The Utilisation of Solid Carbon The Utilisation of Solid Carbon Dioxide in the Extraction of Dioxide in the Extraction of

Extravirgin Olive OilExtravirgin Olive OilVenturi FVenturi F11 Andrich G Andrich G11 Sanmartin C Sanmartin C11 Zoani C Zoani C22 Zappa G Zappa G22 Zinnai A Zinnai A11

1DAFE University of Pisa 2UTAGRI ENEA

3rd International Conference and Exhibition on Food Processing amp

Technology

3rd International Conference and Exhibition on Food Processing amp

Technology

21-23 July Las Vegas USA

Health benefits of EVOO intake

Anti-inflammatory effect

Cardiovascular protection

Digestive health benefits

Anti-cancer activity

Anti-inflammatory effect

Cardiovascular protection

Digestive health benefits

Anti-cancer activity

EVOO is one of the main elements of the Mediterranean diet

EVOO is one of the main elements of the Mediterranean diet

OLIVES

WASHING

CRUSHING

OILWET

RESIDUES

MALAXATION

2-PHASE DECANTER

Extraction Extraction TechnologyTechnology

Yield = Yield = amount of amount of

extracted oilextracted oil

Oil QualityOil Quality

The addition of carbonic snow to grapes to produce The addition of carbonic snow to grapes to produce high quality wines is a largely diffused oenological high quality wines is a largely diffused oenological

practicepractice

CouldCould this technology be usefully this technology be usefully applied in extravirgin olive oil extraction applied in extravirgin olive oil extraction

In order to advance in VOO technology at DAFE of In order to advance in VOO technology at DAFE of University of Pisa an University of Pisa an innovative EVOO extraction innovative EVOO extraction technologytechnology ( (Patent ndeg IT1405173-BPatent ndeg IT1405173-B) involving the ) involving the addition of a cryogen (solid COaddition of a cryogen (solid CO22) to the olives) to the olives were were developed in order to developed in order to increase the extraction increase the extraction yieldyield and to and to obtain an oil characterized by an obtain an oil characterized by an higher concentration of phenolic compounds and a higher concentration of phenolic compounds and a stronger link with the raw material and its stronger link with the raw material and its production areaproduction area

Diffusion of cellular components in the Diffusion of cellular components in the extracellular liquid phase extracellular liquid phase

CELLULAR

CRASH

WATER FREEZING

WATER VOLUME INCREASES

ADDITION CO2s

Mechanical action

Mechanical action

bull Nontoxic and does not leave Nontoxic and does not leave residualresidual

bull Inflammable and less reactiveInflammable and less reactive

bull Good solvent (non-polar)Good solvent (non-polar)

bull Inert by an organoleptic point of Inert by an organoleptic point of viewview

bull Triple point easy to reach (-Triple point easy to reach (-575degC 51atm)575degC 51atm)

bull Easy to find and to useEasy to find and to use

bull Reduced costsReduced costs

bull Anti-microbial and anti-oxidant Anti-microbial and anti-oxidant actionaction

Among all the Among all the possible possible cryogens cryogens

suitable for food suitable for food technology technology

(N(N2L2L He HeLL Ar ArLL etc) etc)

COCO2s2s (or carbonic snow) (or carbonic snow)shows a lot of advantagesshows a lot of advantages

COCO2s2s + Olivesolive paste + Olivesolive paste

Able to prevent Able to prevent the possible the possible oxidation of oxidation of extracted oilextracted oil

Increase of the Increase of the extraction yieldextraction yield

Wished Wished aromatic aromatic profile profile

Higher Higher antioxidant antioxidant

contentcontent

COCO2g2g

Modulation of Modulation of the working the working

variables related variables related toto thethe

MALAXATION MALAXATION

Inert gaseous layer Inert gaseous layer

((COCO22gg airair = 15) = 15)

b) the second goal was to develop specific analytical b) the second goal was to develop specific analytical methods for evaluating the elemental profile of olive methods for evaluating the elemental profile of olive

oil and to collect some preliminary data about the oil and to collect some preliminary data about the possibility to use these methods in order to put in possibility to use these methods in order to put in

evidence the possible influence of different process evidence the possible influence of different process conditions (extraction with or without addition of conditions (extraction with or without addition of carbonic snow) on the olive oil elemental profilecarbonic snow) on the olive oil elemental profile

b) the second goal was to develop specific analytical b) the second goal was to develop specific analytical methods for evaluating the elemental profile of olive methods for evaluating the elemental profile of olive

oil and to collect some preliminary data about the oil and to collect some preliminary data about the possibility to use these methods in order to put in possibility to use these methods in order to put in

evidence the possible influence of different process evidence the possible influence of different process conditions (extraction with or without addition of conditions (extraction with or without addition of carbonic snow) on the olive oil elemental profilecarbonic snow) on the olive oil elemental profile

Aim of the workAim of the work

a) the first goal was to verify the influence of the a) the first goal was to verify the influence of the addition of cryogen (COaddition of cryogen (CO2s2s) directly to olives during ) directly to olives during pre-milling phase on the yield of the oil production pre-milling phase on the yield of the oil production

in order to obtain a preliminary evaluation of the in order to obtain a preliminary evaluation of the suitability of the new proposed methodology for suitability of the new proposed methodology for

EVOO productionEVOO production

The main object of this The main object of this research work is twofoldresearch work is twofold

The main object of this The main object of this research work is twofoldresearch work is twofold

Materials and methodsMaterials and methodsMaterials and methodsMaterials and methods

OIL

1

2

3

4

7

20-30 kg of olivesh

5

The olive crusher utilized Oliomio Baby reg The olive crusher utilized Oliomio Baby reg (TEM)(TEM)

6

Water

CO2(s)

ldquomass cryogenrdquordquomass of fruitsrdquo 02

Wet olive residues

Knife crusher

Horizontal continuous

malaxer 2-phase decanter

Circulation of the thermal fluid

Circulation of the thermal fluid

Addition of cryogen

Addition of cryogen

Thermal probes Thermal probes

Olives Olives

The study were conducted on samples of olive The study were conducted on samples of olive oil produced from monovarietal and oil produced from monovarietal and

polyvarietal (polyvarietal (mixmix) olives collected in two ) olives collected in two different Italian regions (from Tuscany and different Italian regions (from Tuscany and

Basilicata) during the same season Basilicata) during the same season

The study were conducted on samples of olive The study were conducted on samples of olive oil produced from monovarietal and oil produced from monovarietal and

polyvarietal (polyvarietal (mixmix) olives collected in two ) olives collected in two different Italian regions (from Tuscany and different Italian regions (from Tuscany and

Basilicata) during the same season Basilicata) during the same season

The olive fruits utilized in each experimental The olive fruits utilized in each experimental runs (runs ( 60 kg) were preliminary and suitably 60 kg) were preliminary and suitably mixed to ensure homogeneous feeds Each mixed to ensure homogeneous feeds Each sample was split in two fractions (30 kg)sample was split in two fractions (30 kg)

The olive fruits utilized in each experimental The olive fruits utilized in each experimental runs (runs ( 60 kg) were preliminary and suitably 60 kg) were preliminary and suitably mixed to ensure homogeneous feeds Each mixed to ensure homogeneous feeds Each sample was split in two fractions (30 kg)sample was split in two fractions (30 kg)

Traditional extraction

process

Traditional extraction

process

Addition of CO2s

Addition of CO2s

Origin and cultivar of the raw matter Origin and cultivar of the raw matter utilizedutilized

Origin and cultivar of the raw matter Origin and cultivar of the raw matter utilizedutilized

Sample ID Geographical

Cultivar

Traditional

Cryo origin

A 1 Tuscany (GR)

Frantoio

B 2 Tuscany (SI) mix

C 3 Tuscany (SI) mix

D 4 Tuscany (SI) mix

E 5 Basilicata (PZ)

Coratina

F 6 Basilicata (PZ)

Coratina

G 7 Basilicata (PZ)

Coratina

Frantoio Leccino Correggiolo Frantoio Leccino Correggiolo

CryoCryo TraditionalTraditional

Cryogenolives (ww)Cryogenolives (ww) 02 02 00

Temperature of olivesTemperature of olives (degC)(degC) ~-2~-2 115115

Temperature of pasteTemperature of paste (degC)(degC) ~240~240 ~240~240

Time of MalaxationTime of Malaxation (s)(s) 24002400 24002400

Time of ExtractionTime of Extraction (s)(s) 49004900 43004300

Water addedolivesWater addedolives ()() 8585 9393

Main operating variables adopted Main operating variables adopted during the experimental runs during the experimental runs

Total OIL entrance(kg of crushed fruits x of oil inside the olives)

= Total OIL output

(kg of the olive residues x of oil inside the olive residues)

+EXTRACTED OIL

Total OIL entrance(kg of crushed fruits x of oil inside the olives)

= Total OIL output

(kg of the olive residues x of oil inside the olive residues)

+EXTRACTED OIL

MASS BALANCE during extraction MASS BALANCE during extraction processprocess

In order to evaluate the effect induced by the addition of cryogen on the oil extraction yield

the Extractability Index Variation (EIV) was determined as the percentage of the variation of oil extractability using CO2s compared with the same parameter obtained by a traditional

extraction process

In order to evaluate the effect induced by the addition of cryogen on the oil extraction yield

the Extractability Index Variation (EIV) was determined as the percentage of the variation of oil extractability using CO2s compared with the same parameter obtained by a traditional

extraction process EIV = (EC-ET)ET EIV = (EC-ET)ET 100 100EIV = (EC-ET)ET EIV = (EC-ET)ET 100 100

Results and Results and discussiondiscussion

Results and Results and discussiondiscussion

Oil extraction Oil extraction yield yield

preliminary preliminary resultsresults

Oil extraction yield Oil extraction yield preliminary preliminary resultsresults

Oil extraction yield Oil extraction yield preliminary preliminary resultsresults

Run EC ET

1A 858 825

2B 855 772

3C 912 827

4D 841 748

5E 808 793

6F 736 689

7G 844 774

The direct addition of cryogen to the olives during pre-milling phase could induce a general increase in the oil extraction yield ranging from 2 to

124

The direct addition of cryogen to the olives during pre-milling phase could induce a general increase in the oil extraction yield ranging from 2 to

124

[(EC-ET)ET]10040 108 103 124 19 68 90

[(EC-ET)ET]10040 108 103 124 19 68 90

Preliminary results about oil extraction Preliminary results about oil extraction yield yield discussion Idiscussion I

Preliminary results about oil extraction Preliminary results about oil extraction yield yield discussion Idiscussion I

The number of the experimental runs carried out until now is quite reduced

The number of the experimental runs carried out until now is quite reduced

BUTBUT

The results appear very encouraging and the new method seems very suitable for olive oil extraction

The results appear very encouraging and the new method seems very suitable for olive oil extraction

During the next crop season we will increase the number of experimental runs adopting several combinations of the working parameters (ie amount of cryogenamount of olives fruit ripening stage etc)

During the next crop season we will increase the number of experimental runs adopting several combinations of the working parameters (ie amount of cryogenamount of olives fruit ripening stage etc)

Preliminary results about oil extraction Preliminary results about oil extraction yield yield discussion IIdiscussion II

Preliminary results about oil extraction Preliminary results about oil extraction yield yield discussion IIdiscussion II

If necessary this method allows to move up the olive harvest time in order to greatly reduce the damages due to the third fly attack of Bactrocera oleae that can induce a significant loss in oil production (up to 60) as well as a decrease in oil quality

If necessary this method allows to move up the olive harvest time in order to greatly reduce the damages due to the third fly attack of Bactrocera oleae that can induce a significant loss in oil production (up to 60) as well as a decrease in oil quality

Water content

inside the fruit

Water content

inside the fruit

CELLULAR CRASH

We need 08 kg of CO2s to lower 100 kg of olives temperature by 1degC

Cost of 1 kg of CO2s= euro050 $ 037

Cost to turn down the average temperature of 100

kg of olives by 10degC(15degC 5degC )

08kgdegC x 10degC x 037 $kg=

3 $

Considering an average oil yield of 15

The addition cost for a kg of extravirgin olive oil is

3 $100 kg olives x 15100kg oilkg olives

lt 02$kg oil

Oil elemental Oil elemental profile profile

preliminary preliminary resultsresults

ICP-AES and ICP-MS techniques are particularly advantageous for the application in the definition of the elemental profiles of olive oil since they allow simultaneous multi-elemental analysis and are characterized by wide linear ranges and (especially ICP-MS) very low Detection Limits

Main analytical issues are related to the hard organic content of the oil matrix which requires appropriate sample pre-treatments Microwave-assisted digestion permitted to obtain a complete dissolution of olive oil samples but resulted in the obtainment of highly acidic solutions not directly analyzable by ICP-MS with a consequent reduction of sensitivity (due to the preliminary 110 dilution of the mineralized olive oil)

ETV

LA

Preliminary results about oil elemental Preliminary results about oil elemental profileprofile

Preliminary results about oil elemental Preliminary results about oil elemental profileprofile

Preliminary results show a rather homogeneous elemental content among all the analyzed samples of olive oil

For all elements experimental concentrations fall within the ranges reported in literature In respect to these ranges analyzed samples show a high content of B S and Si while Fe Na Pb Ba Cr and Cu contents are quite low

Samples of olive oil obtained by the traditionalldquo process show - in general - a higher content of Ca Cr Mg Si (except those originating from Basilicata) and Zn compared to those obtained by the addition of ldquocarbonic snowldquo

0

20

40

60

80

100

120

140

B Ca Fe Na S Si

mgk

g

000

050

100

150

200

250

300

350

400

450

500

Al K Mg P Zn

mgk

g

0

500

1000

1500

2000

2500

3000

3500

Co Cr Cu Ni Pb

microgk

g

0

2

4

6

8

10

12

14

16

Ce Er Eu Gd La Nd Pr Sm Y Yb

microgk

g

0

100

200

300

400

500

600

700

800

As Ba Cd Li Mn Rb Sb Sc Se Sr Th Ti V

microgk

g

4000 25000

0

20

40

60

80

100

120

140

160

Ca

Na

Si

concentration range obtained from literature [2]

experimental concentration range ICP-AESDetection LimitICP-MSDetection Limit - Normal Sensitivity modeICP-MSDetection Limit - High Sensitivitymode

S B Yasar E K Baran M Alkan Metal determinations in olive oil In Olive Oil ndash Constituents Quality Health Properties and Bioconversions Ed by Boskou Dimitrios 5 89-108 2012

Preliminary results about oil elemental Preliminary results about oil elemental profileprofile

Preliminary results about oil elemental Preliminary results about oil elemental profileprofile

For any further details about the second part of the research you can contact our colleagues in ENEA

claudiazoanieneait giovannazappaeneait

For any further details about the second part of the research you can contact our colleagues in ENEA

claudiazoanieneait giovannazappaeneait

ReferencesReferencesReferencesReferences

The Utilization of Solid Carbon Dioxide in the Production of Extravirgin Olive Oil

Sanmartin C Zinnai A Venturi F Andrich G Proceedings of EFFOST 2011 9-11 November 2011 Berlino

(D)

Analytical methods for olive oil elemental profile and influence of carbonic snow addition in the extraction

phase C Zoani G Zappa A Zinnai F Venturi C Sanmartin

11th Euro Fed Lipid Congress ndash Antalya (Turkey) 27-30 October 2013

Preliminary results on the influence of carbonic snow addition during the olive processing oil extraction yield

and elemental profile C Zoani G Zappa F Venturi C Sanmartin G Andrich and

A ZinnaiJournal of Nutrition and Food Sciences 4 277 (2014)

doi 1041722155-96001000277

The Utilization of Solid Carbon Dioxide in the Production of Extravirgin Olive Oil

Sanmartin C Zinnai A Venturi F Andrich G Proceedings of EFFOST 2011 9-11 November 2011 Berlino

(D)

Analytical methods for olive oil elemental profile and influence of carbonic snow addition in the extraction

phase C Zoani G Zappa A Zinnai F Venturi C Sanmartin

11th Euro Fed Lipid Congress ndash Antalya (Turkey) 27-30 October 2013

Preliminary results on the influence of carbonic snow addition during the olive processing oil extraction yield

and elemental profile C Zoani G Zappa F Venturi C Sanmartin G Andrich and

A ZinnaiJournal of Nutrition and Food Sciences 4 277 (2014)

doi 1041722155-96001000277

Research in progresshellipResearch in progresshellip

Thank you for your attention

Thank you for your attention

research supported by

It will be possible to apply matrix modification procedures (eg solvent extraction ndash also ultrasound assisted - addition of organic solvents or emulsification) or to employ systems for direct oil sample introduction in torch (eg Flow Injection Analysis systems)

We are conducting experimental tests for evaluating the possibility to employ a Laser Ablation system or an ElectroThermal Vaporization system for direct sample introduction in ICP-AES and ICP-MS

ETV

LA

Future developmentsFuture developmentsFuture developmentsFuture developments

Determination of oil elemental profile sample pre-treatment

High PressureMicrowave Digestion

Milestone 1200 Mega

05 golive oil

Mineralized oil sample

(final V = 25 ml)

2 ml H2O2 + 6 ml HNO3

Different mixtures testedH2O2 30vv (1 divide 2 ml)+ HNO3 699vv (2 divide

6 ml)

Total dissoluti

on

high-purity water

(gt 18 MΩ)

time Power Pressure

1 min 250 WFree

pressure race

1 min 0 W

5 min 400 W

5 min 650 W

Vent = 5 min

TQ mineralized

olive oil solution

Varian Vista MPX(axial configuration

simultaneous 112 Mpixel CCD detector)

study of spectral interferencesstudy of spectral interferences

preliminary qualitative analysis72 elements

preliminary qualitative analysis72 elements

quantitative analysisquantitative analysis

Gas flows optimization based on signal-to-background ratio (SB)

Auxiliary flow (lmin)

Nebulizer flow(lmin)

10 15 09 10 11 12

SBMg 3296 11720 13948 17998 19921 18412Mn 0128 0197 0245 0312 0303 0294Na 1827 1940 1827 3187 6121 4371

Zn - 213857 nm more sensitive but interfered by Fe

Zn - 206200 nm - less sensitive but without interferences

Analytical wavelengths (nm)

Al - 396152 nm K - 766491 nm Rb - 780026 nm

As - 188980 nm Li - 670783 nm S - 181972 nm

B - 249772 nm Mg - 279553 nm Sb - 206834 nm

Ba - 455403 nm Mn - 257610 nm Si - 251611 nm

Ca - 396847 nm Na - 589592 nm Sr - 407771 nm

Cr - 267716 nm Ni - 231604 nm Ti - 334941 nm

Cu - 327395 nm P - 213618 nm V - 311837 nm

Fe - 238204 nm Pb - 220353 nm Zn ndash 206200 nm

Instrumental conditions

RF Frequency 40 MHz (free running air-cooled)

RF Power 12 kW

Gas (plasma auxiliary nebulizer) Argon

Plasma flow 150 lmin

Auxiliary flow 15 lmin

Nebulizer flow 110 lmin

Replicates 5

Replicate read time 5 s

Operating parameters for ICP-AES quantitative analysis

ICP-AES Analysis

Bruker Aurora M90 (90 degree ion mirror ion optics Collision Reaction Interface)110 diluted

mineralized olive oil solution

Tuning with a 5 microgl Be Mg Co In Ba Ce Ti Pb and Th solution for

sensitivity and resolution optimization and mass calibration

Tuning with a 5 microgl Be Mg Co In Ba Ce Ti Pb and Th solution for

sensitivity and resolution optimization and mass calibration

Check of the level of oxide ions by the CeO+Ce+ ratio lt 2

Check of the level of oxide ions by the CeO+Ce+ ratio lt 2

Monitoring of double charged ions by the signal 137Ba++137Ba+ lt 3

Monitoring of double charged ions by the signal 137Ba++137Ba+ lt 3

CheckCorrection of isobaric interferences examination of more isotopes of the same element(eg Rb85 Rb 87 Sr88Sr87 Nd142 Nd146 Nd144 Se77 Se78 Sn147 Sm148 Sm152 Gd157 Gd154 Er166 Er168 Yb170 Yb172) application of correction equations with respect to isotopes of other elements potentially interfering (eg Nd142 corrected by analyzing Ce140 Nd144 by Sm147 Sm152 by Gd157 Rb87 by Sr88 ) use of the Collision Reaction Interface ndash CRI (for As and Se)

CheckCorrection of isobaric interferences examination of more isotopes of the same element(eg Rb85 Rb 87 Sr88Sr87 Nd142 Nd146 Nd144 Se77 Se78 Sn147 Sm148 Sm152 Gd157 Gd154 Er166 Er168 Yb170 Yb172) application of correction equations with respect to isotopes of other elements potentially interfering (eg Nd142 corrected by analyzing Ce140 Nd144 by Sm147 Sm152 by Gd157 Rb87 by Sr88 ) use of the Collision Reaction Interface ndash CRI (for As and Se)

Working rangesbull005 divide 5 microgl - As Cd Ce Er Eu Gd La Mn Nd Pb Pr Rb Sb Sc Se Sm Sr Th V Y Ybbull01 divide 10 microgl - Co Cr Cu Mg Ni

Working rangesbull005 divide 5 microgl - As Cd Ce Er Eu Gd La Mn Nd Pb Pr Rb Sb Sc Se Sm Sr Th V Y Ybbull01 divide 10 microgl - Co Cr Cu Mg Ni

External calibration5 standard solutions + blankCurve Fit LinearWeighted Fit NoCorrelation coefficientsR gt 09999

Normal Sensitivity Mode (without CRI) High Sensitivity Mode As and Se ndash Normal mode with CRI

ICP-MS Analysis

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• Slide 27
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• Slide 33
• Slide 34
• Slide 35

Health benefits of EVOO intake

Anti-inflammatory effect

Cardiovascular protection

Digestive health benefits

Anti-cancer activity

Anti-inflammatory effect

Cardiovascular protection

Digestive health benefits

Anti-cancer activity

EVOO is one of the main elements of the Mediterranean diet

EVOO is one of the main elements of the Mediterranean diet

OLIVES

WASHING

CRUSHING

OILWET

RESIDUES

MALAXATION

2-PHASE DECANTER

Extraction Extraction TechnologyTechnology

Yield = Yield = amount of amount of

extracted oilextracted oil

Oil QualityOil Quality

The addition of carbonic snow to grapes to produce The addition of carbonic snow to grapes to produce high quality wines is a largely diffused oenological high quality wines is a largely diffused oenological

practicepractice

CouldCould this technology be usefully this technology be usefully applied in extravirgin olive oil extraction applied in extravirgin olive oil extraction

In order to advance in VOO technology at DAFE of In order to advance in VOO technology at DAFE of University of Pisa an University of Pisa an innovative EVOO extraction innovative EVOO extraction technologytechnology ( (Patent ndeg IT1405173-BPatent ndeg IT1405173-B) involving the ) involving the addition of a cryogen (solid COaddition of a cryogen (solid CO22) to the olives) to the olives were were developed in order to developed in order to increase the extraction increase the extraction yieldyield and to and to obtain an oil characterized by an obtain an oil characterized by an higher concentration of phenolic compounds and a higher concentration of phenolic compounds and a stronger link with the raw material and its stronger link with the raw material and its production areaproduction area

Diffusion of cellular components in the Diffusion of cellular components in the extracellular liquid phase extracellular liquid phase

CELLULAR

CRASH

WATER FREEZING

WATER VOLUME INCREASES

ADDITION CO2s

Mechanical action

Mechanical action

bull Nontoxic and does not leave Nontoxic and does not leave residualresidual

bull Inflammable and less reactiveInflammable and less reactive

bull Good solvent (non-polar)Good solvent (non-polar)

bull Inert by an organoleptic point of Inert by an organoleptic point of viewview

bull Triple point easy to reach (-Triple point easy to reach (-575degC 51atm)575degC 51atm)

bull Easy to find and to useEasy to find and to use

bull Reduced costsReduced costs

bull Anti-microbial and anti-oxidant Anti-microbial and anti-oxidant actionaction

Among all the Among all the possible possible cryogens cryogens

suitable for food suitable for food technology technology

(N(N2L2L He HeLL Ar ArLL etc) etc)

COCO2s2s (or carbonic snow) (or carbonic snow)shows a lot of advantagesshows a lot of advantages

COCO2s2s + Olivesolive paste + Olivesolive paste

Able to prevent Able to prevent the possible the possible oxidation of oxidation of extracted oilextracted oil

Increase of the Increase of the extraction yieldextraction yield

Wished Wished aromatic aromatic profile profile

Higher Higher antioxidant antioxidant

contentcontent

COCO2g2g

Modulation of Modulation of the working the working

variables related variables related toto thethe

MALAXATION MALAXATION

Inert gaseous layer Inert gaseous layer

((COCO22gg airair = 15) = 15)

b) the second goal was to develop specific analytical b) the second goal was to develop specific analytical methods for evaluating the elemental profile of olive methods for evaluating the elemental profile of olive

oil and to collect some preliminary data about the oil and to collect some preliminary data about the possibility to use these methods in order to put in possibility to use these methods in order to put in

evidence the possible influence of different process evidence the possible influence of different process conditions (extraction with or without addition of conditions (extraction with or without addition of carbonic snow) on the olive oil elemental profilecarbonic snow) on the olive oil elemental profile

b) the second goal was to develop specific analytical b) the second goal was to develop specific analytical methods for evaluating the elemental profile of olive methods for evaluating the elemental profile of olive

oil and to collect some preliminary data about the oil and to collect some preliminary data about the possibility to use these methods in order to put in possibility to use these methods in order to put in

evidence the possible influence of different process evidence the possible influence of different process conditions (extraction with or without addition of conditions (extraction with or without addition of carbonic snow) on the olive oil elemental profilecarbonic snow) on the olive oil elemental profile

Aim of the workAim of the work

a) the first goal was to verify the influence of the a) the first goal was to verify the influence of the addition of cryogen (COaddition of cryogen (CO2s2s) directly to olives during ) directly to olives during pre-milling phase on the yield of the oil production pre-milling phase on the yield of the oil production

in order to obtain a preliminary evaluation of the in order to obtain a preliminary evaluation of the suitability of the new proposed methodology for suitability of the new proposed methodology for

EVOO productionEVOO production

The main object of this The main object of this research work is twofoldresearch work is twofold

The main object of this The main object of this research work is twofoldresearch work is twofold

Materials and methodsMaterials and methodsMaterials and methodsMaterials and methods

OIL

1

2

3

4

7

20-30 kg of olivesh

5

The olive crusher utilized Oliomio Baby reg The olive crusher utilized Oliomio Baby reg (TEM)(TEM)

6

Water

CO2(s)

ldquomass cryogenrdquordquomass of fruitsrdquo 02

Wet olive residues

Knife crusher

Horizontal continuous

malaxer 2-phase decanter

Circulation of the thermal fluid

Circulation of the thermal fluid

Addition of cryogen

Addition of cryogen

Thermal probes Thermal probes

Olives Olives

The study were conducted on samples of olive The study were conducted on samples of olive oil produced from monovarietal and oil produced from monovarietal and

polyvarietal (polyvarietal (mixmix) olives collected in two ) olives collected in two different Italian regions (from Tuscany and different Italian regions (from Tuscany and

Basilicata) during the same season Basilicata) during the same season

The study were conducted on samples of olive The study were conducted on samples of olive oil produced from monovarietal and oil produced from monovarietal and

polyvarietal (polyvarietal (mixmix) olives collected in two ) olives collected in two different Italian regions (from Tuscany and different Italian regions (from Tuscany and

Basilicata) during the same season Basilicata) during the same season

The olive fruits utilized in each experimental The olive fruits utilized in each experimental runs (runs ( 60 kg) were preliminary and suitably 60 kg) were preliminary and suitably mixed to ensure homogeneous feeds Each mixed to ensure homogeneous feeds Each sample was split in two fractions (30 kg)sample was split in two fractions (30 kg)

The olive fruits utilized in each experimental The olive fruits utilized in each experimental runs (runs ( 60 kg) were preliminary and suitably 60 kg) were preliminary and suitably mixed to ensure homogeneous feeds Each mixed to ensure homogeneous feeds Each sample was split in two fractions (30 kg)sample was split in two fractions (30 kg)

Traditional extraction

process

Traditional extraction

process

Addition of CO2s

Addition of CO2s

Origin and cultivar of the raw matter Origin and cultivar of the raw matter utilizedutilized

Origin and cultivar of the raw matter Origin and cultivar of the raw matter utilizedutilized

Sample ID Geographical

Cultivar

Traditional

Cryo origin

A 1 Tuscany (GR)

Frantoio

B 2 Tuscany (SI) mix

C 3 Tuscany (SI) mix

D 4 Tuscany (SI) mix

E 5 Basilicata (PZ)

Coratina

F 6 Basilicata (PZ)

Coratina

G 7 Basilicata (PZ)

Coratina

Frantoio Leccino Correggiolo Frantoio Leccino Correggiolo

CryoCryo TraditionalTraditional

Cryogenolives (ww)Cryogenolives (ww) 02 02 00

Temperature of olivesTemperature of olives (degC)(degC) ~-2~-2 115115

Temperature of pasteTemperature of paste (degC)(degC) ~240~240 ~240~240

Time of MalaxationTime of Malaxation (s)(s) 24002400 24002400

Time of ExtractionTime of Extraction (s)(s) 49004900 43004300

Water addedolivesWater addedolives ()() 8585 9393

Main operating variables adopted Main operating variables adopted during the experimental runs during the experimental runs

Total OIL entrance(kg of crushed fruits x of oil inside the olives)

= Total OIL output

(kg of the olive residues x of oil inside the olive residues)

+EXTRACTED OIL

Total OIL entrance(kg of crushed fruits x of oil inside the olives)

= Total OIL output

(kg of the olive residues x of oil inside the olive residues)

+EXTRACTED OIL

MASS BALANCE during extraction MASS BALANCE during extraction processprocess

In order to evaluate the effect induced by the addition of cryogen on the oil extraction yield

the Extractability Index Variation (EIV) was determined as the percentage of the variation of oil extractability using CO2s compared with the same parameter obtained by a traditional

extraction process

In order to evaluate the effect induced by the addition of cryogen on the oil extraction yield

the Extractability Index Variation (EIV) was determined as the percentage of the variation of oil extractability using CO2s compared with the same parameter obtained by a traditional

extraction process EIV = (EC-ET)ET EIV = (EC-ET)ET 100 100EIV = (EC-ET)ET EIV = (EC-ET)ET 100 100

Results and Results and discussiondiscussion

Results and Results and discussiondiscussion

Oil extraction Oil extraction yield yield

preliminary preliminary resultsresults

Oil extraction yield Oil extraction yield preliminary preliminary resultsresults

Oil extraction yield Oil extraction yield preliminary preliminary resultsresults

Run EC ET

1A 858 825

2B 855 772

3C 912 827

4D 841 748

5E 808 793

6F 736 689

7G 844 774

The direct addition of cryogen to the olives during pre-milling phase could induce a general increase in the oil extraction yield ranging from 2 to

124

The direct addition of cryogen to the olives during pre-milling phase could induce a general increase in the oil extraction yield ranging from 2 to

124

[(EC-ET)ET]10040 108 103 124 19 68 90

[(EC-ET)ET]10040 108 103 124 19 68 90

Preliminary results about oil extraction Preliminary results about oil extraction yield yield discussion Idiscussion I

Preliminary results about oil extraction Preliminary results about oil extraction yield yield discussion Idiscussion I

The number of the experimental runs carried out until now is quite reduced

The number of the experimental runs carried out until now is quite reduced

BUTBUT

The results appear very encouraging and the new method seems very suitable for olive oil extraction

The results appear very encouraging and the new method seems very suitable for olive oil extraction

During the next crop season we will increase the number of experimental runs adopting several combinations of the working parameters (ie amount of cryogenamount of olives fruit ripening stage etc)

During the next crop season we will increase the number of experimental runs adopting several combinations of the working parameters (ie amount of cryogenamount of olives fruit ripening stage etc)

Preliminary results about oil extraction Preliminary results about oil extraction yield yield discussion IIdiscussion II

Preliminary results about oil extraction Preliminary results about oil extraction yield yield discussion IIdiscussion II

If necessary this method allows to move up the olive harvest time in order to greatly reduce the damages due to the third fly attack of Bactrocera oleae that can induce a significant loss in oil production (up to 60) as well as a decrease in oil quality

If necessary this method allows to move up the olive harvest time in order to greatly reduce the damages due to the third fly attack of Bactrocera oleae that can induce a significant loss in oil production (up to 60) as well as a decrease in oil quality

Water content

inside the fruit

Water content

inside the fruit

CELLULAR CRASH

We need 08 kg of CO2s to lower 100 kg of olives temperature by 1degC

Cost of 1 kg of CO2s= euro050 $ 037

Cost to turn down the average temperature of 100

kg of olives by 10degC(15degC 5degC )

08kgdegC x 10degC x 037 $kg=

3 $

Considering an average oil yield of 15

The addition cost for a kg of extravirgin olive oil is

3 $100 kg olives x 15100kg oilkg olives

lt 02$kg oil

Oil elemental Oil elemental profile profile

preliminary preliminary resultsresults

ICP-AES and ICP-MS techniques are particularly advantageous for the application in the definition of the elemental profiles of olive oil since they allow simultaneous multi-elemental analysis and are characterized by wide linear ranges and (especially ICP-MS) very low Detection Limits

Main analytical issues are related to the hard organic content of the oil matrix which requires appropriate sample pre-treatments Microwave-assisted digestion permitted to obtain a complete dissolution of olive oil samples but resulted in the obtainment of highly acidic solutions not directly analyzable by ICP-MS with a consequent reduction of sensitivity (due to the preliminary 110 dilution of the mineralized olive oil)

ETV

LA

Preliminary results about oil elemental Preliminary results about oil elemental profileprofile

Preliminary results about oil elemental Preliminary results about oil elemental profileprofile

Preliminary results show a rather homogeneous elemental content among all the analyzed samples of olive oil

For all elements experimental concentrations fall within the ranges reported in literature In respect to these ranges analyzed samples show a high content of B S and Si while Fe Na Pb Ba Cr and Cu contents are quite low

Samples of olive oil obtained by the traditionalldquo process show - in general - a higher content of Ca Cr Mg Si (except those originating from Basilicata) and Zn compared to those obtained by the addition of ldquocarbonic snowldquo

0

20

40

60

80

100

120

140

B Ca Fe Na S Si

mgk

g

000

050

100

150

200

250

300

350

400

450

500

Al K Mg P Zn

mgk

g

0

500

1000

1500

2000

2500

3000

3500

Co Cr Cu Ni Pb

microgk

g

0

2

4

6

8

10

12

14

16

Ce Er Eu Gd La Nd Pr Sm Y Yb

microgk

g

0

100

200

300

400

500

600

700

800

As Ba Cd Li Mn Rb Sb Sc Se Sr Th Ti V

microgk

g

4000 25000

0

20

40

60

80

100

120

140

160

Ca

Na

Si

concentration range obtained from literature [2]

experimental concentration range ICP-AESDetection LimitICP-MSDetection Limit - Normal Sensitivity modeICP-MSDetection Limit - High Sensitivitymode

S B Yasar E K Baran M Alkan Metal determinations in olive oil In Olive Oil ndash Constituents Quality Health Properties and Bioconversions Ed by Boskou Dimitrios 5 89-108 2012

Preliminary results about oil elemental Preliminary results about oil elemental profileprofile

Preliminary results about oil elemental Preliminary results about oil elemental profileprofile

For any further details about the second part of the research you can contact our colleagues in ENEA

claudiazoanieneait giovannazappaeneait

For any further details about the second part of the research you can contact our colleagues in ENEA

claudiazoanieneait giovannazappaeneait

ReferencesReferencesReferencesReferences

The Utilization of Solid Carbon Dioxide in the Production of Extravirgin Olive Oil

Sanmartin C Zinnai A Venturi F Andrich G Proceedings of EFFOST 2011 9-11 November 2011 Berlino

(D)

Analytical methods for olive oil elemental profile and influence of carbonic snow addition in the extraction

phase C Zoani G Zappa A Zinnai F Venturi C Sanmartin

11th Euro Fed Lipid Congress ndash Antalya (Turkey) 27-30 October 2013

Preliminary results on the influence of carbonic snow addition during the olive processing oil extraction yield

and elemental profile C Zoani G Zappa F Venturi C Sanmartin G Andrich and

A ZinnaiJournal of Nutrition and Food Sciences 4 277 (2014)

doi 1041722155-96001000277

The Utilization of Solid Carbon Dioxide in the Production of Extravirgin Olive Oil

Sanmartin C Zinnai A Venturi F Andrich G Proceedings of EFFOST 2011 9-11 November 2011 Berlino

(D)

Analytical methods for olive oil elemental profile and influence of carbonic snow addition in the extraction

phase C Zoani G Zappa A Zinnai F Venturi C Sanmartin

11th Euro Fed Lipid Congress ndash Antalya (Turkey) 27-30 October 2013

Preliminary results on the influence of carbonic snow addition during the olive processing oil extraction yield

and elemental profile C Zoani G Zappa F Venturi C Sanmartin G Andrich and

A ZinnaiJournal of Nutrition and Food Sciences 4 277 (2014)

doi 1041722155-96001000277

Research in progresshellipResearch in progresshellip

Thank you for your attention

Thank you for your attention

research supported by

It will be possible to apply matrix modification procedures (eg solvent extraction ndash also ultrasound assisted - addition of organic solvents or emulsification) or to employ systems for direct oil sample introduction in torch (eg Flow Injection Analysis systems)

We are conducting experimental tests for evaluating the possibility to employ a Laser Ablation system or an ElectroThermal Vaporization system for direct sample introduction in ICP-AES and ICP-MS

ETV

LA

Future developmentsFuture developmentsFuture developmentsFuture developments

Determination of oil elemental profile sample pre-treatment

High PressureMicrowave Digestion

Milestone 1200 Mega

05 golive oil

Mineralized oil sample

(final V = 25 ml)

2 ml H2O2 + 6 ml HNO3

Different mixtures testedH2O2 30vv (1 divide 2 ml)+ HNO3 699vv (2 divide

6 ml)

Total dissoluti

on

high-purity water

(gt 18 MΩ)

time Power Pressure

1 min 250 WFree

pressure race

1 min 0 W

5 min 400 W

5 min 650 W

Vent = 5 min

TQ mineralized

olive oil solution

Varian Vista MPX(axial configuration

simultaneous 112 Mpixel CCD detector)

study of spectral interferencesstudy of spectral interferences

preliminary qualitative analysis72 elements

preliminary qualitative analysis72 elements

quantitative analysisquantitative analysis

Gas flows optimization based on signal-to-background ratio (SB)

Auxiliary flow (lmin)

Nebulizer flow(lmin)

10 15 09 10 11 12

SBMg 3296 11720 13948 17998 19921 18412Mn 0128 0197 0245 0312 0303 0294Na 1827 1940 1827 3187 6121 4371

Zn - 213857 nm more sensitive but interfered by Fe

Zn - 206200 nm - less sensitive but without interferences

Analytical wavelengths (nm)

Al - 396152 nm K - 766491 nm Rb - 780026 nm

As - 188980 nm Li - 670783 nm S - 181972 nm

B - 249772 nm Mg - 279553 nm Sb - 206834 nm

Ba - 455403 nm Mn - 257610 nm Si - 251611 nm

Ca - 396847 nm Na - 589592 nm Sr - 407771 nm

Cr - 267716 nm Ni - 231604 nm Ti - 334941 nm

Cu - 327395 nm P - 213618 nm V - 311837 nm

Fe - 238204 nm Pb - 220353 nm Zn ndash 206200 nm

Instrumental conditions

RF Frequency 40 MHz (free running air-cooled)

RF Power 12 kW

Gas (plasma auxiliary nebulizer) Argon

Plasma flow 150 lmin

Auxiliary flow 15 lmin

Nebulizer flow 110 lmin

Replicates 5

Replicate read time 5 s

Operating parameters for ICP-AES quantitative analysis

ICP-AES Analysis

Bruker Aurora M90 (90 degree ion mirror ion optics Collision Reaction Interface)110 diluted

mineralized olive oil solution

Tuning with a 5 microgl Be Mg Co In Ba Ce Ti Pb and Th solution for

sensitivity and resolution optimization and mass calibration

Tuning with a 5 microgl Be Mg Co In Ba Ce Ti Pb and Th solution for

sensitivity and resolution optimization and mass calibration

Check of the level of oxide ions by the CeO+Ce+ ratio lt 2

Check of the level of oxide ions by the CeO+Ce+ ratio lt 2

Monitoring of double charged ions by the signal 137Ba++137Ba+ lt 3

Monitoring of double charged ions by the signal 137Ba++137Ba+ lt 3

CheckCorrection of isobaric interferences examination of more isotopes of the same element(eg Rb85 Rb 87 Sr88Sr87 Nd142 Nd146 Nd144 Se77 Se78 Sn147 Sm148 Sm152 Gd157 Gd154 Er166 Er168 Yb170 Yb172) application of correction equations with respect to isotopes of other elements potentially interfering (eg Nd142 corrected by analyzing Ce140 Nd144 by Sm147 Sm152 by Gd157 Rb87 by Sr88 ) use of the Collision Reaction Interface ndash CRI (for As and Se)

CheckCorrection of isobaric interferences examination of more isotopes of the same element(eg Rb85 Rb 87 Sr88Sr87 Nd142 Nd146 Nd144 Se77 Se78 Sn147 Sm148 Sm152 Gd157 Gd154 Er166 Er168 Yb170 Yb172) application of correction equations with respect to isotopes of other elements potentially interfering (eg Nd142 corrected by analyzing Ce140 Nd144 by Sm147 Sm152 by Gd157 Rb87 by Sr88 ) use of the Collision Reaction Interface ndash CRI (for As and Se)

Working rangesbull005 divide 5 microgl - As Cd Ce Er Eu Gd La Mn Nd Pb Pr Rb Sb Sc Se Sm Sr Th V Y Ybbull01 divide 10 microgl - Co Cr Cu Mg Ni

Working rangesbull005 divide 5 microgl - As Cd Ce Er Eu Gd La Mn Nd Pb Pr Rb Sb Sc Se Sm Sr Th V Y Ybbull01 divide 10 microgl - Co Cr Cu Mg Ni

External calibration5 standard solutions + blankCurve Fit LinearWeighted Fit NoCorrelation coefficientsR gt 09999

Normal Sensitivity Mode (without CRI) High Sensitivity Mode As and Se ndash Normal mode with CRI

ICP-MS Analysis

• Slide 1
• Slide 2
• Slide 3
• Slide 4
• Slide 5
• Slide 6
• Slide 7
• Slide 8
• Slide 9
• Slide 10
• Slide 11
• Slide 12
• Slide 13
• Slide 14
• Slide 15
• Slide 16
• Slide 17
• Slide 18
• Slide 19
• Slide 20
• Slide 21
• Slide 22
• Slide 23
• Slide 24
• Slide 25
• Slide 26
• Slide 27
• Slide 28
• Slide 29
• Slide 30
• Slide 31
• Slide 32
• Slide 33
• Slide 34
• Slide 35

OLIVES

WASHING

CRUSHING

OILWET

RESIDUES

MALAXATION

2-PHASE DECANTER

Extraction Extraction TechnologyTechnology

Yield = Yield = amount of amount of

extracted oilextracted oil

Oil QualityOil Quality

The addition of carbonic snow to grapes to produce The addition of carbonic snow to grapes to produce high quality wines is a largely diffused oenological high quality wines is a largely diffused oenological

practicepractice

CouldCould this technology be usefully this technology be usefully applied in extravirgin olive oil extraction applied in extravirgin olive oil extraction

In order to advance in VOO technology at DAFE of In order to advance in VOO technology at DAFE of University of Pisa an University of Pisa an innovative EVOO extraction innovative EVOO extraction technologytechnology ( (Patent ndeg IT1405173-BPatent ndeg IT1405173-B) involving the ) involving the addition of a cryogen (solid COaddition of a cryogen (solid CO22) to the olives) to the olives were were developed in order to developed in order to increase the extraction increase the extraction yieldyield and to and to obtain an oil characterized by an obtain an oil characterized by an higher concentration of phenolic compounds and a higher concentration of phenolic compounds and a stronger link with the raw material and its stronger link with the raw material and its production areaproduction area

Diffusion of cellular components in the Diffusion of cellular components in the extracellular liquid phase extracellular liquid phase

CELLULAR

CRASH

WATER FREEZING

WATER VOLUME INCREASES

ADDITION CO2s

Mechanical action

Mechanical action

bull Nontoxic and does not leave Nontoxic and does not leave residualresidual

bull Inflammable and less reactiveInflammable and less reactive

bull Good solvent (non-polar)Good solvent (non-polar)

bull Inert by an organoleptic point of Inert by an organoleptic point of viewview

bull Triple point easy to reach (-Triple point easy to reach (-575degC 51atm)575degC 51atm)

bull Easy to find and to useEasy to find and to use

bull Reduced costsReduced costs

bull Anti-microbial and anti-oxidant Anti-microbial and anti-oxidant actionaction

Among all the Among all the possible possible cryogens cryogens

suitable for food suitable for food technology technology

(N(N2L2L He HeLL Ar ArLL etc) etc)

COCO2s2s (or carbonic snow) (or carbonic snow)shows a lot of advantagesshows a lot of advantages

COCO2s2s + Olivesolive paste + Olivesolive paste

Able to prevent Able to prevent the possible the possible oxidation of oxidation of extracted oilextracted oil

Increase of the Increase of the extraction yieldextraction yield

Wished Wished aromatic aromatic profile profile

Higher Higher antioxidant antioxidant

contentcontent

COCO2g2g

Modulation of Modulation of the working the working

variables related variables related toto thethe

MALAXATION MALAXATION

Inert gaseous layer Inert gaseous layer

((COCO22gg airair = 15) = 15)

b) the second goal was to develop specific analytical b) the second goal was to develop specific analytical methods for evaluating the elemental profile of olive methods for evaluating the elemental profile of olive

oil and to collect some preliminary data about the oil and to collect some preliminary data about the possibility to use these methods in order to put in possibility to use these methods in order to put in

evidence the possible influence of different process evidence the possible influence of different process conditions (extraction with or without addition of conditions (extraction with or without addition of carbonic snow) on the olive oil elemental profilecarbonic snow) on the olive oil elemental profile

b) the second goal was to develop specific analytical b) the second goal was to develop specific analytical methods for evaluating the elemental profile of olive methods for evaluating the elemental profile of olive

oil and to collect some preliminary data about the oil and to collect some preliminary data about the possibility to use these methods in order to put in possibility to use these methods in order to put in

evidence the possible influence of different process evidence the possible influence of different process conditions (extraction with or without addition of conditions (extraction with or without addition of carbonic snow) on the olive oil elemental profilecarbonic snow) on the olive oil elemental profile

Aim of the workAim of the work

a) the first goal was to verify the influence of the a) the first goal was to verify the influence of the addition of cryogen (COaddition of cryogen (CO2s2s) directly to olives during ) directly to olives during pre-milling phase on the yield of the oil production pre-milling phase on the yield of the oil production

in order to obtain a preliminary evaluation of the in order to obtain a preliminary evaluation of the suitability of the new proposed methodology for suitability of the new proposed methodology for

EVOO productionEVOO production

The main object of this The main object of this research work is twofoldresearch work is twofold

The main object of this The main object of this research work is twofoldresearch work is twofold

Materials and methodsMaterials and methodsMaterials and methodsMaterials and methods

OIL

1

2

3

4

7

20-30 kg of olivesh

5

The olive crusher utilized Oliomio Baby reg The olive crusher utilized Oliomio Baby reg (TEM)(TEM)

6

Water

CO2(s)

ldquomass cryogenrdquordquomass of fruitsrdquo 02

Wet olive residues

Knife crusher

Horizontal continuous

malaxer 2-phase decanter

Circulation of the thermal fluid

Circulation of the thermal fluid

Addition of cryogen

Addition of cryogen

Thermal probes Thermal probes

Olives Olives

The study were conducted on samples of olive The study were conducted on samples of olive oil produced from monovarietal and oil produced from monovarietal and

polyvarietal (polyvarietal (mixmix) olives collected in two ) olives collected in two different Italian regions (from Tuscany and different Italian regions (from Tuscany and

Basilicata) during the same season Basilicata) during the same season

The study were conducted on samples of olive The study were conducted on samples of olive oil produced from monovarietal and oil produced from monovarietal and

polyvarietal (polyvarietal (mixmix) olives collected in two ) olives collected in two different Italian regions (from Tuscany and different Italian regions (from Tuscany and

Basilicata) during the same season Basilicata) during the same season

The olive fruits utilized in each experimental The olive fruits utilized in each experimental runs (runs ( 60 kg) were preliminary and suitably 60 kg) were preliminary and suitably mixed to ensure homogeneous feeds Each mixed to ensure homogeneous feeds Each sample was split in two fractions (30 kg)sample was split in two fractions (30 kg)

The olive fruits utilized in each experimental The olive fruits utilized in each experimental runs (runs ( 60 kg) were preliminary and suitably 60 kg) were preliminary and suitably mixed to ensure homogeneous feeds Each mixed to ensure homogeneous feeds Each sample was split in two fractions (30 kg)sample was split in two fractions (30 kg)

Traditional extraction

process

Traditional extraction

process

Addition of CO2s

Addition of CO2s

Origin and cultivar of the raw matter Origin and cultivar of the raw matter utilizedutilized

Origin and cultivar of the raw matter Origin and cultivar of the raw matter utilizedutilized

Sample ID Geographical

Cultivar

Traditional

Cryo origin

A 1 Tuscany (GR)

Frantoio

B 2 Tuscany (SI) mix

C 3 Tuscany (SI) mix

D 4 Tuscany (SI) mix

E 5 Basilicata (PZ)

Coratina

F 6 Basilicata (PZ)

Coratina

G 7 Basilicata (PZ)

Coratina

Frantoio Leccino Correggiolo Frantoio Leccino Correggiolo

CryoCryo TraditionalTraditional

Cryogenolives (ww)Cryogenolives (ww) 02 02 00

Temperature of olivesTemperature of olives (degC)(degC) ~-2~-2 115115

Temperature of pasteTemperature of paste (degC)(degC) ~240~240 ~240~240

Time of MalaxationTime of Malaxation (s)(s) 24002400 24002400

Time of ExtractionTime of Extraction (s)(s) 49004900 43004300

Water addedolivesWater addedolives ()() 8585 9393

Main operating variables adopted Main operating variables adopted during the experimental runs during the experimental runs

Total OIL entrance(kg of crushed fruits x of oil inside the olives)

= Total OIL output

(kg of the olive residues x of oil inside the olive residues)

+EXTRACTED OIL

Total OIL entrance(kg of crushed fruits x of oil inside the olives)

= Total OIL output

(kg of the olive residues x of oil inside the olive residues)

+EXTRACTED OIL

MASS BALANCE during extraction MASS BALANCE during extraction processprocess

In order to evaluate the effect induced by the addition of cryogen on the oil extraction yield

the Extractability Index Variation (EIV) was determined as the percentage of the variation of oil extractability using CO2s compared with the same parameter obtained by a traditional

extraction process

In order to evaluate the effect induced by the addition of cryogen on the oil extraction yield

the Extractability Index Variation (EIV) was determined as the percentage of the variation of oil extractability using CO2s compared with the same parameter obtained by a traditional

extraction process EIV = (EC-ET)ET EIV = (EC-ET)ET 100 100EIV = (EC-ET)ET EIV = (EC-ET)ET 100 100

Results and Results and discussiondiscussion

Results and Results and discussiondiscussion

Oil extraction Oil extraction yield yield

preliminary preliminary resultsresults

Oil extraction yield Oil extraction yield preliminary preliminary resultsresults

Oil extraction yield Oil extraction yield preliminary preliminary resultsresults

Run EC ET

1A 858 825

2B 855 772

3C 912 827

4D 841 748

5E 808 793

6F 736 689

7G 844 774

The direct addition of cryogen to the olives during pre-milling phase could induce a general increase in the oil extraction yield ranging from 2 to

124

The direct addition of cryogen to the olives during pre-milling phase could induce a general increase in the oil extraction yield ranging from 2 to

124

[(EC-ET)ET]10040 108 103 124 19 68 90

[(EC-ET)ET]10040 108 103 124 19 68 90

Preliminary results about oil extraction Preliminary results about oil extraction yield yield discussion Idiscussion I

Preliminary results about oil extraction Preliminary results about oil extraction yield yield discussion Idiscussion I

The number of the experimental runs carried out until now is quite reduced

The number of the experimental runs carried out until now is quite reduced

BUTBUT

The results appear very encouraging and the new method seems very suitable for olive oil extraction

The results appear very encouraging and the new method seems very suitable for olive oil extraction

During the next crop season we will increase the number of experimental runs adopting several combinations of the working parameters (ie amount of cryogenamount of olives fruit ripening stage etc)

During the next crop season we will increase the number of experimental runs adopting several combinations of the working parameters (ie amount of cryogenamount of olives fruit ripening stage etc)

Preliminary results about oil extraction Preliminary results about oil extraction yield yield discussion IIdiscussion II

Preliminary results about oil extraction Preliminary results about oil extraction yield yield discussion IIdiscussion II

If necessary this method allows to move up the olive harvest time in order to greatly reduce the damages due to the third fly attack of Bactrocera oleae that can induce a significant loss in oil production (up to 60) as well as a decrease in oil quality

If necessary this method allows to move up the olive harvest time in order to greatly reduce the damages due to the third fly attack of Bactrocera oleae that can induce a significant loss in oil production (up to 60) as well as a decrease in oil quality

Water content

inside the fruit

Water content

inside the fruit

CELLULAR CRASH

We need 08 kg of CO2s to lower 100 kg of olives temperature by 1degC

Cost of 1 kg of CO2s= euro050 $ 037

Cost to turn down the average temperature of 100

kg of olives by 10degC(15degC 5degC )

08kgdegC x 10degC x 037 $kg=

3 $

Considering an average oil yield of 15

The addition cost for a kg of extravirgin olive oil is

3 $100 kg olives x 15100kg oilkg olives

lt 02$kg oil

Oil elemental Oil elemental profile profile

preliminary preliminary resultsresults

ICP-AES and ICP-MS techniques are particularly advantageous for the application in the definition of the elemental profiles of olive oil since they allow simultaneous multi-elemental analysis and are characterized by wide linear ranges and (especially ICP-MS) very low Detection Limits

Main analytical issues are related to the hard organic content of the oil matrix which requires appropriate sample pre-treatments Microwave-assisted digestion permitted to obtain a complete dissolution of olive oil samples but resulted in the obtainment of highly acidic solutions not directly analyzable by ICP-MS with a consequent reduction of sensitivity (due to the preliminary 110 dilution of the mineralized olive oil)

ETV

LA

Preliminary results about oil elemental Preliminary results about oil elemental profileprofile

Preliminary results about oil elemental Preliminary results about oil elemental profileprofile

Preliminary results show a rather homogeneous elemental content among all the analyzed samples of olive oil

For all elements experimental concentrations fall within the ranges reported in literature In respect to these ranges analyzed samples show a high content of B S and Si while Fe Na Pb Ba Cr and Cu contents are quite low

Samples of olive oil obtained by the traditionalldquo process show - in general - a higher content of Ca Cr Mg Si (except those originating from Basilicata) and Zn compared to those obtained by the addition of ldquocarbonic snowldquo

0

20

40

60

80

100

120

140

B Ca Fe Na S Si

mgk

g

000

050

100

150

200

250

300

350

400

450

500

Al K Mg P Zn

mgk

g

0

500

1000

1500

2000

2500

3000

3500

Co Cr Cu Ni Pb

microgk

g

0

2

4

6

8

10

12

14

16

Ce Er Eu Gd La Nd Pr Sm Y Yb

microgk

g

0

100

200

300

400

500

600

700

800

As Ba Cd Li Mn Rb Sb Sc Se Sr Th Ti V

microgk

g

4000 25000

0

20

40

60

80

100

120

140

160

Ca

Na

Si

concentration range obtained from literature [2]

experimental concentration range ICP-AESDetection LimitICP-MSDetection Limit - Normal Sensitivity modeICP-MSDetection Limit - High Sensitivitymode

S B Yasar E K Baran M Alkan Metal determinations in olive oil In Olive Oil ndash Constituents Quality Health Properties and Bioconversions Ed by Boskou Dimitrios 5 89-108 2012

Preliminary results about oil elemental Preliminary results about oil elemental profileprofile

Preliminary results about oil elemental Preliminary results about oil elemental profileprofile

For any further details about the second part of the research you can contact our colleagues in ENEA

claudiazoanieneait giovannazappaeneait

For any further details about the second part of the research you can contact our colleagues in ENEA

claudiazoanieneait giovannazappaeneait

ReferencesReferencesReferencesReferences

The Utilization of Solid Carbon Dioxide in the Production of Extravirgin Olive Oil

Sanmartin C Zinnai A Venturi F Andrich G Proceedings of EFFOST 2011 9-11 November 2011 Berlino

(D)

Analytical methods for olive oil elemental profile and influence of carbonic snow addition in the extraction

phase C Zoani G Zappa A Zinnai F Venturi C Sanmartin

11th Euro Fed Lipid Congress ndash Antalya (Turkey) 27-30 October 2013

Preliminary results on the influence of carbonic snow addition during the olive processing oil extraction yield

and elemental profile C Zoani G Zappa F Venturi C Sanmartin G Andrich and

A ZinnaiJournal of Nutrition and Food Sciences 4 277 (2014)

doi 1041722155-96001000277

The Utilization of Solid Carbon Dioxide in the Production of Extravirgin Olive Oil

Sanmartin C Zinnai A Venturi F Andrich G Proceedings of EFFOST 2011 9-11 November 2011 Berlino

(D)

Analytical methods for olive oil elemental profile and influence of carbonic snow addition in the extraction

phase C Zoani G Zappa A Zinnai F Venturi C Sanmartin

11th Euro Fed Lipid Congress ndash Antalya (Turkey) 27-30 October 2013

Preliminary results on the influence of carbonic snow addition during the olive processing oil extraction yield

and elemental profile C Zoani G Zappa F Venturi C Sanmartin G Andrich and

A ZinnaiJournal of Nutrition and Food Sciences 4 277 (2014)

doi 1041722155-96001000277

Research in progresshellipResearch in progresshellip

Thank you for your attention

Thank you for your attention

research supported by

It will be possible to apply matrix modification procedures (eg solvent extraction ndash also ultrasound assisted - addition of organic solvents or emulsification) or to employ systems for direct oil sample introduction in torch (eg Flow Injection Analysis systems)

We are conducting experimental tests for evaluating the possibility to employ a Laser Ablation system or an ElectroThermal Vaporization system for direct sample introduction in ICP-AES and ICP-MS

ETV

LA

Future developmentsFuture developmentsFuture developmentsFuture developments

Determination of oil elemental profile sample pre-treatment

High PressureMicrowave Digestion

Milestone 1200 Mega

05 golive oil

Mineralized oil sample

(final V = 25 ml)

2 ml H2O2 + 6 ml HNO3

Different mixtures testedH2O2 30vv (1 divide 2 ml)+ HNO3 699vv (2 divide

6 ml)

Total dissoluti

on

high-purity water

(gt 18 MΩ)

time Power Pressure

1 min 250 WFree

pressure race

1 min 0 W

5 min 400 W

5 min 650 W

Vent = 5 min

TQ mineralized

olive oil solution

Varian Vista MPX(axial configuration

simultaneous 112 Mpixel CCD detector)

study of spectral interferencesstudy of spectral interferences

preliminary qualitative analysis72 elements

preliminary qualitative analysis72 elements

quantitative analysisquantitative analysis

Gas flows optimization based on signal-to-background ratio (SB)

Auxiliary flow (lmin)

Nebulizer flow(lmin)

10 15 09 10 11 12

SBMg 3296 11720 13948 17998 19921 18412Mn 0128 0197 0245 0312 0303 0294Na 1827 1940 1827 3187 6121 4371

Zn - 213857 nm more sensitive but interfered by Fe

Zn - 206200 nm - less sensitive but without interferences

Analytical wavelengths (nm)

Al - 396152 nm K - 766491 nm Rb - 780026 nm

As - 188980 nm Li - 670783 nm S - 181972 nm

B - 249772 nm Mg - 279553 nm Sb - 206834 nm

Ba - 455403 nm Mn - 257610 nm Si - 251611 nm

Ca - 396847 nm Na - 589592 nm Sr - 407771 nm

Cr - 267716 nm Ni - 231604 nm Ti - 334941 nm

Cu - 327395 nm P - 213618 nm V - 311837 nm

Fe - 238204 nm Pb - 220353 nm Zn ndash 206200 nm

Instrumental conditions

RF Frequency 40 MHz (free running air-cooled)

RF Power 12 kW

Gas (plasma auxiliary nebulizer) Argon

Plasma flow 150 lmin

Auxiliary flow 15 lmin

Nebulizer flow 110 lmin

Replicates 5

Replicate read time 5 s

Operating parameters for ICP-AES quantitative analysis

ICP-AES Analysis

Bruker Aurora M90 (90 degree ion mirror ion optics Collision Reaction Interface)110 diluted

mineralized olive oil solution

Tuning with a 5 microgl Be Mg Co In Ba Ce Ti Pb and Th solution for

sensitivity and resolution optimization and mass calibration

Tuning with a 5 microgl Be Mg Co In Ba Ce Ti Pb and Th solution for

sensitivity and resolution optimization and mass calibration

Check of the level of oxide ions by the CeO+Ce+ ratio lt 2

Check of the level of oxide ions by the CeO+Ce+ ratio lt 2

Monitoring of double charged ions by the signal 137Ba++137Ba+ lt 3

Monitoring of double charged ions by the signal 137Ba++137Ba+ lt 3

CheckCorrection of isobaric interferences examination of more isotopes of the same element(eg Rb85 Rb 87 Sr88Sr87 Nd142 Nd146 Nd144 Se77 Se78 Sn147 Sm148 Sm152 Gd157 Gd154 Er166 Er168 Yb170 Yb172) application of correction equations with respect to isotopes of other elements potentially interfering (eg Nd142 corrected by analyzing Ce140 Nd144 by Sm147 Sm152 by Gd157 Rb87 by Sr88 ) use of the Collision Reaction Interface ndash CRI (for As and Se)

CheckCorrection of isobaric interferences examination of more isotopes of the same element(eg Rb85 Rb 87 Sr88Sr87 Nd142 Nd146 Nd144 Se77 Se78 Sn147 Sm148 Sm152 Gd157 Gd154 Er166 Er168 Yb170 Yb172) application of correction equations with respect to isotopes of other elements potentially interfering (eg Nd142 corrected by analyzing Ce140 Nd144 by Sm147 Sm152 by Gd157 Rb87 by Sr88 ) use of the Collision Reaction Interface ndash CRI (for As and Se)

Working rangesbull005 divide 5 microgl - As Cd Ce Er Eu Gd La Mn Nd Pb Pr Rb Sb Sc Se Sm Sr Th V Y Ybbull01 divide 10 microgl - Co Cr Cu Mg Ni

Working rangesbull005 divide 5 microgl - As Cd Ce Er Eu Gd La Mn Nd Pb Pr Rb Sb Sc Se Sm Sr Th V Y Ybbull01 divide 10 microgl - Co Cr Cu Mg Ni

External calibration5 standard solutions + blankCurve Fit LinearWeighted Fit NoCorrelation coefficientsR gt 09999

Normal Sensitivity Mode (without CRI) High Sensitivity Mode As and Se ndash Normal mode with CRI

ICP-MS Analysis

• Slide 1
• Slide 2
• Slide 3
• Slide 4
• Slide 5
• Slide 6
• Slide 7
• Slide 8
• Slide 9
• Slide 10
• Slide 11
• Slide 12
• Slide 13
• Slide 14
• Slide 15
• Slide 16
• Slide 17
• Slide 18
• Slide 19
• Slide 20
• Slide 21
• Slide 22
• Slide 23
• Slide 24
• Slide 25
• Slide 26
• Slide 27
• Slide 28
• Slide 29
• Slide 30
• Slide 31
• Slide 32
• Slide 33
• Slide 34
• Slide 35

Extraction Extraction TechnologyTechnology

Yield = Yield = amount of amount of

extracted oilextracted oil

Oil QualityOil Quality

The addition of carbonic snow to grapes to produce The addition of carbonic snow to grapes to produce high quality wines is a largely diffused oenological high quality wines is a largely diffused oenological

practicepractice

CouldCould this technology be usefully this technology be usefully applied in extravirgin olive oil extraction applied in extravirgin olive oil extraction

In order to advance in VOO technology at DAFE of In order to advance in VOO technology at DAFE of University of Pisa an University of Pisa an innovative EVOO extraction innovative EVOO extraction technologytechnology ( (Patent ndeg IT1405173-BPatent ndeg IT1405173-B) involving the ) involving the addition of a cryogen (solid COaddition of a cryogen (solid CO22) to the olives) to the olives were were developed in order to developed in order to increase the extraction increase the extraction yieldyield and to and to obtain an oil characterized by an obtain an oil characterized by an higher concentration of phenolic compounds and a higher concentration of phenolic compounds and a stronger link with the raw material and its stronger link with the raw material and its production areaproduction area

Diffusion of cellular components in the Diffusion of cellular components in the extracellular liquid phase extracellular liquid phase

CELLULAR

CRASH

WATER FREEZING

WATER VOLUME INCREASES

ADDITION CO2s

Mechanical action

Mechanical action

bull Nontoxic and does not leave Nontoxic and does not leave residualresidual

bull Inflammable and less reactiveInflammable and less reactive

bull Good solvent (non-polar)Good solvent (non-polar)

bull Inert by an organoleptic point of Inert by an organoleptic point of viewview

bull Triple point easy to reach (-Triple point easy to reach (-575degC 51atm)575degC 51atm)

bull Easy to find and to useEasy to find and to use

bull Reduced costsReduced costs

bull Anti-microbial and anti-oxidant Anti-microbial and anti-oxidant actionaction

Among all the Among all the possible possible cryogens cryogens

suitable for food suitable for food technology technology

(N(N2L2L He HeLL Ar ArLL etc) etc)

COCO2s2s (or carbonic snow) (or carbonic snow)shows a lot of advantagesshows a lot of advantages

COCO2s2s + Olivesolive paste + Olivesolive paste

Able to prevent Able to prevent the possible the possible oxidation of oxidation of extracted oilextracted oil

Increase of the Increase of the extraction yieldextraction yield

Wished Wished aromatic aromatic profile profile

Higher Higher antioxidant antioxidant

contentcontent

COCO2g2g

Modulation of Modulation of the working the working

variables related variables related toto thethe

MALAXATION MALAXATION

Inert gaseous layer Inert gaseous layer

((COCO22gg airair = 15) = 15)

b) the second goal was to develop specific analytical b) the second goal was to develop specific analytical methods for evaluating the elemental profile of olive methods for evaluating the elemental profile of olive

oil and to collect some preliminary data about the oil and to collect some preliminary data about the possibility to use these methods in order to put in possibility to use these methods in order to put in

evidence the possible influence of different process evidence the possible influence of different process conditions (extraction with or without addition of conditions (extraction with or without addition of carbonic snow) on the olive oil elemental profilecarbonic snow) on the olive oil elemental profile

b) the second goal was to develop specific analytical b) the second goal was to develop specific analytical methods for evaluating the elemental profile of olive methods for evaluating the elemental profile of olive

oil and to collect some preliminary data about the oil and to collect some preliminary data about the possibility to use these methods in order to put in possibility to use these methods in order to put in

evidence the possible influence of different process evidence the possible influence of different process conditions (extraction with or without addition of conditions (extraction with or without addition of carbonic snow) on the olive oil elemental profilecarbonic snow) on the olive oil elemental profile

Aim of the workAim of the work

a) the first goal was to verify the influence of the a) the first goal was to verify the influence of the addition of cryogen (COaddition of cryogen (CO2s2s) directly to olives during ) directly to olives during pre-milling phase on the yield of the oil production pre-milling phase on the yield of the oil production

in order to obtain a preliminary evaluation of the in order to obtain a preliminary evaluation of the suitability of the new proposed methodology for suitability of the new proposed methodology for

EVOO productionEVOO production

The main object of this The main object of this research work is twofoldresearch work is twofold

The main object of this The main object of this research work is twofoldresearch work is twofold

Materials and methodsMaterials and methodsMaterials and methodsMaterials and methods

OIL

1

2

3

4

7

20-30 kg of olivesh

5

The olive crusher utilized Oliomio Baby reg The olive crusher utilized Oliomio Baby reg (TEM)(TEM)

6

Water

CO2(s)

ldquomass cryogenrdquordquomass of fruitsrdquo 02

Wet olive residues

Knife crusher

Horizontal continuous

malaxer 2-phase decanter

Circulation of the thermal fluid

Circulation of the thermal fluid

Addition of cryogen

Addition of cryogen

Thermal probes Thermal probes

Olives Olives

The study were conducted on samples of olive The study were conducted on samples of olive oil produced from monovarietal and oil produced from monovarietal and

polyvarietal (polyvarietal (mixmix) olives collected in two ) olives collected in two different Italian regions (from Tuscany and different Italian regions (from Tuscany and

Basilicata) during the same season Basilicata) during the same season

The study were conducted on samples of olive The study were conducted on samples of olive oil produced from monovarietal and oil produced from monovarietal and

polyvarietal (polyvarietal (mixmix) olives collected in two ) olives collected in two different Italian regions (from Tuscany and different Italian regions (from Tuscany and

Basilicata) during the same season Basilicata) during the same season

The olive fruits utilized in each experimental The olive fruits utilized in each experimental runs (runs ( 60 kg) were preliminary and suitably 60 kg) were preliminary and suitably mixed to ensure homogeneous feeds Each mixed to ensure homogeneous feeds Each sample was split in two fractions (30 kg)sample was split in two fractions (30 kg)

The olive fruits utilized in each experimental The olive fruits utilized in each experimental runs (runs ( 60 kg) were preliminary and suitably 60 kg) were preliminary and suitably mixed to ensure homogeneous feeds Each mixed to ensure homogeneous feeds Each sample was split in two fractions (30 kg)sample was split in two fractions (30 kg)

Traditional extraction

process

Traditional extraction

process

Addition of CO2s

Addition of CO2s

Origin and cultivar of the raw matter Origin and cultivar of the raw matter utilizedutilized

Origin and cultivar of the raw matter Origin and cultivar of the raw matter utilizedutilized

Sample ID Geographical

Cultivar

Traditional

Cryo origin

A 1 Tuscany (GR)

Frantoio

B 2 Tuscany (SI) mix

C 3 Tuscany (SI) mix

D 4 Tuscany (SI) mix

E 5 Basilicata (PZ)

Coratina

F 6 Basilicata (PZ)

Coratina

G 7 Basilicata (PZ)

Coratina

Frantoio Leccino Correggiolo Frantoio Leccino Correggiolo

CryoCryo TraditionalTraditional

Cryogenolives (ww)Cryogenolives (ww) 02 02 00

Temperature of olivesTemperature of olives (degC)(degC) ~-2~-2 115115

Temperature of pasteTemperature of paste (degC)(degC) ~240~240 ~240~240

Time of MalaxationTime of Malaxation (s)(s) 24002400 24002400

Time of ExtractionTime of Extraction (s)(s) 49004900 43004300

Water addedolivesWater addedolives ()() 8585 9393

Main operating variables adopted Main operating variables adopted during the experimental runs during the experimental runs

Total OIL entrance(kg of crushed fruits x of oil inside the olives)

= Total OIL output

(kg of the olive residues x of oil inside the olive residues)

+EXTRACTED OIL

Total OIL entrance(kg of crushed fruits x of oil inside the olives)

= Total OIL output

(kg of the olive residues x of oil inside the olive residues)

+EXTRACTED OIL

MASS BALANCE during extraction MASS BALANCE during extraction processprocess

In order to evaluate the effect induced by the addition of cryogen on the oil extraction yield

the Extractability Index Variation (EIV) was determined as the percentage of the variation of oil extractability using CO2s compared with the same parameter obtained by a traditional

extraction process

In order to evaluate the effect induced by the addition of cryogen on the oil extraction yield

the Extractability Index Variation (EIV) was determined as the percentage of the variation of oil extractability using CO2s compared with the same parameter obtained by a traditional

extraction process EIV = (EC-ET)ET EIV = (EC-ET)ET 100 100EIV = (EC-ET)ET EIV = (EC-ET)ET 100 100

Results and Results and discussiondiscussion

Results and Results and discussiondiscussion

Oil extraction Oil extraction yield yield

preliminary preliminary resultsresults

Oil extraction yield Oil extraction yield preliminary preliminary resultsresults

Oil extraction yield Oil extraction yield preliminary preliminary resultsresults

Run EC ET

1A 858 825

2B 855 772

3C 912 827

4D 841 748

5E 808 793

6F 736 689

7G 844 774

The direct addition of cryogen to the olives during pre-milling phase could induce a general increase in the oil extraction yield ranging from 2 to

124

The direct addition of cryogen to the olives during pre-milling phase could induce a general increase in the oil extraction yield ranging from 2 to

124

[(EC-ET)ET]10040 108 103 124 19 68 90

[(EC-ET)ET]10040 108 103 124 19 68 90

Preliminary results about oil extraction Preliminary results about oil extraction yield yield discussion Idiscussion I

Preliminary results about oil extraction Preliminary results about oil extraction yield yield discussion Idiscussion I

The number of the experimental runs carried out until now is quite reduced

The number of the experimental runs carried out until now is quite reduced

BUTBUT

The results appear very encouraging and the new method seems very suitable for olive oil extraction

The results appear very encouraging and the new method seems very suitable for olive oil extraction

During the next crop season we will increase the number of experimental runs adopting several combinations of the working parameters (ie amount of cryogenamount of olives fruit ripening stage etc)

During the next crop season we will increase the number of experimental runs adopting several combinations of the working parameters (ie amount of cryogenamount of olives fruit ripening stage etc)

Preliminary results about oil extraction Preliminary results about oil extraction yield yield discussion IIdiscussion II

Preliminary results about oil extraction Preliminary results about oil extraction yield yield discussion IIdiscussion II

If necessary this method allows to move up the olive harvest time in order to greatly reduce the damages due to the third fly attack of Bactrocera oleae that can induce a significant loss in oil production (up to 60) as well as a decrease in oil quality

If necessary this method allows to move up the olive harvest time in order to greatly reduce the damages due to the third fly attack of Bactrocera oleae that can induce a significant loss in oil production (up to 60) as well as a decrease in oil quality

Water content

inside the fruit

Water content

inside the fruit

CELLULAR CRASH

We need 08 kg of CO2s to lower 100 kg of olives temperature by 1degC

Cost of 1 kg of CO2s= euro050 $ 037

Cost to turn down the average temperature of 100

kg of olives by 10degC(15degC 5degC )

08kgdegC x 10degC x 037 $kg=

3 $

Considering an average oil yield of 15

The addition cost for a kg of extravirgin olive oil is

3 $100 kg olives x 15100kg oilkg olives

lt 02$kg oil

Oil elemental Oil elemental profile profile

preliminary preliminary resultsresults

ICP-AES and ICP-MS techniques are particularly advantageous for the application in the definition of the elemental profiles of olive oil since they allow simultaneous multi-elemental analysis and are characterized by wide linear ranges and (especially ICP-MS) very low Detection Limits

Main analytical issues are related to the hard organic content of the oil matrix which requires appropriate sample pre-treatments Microwave-assisted digestion permitted to obtain a complete dissolution of olive oil samples but resulted in the obtainment of highly acidic solutions not directly analyzable by ICP-MS with a consequent reduction of sensitivity (due to the preliminary 110 dilution of the mineralized olive oil)

ETV

LA

Preliminary results about oil elemental Preliminary results about oil elemental profileprofile

Preliminary results about oil elemental Preliminary results about oil elemental profileprofile

Preliminary results show a rather homogeneous elemental content among all the analyzed samples of olive oil

For all elements experimental concentrations fall within the ranges reported in literature In respect to these ranges analyzed samples show a high content of B S and Si while Fe Na Pb Ba Cr and Cu contents are quite low

Samples of olive oil obtained by the traditionalldquo process show - in general - a higher content of Ca Cr Mg Si (except those originating from Basilicata) and Zn compared to those obtained by the addition of ldquocarbonic snowldquo

0

20

40

60

80

100

120

140

B Ca Fe Na S Si

mgk

g

000

050

100

150

200

250

300

350

400

450

500

Al K Mg P Zn

mgk

g

0

500

1000

1500

2000

2500

3000

3500

Co Cr Cu Ni Pb

microgk

g

0

2

4

6

8

10

12

14

16

Ce Er Eu Gd La Nd Pr Sm Y Yb

microgk

g

0

100

200

300

400

500

600

700

800

As Ba Cd Li Mn Rb Sb Sc Se Sr Th Ti V

microgk

g

4000 25000

0

20

40

60

80

100

120

140

160

Ca

Na

Si

concentration range obtained from literature [2]

experimental concentration range ICP-AESDetection LimitICP-MSDetection Limit - Normal Sensitivity modeICP-MSDetection Limit - High Sensitivitymode

S B Yasar E K Baran M Alkan Metal determinations in olive oil In Olive Oil ndash Constituents Quality Health Properties and Bioconversions Ed by Boskou Dimitrios 5 89-108 2012

Preliminary results about oil elemental Preliminary results about oil elemental profileprofile

Preliminary results about oil elemental Preliminary results about oil elemental profileprofile

For any further details about the second part of the research you can contact our colleagues in ENEA

claudiazoanieneait giovannazappaeneait

For any further details about the second part of the research you can contact our colleagues in ENEA

claudiazoanieneait giovannazappaeneait

ReferencesReferencesReferencesReferences

The Utilization of Solid Carbon Dioxide in the Production of Extravirgin Olive Oil

Sanmartin C Zinnai A Venturi F Andrich G Proceedings of EFFOST 2011 9-11 November 2011 Berlino

(D)

Analytical methods for olive oil elemental profile and influence of carbonic snow addition in the extraction

phase C Zoani G Zappa A Zinnai F Venturi C Sanmartin

11th Euro Fed Lipid Congress ndash Antalya (Turkey) 27-30 October 2013

Preliminary results on the influence of carbonic snow addition during the olive processing oil extraction yield

and elemental profile C Zoani G Zappa F Venturi C Sanmartin G Andrich and

A ZinnaiJournal of Nutrition and Food Sciences 4 277 (2014)

doi 1041722155-96001000277

The Utilization of Solid Carbon Dioxide in the Production of Extravirgin Olive Oil

Sanmartin C Zinnai A Venturi F Andrich G Proceedings of EFFOST 2011 9-11 November 2011 Berlino

(D)

Analytical methods for olive oil elemental profile and influence of carbonic snow addition in the extraction

phase C Zoani G Zappa A Zinnai F Venturi C Sanmartin

11th Euro Fed Lipid Congress ndash Antalya (Turkey) 27-30 October 2013

Preliminary results on the influence of carbonic snow addition during the olive processing oil extraction yield

and elemental profile C Zoani G Zappa F Venturi C Sanmartin G Andrich and

A ZinnaiJournal of Nutrition and Food Sciences 4 277 (2014)

doi 1041722155-96001000277

Research in progresshellipResearch in progresshellip

Thank you for your attention

Thank you for your attention

research supported by

It will be possible to apply matrix modification procedures (eg solvent extraction ndash also ultrasound assisted - addition of organic solvents or emulsification) or to employ systems for direct oil sample introduction in torch (eg Flow Injection Analysis systems)

We are conducting experimental tests for evaluating the possibility to employ a Laser Ablation system or an ElectroThermal Vaporization system for direct sample introduction in ICP-AES and ICP-MS

ETV

LA

Future developmentsFuture developmentsFuture developmentsFuture developments

Determination of oil elemental profile sample pre-treatment

High PressureMicrowave Digestion

Milestone 1200 Mega

05 golive oil

Mineralized oil sample

(final V = 25 ml)

2 ml H2O2 + 6 ml HNO3

Different mixtures testedH2O2 30vv (1 divide 2 ml)+ HNO3 699vv (2 divide

6 ml)

Total dissoluti

on

high-purity water

(gt 18 MΩ)

time Power Pressure

1 min 250 WFree

pressure race

1 min 0 W

5 min 400 W

5 min 650 W

Vent = 5 min

TQ mineralized

olive oil solution

Varian Vista MPX(axial configuration

simultaneous 112 Mpixel CCD detector)

study of spectral interferencesstudy of spectral interferences

preliminary qualitative analysis72 elements

preliminary qualitative analysis72 elements

quantitative analysisquantitative analysis

Gas flows optimization based on signal-to-background ratio (SB)

Auxiliary flow (lmin)

Nebulizer flow(lmin)

10 15 09 10 11 12

SBMg 3296 11720 13948 17998 19921 18412Mn 0128 0197 0245 0312 0303 0294Na 1827 1940 1827 3187 6121 4371

Zn - 213857 nm more sensitive but interfered by Fe

Zn - 206200 nm - less sensitive but without interferences

Analytical wavelengths (nm)

Al - 396152 nm K - 766491 nm Rb - 780026 nm

As - 188980 nm Li - 670783 nm S - 181972 nm

B - 249772 nm Mg - 279553 nm Sb - 206834 nm

Ba - 455403 nm Mn - 257610 nm Si - 251611 nm

Ca - 396847 nm Na - 589592 nm Sr - 407771 nm

Cr - 267716 nm Ni - 231604 nm Ti - 334941 nm

Cu - 327395 nm P - 213618 nm V - 311837 nm

Fe - 238204 nm Pb - 220353 nm Zn ndash 206200 nm

Instrumental conditions

RF Frequency 40 MHz (free running air-cooled)

RF Power 12 kW

Gas (plasma auxiliary nebulizer) Argon

Plasma flow 150 lmin

Auxiliary flow 15 lmin

Nebulizer flow 110 lmin

Replicates 5

Replicate read time 5 s

Operating parameters for ICP-AES quantitative analysis

ICP-AES Analysis

Bruker Aurora M90 (90 degree ion mirror ion optics Collision Reaction Interface)110 diluted

mineralized olive oil solution

Tuning with a 5 microgl Be Mg Co In Ba Ce Ti Pb and Th solution for

sensitivity and resolution optimization and mass calibration

Tuning with a 5 microgl Be Mg Co In Ba Ce Ti Pb and Th solution for

sensitivity and resolution optimization and mass calibration

Check of the level of oxide ions by the CeO+Ce+ ratio lt 2

Check of the level of oxide ions by the CeO+Ce+ ratio lt 2

Monitoring of double charged ions by the signal 137Ba++137Ba+ lt 3

Monitoring of double charged ions by the signal 137Ba++137Ba+ lt 3

CheckCorrection of isobaric interferences examination of more isotopes of the same element(eg Rb85 Rb 87 Sr88Sr87 Nd142 Nd146 Nd144 Se77 Se78 Sn147 Sm148 Sm152 Gd157 Gd154 Er166 Er168 Yb170 Yb172) application of correction equations with respect to isotopes of other elements potentially interfering (eg Nd142 corrected by analyzing Ce140 Nd144 by Sm147 Sm152 by Gd157 Rb87 by Sr88 ) use of the Collision Reaction Interface ndash CRI (for As and Se)

CheckCorrection of isobaric interferences examination of more isotopes of the same element(eg Rb85 Rb 87 Sr88Sr87 Nd142 Nd146 Nd144 Se77 Se78 Sn147 Sm148 Sm152 Gd157 Gd154 Er166 Er168 Yb170 Yb172) application of correction equations with respect to isotopes of other elements potentially interfering (eg Nd142 corrected by analyzing Ce140 Nd144 by Sm147 Sm152 by Gd157 Rb87 by Sr88 ) use of the Collision Reaction Interface ndash CRI (for As and Se)

Working rangesbull005 divide 5 microgl - As Cd Ce Er Eu Gd La Mn Nd Pb Pr Rb Sb Sc Se Sm Sr Th V Y Ybbull01 divide 10 microgl - Co Cr Cu Mg Ni

Working rangesbull005 divide 5 microgl - As Cd Ce Er Eu Gd La Mn Nd Pb Pr Rb Sb Sc Se Sm Sr Th V Y Ybbull01 divide 10 microgl - Co Cr Cu Mg Ni

External calibration5 standard solutions + blankCurve Fit LinearWeighted Fit NoCorrelation coefficientsR gt 09999

Normal Sensitivity Mode (without CRI) High Sensitivity Mode As and Se ndash Normal mode with CRI

ICP-MS Analysis

• Slide 1
• Slide 2
• Slide 3
• Slide 4
• Slide 5
• Slide 6
• Slide 7
• Slide 8
• Slide 9
• Slide 10
• Slide 11
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• Slide 13
• Slide 14
• Slide 15
• Slide 16
• Slide 17
• Slide 18
• Slide 19
• Slide 20
• Slide 21
• Slide 22
• Slide 23
• Slide 24
• Slide 25
• Slide 26
• Slide 27
• Slide 28
• Slide 29
• Slide 30
• Slide 31
• Slide 32
• Slide 33
• Slide 34
• Slide 35

The addition of carbonic snow to grapes to produce The addition of carbonic snow to grapes to produce high quality wines is a largely diffused oenological high quality wines is a largely diffused oenological

practicepractice

CouldCould this technology be usefully this technology be usefully applied in extravirgin olive oil extraction applied in extravirgin olive oil extraction

In order to advance in VOO technology at DAFE of In order to advance in VOO technology at DAFE of University of Pisa an University of Pisa an innovative EVOO extraction innovative EVOO extraction technologytechnology ( (Patent ndeg IT1405173-BPatent ndeg IT1405173-B) involving the ) involving the addition of a cryogen (solid COaddition of a cryogen (solid CO22) to the olives) to the olives were were developed in order to developed in order to increase the extraction increase the extraction yieldyield and to and to obtain an oil characterized by an obtain an oil characterized by an higher concentration of phenolic compounds and a higher concentration of phenolic compounds and a stronger link with the raw material and its stronger link with the raw material and its production areaproduction area

Diffusion of cellular components in the Diffusion of cellular components in the extracellular liquid phase extracellular liquid phase

CELLULAR

CRASH

WATER FREEZING

WATER VOLUME INCREASES

ADDITION CO2s

Mechanical action

Mechanical action

bull Nontoxic and does not leave Nontoxic and does not leave residualresidual

bull Inflammable and less reactiveInflammable and less reactive

bull Good solvent (non-polar)Good solvent (non-polar)

bull Inert by an organoleptic point of Inert by an organoleptic point of viewview

bull Triple point easy to reach (-Triple point easy to reach (-575degC 51atm)575degC 51atm)

bull Easy to find and to useEasy to find and to use

bull Reduced costsReduced costs

bull Anti-microbial and anti-oxidant Anti-microbial and anti-oxidant actionaction

Among all the Among all the possible possible cryogens cryogens

suitable for food suitable for food technology technology

(N(N2L2L He HeLL Ar ArLL etc) etc)

COCO2s2s (or carbonic snow) (or carbonic snow)shows a lot of advantagesshows a lot of advantages

COCO2s2s + Olivesolive paste + Olivesolive paste

Able to prevent Able to prevent the possible the possible oxidation of oxidation of extracted oilextracted oil

Increase of the Increase of the extraction yieldextraction yield

Wished Wished aromatic aromatic profile profile

Higher Higher antioxidant antioxidant

contentcontent

COCO2g2g

Modulation of Modulation of the working the working

variables related variables related toto thethe

MALAXATION MALAXATION

Inert gaseous layer Inert gaseous layer

((COCO22gg airair = 15) = 15)

b) the second goal was to develop specific analytical b) the second goal was to develop specific analytical methods for evaluating the elemental profile of olive methods for evaluating the elemental profile of olive

oil and to collect some preliminary data about the oil and to collect some preliminary data about the possibility to use these methods in order to put in possibility to use these methods in order to put in

evidence the possible influence of different process evidence the possible influence of different process conditions (extraction with or without addition of conditions (extraction with or without addition of carbonic snow) on the olive oil elemental profilecarbonic snow) on the olive oil elemental profile

b) the second goal was to develop specific analytical b) the second goal was to develop specific analytical methods for evaluating the elemental profile of olive methods for evaluating the elemental profile of olive

oil and to collect some preliminary data about the oil and to collect some preliminary data about the possibility to use these methods in order to put in possibility to use these methods in order to put in

evidence the possible influence of different process evidence the possible influence of different process conditions (extraction with or without addition of conditions (extraction with or without addition of carbonic snow) on the olive oil elemental profilecarbonic snow) on the olive oil elemental profile

Aim of the workAim of the work

a) the first goal was to verify the influence of the a) the first goal was to verify the influence of the addition of cryogen (COaddition of cryogen (CO2s2s) directly to olives during ) directly to olives during pre-milling phase on the yield of the oil production pre-milling phase on the yield of the oil production

in order to obtain a preliminary evaluation of the in order to obtain a preliminary evaluation of the suitability of the new proposed methodology for suitability of the new proposed methodology for

EVOO productionEVOO production

The main object of this The main object of this research work is twofoldresearch work is twofold

The main object of this The main object of this research work is twofoldresearch work is twofold

Materials and methodsMaterials and methodsMaterials and methodsMaterials and methods

OIL

1

2

3

4

7

20-30 kg of olivesh

5

The olive crusher utilized Oliomio Baby reg The olive crusher utilized Oliomio Baby reg (TEM)(TEM)

6

Water

CO2(s)

ldquomass cryogenrdquordquomass of fruitsrdquo 02

Wet olive residues

Knife crusher

Horizontal continuous

malaxer 2-phase decanter

Circulation of the thermal fluid

Circulation of the thermal fluid

Addition of cryogen

Addition of cryogen

Thermal probes Thermal probes

Olives Olives

The study were conducted on samples of olive The study were conducted on samples of olive oil produced from monovarietal and oil produced from monovarietal and

polyvarietal (polyvarietal (mixmix) olives collected in two ) olives collected in two different Italian regions (from Tuscany and different Italian regions (from Tuscany and

Basilicata) during the same season Basilicata) during the same season

The study were conducted on samples of olive The study were conducted on samples of olive oil produced from monovarietal and oil produced from monovarietal and

polyvarietal (polyvarietal (mixmix) olives collected in two ) olives collected in two different Italian regions (from Tuscany and different Italian regions (from Tuscany and

Basilicata) during the same season Basilicata) during the same season

The olive fruits utilized in each experimental The olive fruits utilized in each experimental runs (runs ( 60 kg) were preliminary and suitably 60 kg) were preliminary and suitably mixed to ensure homogeneous feeds Each mixed to ensure homogeneous feeds Each sample was split in two fractions (30 kg)sample was split in two fractions (30 kg)

The olive fruits utilized in each experimental The olive fruits utilized in each experimental runs (runs ( 60 kg) were preliminary and suitably 60 kg) were preliminary and suitably mixed to ensure homogeneous feeds Each mixed to ensure homogeneous feeds Each sample was split in two fractions (30 kg)sample was split in two fractions (30 kg)

Traditional extraction

process

Traditional extraction

process

Addition of CO2s

Addition of CO2s

Origin and cultivar of the raw matter Origin and cultivar of the raw matter utilizedutilized

Origin and cultivar of the raw matter Origin and cultivar of the raw matter utilizedutilized

Sample ID Geographical

Cultivar

Traditional

Cryo origin

A 1 Tuscany (GR)

Frantoio

B 2 Tuscany (SI) mix

C 3 Tuscany (SI) mix

D 4 Tuscany (SI) mix

E 5 Basilicata (PZ)

Coratina

F 6 Basilicata (PZ)

Coratina

G 7 Basilicata (PZ)

Coratina

Frantoio Leccino Correggiolo Frantoio Leccino Correggiolo

CryoCryo TraditionalTraditional

Cryogenolives (ww)Cryogenolives (ww) 02 02 00

Temperature of olivesTemperature of olives (degC)(degC) ~-2~-2 115115

Temperature of pasteTemperature of paste (degC)(degC) ~240~240 ~240~240

Time of MalaxationTime of Malaxation (s)(s) 24002400 24002400

Time of ExtractionTime of Extraction (s)(s) 49004900 43004300

Water addedolivesWater addedolives ()() 8585 9393

Main operating variables adopted Main operating variables adopted during the experimental runs during the experimental runs

Total OIL entrance(kg of crushed fruits x of oil inside the olives)

= Total OIL output

(kg of the olive residues x of oil inside the olive residues)

+EXTRACTED OIL

Total OIL entrance(kg of crushed fruits x of oil inside the olives)

= Total OIL output

(kg of the olive residues x of oil inside the olive residues)

+EXTRACTED OIL

MASS BALANCE during extraction MASS BALANCE during extraction processprocess

In order to evaluate the effect induced by the addition of cryogen on the oil extraction yield

the Extractability Index Variation (EIV) was determined as the percentage of the variation of oil extractability using CO2s compared with the same parameter obtained by a traditional

extraction process

In order to evaluate the effect induced by the addition of cryogen on the oil extraction yield

the Extractability Index Variation (EIV) was determined as the percentage of the variation of oil extractability using CO2s compared with the same parameter obtained by a traditional

extraction process EIV = (EC-ET)ET EIV = (EC-ET)ET 100 100EIV = (EC-ET)ET EIV = (EC-ET)ET 100 100

Results and Results and discussiondiscussion

Results and Results and discussiondiscussion

Oil extraction Oil extraction yield yield

preliminary preliminary resultsresults

Oil extraction yield Oil extraction yield preliminary preliminary resultsresults

Oil extraction yield Oil extraction yield preliminary preliminary resultsresults

Run EC ET

1A 858 825

2B 855 772

3C 912 827

4D 841 748

5E 808 793

6F 736 689

7G 844 774

The direct addition of cryogen to the olives during pre-milling phase could induce a general increase in the oil extraction yield ranging from 2 to

124

The direct addition of cryogen to the olives during pre-milling phase could induce a general increase in the oil extraction yield ranging from 2 to

124

[(EC-ET)ET]10040 108 103 124 19 68 90

[(EC-ET)ET]10040 108 103 124 19 68 90

Preliminary results about oil extraction Preliminary results about oil extraction yield yield discussion Idiscussion I

Preliminary results about oil extraction Preliminary results about oil extraction yield yield discussion Idiscussion I

The number of the experimental runs carried out until now is quite reduced

The number of the experimental runs carried out until now is quite reduced

BUTBUT

The results appear very encouraging and the new method seems very suitable for olive oil extraction

The results appear very encouraging and the new method seems very suitable for olive oil extraction

During the next crop season we will increase the number of experimental runs adopting several combinations of the working parameters (ie amount of cryogenamount of olives fruit ripening stage etc)

During the next crop season we will increase the number of experimental runs adopting several combinations of the working parameters (ie amount of cryogenamount of olives fruit ripening stage etc)

Preliminary results about oil extraction Preliminary results about oil extraction yield yield discussion IIdiscussion II

Preliminary results about oil extraction Preliminary results about oil extraction yield yield discussion IIdiscussion II

If necessary this method allows to move up the olive harvest time in order to greatly reduce the damages due to the third fly attack of Bactrocera oleae that can induce a significant loss in oil production (up to 60) as well as a decrease in oil quality

If necessary this method allows to move up the olive harvest time in order to greatly reduce the damages due to the third fly attack of Bactrocera oleae that can induce a significant loss in oil production (up to 60) as well as a decrease in oil quality

Water content

inside the fruit

Water content

inside the fruit

CELLULAR CRASH

We need 08 kg of CO2s to lower 100 kg of olives temperature by 1degC

Cost of 1 kg of CO2s= euro050 $ 037

Cost to turn down the average temperature of 100

kg of olives by 10degC(15degC 5degC )

08kgdegC x 10degC x 037 $kg=

3 $

Considering an average oil yield of 15

The addition cost for a kg of extravirgin olive oil is

3 $100 kg olives x 15100kg oilkg olives

lt 02$kg oil

Oil elemental Oil elemental profile profile

preliminary preliminary resultsresults

ICP-AES and ICP-MS techniques are particularly advantageous for the application in the definition of the elemental profiles of olive oil since they allow simultaneous multi-elemental analysis and are characterized by wide linear ranges and (especially ICP-MS) very low Detection Limits

Main analytical issues are related to the hard organic content of the oil matrix which requires appropriate sample pre-treatments Microwave-assisted digestion permitted to obtain a complete dissolution of olive oil samples but resulted in the obtainment of highly acidic solutions not directly analyzable by ICP-MS with a consequent reduction of sensitivity (due to the preliminary 110 dilution of the mineralized olive oil)

ETV

LA

Preliminary results about oil elemental Preliminary results about oil elemental profileprofile

Preliminary results about oil elemental Preliminary results about oil elemental profileprofile

Preliminary results show a rather homogeneous elemental content among all the analyzed samples of olive oil

For all elements experimental concentrations fall within the ranges reported in literature In respect to these ranges analyzed samples show a high content of B S and Si while Fe Na Pb Ba Cr and Cu contents are quite low

Samples of olive oil obtained by the traditionalldquo process show - in general - a higher content of Ca Cr Mg Si (except those originating from Basilicata) and Zn compared to those obtained by the addition of ldquocarbonic snowldquo

0

20

40

60

80

100

120

140

B Ca Fe Na S Si

mgk

g

000

050

100

150

200

250

300

350

400

450

500

Al K Mg P Zn

mgk

g

0

500

1000

1500

2000

2500

3000

3500

Co Cr Cu Ni Pb

microgk

g

0

2

4

6

8

10

12

14

16

Ce Er Eu Gd La Nd Pr Sm Y Yb

microgk

g

0

100

200

300

400

500

600

700

800

As Ba Cd Li Mn Rb Sb Sc Se Sr Th Ti V

microgk

g

4000 25000

0

20

40

60

80

100

120

140

160

Ca

Na

Si

concentration range obtained from literature [2]

experimental concentration range ICP-AESDetection LimitICP-MSDetection Limit - Normal Sensitivity modeICP-MSDetection Limit - High Sensitivitymode

S B Yasar E K Baran M Alkan Metal determinations in olive oil In Olive Oil ndash Constituents Quality Health Properties and Bioconversions Ed by Boskou Dimitrios 5 89-108 2012

Preliminary results about oil elemental Preliminary results about oil elemental profileprofile

Preliminary results about oil elemental Preliminary results about oil elemental profileprofile

For any further details about the second part of the research you can contact our colleagues in ENEA

claudiazoanieneait giovannazappaeneait

For any further details about the second part of the research you can contact our colleagues in ENEA

claudiazoanieneait giovannazappaeneait

ReferencesReferencesReferencesReferences

The Utilization of Solid Carbon Dioxide in the Production of Extravirgin Olive Oil

Sanmartin C Zinnai A Venturi F Andrich G Proceedings of EFFOST 2011 9-11 November 2011 Berlino

(D)

Analytical methods for olive oil elemental profile and influence of carbonic snow addition in the extraction

phase C Zoani G Zappa A Zinnai F Venturi C Sanmartin

11th Euro Fed Lipid Congress ndash Antalya (Turkey) 27-30 October 2013

Preliminary results on the influence of carbonic snow addition during the olive processing oil extraction yield

and elemental profile C Zoani G Zappa F Venturi C Sanmartin G Andrich and

A ZinnaiJournal of Nutrition and Food Sciences 4 277 (2014)

doi 1041722155-96001000277

The Utilization of Solid Carbon Dioxide in the Production of Extravirgin Olive Oil

Sanmartin C Zinnai A Venturi F Andrich G Proceedings of EFFOST 2011 9-11 November 2011 Berlino

(D)

Analytical methods for olive oil elemental profile and influence of carbonic snow addition in the extraction

phase C Zoani G Zappa A Zinnai F Venturi C Sanmartin

11th Euro Fed Lipid Congress ndash Antalya (Turkey) 27-30 October 2013

Preliminary results on the influence of carbonic snow addition during the olive processing oil extraction yield

and elemental profile C Zoani G Zappa F Venturi C Sanmartin G Andrich and

A ZinnaiJournal of Nutrition and Food Sciences 4 277 (2014)

doi 1041722155-96001000277

Research in progresshellipResearch in progresshellip

Thank you for your attention

Thank you for your attention

research supported by

It will be possible to apply matrix modification procedures (eg solvent extraction ndash also ultrasound assisted - addition of organic solvents or emulsification) or to employ systems for direct oil sample introduction in torch (eg Flow Injection Analysis systems)

We are conducting experimental tests for evaluating the possibility to employ a Laser Ablation system or an ElectroThermal Vaporization system for direct sample introduction in ICP-AES and ICP-MS

ETV

LA

Future developmentsFuture developmentsFuture developmentsFuture developments

Determination of oil elemental profile sample pre-treatment

High PressureMicrowave Digestion

Milestone 1200 Mega

05 golive oil

Mineralized oil sample

(final V = 25 ml)

2 ml H2O2 + 6 ml HNO3

Different mixtures testedH2O2 30vv (1 divide 2 ml)+ HNO3 699vv (2 divide

6 ml)

Total dissoluti

on

high-purity water

(gt 18 MΩ)

time Power Pressure

1 min 250 WFree

pressure race

1 min 0 W

5 min 400 W

5 min 650 W

Vent = 5 min

TQ mineralized

olive oil solution

Varian Vista MPX(axial configuration

simultaneous 112 Mpixel CCD detector)

study of spectral interferencesstudy of spectral interferences

preliminary qualitative analysis72 elements

preliminary qualitative analysis72 elements

quantitative analysisquantitative analysis

Gas flows optimization based on signal-to-background ratio (SB)

Auxiliary flow (lmin)

Nebulizer flow(lmin)

10 15 09 10 11 12

SBMg 3296 11720 13948 17998 19921 18412Mn 0128 0197 0245 0312 0303 0294Na 1827 1940 1827 3187 6121 4371

Zn - 213857 nm more sensitive but interfered by Fe

Zn - 206200 nm - less sensitive but without interferences

Analytical wavelengths (nm)

Al - 396152 nm K - 766491 nm Rb - 780026 nm

As - 188980 nm Li - 670783 nm S - 181972 nm

B - 249772 nm Mg - 279553 nm Sb - 206834 nm

Ba - 455403 nm Mn - 257610 nm Si - 251611 nm

Ca - 396847 nm Na - 589592 nm Sr - 407771 nm

Cr - 267716 nm Ni - 231604 nm Ti - 334941 nm

Cu - 327395 nm P - 213618 nm V - 311837 nm

Fe - 238204 nm Pb - 220353 nm Zn ndash 206200 nm

Instrumental conditions

RF Frequency 40 MHz (free running air-cooled)

RF Power 12 kW

Gas (plasma auxiliary nebulizer) Argon

Plasma flow 150 lmin

Auxiliary flow 15 lmin

Nebulizer flow 110 lmin

Replicates 5

Replicate read time 5 s

Operating parameters for ICP-AES quantitative analysis

ICP-AES Analysis

Bruker Aurora M90 (90 degree ion mirror ion optics Collision Reaction Interface)110 diluted

mineralized olive oil solution

Tuning with a 5 microgl Be Mg Co In Ba Ce Ti Pb and Th solution for

sensitivity and resolution optimization and mass calibration

Tuning with a 5 microgl Be Mg Co In Ba Ce Ti Pb and Th solution for

sensitivity and resolution optimization and mass calibration

Check of the level of oxide ions by the CeO+Ce+ ratio lt 2

Check of the level of oxide ions by the CeO+Ce+ ratio lt 2

Monitoring of double charged ions by the signal 137Ba++137Ba+ lt 3

Monitoring of double charged ions by the signal 137Ba++137Ba+ lt 3

CheckCorrection of isobaric interferences examination of more isotopes of the same element(eg Rb85 Rb 87 Sr88Sr87 Nd142 Nd146 Nd144 Se77 Se78 Sn147 Sm148 Sm152 Gd157 Gd154 Er166 Er168 Yb170 Yb172) application of correction equations with respect to isotopes of other elements potentially interfering (eg Nd142 corrected by analyzing Ce140 Nd144 by Sm147 Sm152 by Gd157 Rb87 by Sr88 ) use of the Collision Reaction Interface ndash CRI (for As and Se)

CheckCorrection of isobaric interferences examination of more isotopes of the same element(eg Rb85 Rb 87 Sr88Sr87 Nd142 Nd146 Nd144 Se77 Se78 Sn147 Sm148 Sm152 Gd157 Gd154 Er166 Er168 Yb170 Yb172) application of correction equations with respect to isotopes of other elements potentially interfering (eg Nd142 corrected by analyzing Ce140 Nd144 by Sm147 Sm152 by Gd157 Rb87 by Sr88 ) use of the Collision Reaction Interface ndash CRI (for As and Se)

Working rangesbull005 divide 5 microgl - As Cd Ce Er Eu Gd La Mn Nd Pb Pr Rb Sb Sc Se Sm Sr Th V Y Ybbull01 divide 10 microgl - Co Cr Cu Mg Ni

Working rangesbull005 divide 5 microgl - As Cd Ce Er Eu Gd La Mn Nd Pb Pr Rb Sb Sc Se Sm Sr Th V Y Ybbull01 divide 10 microgl - Co Cr Cu Mg Ni

External calibration5 standard solutions + blankCurve Fit LinearWeighted Fit NoCorrelation coefficientsR gt 09999

Normal Sensitivity Mode (without CRI) High Sensitivity Mode As and Se ndash Normal mode with CRI

ICP-MS Analysis

• Slide 1
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• Slide 10
• Slide 11
• Slide 12
• Slide 13
• Slide 14
• Slide 15
• Slide 16
• Slide 17
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• Slide 19
• Slide 20
• Slide 21
• Slide 22
• Slide 23
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• Slide 26
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• Slide 29
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• Slide 34
• Slide 35

In order to advance in VOO technology at DAFE of In order to advance in VOO technology at DAFE of University of Pisa an University of Pisa an innovative EVOO extraction innovative EVOO extraction technologytechnology ( (Patent ndeg IT1405173-BPatent ndeg IT1405173-B) involving the ) involving the addition of a cryogen (solid COaddition of a cryogen (solid CO22) to the olives) to the olives were were developed in order to developed in order to increase the extraction increase the extraction yieldyield and to and to obtain an oil characterized by an obtain an oil characterized by an higher concentration of phenolic compounds and a higher concentration of phenolic compounds and a stronger link with the raw material and its stronger link with the raw material and its production areaproduction area

Diffusion of cellular components in the Diffusion of cellular components in the extracellular liquid phase extracellular liquid phase

CELLULAR

CRASH

WATER FREEZING

WATER VOLUME INCREASES

ADDITION CO2s

Mechanical action

Mechanical action

bull Nontoxic and does not leave Nontoxic and does not leave residualresidual

bull Inflammable and less reactiveInflammable and less reactive

bull Good solvent (non-polar)Good solvent (non-polar)

bull Inert by an organoleptic point of Inert by an organoleptic point of viewview

bull Triple point easy to reach (-Triple point easy to reach (-575degC 51atm)575degC 51atm)

bull Easy to find and to useEasy to find and to use

bull Reduced costsReduced costs

bull Anti-microbial and anti-oxidant Anti-microbial and anti-oxidant actionaction

Among all the Among all the possible possible cryogens cryogens

suitable for food suitable for food technology technology

(N(N2L2L He HeLL Ar ArLL etc) etc)

COCO2s2s (or carbonic snow) (or carbonic snow)shows a lot of advantagesshows a lot of advantages

COCO2s2s + Olivesolive paste + Olivesolive paste

Able to prevent Able to prevent the possible the possible oxidation of oxidation of extracted oilextracted oil

Increase of the Increase of the extraction yieldextraction yield

Wished Wished aromatic aromatic profile profile

Higher Higher antioxidant antioxidant

contentcontent

COCO2g2g

Modulation of Modulation of the working the working

variables related variables related toto thethe

MALAXATION MALAXATION

Inert gaseous layer Inert gaseous layer

((COCO22gg airair = 15) = 15)

b) the second goal was to develop specific analytical b) the second goal was to develop specific analytical methods for evaluating the elemental profile of olive methods for evaluating the elemental profile of olive

oil and to collect some preliminary data about the oil and to collect some preliminary data about the possibility to use these methods in order to put in possibility to use these methods in order to put in

evidence the possible influence of different process evidence the possible influence of different process conditions (extraction with or without addition of conditions (extraction with or without addition of carbonic snow) on the olive oil elemental profilecarbonic snow) on the olive oil elemental profile

b) the second goal was to develop specific analytical b) the second goal was to develop specific analytical methods for evaluating the elemental profile of olive methods for evaluating the elemental profile of olive

oil and to collect some preliminary data about the oil and to collect some preliminary data about the possibility to use these methods in order to put in possibility to use these methods in order to put in

evidence the possible influence of different process evidence the possible influence of different process conditions (extraction with or without addition of conditions (extraction with or without addition of carbonic snow) on the olive oil elemental profilecarbonic snow) on the olive oil elemental profile

Aim of the workAim of the work

a) the first goal was to verify the influence of the a) the first goal was to verify the influence of the addition of cryogen (COaddition of cryogen (CO2s2s) directly to olives during ) directly to olives during pre-milling phase on the yield of the oil production pre-milling phase on the yield of the oil production

in order to obtain a preliminary evaluation of the in order to obtain a preliminary evaluation of the suitability of the new proposed methodology for suitability of the new proposed methodology for

EVOO productionEVOO production

The main object of this The main object of this research work is twofoldresearch work is twofold

The main object of this The main object of this research work is twofoldresearch work is twofold

Materials and methodsMaterials and methodsMaterials and methodsMaterials and methods

OIL

1

2

3

4

7

20-30 kg of olivesh

5

The olive crusher utilized Oliomio Baby reg The olive crusher utilized Oliomio Baby reg (TEM)(TEM)

6

Water

CO2(s)

ldquomass cryogenrdquordquomass of fruitsrdquo 02

Wet olive residues

Knife crusher

Horizontal continuous

malaxer 2-phase decanter

Circulation of the thermal fluid

Circulation of the thermal fluid

Addition of cryogen

Addition of cryogen

Thermal probes Thermal probes

Olives Olives

The study were conducted on samples of olive The study were conducted on samples of olive oil produced from monovarietal and oil produced from monovarietal and

polyvarietal (polyvarietal (mixmix) olives collected in two ) olives collected in two different Italian regions (from Tuscany and different Italian regions (from Tuscany and

Basilicata) during the same season Basilicata) during the same season

The study were conducted on samples of olive The study were conducted on samples of olive oil produced from monovarietal and oil produced from monovarietal and

polyvarietal (polyvarietal (mixmix) olives collected in two ) olives collected in two different Italian regions (from Tuscany and different Italian regions (from Tuscany and

Basilicata) during the same season Basilicata) during the same season

The olive fruits utilized in each experimental The olive fruits utilized in each experimental runs (runs ( 60 kg) were preliminary and suitably 60 kg) were preliminary and suitably mixed to ensure homogeneous feeds Each mixed to ensure homogeneous feeds Each sample was split in two fractions (30 kg)sample was split in two fractions (30 kg)

The olive fruits utilized in each experimental The olive fruits utilized in each experimental runs (runs ( 60 kg) were preliminary and suitably 60 kg) were preliminary and suitably mixed to ensure homogeneous feeds Each mixed to ensure homogeneous feeds Each sample was split in two fractions (30 kg)sample was split in two fractions (30 kg)

Traditional extraction

process

Traditional extraction

process

Addition of CO2s

Addition of CO2s

Origin and cultivar of the raw matter Origin and cultivar of the raw matter utilizedutilized

Origin and cultivar of the raw matter Origin and cultivar of the raw matter utilizedutilized

Sample ID Geographical

Cultivar

Traditional

Cryo origin

A 1 Tuscany (GR)

Frantoio

B 2 Tuscany (SI) mix

C 3 Tuscany (SI) mix

D 4 Tuscany (SI) mix

E 5 Basilicata (PZ)

Coratina

F 6 Basilicata (PZ)

Coratina

G 7 Basilicata (PZ)

Coratina

Frantoio Leccino Correggiolo Frantoio Leccino Correggiolo

CryoCryo TraditionalTraditional

Cryogenolives (ww)Cryogenolives (ww) 02 02 00

Temperature of olivesTemperature of olives (degC)(degC) ~-2~-2 115115

Temperature of pasteTemperature of paste (degC)(degC) ~240~240 ~240~240

Time of MalaxationTime of Malaxation (s)(s) 24002400 24002400

Time of ExtractionTime of Extraction (s)(s) 49004900 43004300

Water addedolivesWater addedolives ()() 8585 9393

Main operating variables adopted Main operating variables adopted during the experimental runs during the experimental runs

Total OIL entrance(kg of crushed fruits x of oil inside the olives)

= Total OIL output

(kg of the olive residues x of oil inside the olive residues)

+EXTRACTED OIL

Total OIL entrance(kg of crushed fruits x of oil inside the olives)

= Total OIL output

(kg of the olive residues x of oil inside the olive residues)

+EXTRACTED OIL

MASS BALANCE during extraction MASS BALANCE during extraction processprocess

In order to evaluate the effect induced by the addition of cryogen on the oil extraction yield

the Extractability Index Variation (EIV) was determined as the percentage of the variation of oil extractability using CO2s compared with the same parameter obtained by a traditional

extraction process

In order to evaluate the effect induced by the addition of cryogen on the oil extraction yield

the Extractability Index Variation (EIV) was determined as the percentage of the variation of oil extractability using CO2s compared with the same parameter obtained by a traditional

extraction process EIV = (EC-ET)ET EIV = (EC-ET)ET 100 100EIV = (EC-ET)ET EIV = (EC-ET)ET 100 100

Results and Results and discussiondiscussion

Results and Results and discussiondiscussion

Oil extraction Oil extraction yield yield

preliminary preliminary resultsresults

Oil extraction yield Oil extraction yield preliminary preliminary resultsresults

Oil extraction yield Oil extraction yield preliminary preliminary resultsresults

Run EC ET

1A 858 825

2B 855 772

3C 912 827

4D 841 748

5E 808 793

6F 736 689

7G 844 774

The direct addition of cryogen to the olives during pre-milling phase could induce a general increase in the oil extraction yield ranging from 2 to

124

The direct addition of cryogen to the olives during pre-milling phase could induce a general increase in the oil extraction yield ranging from 2 to

124

[(EC-ET)ET]10040 108 103 124 19 68 90

[(EC-ET)ET]10040 108 103 124 19 68 90

Preliminary results about oil extraction Preliminary results about oil extraction yield yield discussion Idiscussion I

Preliminary results about oil extraction Preliminary results about oil extraction yield yield discussion Idiscussion I

The number of the experimental runs carried out until now is quite reduced

The number of the experimental runs carried out until now is quite reduced

BUTBUT

The results appear very encouraging and the new method seems very suitable for olive oil extraction

The results appear very encouraging and the new method seems very suitable for olive oil extraction

During the next crop season we will increase the number of experimental runs adopting several combinations of the working parameters (ie amount of cryogenamount of olives fruit ripening stage etc)

During the next crop season we will increase the number of experimental runs adopting several combinations of the working parameters (ie amount of cryogenamount of olives fruit ripening stage etc)

Preliminary results about oil extraction Preliminary results about oil extraction yield yield discussion IIdiscussion II

Preliminary results about oil extraction Preliminary results about oil extraction yield yield discussion IIdiscussion II

If necessary this method allows to move up the olive harvest time in order to greatly reduce the damages due to the third fly attack of Bactrocera oleae that can induce a significant loss in oil production (up to 60) as well as a decrease in oil quality

If necessary this method allows to move up the olive harvest time in order to greatly reduce the damages due to the third fly attack of Bactrocera oleae that can induce a significant loss in oil production (up to 60) as well as a decrease in oil quality

Water content

inside the fruit

Water content

inside the fruit

CELLULAR CRASH

We need 08 kg of CO2s to lower 100 kg of olives temperature by 1degC

Cost of 1 kg of CO2s= euro050 $ 037

Cost to turn down the average temperature of 100

kg of olives by 10degC(15degC 5degC )

08kgdegC x 10degC x 037 $kg=

3 $

Considering an average oil yield of 15

The addition cost for a kg of extravirgin olive oil is

3 $100 kg olives x 15100kg oilkg olives

lt 02$kg oil

Oil elemental Oil elemental profile profile

preliminary preliminary resultsresults

ICP-AES and ICP-MS techniques are particularly advantageous for the application in the definition of the elemental profiles of olive oil since they allow simultaneous multi-elemental analysis and are characterized by wide linear ranges and (especially ICP-MS) very low Detection Limits

Main analytical issues are related to the hard organic content of the oil matrix which requires appropriate sample pre-treatments Microwave-assisted digestion permitted to obtain a complete dissolution of olive oil samples but resulted in the obtainment of highly acidic solutions not directly analyzable by ICP-MS with a consequent reduction of sensitivity (due to the preliminary 110 dilution of the mineralized olive oil)

ETV

LA

Preliminary results about oil elemental Preliminary results about oil elemental profileprofile

Preliminary results about oil elemental Preliminary results about oil elemental profileprofile

Preliminary results show a rather homogeneous elemental content among all the analyzed samples of olive oil

For all elements experimental concentrations fall within the ranges reported in literature In respect to these ranges analyzed samples show a high content of B S and Si while Fe Na Pb Ba Cr and Cu contents are quite low

Samples of olive oil obtained by the traditionalldquo process show - in general - a higher content of Ca Cr Mg Si (except those originating from Basilicata) and Zn compared to those obtained by the addition of ldquocarbonic snowldquo

0

20

40

60

80

100

120

140

B Ca Fe Na S Si

mgk

g

000

050

100

150

200

250

300

350

400

450

500

Al K Mg P Zn

mgk

g

0

500

1000

1500

2000

2500

3000

3500

Co Cr Cu Ni Pb

microgk

g

0

2

4

6

8

10

12

14

16

Ce Er Eu Gd La Nd Pr Sm Y Yb

microgk

g

0

100

200

300

400

500

600

700

800

As Ba Cd Li Mn Rb Sb Sc Se Sr Th Ti V

microgk

g

4000 25000

0

20

40

60

80

100

120

140

160

Ca

Na

Si

concentration range obtained from literature [2]

experimental concentration range ICP-AESDetection LimitICP-MSDetection Limit - Normal Sensitivity modeICP-MSDetection Limit - High Sensitivitymode

S B Yasar E K Baran M Alkan Metal determinations in olive oil In Olive Oil ndash Constituents Quality Health Properties and Bioconversions Ed by Boskou Dimitrios 5 89-108 2012

Preliminary results about oil elemental Preliminary results about oil elemental profileprofile

Preliminary results about oil elemental Preliminary results about oil elemental profileprofile

For any further details about the second part of the research you can contact our colleagues in ENEA

claudiazoanieneait giovannazappaeneait

For any further details about the second part of the research you can contact our colleagues in ENEA

claudiazoanieneait giovannazappaeneait

ReferencesReferencesReferencesReferences

The Utilization of Solid Carbon Dioxide in the Production of Extravirgin Olive Oil

Sanmartin C Zinnai A Venturi F Andrich G Proceedings of EFFOST 2011 9-11 November 2011 Berlino

(D)

Analytical methods for olive oil elemental profile and influence of carbonic snow addition in the extraction

phase C Zoani G Zappa A Zinnai F Venturi C Sanmartin

11th Euro Fed Lipid Congress ndash Antalya (Turkey) 27-30 October 2013

Preliminary results on the influence of carbonic snow addition during the olive processing oil extraction yield

and elemental profile C Zoani G Zappa F Venturi C Sanmartin G Andrich and

A ZinnaiJournal of Nutrition and Food Sciences 4 277 (2014)

doi 1041722155-96001000277

The Utilization of Solid Carbon Dioxide in the Production of Extravirgin Olive Oil

Sanmartin C Zinnai A Venturi F Andrich G Proceedings of EFFOST 2011 9-11 November 2011 Berlino

(D)

Analytical methods for olive oil elemental profile and influence of carbonic snow addition in the extraction

phase C Zoani G Zappa A Zinnai F Venturi C Sanmartin

11th Euro Fed Lipid Congress ndash Antalya (Turkey) 27-30 October 2013

Preliminary results on the influence of carbonic snow addition during the olive processing oil extraction yield

and elemental profile C Zoani G Zappa F Venturi C Sanmartin G Andrich and

A ZinnaiJournal of Nutrition and Food Sciences 4 277 (2014)

doi 1041722155-96001000277

Research in progresshellipResearch in progresshellip

Thank you for your attention

Thank you for your attention

research supported by

It will be possible to apply matrix modification procedures (eg solvent extraction ndash also ultrasound assisted - addition of organic solvents or emulsification) or to employ systems for direct oil sample introduction in torch (eg Flow Injection Analysis systems)

We are conducting experimental tests for evaluating the possibility to employ a Laser Ablation system or an ElectroThermal Vaporization system for direct sample introduction in ICP-AES and ICP-MS

ETV

LA

Future developmentsFuture developmentsFuture developmentsFuture developments

Determination of oil elemental profile sample pre-treatment

High PressureMicrowave Digestion

Milestone 1200 Mega

05 golive oil

Mineralized oil sample

(final V = 25 ml)

2 ml H2O2 + 6 ml HNO3

Different mixtures testedH2O2 30vv (1 divide 2 ml)+ HNO3 699vv (2 divide

6 ml)

Total dissoluti

on

high-purity water

(gt 18 MΩ)

time Power Pressure

1 min 250 WFree

pressure race

1 min 0 W

5 min 400 W

5 min 650 W

Vent = 5 min

TQ mineralized

olive oil solution

Varian Vista MPX(axial configuration

simultaneous 112 Mpixel CCD detector)

study of spectral interferencesstudy of spectral interferences

preliminary qualitative analysis72 elements

preliminary qualitative analysis72 elements

quantitative analysisquantitative analysis

Gas flows optimization based on signal-to-background ratio (SB)

Auxiliary flow (lmin)

Nebulizer flow(lmin)

10 15 09 10 11 12

SBMg 3296 11720 13948 17998 19921 18412Mn 0128 0197 0245 0312 0303 0294Na 1827 1940 1827 3187 6121 4371

Zn - 213857 nm more sensitive but interfered by Fe

Zn - 206200 nm - less sensitive but without interferences

Analytical wavelengths (nm)

Al - 396152 nm K - 766491 nm Rb - 780026 nm

As - 188980 nm Li - 670783 nm S - 181972 nm

B - 249772 nm Mg - 279553 nm Sb - 206834 nm

Ba - 455403 nm Mn - 257610 nm Si - 251611 nm

Ca - 396847 nm Na - 589592 nm Sr - 407771 nm

Cr - 267716 nm Ni - 231604 nm Ti - 334941 nm

Cu - 327395 nm P - 213618 nm V - 311837 nm

Fe - 238204 nm Pb - 220353 nm Zn ndash 206200 nm

Instrumental conditions

RF Frequency 40 MHz (free running air-cooled)

RF Power 12 kW

Gas (plasma auxiliary nebulizer) Argon

Plasma flow 150 lmin

Auxiliary flow 15 lmin

Nebulizer flow 110 lmin

Replicates 5

Replicate read time 5 s

Operating parameters for ICP-AES quantitative analysis

ICP-AES Analysis

Bruker Aurora M90 (90 degree ion mirror ion optics Collision Reaction Interface)110 diluted

mineralized olive oil solution

Tuning with a 5 microgl Be Mg Co In Ba Ce Ti Pb and Th solution for

sensitivity and resolution optimization and mass calibration

Tuning with a 5 microgl Be Mg Co In Ba Ce Ti Pb and Th solution for

sensitivity and resolution optimization and mass calibration

Check of the level of oxide ions by the CeO+Ce+ ratio lt 2

Check of the level of oxide ions by the CeO+Ce+ ratio lt 2

Monitoring of double charged ions by the signal 137Ba++137Ba+ lt 3

Monitoring of double charged ions by the signal 137Ba++137Ba+ lt 3

CheckCorrection of isobaric interferences examination of more isotopes of the same element(eg Rb85 Rb 87 Sr88Sr87 Nd142 Nd146 Nd144 Se77 Se78 Sn147 Sm148 Sm152 Gd157 Gd154 Er166 Er168 Yb170 Yb172) application of correction equations with respect to isotopes of other elements potentially interfering (eg Nd142 corrected by analyzing Ce140 Nd144 by Sm147 Sm152 by Gd157 Rb87 by Sr88 ) use of the Collision Reaction Interface ndash CRI (for As and Se)

CheckCorrection of isobaric interferences examination of more isotopes of the same element(eg Rb85 Rb 87 Sr88Sr87 Nd142 Nd146 Nd144 Se77 Se78 Sn147 Sm148 Sm152 Gd157 Gd154 Er166 Er168 Yb170 Yb172) application of correction equations with respect to isotopes of other elements potentially interfering (eg Nd142 corrected by analyzing Ce140 Nd144 by Sm147 Sm152 by Gd157 Rb87 by Sr88 ) use of the Collision Reaction Interface ndash CRI (for As and Se)

Working rangesbull005 divide 5 microgl - As Cd Ce Er Eu Gd La Mn Nd Pb Pr Rb Sb Sc Se Sm Sr Th V Y Ybbull01 divide 10 microgl - Co Cr Cu Mg Ni

Working rangesbull005 divide 5 microgl - As Cd Ce Er Eu Gd La Mn Nd Pb Pr Rb Sb Sc Se Sm Sr Th V Y Ybbull01 divide 10 microgl - Co Cr Cu Mg Ni

External calibration5 standard solutions + blankCurve Fit LinearWeighted Fit NoCorrelation coefficientsR gt 09999

Normal Sensitivity Mode (without CRI) High Sensitivity Mode As and Se ndash Normal mode with CRI

ICP-MS Analysis

• Slide 1
• Slide 2
• Slide 3
• Slide 4
• Slide 5
• Slide 6
• Slide 7
• Slide 8
• Slide 9
• Slide 10
• Slide 11
• Slide 12
• Slide 13
• Slide 14
• Slide 15
• Slide 16
• Slide 17
• Slide 18
• Slide 19
• Slide 20
• Slide 21
• Slide 22
• Slide 23
• Slide 24
• Slide 25
• Slide 26
• Slide 27
• Slide 28
• Slide 29
• Slide 30
• Slide 31
• Slide 32
• Slide 33
• Slide 34
• Slide 35

Diffusion of cellular components in the Diffusion of cellular components in the extracellular liquid phase extracellular liquid phase

CELLULAR

CRASH

WATER FREEZING

WATER VOLUME INCREASES

ADDITION CO2s

Mechanical action

Mechanical action

bull Nontoxic and does not leave Nontoxic and does not leave residualresidual

bull Inflammable and less reactiveInflammable and less reactive

bull Good solvent (non-polar)Good solvent (non-polar)

bull Inert by an organoleptic point of Inert by an organoleptic point of viewview

bull Triple point easy to reach (-Triple point easy to reach (-575degC 51atm)575degC 51atm)

bull Easy to find and to useEasy to find and to use

bull Reduced costsReduced costs

bull Anti-microbial and anti-oxidant Anti-microbial and anti-oxidant actionaction

Among all the Among all the possible possible cryogens cryogens

suitable for food suitable for food technology technology

(N(N2L2L He HeLL Ar ArLL etc) etc)

COCO2s2s (or carbonic snow) (or carbonic snow)shows a lot of advantagesshows a lot of advantages

COCO2s2s + Olivesolive paste + Olivesolive paste

Able to prevent Able to prevent the possible the possible oxidation of oxidation of extracted oilextracted oil

Increase of the Increase of the extraction yieldextraction yield

Wished Wished aromatic aromatic profile profile

Higher Higher antioxidant antioxidant

contentcontent

COCO2g2g

Modulation of Modulation of the working the working

variables related variables related toto thethe

MALAXATION MALAXATION

Inert gaseous layer Inert gaseous layer

((COCO22gg airair = 15) = 15)

b) the second goal was to develop specific analytical b) the second goal was to develop specific analytical methods for evaluating the elemental profile of olive methods for evaluating the elemental profile of olive

oil and to collect some preliminary data about the oil and to collect some preliminary data about the possibility to use these methods in order to put in possibility to use these methods in order to put in

evidence the possible influence of different process evidence the possible influence of different process conditions (extraction with or without addition of conditions (extraction with or without addition of carbonic snow) on the olive oil elemental profilecarbonic snow) on the olive oil elemental profile

b) the second goal was to develop specific analytical b) the second goal was to develop specific analytical methods for evaluating the elemental profile of olive methods for evaluating the elemental profile of olive

oil and to collect some preliminary data about the oil and to collect some preliminary data about the possibility to use these methods in order to put in possibility to use these methods in order to put in

evidence the possible influence of different process evidence the possible influence of different process conditions (extraction with or without addition of conditions (extraction with or without addition of carbonic snow) on the olive oil elemental profilecarbonic snow) on the olive oil elemental profile

Aim of the workAim of the work

a) the first goal was to verify the influence of the a) the first goal was to verify the influence of the addition of cryogen (COaddition of cryogen (CO2s2s) directly to olives during ) directly to olives during pre-milling phase on the yield of the oil production pre-milling phase on the yield of the oil production

in order to obtain a preliminary evaluation of the in order to obtain a preliminary evaluation of the suitability of the new proposed methodology for suitability of the new proposed methodology for

EVOO productionEVOO production

The main object of this The main object of this research work is twofoldresearch work is twofold

The main object of this The main object of this research work is twofoldresearch work is twofold

Materials and methodsMaterials and methodsMaterials and methodsMaterials and methods

OIL

1

2

3

4

7

20-30 kg of olivesh

5

The olive crusher utilized Oliomio Baby reg The olive crusher utilized Oliomio Baby reg (TEM)(TEM)

6

Water

CO2(s)

ldquomass cryogenrdquordquomass of fruitsrdquo 02

Wet olive residues

Knife crusher

Horizontal continuous

malaxer 2-phase decanter

Circulation of the thermal fluid

Circulation of the thermal fluid

Addition of cryogen

Addition of cryogen

Thermal probes Thermal probes

Olives Olives

The study were conducted on samples of olive The study were conducted on samples of olive oil produced from monovarietal and oil produced from monovarietal and

polyvarietal (polyvarietal (mixmix) olives collected in two ) olives collected in two different Italian regions (from Tuscany and different Italian regions (from Tuscany and

Basilicata) during the same season Basilicata) during the same season

The study were conducted on samples of olive The study were conducted on samples of olive oil produced from monovarietal and oil produced from monovarietal and

polyvarietal (polyvarietal (mixmix) olives collected in two ) olives collected in two different Italian regions (from Tuscany and different Italian regions (from Tuscany and

Basilicata) during the same season Basilicata) during the same season

The olive fruits utilized in each experimental The olive fruits utilized in each experimental runs (runs ( 60 kg) were preliminary and suitably 60 kg) were preliminary and suitably mixed to ensure homogeneous feeds Each mixed to ensure homogeneous feeds Each sample was split in two fractions (30 kg)sample was split in two fractions (30 kg)

The olive fruits utilized in each experimental The olive fruits utilized in each experimental runs (runs ( 60 kg) were preliminary and suitably 60 kg) were preliminary and suitably mixed to ensure homogeneous feeds Each mixed to ensure homogeneous feeds Each sample was split in two fractions (30 kg)sample was split in two fractions (30 kg)

Traditional extraction

process

Traditional extraction

process

Addition of CO2s

Addition of CO2s

Origin and cultivar of the raw matter Origin and cultivar of the raw matter utilizedutilized

Origin and cultivar of the raw matter Origin and cultivar of the raw matter utilizedutilized

Sample ID Geographical

Cultivar

Traditional

Cryo origin

A 1 Tuscany (GR)

Frantoio

B 2 Tuscany (SI) mix

C 3 Tuscany (SI) mix

D 4 Tuscany (SI) mix

E 5 Basilicata (PZ)

Coratina

F 6 Basilicata (PZ)

Coratina

G 7 Basilicata (PZ)

Coratina

Frantoio Leccino Correggiolo Frantoio Leccino Correggiolo

CryoCryo TraditionalTraditional

Cryogenolives (ww)Cryogenolives (ww) 02 02 00

Temperature of olivesTemperature of olives (degC)(degC) ~-2~-2 115115

Temperature of pasteTemperature of paste (degC)(degC) ~240~240 ~240~240

Time of MalaxationTime of Malaxation (s)(s) 24002400 24002400

Time of ExtractionTime of Extraction (s)(s) 49004900 43004300

Water addedolivesWater addedolives ()() 8585 9393

Main operating variables adopted Main operating variables adopted during the experimental runs during the experimental runs

Total OIL entrance(kg of crushed fruits x of oil inside the olives)

= Total OIL output

(kg of the olive residues x of oil inside the olive residues)

+EXTRACTED OIL

Total OIL entrance(kg of crushed fruits x of oil inside the olives)

= Total OIL output

(kg of the olive residues x of oil inside the olive residues)

+EXTRACTED OIL

MASS BALANCE during extraction MASS BALANCE during extraction processprocess

In order to evaluate the effect induced by the addition of cryogen on the oil extraction yield

the Extractability Index Variation (EIV) was determined as the percentage of the variation of oil extractability using CO2s compared with the same parameter obtained by a traditional

extraction process

In order to evaluate the effect induced by the addition of cryogen on the oil extraction yield

the Extractability Index Variation (EIV) was determined as the percentage of the variation of oil extractability using CO2s compared with the same parameter obtained by a traditional

extraction process EIV = (EC-ET)ET EIV = (EC-ET)ET 100 100EIV = (EC-ET)ET EIV = (EC-ET)ET 100 100

Results and Results and discussiondiscussion

Results and Results and discussiondiscussion

Oil extraction Oil extraction yield yield

preliminary preliminary resultsresults

Oil extraction yield Oil extraction yield preliminary preliminary resultsresults

Oil extraction yield Oil extraction yield preliminary preliminary resultsresults

Run EC ET

1A 858 825

2B 855 772

3C 912 827

4D 841 748

5E 808 793

6F 736 689

7G 844 774

The direct addition of cryogen to the olives during pre-milling phase could induce a general increase in the oil extraction yield ranging from 2 to

124

The direct addition of cryogen to the olives during pre-milling phase could induce a general increase in the oil extraction yield ranging from 2 to

124

[(EC-ET)ET]10040 108 103 124 19 68 90

[(EC-ET)ET]10040 108 103 124 19 68 90

Preliminary results about oil extraction Preliminary results about oil extraction yield yield discussion Idiscussion I

Preliminary results about oil extraction Preliminary results about oil extraction yield yield discussion Idiscussion I

The number of the experimental runs carried out until now is quite reduced

The number of the experimental runs carried out until now is quite reduced

BUTBUT

The results appear very encouraging and the new method seems very suitable for olive oil extraction

The results appear very encouraging and the new method seems very suitable for olive oil extraction

During the next crop season we will increase the number of experimental runs adopting several combinations of the working parameters (ie amount of cryogenamount of olives fruit ripening stage etc)

During the next crop season we will increase the number of experimental runs adopting several combinations of the working parameters (ie amount of cryogenamount of olives fruit ripening stage etc)

Preliminary results about oil extraction Preliminary results about oil extraction yield yield discussion IIdiscussion II

Preliminary results about oil extraction Preliminary results about oil extraction yield yield discussion IIdiscussion II

If necessary this method allows to move up the olive harvest time in order to greatly reduce the damages due to the third fly attack of Bactrocera oleae that can induce a significant loss in oil production (up to 60) as well as a decrease in oil quality

If necessary this method allows to move up the olive harvest time in order to greatly reduce the damages due to the third fly attack of Bactrocera oleae that can induce a significant loss in oil production (up to 60) as well as a decrease in oil quality

Water content

inside the fruit

Water content

inside the fruit

CELLULAR CRASH

We need 08 kg of CO2s to lower 100 kg of olives temperature by 1degC

Cost of 1 kg of CO2s= euro050 $ 037

Cost to turn down the average temperature of 100

kg of olives by 10degC(15degC 5degC )

08kgdegC x 10degC x 037 $kg=

3 $

Considering an average oil yield of 15

The addition cost for a kg of extravirgin olive oil is

3 $100 kg olives x 15100kg oilkg olives

lt 02$kg oil

Oil elemental Oil elemental profile profile

preliminary preliminary resultsresults

ICP-AES and ICP-MS techniques are particularly advantageous for the application in the definition of the elemental profiles of olive oil since they allow simultaneous multi-elemental analysis and are characterized by wide linear ranges and (especially ICP-MS) very low Detection Limits

Main analytical issues are related to the hard organic content of the oil matrix which requires appropriate sample pre-treatments Microwave-assisted digestion permitted to obtain a complete dissolution of olive oil samples but resulted in the obtainment of highly acidic solutions not directly analyzable by ICP-MS with a consequent reduction of sensitivity (due to the preliminary 110 dilution of the mineralized olive oil)

ETV

LA

Preliminary results about oil elemental Preliminary results about oil elemental profileprofile

Preliminary results about oil elemental Preliminary results about oil elemental profileprofile

Preliminary results show a rather homogeneous elemental content among all the analyzed samples of olive oil

For all elements experimental concentrations fall within the ranges reported in literature In respect to these ranges analyzed samples show a high content of B S and Si while Fe Na Pb Ba Cr and Cu contents are quite low

Samples of olive oil obtained by the traditionalldquo process show - in general - a higher content of Ca Cr Mg Si (except those originating from Basilicata) and Zn compared to those obtained by the addition of ldquocarbonic snowldquo

0

20

40

60

80

100

120

140

B Ca Fe Na S Si

mgk

g

000

050

100

150

200

250

300

350

400

450

500

Al K Mg P Zn

mgk

g

0

500

1000

1500

2000

2500

3000

3500

Co Cr Cu Ni Pb

microgk

g

0

2

4

6

8

10

12

14

16

Ce Er Eu Gd La Nd Pr Sm Y Yb

microgk

g

0

100

200

300

400

500

600

700

800

As Ba Cd Li Mn Rb Sb Sc Se Sr Th Ti V

microgk

g

4000 25000

0

20

40

60

80

100

120

140

160

Ca

Na

Si

concentration range obtained from literature [2]

experimental concentration range ICP-AESDetection LimitICP-MSDetection Limit - Normal Sensitivity modeICP-MSDetection Limit - High Sensitivitymode

S B Yasar E K Baran M Alkan Metal determinations in olive oil In Olive Oil ndash Constituents Quality Health Properties and Bioconversions Ed by Boskou Dimitrios 5 89-108 2012

Preliminary results about oil elemental Preliminary results about oil elemental profileprofile

Preliminary results about oil elemental Preliminary results about oil elemental profileprofile

For any further details about the second part of the research you can contact our colleagues in ENEA

claudiazoanieneait giovannazappaeneait

For any further details about the second part of the research you can contact our colleagues in ENEA

claudiazoanieneait giovannazappaeneait

ReferencesReferencesReferencesReferences

The Utilization of Solid Carbon Dioxide in the Production of Extravirgin Olive Oil

Sanmartin C Zinnai A Venturi F Andrich G Proceedings of EFFOST 2011 9-11 November 2011 Berlino

(D)

Analytical methods for olive oil elemental profile and influence of carbonic snow addition in the extraction

phase C Zoani G Zappa A Zinnai F Venturi C Sanmartin

11th Euro Fed Lipid Congress ndash Antalya (Turkey) 27-30 October 2013

Preliminary results on the influence of carbonic snow addition during the olive processing oil extraction yield

and elemental profile C Zoani G Zappa F Venturi C Sanmartin G Andrich and

A ZinnaiJournal of Nutrition and Food Sciences 4 277 (2014)

doi 1041722155-96001000277

The Utilization of Solid Carbon Dioxide in the Production of Extravirgin Olive Oil

Sanmartin C Zinnai A Venturi F Andrich G Proceedings of EFFOST 2011 9-11 November 2011 Berlino

(D)

Analytical methods for olive oil elemental profile and influence of carbonic snow addition in the extraction

phase C Zoani G Zappa A Zinnai F Venturi C Sanmartin

11th Euro Fed Lipid Congress ndash Antalya (Turkey) 27-30 October 2013

Preliminary results on the influence of carbonic snow addition during the olive processing oil extraction yield

and elemental profile C Zoani G Zappa F Venturi C Sanmartin G Andrich and

A ZinnaiJournal of Nutrition and Food Sciences 4 277 (2014)

doi 1041722155-96001000277

Research in progresshellipResearch in progresshellip

Thank you for your attention

Thank you for your attention

research supported by

It will be possible to apply matrix modification procedures (eg solvent extraction ndash also ultrasound assisted - addition of organic solvents or emulsification) or to employ systems for direct oil sample introduction in torch (eg Flow Injection Analysis systems)

We are conducting experimental tests for evaluating the possibility to employ a Laser Ablation system or an ElectroThermal Vaporization system for direct sample introduction in ICP-AES and ICP-MS

ETV

LA

Future developmentsFuture developmentsFuture developmentsFuture developments

Determination of oil elemental profile sample pre-treatment

High PressureMicrowave Digestion

Milestone 1200 Mega

05 golive oil

Mineralized oil sample

(final V = 25 ml)

2 ml H2O2 + 6 ml HNO3

Different mixtures testedH2O2 30vv (1 divide 2 ml)+ HNO3 699vv (2 divide

6 ml)

Total dissoluti

on

high-purity water

(gt 18 MΩ)

time Power Pressure

1 min 250 WFree

pressure race

1 min 0 W

5 min 400 W

5 min 650 W

Vent = 5 min

TQ mineralized

olive oil solution

Varian Vista MPX(axial configuration

simultaneous 112 Mpixel CCD detector)

study of spectral interferencesstudy of spectral interferences

preliminary qualitative analysis72 elements

preliminary qualitative analysis72 elements

quantitative analysisquantitative analysis

Gas flows optimization based on signal-to-background ratio (SB)

Auxiliary flow (lmin)

Nebulizer flow(lmin)

10 15 09 10 11 12

SBMg 3296 11720 13948 17998 19921 18412Mn 0128 0197 0245 0312 0303 0294Na 1827 1940 1827 3187 6121 4371

Zn - 213857 nm more sensitive but interfered by Fe

Zn - 206200 nm - less sensitive but without interferences

Analytical wavelengths (nm)

Al - 396152 nm K - 766491 nm Rb - 780026 nm

As - 188980 nm Li - 670783 nm S - 181972 nm

B - 249772 nm Mg - 279553 nm Sb - 206834 nm

Ba - 455403 nm Mn - 257610 nm Si - 251611 nm

Ca - 396847 nm Na - 589592 nm Sr - 407771 nm

Cr - 267716 nm Ni - 231604 nm Ti - 334941 nm

Cu - 327395 nm P - 213618 nm V - 311837 nm

Fe - 238204 nm Pb - 220353 nm Zn ndash 206200 nm

Instrumental conditions

RF Frequency 40 MHz (free running air-cooled)

RF Power 12 kW

Gas (plasma auxiliary nebulizer) Argon

Plasma flow 150 lmin

Auxiliary flow 15 lmin

Nebulizer flow 110 lmin

Replicates 5

Replicate read time 5 s

Operating parameters for ICP-AES quantitative analysis

ICP-AES Analysis

Bruker Aurora M90 (90 degree ion mirror ion optics Collision Reaction Interface)110 diluted

mineralized olive oil solution

Tuning with a 5 microgl Be Mg Co In Ba Ce Ti Pb and Th solution for

sensitivity and resolution optimization and mass calibration

Tuning with a 5 microgl Be Mg Co In Ba Ce Ti Pb and Th solution for

sensitivity and resolution optimization and mass calibration

Check of the level of oxide ions by the CeO+Ce+ ratio lt 2

Check of the level of oxide ions by the CeO+Ce+ ratio lt 2

Monitoring of double charged ions by the signal 137Ba++137Ba+ lt 3

Monitoring of double charged ions by the signal 137Ba++137Ba+ lt 3

CheckCorrection of isobaric interferences examination of more isotopes of the same element(eg Rb85 Rb 87 Sr88Sr87 Nd142 Nd146 Nd144 Se77 Se78 Sn147 Sm148 Sm152 Gd157 Gd154 Er166 Er168 Yb170 Yb172) application of correction equations with respect to isotopes of other elements potentially interfering (eg Nd142 corrected by analyzing Ce140 Nd144 by Sm147 Sm152 by Gd157 Rb87 by Sr88 ) use of the Collision Reaction Interface ndash CRI (for As and Se)

CheckCorrection of isobaric interferences examination of more isotopes of the same element(eg Rb85 Rb 87 Sr88Sr87 Nd142 Nd146 Nd144 Se77 Se78 Sn147 Sm148 Sm152 Gd157 Gd154 Er166 Er168 Yb170 Yb172) application of correction equations with respect to isotopes of other elements potentially interfering (eg Nd142 corrected by analyzing Ce140 Nd144 by Sm147 Sm152 by Gd157 Rb87 by Sr88 ) use of the Collision Reaction Interface ndash CRI (for As and Se)

Working rangesbull005 divide 5 microgl - As Cd Ce Er Eu Gd La Mn Nd Pb Pr Rb Sb Sc Se Sm Sr Th V Y Ybbull01 divide 10 microgl - Co Cr Cu Mg Ni

Working rangesbull005 divide 5 microgl - As Cd Ce Er Eu Gd La Mn Nd Pb Pr Rb Sb Sc Se Sm Sr Th V Y Ybbull01 divide 10 microgl - Co Cr Cu Mg Ni

External calibration5 standard solutions + blankCurve Fit LinearWeighted Fit NoCorrelation coefficientsR gt 09999

Normal Sensitivity Mode (without CRI) High Sensitivity Mode As and Se ndash Normal mode with CRI

ICP-MS Analysis

• Slide 1
• Slide 2
• Slide 3
• Slide 4
• Slide 5
• Slide 6
• Slide 7
• Slide 8
• Slide 9
• Slide 10
• Slide 11
• Slide 12
• Slide 13
• Slide 14
• Slide 15
• Slide 16
• Slide 17
• Slide 18
• Slide 19
• Slide 20
• Slide 21
• Slide 22
• Slide 23
• Slide 24
• Slide 25
• Slide 26
• Slide 27
• Slide 28
• Slide 29
• Slide 30
• Slide 31
• Slide 32
• Slide 33
• Slide 34
• Slide 35

bull Nontoxic and does not leave Nontoxic and does not leave residualresidual

bull Inflammable and less reactiveInflammable and less reactive

bull Good solvent (non-polar)Good solvent (non-polar)

bull Inert by an organoleptic point of Inert by an organoleptic point of viewview

bull Triple point easy to reach (-Triple point easy to reach (-575degC 51atm)575degC 51atm)

bull Easy to find and to useEasy to find and to use

bull Reduced costsReduced costs

bull Anti-microbial and anti-oxidant Anti-microbial and anti-oxidant actionaction

Among all the Among all the possible possible cryogens cryogens

suitable for food suitable for food technology technology

(N(N2L2L He HeLL Ar ArLL etc) etc)

COCO2s2s (or carbonic snow) (or carbonic snow)shows a lot of advantagesshows a lot of advantages

COCO2s2s + Olivesolive paste + Olivesolive paste

Able to prevent Able to prevent the possible the possible oxidation of oxidation of extracted oilextracted oil

Increase of the Increase of the extraction yieldextraction yield

Wished Wished aromatic aromatic profile profile

Higher Higher antioxidant antioxidant

contentcontent

COCO2g2g

Modulation of Modulation of the working the working

variables related variables related toto thethe

MALAXATION MALAXATION

Inert gaseous layer Inert gaseous layer

((COCO22gg airair = 15) = 15)

b) the second goal was to develop specific analytical b) the second goal was to develop specific analytical methods for evaluating the elemental profile of olive methods for evaluating the elemental profile of olive

oil and to collect some preliminary data about the oil and to collect some preliminary data about the possibility to use these methods in order to put in possibility to use these methods in order to put in

evidence the possible influence of different process evidence the possible influence of different process conditions (extraction with or without addition of conditions (extraction with or without addition of carbonic snow) on the olive oil elemental profilecarbonic snow) on the olive oil elemental profile

b) the second goal was to develop specific analytical b) the second goal was to develop specific analytical methods for evaluating the elemental profile of olive methods for evaluating the elemental profile of olive

oil and to collect some preliminary data about the oil and to collect some preliminary data about the possibility to use these methods in order to put in possibility to use these methods in order to put in

evidence the possible influence of different process evidence the possible influence of different process conditions (extraction with or without addition of conditions (extraction with or without addition of carbonic snow) on the olive oil elemental profilecarbonic snow) on the olive oil elemental profile

Aim of the workAim of the work

a) the first goal was to verify the influence of the a) the first goal was to verify the influence of the addition of cryogen (COaddition of cryogen (CO2s2s) directly to olives during ) directly to olives during pre-milling phase on the yield of the oil production pre-milling phase on the yield of the oil production

in order to obtain a preliminary evaluation of the in order to obtain a preliminary evaluation of the suitability of the new proposed methodology for suitability of the new proposed methodology for

EVOO productionEVOO production

The main object of this The main object of this research work is twofoldresearch work is twofold

The main object of this The main object of this research work is twofoldresearch work is twofold

Materials and methodsMaterials and methodsMaterials and methodsMaterials and methods

OIL

1

2

3

4

7

20-30 kg of olivesh

5

The olive crusher utilized Oliomio Baby reg The olive crusher utilized Oliomio Baby reg (TEM)(TEM)

6

Water

CO2(s)

ldquomass cryogenrdquordquomass of fruitsrdquo 02

Wet olive residues

Knife crusher

Horizontal continuous

malaxer 2-phase decanter

Circulation of the thermal fluid

Circulation of the thermal fluid

Addition of cryogen

Addition of cryogen

Thermal probes Thermal probes

Olives Olives

The study were conducted on samples of olive The study were conducted on samples of olive oil produced from monovarietal and oil produced from monovarietal and

polyvarietal (polyvarietal (mixmix) olives collected in two ) olives collected in two different Italian regions (from Tuscany and different Italian regions (from Tuscany and

Basilicata) during the same season Basilicata) during the same season

The study were conducted on samples of olive The study were conducted on samples of olive oil produced from monovarietal and oil produced from monovarietal and

polyvarietal (polyvarietal (mixmix) olives collected in two ) olives collected in two different Italian regions (from Tuscany and different Italian regions (from Tuscany and

Basilicata) during the same season Basilicata) during the same season

The olive fruits utilized in each experimental The olive fruits utilized in each experimental runs (runs ( 60 kg) were preliminary and suitably 60 kg) were preliminary and suitably mixed to ensure homogeneous feeds Each mixed to ensure homogeneous feeds Each sample was split in two fractions (30 kg)sample was split in two fractions (30 kg)

The olive fruits utilized in each experimental The olive fruits utilized in each experimental runs (runs ( 60 kg) were preliminary and suitably 60 kg) were preliminary and suitably mixed to ensure homogeneous feeds Each mixed to ensure homogeneous feeds Each sample was split in two fractions (30 kg)sample was split in two fractions (30 kg)

Traditional extraction

process

Traditional extraction

process

Addition of CO2s

Addition of CO2s

Origin and cultivar of the raw matter Origin and cultivar of the raw matter utilizedutilized

Origin and cultivar of the raw matter Origin and cultivar of the raw matter utilizedutilized

Sample ID Geographical

Cultivar

Traditional

Cryo origin

A 1 Tuscany (GR)

Frantoio

B 2 Tuscany (SI) mix

C 3 Tuscany (SI) mix

D 4 Tuscany (SI) mix

E 5 Basilicata (PZ)

Coratina

F 6 Basilicata (PZ)

Coratina

G 7 Basilicata (PZ)

Coratina

Frantoio Leccino Correggiolo Frantoio Leccino Correggiolo

CryoCryo TraditionalTraditional

Cryogenolives (ww)Cryogenolives (ww) 02 02 00

Temperature of olivesTemperature of olives (degC)(degC) ~-2~-2 115115

Temperature of pasteTemperature of paste (degC)(degC) ~240~240 ~240~240

Time of MalaxationTime of Malaxation (s)(s) 24002400 24002400

Time of ExtractionTime of Extraction (s)(s) 49004900 43004300

Water addedolivesWater addedolives ()() 8585 9393

Main operating variables adopted Main operating variables adopted during the experimental runs during the experimental runs

Total OIL entrance(kg of crushed fruits x of oil inside the olives)

= Total OIL output

(kg of the olive residues x of oil inside the olive residues)

+EXTRACTED OIL

Total OIL entrance(kg of crushed fruits x of oil inside the olives)

= Total OIL output

(kg of the olive residues x of oil inside the olive residues)

+EXTRACTED OIL

MASS BALANCE during extraction MASS BALANCE during extraction processprocess

In order to evaluate the effect induced by the addition of cryogen on the oil extraction yield

the Extractability Index Variation (EIV) was determined as the percentage of the variation of oil extractability using CO2s compared with the same parameter obtained by a traditional

extraction process

In order to evaluate the effect induced by the addition of cryogen on the oil extraction yield

the Extractability Index Variation (EIV) was determined as the percentage of the variation of oil extractability using CO2s compared with the same parameter obtained by a traditional

extraction process EIV = (EC-ET)ET EIV = (EC-ET)ET 100 100EIV = (EC-ET)ET EIV = (EC-ET)ET 100 100

Results and Results and discussiondiscussion

Results and Results and discussiondiscussion

Oil extraction Oil extraction yield yield

preliminary preliminary resultsresults

Oil extraction yield Oil extraction yield preliminary preliminary resultsresults

Oil extraction yield Oil extraction yield preliminary preliminary resultsresults

Run EC ET

1A 858 825

2B 855 772

3C 912 827

4D 841 748

5E 808 793

6F 736 689

7G 844 774

The direct addition of cryogen to the olives during pre-milling phase could induce a general increase in the oil extraction yield ranging from 2 to

124

The direct addition of cryogen to the olives during pre-milling phase could induce a general increase in the oil extraction yield ranging from 2 to

124

[(EC-ET)ET]10040 108 103 124 19 68 90

[(EC-ET)ET]10040 108 103 124 19 68 90

Preliminary results about oil extraction Preliminary results about oil extraction yield yield discussion Idiscussion I

Preliminary results about oil extraction Preliminary results about oil extraction yield yield discussion Idiscussion I

The number of the experimental runs carried out until now is quite reduced

The number of the experimental runs carried out until now is quite reduced

BUTBUT

The results appear very encouraging and the new method seems very suitable for olive oil extraction

The results appear very encouraging and the new method seems very suitable for olive oil extraction

During the next crop season we will increase the number of experimental runs adopting several combinations of the working parameters (ie amount of cryogenamount of olives fruit ripening stage etc)

During the next crop season we will increase the number of experimental runs adopting several combinations of the working parameters (ie amount of cryogenamount of olives fruit ripening stage etc)

Preliminary results about oil extraction Preliminary results about oil extraction yield yield discussion IIdiscussion II

Preliminary results about oil extraction Preliminary results about oil extraction yield yield discussion IIdiscussion II

If necessary this method allows to move up the olive harvest time in order to greatly reduce the damages due to the third fly attack of Bactrocera oleae that can induce a significant loss in oil production (up to 60) as well as a decrease in oil quality

If necessary this method allows to move up the olive harvest time in order to greatly reduce the damages due to the third fly attack of Bactrocera oleae that can induce a significant loss in oil production (up to 60) as well as a decrease in oil quality

Water content

inside the fruit

Water content

inside the fruit

CELLULAR CRASH

We need 08 kg of CO2s to lower 100 kg of olives temperature by 1degC

Cost of 1 kg of CO2s= euro050 $ 037

Cost to turn down the average temperature of 100

kg of olives by 10degC(15degC 5degC )

08kgdegC x 10degC x 037 $kg=

3 $

Considering an average oil yield of 15

The addition cost for a kg of extravirgin olive oil is

3 $100 kg olives x 15100kg oilkg olives

lt 02$kg oil

Oil elemental Oil elemental profile profile

preliminary preliminary resultsresults

ICP-AES and ICP-MS techniques are particularly advantageous for the application in the definition of the elemental profiles of olive oil since they allow simultaneous multi-elemental analysis and are characterized by wide linear ranges and (especially ICP-MS) very low Detection Limits

Main analytical issues are related to the hard organic content of the oil matrix which requires appropriate sample pre-treatments Microwave-assisted digestion permitted to obtain a complete dissolution of olive oil samples but resulted in the obtainment of highly acidic solutions not directly analyzable by ICP-MS with a consequent reduction of sensitivity (due to the preliminary 110 dilution of the mineralized olive oil)

ETV

LA

Preliminary results about oil elemental Preliminary results about oil elemental profileprofile

Preliminary results about oil elemental Preliminary results about oil elemental profileprofile

Preliminary results show a rather homogeneous elemental content among all the analyzed samples of olive oil

For all elements experimental concentrations fall within the ranges reported in literature In respect to these ranges analyzed samples show a high content of B S and Si while Fe Na Pb Ba Cr and Cu contents are quite low

Samples of olive oil obtained by the traditionalldquo process show - in general - a higher content of Ca Cr Mg Si (except those originating from Basilicata) and Zn compared to those obtained by the addition of ldquocarbonic snowldquo

0

20

40

60

80

100

120

140

B Ca Fe Na S Si

mgk

g

000

050

100

150

200

250

300

350

400

450

500

Al K Mg P Zn

mgk

g

0

500

1000

1500

2000

2500

3000

3500

Co Cr Cu Ni Pb

microgk

g

0

2

4

6

8

10

12

14

16

Ce Er Eu Gd La Nd Pr Sm Y Yb

microgk

g

0

100

200

300

400

500

600

700

800

As Ba Cd Li Mn Rb Sb Sc Se Sr Th Ti V

microgk

g

4000 25000

0

20

40

60

80

100

120

140

160

Ca

Na

Si

concentration range obtained from literature [2]

experimental concentration range ICP-AESDetection LimitICP-MSDetection Limit - Normal Sensitivity modeICP-MSDetection Limit - High Sensitivitymode

S B Yasar E K Baran M Alkan Metal determinations in olive oil In Olive Oil ndash Constituents Quality Health Properties and Bioconversions Ed by Boskou Dimitrios 5 89-108 2012

Preliminary results about oil elemental Preliminary results about oil elemental profileprofile

Preliminary results about oil elemental Preliminary results about oil elemental profileprofile

For any further details about the second part of the research you can contact our colleagues in ENEA

claudiazoanieneait giovannazappaeneait

For any further details about the second part of the research you can contact our colleagues in ENEA

claudiazoanieneait giovannazappaeneait

ReferencesReferencesReferencesReferences

The Utilization of Solid Carbon Dioxide in the Production of Extravirgin Olive Oil

Sanmartin C Zinnai A Venturi F Andrich G Proceedings of EFFOST 2011 9-11 November 2011 Berlino

(D)

Analytical methods for olive oil elemental profile and influence of carbonic snow addition in the extraction

phase C Zoani G Zappa A Zinnai F Venturi C Sanmartin

11th Euro Fed Lipid Congress ndash Antalya (Turkey) 27-30 October 2013

Preliminary results on the influence of carbonic snow addition during the olive processing oil extraction yield

and elemental profile C Zoani G Zappa F Venturi C Sanmartin G Andrich and

A ZinnaiJournal of Nutrition and Food Sciences 4 277 (2014)

doi 1041722155-96001000277

The Utilization of Solid Carbon Dioxide in the Production of Extravirgin Olive Oil

Sanmartin C Zinnai A Venturi F Andrich G Proceedings of EFFOST 2011 9-11 November 2011 Berlino

(D)

Analytical methods for olive oil elemental profile and influence of carbonic snow addition in the extraction

phase C Zoani G Zappa A Zinnai F Venturi C Sanmartin

11th Euro Fed Lipid Congress ndash Antalya (Turkey) 27-30 October 2013

Preliminary results on the influence of carbonic snow addition during the olive processing oil extraction yield

and elemental profile C Zoani G Zappa F Venturi C Sanmartin G Andrich and

A ZinnaiJournal of Nutrition and Food Sciences 4 277 (2014)

doi 1041722155-96001000277

Research in progresshellipResearch in progresshellip

Thank you for your attention

Thank you for your attention

research supported by

It will be possible to apply matrix modification procedures (eg solvent extraction ndash also ultrasound assisted - addition of organic solvents or emulsification) or to employ systems for direct oil sample introduction in torch (eg Flow Injection Analysis systems)

We are conducting experimental tests for evaluating the possibility to employ a Laser Ablation system or an ElectroThermal Vaporization system for direct sample introduction in ICP-AES and ICP-MS

ETV

LA

Future developmentsFuture developmentsFuture developmentsFuture developments

Determination of oil elemental profile sample pre-treatment

High PressureMicrowave Digestion

Milestone 1200 Mega

05 golive oil

Mineralized oil sample

(final V = 25 ml)

2 ml H2O2 + 6 ml HNO3

Different mixtures testedH2O2 30vv (1 divide 2 ml)+ HNO3 699vv (2 divide

6 ml)

Total dissoluti

on

high-purity water

(gt 18 MΩ)

time Power Pressure

1 min 250 WFree

pressure race

1 min 0 W

5 min 400 W

5 min 650 W

Vent = 5 min

TQ mineralized

olive oil solution

Varian Vista MPX(axial configuration

simultaneous 112 Mpixel CCD detector)

study of spectral interferencesstudy of spectral interferences

preliminary qualitative analysis72 elements

preliminary qualitative analysis72 elements

quantitative analysisquantitative analysis

Gas flows optimization based on signal-to-background ratio (SB)

Auxiliary flow (lmin)

Nebulizer flow(lmin)

10 15 09 10 11 12

SBMg 3296 11720 13948 17998 19921 18412Mn 0128 0197 0245 0312 0303 0294Na 1827 1940 1827 3187 6121 4371

Zn - 213857 nm more sensitive but interfered by Fe

Zn - 206200 nm - less sensitive but without interferences

Analytical wavelengths (nm)

Al - 396152 nm K - 766491 nm Rb - 780026 nm

As - 188980 nm Li - 670783 nm S - 181972 nm

B - 249772 nm Mg - 279553 nm Sb - 206834 nm

Ba - 455403 nm Mn - 257610 nm Si - 251611 nm

Ca - 396847 nm Na - 589592 nm Sr - 407771 nm

Cr - 267716 nm Ni - 231604 nm Ti - 334941 nm

Cu - 327395 nm P - 213618 nm V - 311837 nm

Fe - 238204 nm Pb - 220353 nm Zn ndash 206200 nm

Instrumental conditions

RF Frequency 40 MHz (free running air-cooled)

RF Power 12 kW

Gas (plasma auxiliary nebulizer) Argon

Plasma flow 150 lmin

Auxiliary flow 15 lmin

Nebulizer flow 110 lmin

Replicates 5

Replicate read time 5 s

Operating parameters for ICP-AES quantitative analysis

ICP-AES Analysis

Bruker Aurora M90 (90 degree ion mirror ion optics Collision Reaction Interface)110 diluted

mineralized olive oil solution

Tuning with a 5 microgl Be Mg Co In Ba Ce Ti Pb and Th solution for

sensitivity and resolution optimization and mass calibration

Tuning with a 5 microgl Be Mg Co In Ba Ce Ti Pb and Th solution for

sensitivity and resolution optimization and mass calibration

Check of the level of oxide ions by the CeO+Ce+ ratio lt 2

Check of the level of oxide ions by the CeO+Ce+ ratio lt 2

Monitoring of double charged ions by the signal 137Ba++137Ba+ lt 3

Monitoring of double charged ions by the signal 137Ba++137Ba+ lt 3

CheckCorrection of isobaric interferences examination of more isotopes of the same element(eg Rb85 Rb 87 Sr88Sr87 Nd142 Nd146 Nd144 Se77 Se78 Sn147 Sm148 Sm152 Gd157 Gd154 Er166 Er168 Yb170 Yb172) application of correction equations with respect to isotopes of other elements potentially interfering (eg Nd142 corrected by analyzing Ce140 Nd144 by Sm147 Sm152 by Gd157 Rb87 by Sr88 ) use of the Collision Reaction Interface ndash CRI (for As and Se)

CheckCorrection of isobaric interferences examination of more isotopes of the same element(eg Rb85 Rb 87 Sr88Sr87 Nd142 Nd146 Nd144 Se77 Se78 Sn147 Sm148 Sm152 Gd157 Gd154 Er166 Er168 Yb170 Yb172) application of correction equations with respect to isotopes of other elements potentially interfering (eg Nd142 corrected by analyzing Ce140 Nd144 by Sm147 Sm152 by Gd157 Rb87 by Sr88 ) use of the Collision Reaction Interface ndash CRI (for As and Se)

Working rangesbull005 divide 5 microgl - As Cd Ce Er Eu Gd La Mn Nd Pb Pr Rb Sb Sc Se Sm Sr Th V Y Ybbull01 divide 10 microgl - Co Cr Cu Mg Ni

Working rangesbull005 divide 5 microgl - As Cd Ce Er Eu Gd La Mn Nd Pb Pr Rb Sb Sc Se Sm Sr Th V Y Ybbull01 divide 10 microgl - Co Cr Cu Mg Ni

External calibration5 standard solutions + blankCurve Fit LinearWeighted Fit NoCorrelation coefficientsR gt 09999

Normal Sensitivity Mode (without CRI) High Sensitivity Mode As and Se ndash Normal mode with CRI

ICP-MS Analysis

• Slide 1
• Slide 2
• Slide 3
• Slide 4
• Slide 5
• Slide 6
• Slide 7
• Slide 8
• Slide 9
• Slide 10
• Slide 11
• Slide 12
• Slide 13
• Slide 14
• Slide 15
• Slide 16
• Slide 17
• Slide 18
• Slide 19
• Slide 20
• Slide 21
• Slide 22
• Slide 23
• Slide 24
• Slide 25
• Slide 26
• Slide 27
• Slide 28
• Slide 29
• Slide 30
• Slide 31
• Slide 32
• Slide 33
• Slide 34
• Slide 35

COCO2s2s + Olivesolive paste + Olivesolive paste

Able to prevent Able to prevent the possible the possible oxidation of oxidation of extracted oilextracted oil

Increase of the Increase of the extraction yieldextraction yield

Wished Wished aromatic aromatic profile profile

Higher Higher antioxidant antioxidant

contentcontent

COCO2g2g

Modulation of Modulation of the working the working

variables related variables related toto thethe

MALAXATION MALAXATION

Inert gaseous layer Inert gaseous layer

((COCO22gg airair = 15) = 15)

b) the second goal was to develop specific analytical b) the second goal was to develop specific analytical methods for evaluating the elemental profile of olive methods for evaluating the elemental profile of olive

oil and to collect some preliminary data about the oil and to collect some preliminary data about the possibility to use these methods in order to put in possibility to use these methods in order to put in

evidence the possible influence of different process evidence the possible influence of different process conditions (extraction with or without addition of conditions (extraction with or without addition of carbonic snow) on the olive oil elemental profilecarbonic snow) on the olive oil elemental profile

b) the second goal was to develop specific analytical b) the second goal was to develop specific analytical methods for evaluating the elemental profile of olive methods for evaluating the elemental profile of olive

oil and to collect some preliminary data about the oil and to collect some preliminary data about the possibility to use these methods in order to put in possibility to use these methods in order to put in

evidence the possible influence of different process evidence the possible influence of different process conditions (extraction with or without addition of conditions (extraction with or without addition of carbonic snow) on the olive oil elemental profilecarbonic snow) on the olive oil elemental profile

Aim of the workAim of the work

a) the first goal was to verify the influence of the a) the first goal was to verify the influence of the addition of cryogen (COaddition of cryogen (CO2s2s) directly to olives during ) directly to olives during pre-milling phase on the yield of the oil production pre-milling phase on the yield of the oil production

in order to obtain a preliminary evaluation of the in order to obtain a preliminary evaluation of the suitability of the new proposed methodology for suitability of the new proposed methodology for

EVOO productionEVOO production

The main object of this The main object of this research work is twofoldresearch work is twofold

The main object of this The main object of this research work is twofoldresearch work is twofold

Materials and methodsMaterials and methodsMaterials and methodsMaterials and methods

OIL

1

2

3

4

7

20-30 kg of olivesh

5

The olive crusher utilized Oliomio Baby reg The olive crusher utilized Oliomio Baby reg (TEM)(TEM)

6

Water

CO2(s)

ldquomass cryogenrdquordquomass of fruitsrdquo 02

Wet olive residues

Knife crusher

Horizontal continuous

malaxer 2-phase decanter

Circulation of the thermal fluid

Circulation of the thermal fluid

Addition of cryogen

Addition of cryogen

Thermal probes Thermal probes

Olives Olives

The study were conducted on samples of olive The study were conducted on samples of olive oil produced from monovarietal and oil produced from monovarietal and

polyvarietal (polyvarietal (mixmix) olives collected in two ) olives collected in two different Italian regions (from Tuscany and different Italian regions (from Tuscany and

Basilicata) during the same season Basilicata) during the same season

The study were conducted on samples of olive The study were conducted on samples of olive oil produced from monovarietal and oil produced from monovarietal and

polyvarietal (polyvarietal (mixmix) olives collected in two ) olives collected in two different Italian regions (from Tuscany and different Italian regions (from Tuscany and

Basilicata) during the same season Basilicata) during the same season

The olive fruits utilized in each experimental The olive fruits utilized in each experimental runs (runs ( 60 kg) were preliminary and suitably 60 kg) were preliminary and suitably mixed to ensure homogeneous feeds Each mixed to ensure homogeneous feeds Each sample was split in two fractions (30 kg)sample was split in two fractions (30 kg)

The olive fruits utilized in each experimental The olive fruits utilized in each experimental runs (runs ( 60 kg) were preliminary and suitably 60 kg) were preliminary and suitably mixed to ensure homogeneous feeds Each mixed to ensure homogeneous feeds Each sample was split in two fractions (30 kg)sample was split in two fractions (30 kg)

Traditional extraction

process

Traditional extraction

process

Addition of CO2s

Addition of CO2s

Origin and cultivar of the raw matter Origin and cultivar of the raw matter utilizedutilized

Origin and cultivar of the raw matter Origin and cultivar of the raw matter utilizedutilized

Sample ID Geographical

Cultivar

Traditional

Cryo origin

A 1 Tuscany (GR)

Frantoio

B 2 Tuscany (SI) mix

C 3 Tuscany (SI) mix

D 4 Tuscany (SI) mix

E 5 Basilicata (PZ)

Coratina

F 6 Basilicata (PZ)

Coratina

G 7 Basilicata (PZ)

Coratina

Frantoio Leccino Correggiolo Frantoio Leccino Correggiolo

CryoCryo TraditionalTraditional

Cryogenolives (ww)Cryogenolives (ww) 02 02 00

Temperature of olivesTemperature of olives (degC)(degC) ~-2~-2 115115

Temperature of pasteTemperature of paste (degC)(degC) ~240~240 ~240~240

Time of MalaxationTime of Malaxation (s)(s) 24002400 24002400

Time of ExtractionTime of Extraction (s)(s) 49004900 43004300

Water addedolivesWater addedolives ()() 8585 9393

Main operating variables adopted Main operating variables adopted during the experimental runs during the experimental runs

Total OIL entrance(kg of crushed fruits x of oil inside the olives)

= Total OIL output

(kg of the olive residues x of oil inside the olive residues)

+EXTRACTED OIL

Total OIL entrance(kg of crushed fruits x of oil inside the olives)

= Total OIL output

(kg of the olive residues x of oil inside the olive residues)

+EXTRACTED OIL

MASS BALANCE during extraction MASS BALANCE during extraction processprocess

In order to evaluate the effect induced by the addition of cryogen on the oil extraction yield

the Extractability Index Variation (EIV) was determined as the percentage of the variation of oil extractability using CO2s compared with the same parameter obtained by a traditional

extraction process

In order to evaluate the effect induced by the addition of cryogen on the oil extraction yield

the Extractability Index Variation (EIV) was determined as the percentage of the variation of oil extractability using CO2s compared with the same parameter obtained by a traditional

extraction process EIV = (EC-ET)ET EIV = (EC-ET)ET 100 100EIV = (EC-ET)ET EIV = (EC-ET)ET 100 100

Results and Results and discussiondiscussion

Results and Results and discussiondiscussion

Oil extraction Oil extraction yield yield

preliminary preliminary resultsresults

Oil extraction yield Oil extraction yield preliminary preliminary resultsresults

Oil extraction yield Oil extraction yield preliminary preliminary resultsresults

Run EC ET

1A 858 825

2B 855 772

3C 912 827

4D 841 748

5E 808 793

6F 736 689

7G 844 774

The direct addition of cryogen to the olives during pre-milling phase could induce a general increase in the oil extraction yield ranging from 2 to

124

The direct addition of cryogen to the olives during pre-milling phase could induce a general increase in the oil extraction yield ranging from 2 to

124

[(EC-ET)ET]10040 108 103 124 19 68 90

[(EC-ET)ET]10040 108 103 124 19 68 90

Preliminary results about oil extraction Preliminary results about oil extraction yield yield discussion Idiscussion I

Preliminary results about oil extraction Preliminary results about oil extraction yield yield discussion Idiscussion I

The number of the experimental runs carried out until now is quite reduced

The number of the experimental runs carried out until now is quite reduced

BUTBUT

The results appear very encouraging and the new method seems very suitable for olive oil extraction

The results appear very encouraging and the new method seems very suitable for olive oil extraction

During the next crop season we will increase the number of experimental runs adopting several combinations of the working parameters (ie amount of cryogenamount of olives fruit ripening stage etc)

During the next crop season we will increase the number of experimental runs adopting several combinations of the working parameters (ie amount of cryogenamount of olives fruit ripening stage etc)

Preliminary results about oil extraction Preliminary results about oil extraction yield yield discussion IIdiscussion II

Preliminary results about oil extraction Preliminary results about oil extraction yield yield discussion IIdiscussion II

If necessary this method allows to move up the olive harvest time in order to greatly reduce the damages due to the third fly attack of Bactrocera oleae that can induce a significant loss in oil production (up to 60) as well as a decrease in oil quality

If necessary this method allows to move up the olive harvest time in order to greatly reduce the damages due to the third fly attack of Bactrocera oleae that can induce a significant loss in oil production (up to 60) as well as a decrease in oil quality

Water content

inside the fruit

Water content

inside the fruit

CELLULAR CRASH

We need 08 kg of CO2s to lower 100 kg of olives temperature by 1degC

Cost of 1 kg of CO2s= euro050 $ 037

Cost to turn down the average temperature of 100

kg of olives by 10degC(15degC 5degC )

08kgdegC x 10degC x 037 $kg=

3 $

Considering an average oil yield of 15

The addition cost for a kg of extravirgin olive oil is

3 $100 kg olives x 15100kg oilkg olives

lt 02$kg oil

Oil elemental Oil elemental profile profile

preliminary preliminary resultsresults

ICP-AES and ICP-MS techniques are particularly advantageous for the application in the definition of the elemental profiles of olive oil since they allow simultaneous multi-elemental analysis and are characterized by wide linear ranges and (especially ICP-MS) very low Detection Limits

Main analytical issues are related to the hard organic content of the oil matrix which requires appropriate sample pre-treatments Microwave-assisted digestion permitted to obtain a complete dissolution of olive oil samples but resulted in the obtainment of highly acidic solutions not directly analyzable by ICP-MS with a consequent reduction of sensitivity (due to the preliminary 110 dilution of the mineralized olive oil)

ETV

LA

Preliminary results about oil elemental Preliminary results about oil elemental profileprofile

Preliminary results about oil elemental Preliminary results about oil elemental profileprofile

Preliminary results show a rather homogeneous elemental content among all the analyzed samples of olive oil

For all elements experimental concentrations fall within the ranges reported in literature In respect to these ranges analyzed samples show a high content of B S and Si while Fe Na Pb Ba Cr and Cu contents are quite low

Samples of olive oil obtained by the traditionalldquo process show - in general - a higher content of Ca Cr Mg Si (except those originating from Basilicata) and Zn compared to those obtained by the addition of ldquocarbonic snowldquo

0

20

40

60

80

100

120

140

B Ca Fe Na S Si

mgk

g

000

050

100

150

200

250

300

350

400

450

500

Al K Mg P Zn

mgk

g

0

500

1000

1500

2000

2500

3000

3500

Co Cr Cu Ni Pb

microgk

g

0

2

4

6

8

10

12

14

16

Ce Er Eu Gd La Nd Pr Sm Y Yb

microgk

g

0

100

200

300

400

500

600

700

800

As Ba Cd Li Mn Rb Sb Sc Se Sr Th Ti V

microgk

g

4000 25000

0

20

40

60

80

100

120

140

160

Ca

Na

Si

concentration range obtained from literature [2]

experimental concentration range ICP-AESDetection LimitICP-MSDetection Limit - Normal Sensitivity modeICP-MSDetection Limit - High Sensitivitymode

S B Yasar E K Baran M Alkan Metal determinations in olive oil In Olive Oil ndash Constituents Quality Health Properties and Bioconversions Ed by Boskou Dimitrios 5 89-108 2012

Preliminary results about oil elemental Preliminary results about oil elemental profileprofile

Preliminary results about oil elemental Preliminary results about oil elemental profileprofile

For any further details about the second part of the research you can contact our colleagues in ENEA

claudiazoanieneait giovannazappaeneait

For any further details about the second part of the research you can contact our colleagues in ENEA

claudiazoanieneait giovannazappaeneait

ReferencesReferencesReferencesReferences

The Utilization of Solid Carbon Dioxide in the Production of Extravirgin Olive Oil

Sanmartin C Zinnai A Venturi F Andrich G Proceedings of EFFOST 2011 9-11 November 2011 Berlino

(D)

Analytical methods for olive oil elemental profile and influence of carbonic snow addition in the extraction

phase C Zoani G Zappa A Zinnai F Venturi C Sanmartin

11th Euro Fed Lipid Congress ndash Antalya (Turkey) 27-30 October 2013

Preliminary results on the influence of carbonic snow addition during the olive processing oil extraction yield

and elemental profile C Zoani G Zappa F Venturi C Sanmartin G Andrich and

A ZinnaiJournal of Nutrition and Food Sciences 4 277 (2014)

doi 1041722155-96001000277

The Utilization of Solid Carbon Dioxide in the Production of Extravirgin Olive Oil

Sanmartin C Zinnai A Venturi F Andrich G Proceedings of EFFOST 2011 9-11 November 2011 Berlino

(D)

Analytical methods for olive oil elemental profile and influence of carbonic snow addition in the extraction

phase C Zoani G Zappa A Zinnai F Venturi C Sanmartin

11th Euro Fed Lipid Congress ndash Antalya (Turkey) 27-30 October 2013

Preliminary results on the influence of carbonic snow addition during the olive processing oil extraction yield

and elemental profile C Zoani G Zappa F Venturi C Sanmartin G Andrich and

A ZinnaiJournal of Nutrition and Food Sciences 4 277 (2014)

doi 1041722155-96001000277

Research in progresshellipResearch in progresshellip

Thank you for your attention

Thank you for your attention

research supported by

It will be possible to apply matrix modification procedures (eg solvent extraction ndash also ultrasound assisted - addition of organic solvents or emulsification) or to employ systems for direct oil sample introduction in torch (eg Flow Injection Analysis systems)

We are conducting experimental tests for evaluating the possibility to employ a Laser Ablation system or an ElectroThermal Vaporization system for direct sample introduction in ICP-AES and ICP-MS

ETV

LA

Future developmentsFuture developmentsFuture developmentsFuture developments

Determination of oil elemental profile sample pre-treatment

High PressureMicrowave Digestion

Milestone 1200 Mega

05 golive oil

Mineralized oil sample

(final V = 25 ml)

2 ml H2O2 + 6 ml HNO3

Different mixtures testedH2O2 30vv (1 divide 2 ml)+ HNO3 699vv (2 divide

6 ml)

Total dissoluti

on

high-purity water

(gt 18 MΩ)

time Power Pressure

1 min 250 WFree

pressure race

1 min 0 W

5 min 400 W

5 min 650 W

Vent = 5 min

TQ mineralized

olive oil solution

Varian Vista MPX(axial configuration

simultaneous 112 Mpixel CCD detector)

study of spectral interferencesstudy of spectral interferences

preliminary qualitative analysis72 elements

preliminary qualitative analysis72 elements

quantitative analysisquantitative analysis

Gas flows optimization based on signal-to-background ratio (SB)

Auxiliary flow (lmin)

Nebulizer flow(lmin)

10 15 09 10 11 12

SBMg 3296 11720 13948 17998 19921 18412Mn 0128 0197 0245 0312 0303 0294Na 1827 1940 1827 3187 6121 4371

Zn - 213857 nm more sensitive but interfered by Fe

Zn - 206200 nm - less sensitive but without interferences

Analytical wavelengths (nm)

Al - 396152 nm K - 766491 nm Rb - 780026 nm

As - 188980 nm Li - 670783 nm S - 181972 nm

B - 249772 nm Mg - 279553 nm Sb - 206834 nm

Ba - 455403 nm Mn - 257610 nm Si - 251611 nm

Ca - 396847 nm Na - 589592 nm Sr - 407771 nm

Cr - 267716 nm Ni - 231604 nm Ti - 334941 nm

Cu - 327395 nm P - 213618 nm V - 311837 nm

Fe - 238204 nm Pb - 220353 nm Zn ndash 206200 nm

Instrumental conditions

RF Frequency 40 MHz (free running air-cooled)

RF Power 12 kW

Gas (plasma auxiliary nebulizer) Argon

Plasma flow 150 lmin

Auxiliary flow 15 lmin

Nebulizer flow 110 lmin

Replicates 5

Replicate read time 5 s

Operating parameters for ICP-AES quantitative analysis

ICP-AES Analysis

Bruker Aurora M90 (90 degree ion mirror ion optics Collision Reaction Interface)110 diluted

mineralized olive oil solution

Tuning with a 5 microgl Be Mg Co In Ba Ce Ti Pb and Th solution for

sensitivity and resolution optimization and mass calibration

Tuning with a 5 microgl Be Mg Co In Ba Ce Ti Pb and Th solution for

sensitivity and resolution optimization and mass calibration

Check of the level of oxide ions by the CeO+Ce+ ratio lt 2

Check of the level of oxide ions by the CeO+Ce+ ratio lt 2

Monitoring of double charged ions by the signal 137Ba++137Ba+ lt 3

Monitoring of double charged ions by the signal 137Ba++137Ba+ lt 3

CheckCorrection of isobaric interferences examination of more isotopes of the same element(eg Rb85 Rb 87 Sr88Sr87 Nd142 Nd146 Nd144 Se77 Se78 Sn147 Sm148 Sm152 Gd157 Gd154 Er166 Er168 Yb170 Yb172) application of correction equations with respect to isotopes of other elements potentially interfering (eg Nd142 corrected by analyzing Ce140 Nd144 by Sm147 Sm152 by Gd157 Rb87 by Sr88 ) use of the Collision Reaction Interface ndash CRI (for As and Se)

CheckCorrection of isobaric interferences examination of more isotopes of the same element(eg Rb85 Rb 87 Sr88Sr87 Nd142 Nd146 Nd144 Se77 Se78 Sn147 Sm148 Sm152 Gd157 Gd154 Er166 Er168 Yb170 Yb172) application of correction equations with respect to isotopes of other elements potentially interfering (eg Nd142 corrected by analyzing Ce140 Nd144 by Sm147 Sm152 by Gd157 Rb87 by Sr88 ) use of the Collision Reaction Interface ndash CRI (for As and Se)

Working rangesbull005 divide 5 microgl - As Cd Ce Er Eu Gd La Mn Nd Pb Pr Rb Sb Sc Se Sm Sr Th V Y Ybbull01 divide 10 microgl - Co Cr Cu Mg Ni

Working rangesbull005 divide 5 microgl - As Cd Ce Er Eu Gd La Mn Nd Pb Pr Rb Sb Sc Se Sm Sr Th V Y Ybbull01 divide 10 microgl - Co Cr Cu Mg Ni

External calibration5 standard solutions + blankCurve Fit LinearWeighted Fit NoCorrelation coefficientsR gt 09999

Normal Sensitivity Mode (without CRI) High Sensitivity Mode As and Se ndash Normal mode with CRI

ICP-MS Analysis

• Slide 1
• Slide 2
• Slide 3
• Slide 4
• Slide 5
• Slide 6
• Slide 7
• Slide 8
• Slide 9
• Slide 10
• Slide 11
• Slide 12
• Slide 13
• Slide 14
• Slide 15
• Slide 16
• Slide 17
• Slide 18
• Slide 19
• Slide 20
• Slide 21
• Slide 22
• Slide 23
• Slide 24
• Slide 25
• Slide 26
• Slide 27
• Slide 28
• Slide 29
• Slide 30
• Slide 31
• Slide 32
• Slide 33
• Slide 34
• Slide 35

b) the second goal was to develop specific analytical b) the second goal was to develop specific analytical methods for evaluating the elemental profile of olive methods for evaluating the elemental profile of olive

oil and to collect some preliminary data about the oil and to collect some preliminary data about the possibility to use these methods in order to put in possibility to use these methods in order to put in

evidence the possible influence of different process evidence the possible influence of different process conditions (extraction with or without addition of conditions (extraction with or without addition of carbonic snow) on the olive oil elemental profilecarbonic snow) on the olive oil elemental profile

b) the second goal was to develop specific analytical b) the second goal was to develop specific analytical methods for evaluating the elemental profile of olive methods for evaluating the elemental profile of olive

oil and to collect some preliminary data about the oil and to collect some preliminary data about the possibility to use these methods in order to put in possibility to use these methods in order to put in

evidence the possible influence of different process evidence the possible influence of different process conditions (extraction with or without addition of conditions (extraction with or without addition of carbonic snow) on the olive oil elemental profilecarbonic snow) on the olive oil elemental profile

Aim of the workAim of the work

a) the first goal was to verify the influence of the a) the first goal was to verify the influence of the addition of cryogen (COaddition of cryogen (CO2s2s) directly to olives during ) directly to olives during pre-milling phase on the yield of the oil production pre-milling phase on the yield of the oil production

in order to obtain a preliminary evaluation of the in order to obtain a preliminary evaluation of the suitability of the new proposed methodology for suitability of the new proposed methodology for

EVOO productionEVOO production

The main object of this The main object of this research work is twofoldresearch work is twofold

The main object of this The main object of this research work is twofoldresearch work is twofold

Materials and methodsMaterials and methodsMaterials and methodsMaterials and methods

OIL

1

2

3

4

7

20-30 kg of olivesh

5

The olive crusher utilized Oliomio Baby reg The olive crusher utilized Oliomio Baby reg (TEM)(TEM)

6

Water

CO2(s)

ldquomass cryogenrdquordquomass of fruitsrdquo 02

Wet olive residues

Knife crusher

Horizontal continuous

malaxer 2-phase decanter

Circulation of the thermal fluid

Circulation of the thermal fluid

Addition of cryogen

Addition of cryogen

Thermal probes Thermal probes

Olives Olives

The study were conducted on samples of olive The study were conducted on samples of olive oil produced from monovarietal and oil produced from monovarietal and

polyvarietal (polyvarietal (mixmix) olives collected in two ) olives collected in two different Italian regions (from Tuscany and different Italian regions (from Tuscany and

Basilicata) during the same season Basilicata) during the same season

The study were conducted on samples of olive The study were conducted on samples of olive oil produced from monovarietal and oil produced from monovarietal and

polyvarietal (polyvarietal (mixmix) olives collected in two ) olives collected in two different Italian regions (from Tuscany and different Italian regions (from Tuscany and

Basilicata) during the same season Basilicata) during the same season

The olive fruits utilized in each experimental The olive fruits utilized in each experimental runs (runs ( 60 kg) were preliminary and suitably 60 kg) were preliminary and suitably mixed to ensure homogeneous feeds Each mixed to ensure homogeneous feeds Each sample was split in two fractions (30 kg)sample was split in two fractions (30 kg)

The olive fruits utilized in each experimental The olive fruits utilized in each experimental runs (runs ( 60 kg) were preliminary and suitably 60 kg) were preliminary and suitably mixed to ensure homogeneous feeds Each mixed to ensure homogeneous feeds Each sample was split in two fractions (30 kg)sample was split in two fractions (30 kg)

Traditional extraction

process

Traditional extraction

process

Addition of CO2s

Addition of CO2s

Origin and cultivar of the raw matter Origin and cultivar of the raw matter utilizedutilized

Origin and cultivar of the raw matter Origin and cultivar of the raw matter utilizedutilized

Sample ID Geographical

Cultivar

Traditional

Cryo origin

A 1 Tuscany (GR)

Frantoio

B 2 Tuscany (SI) mix

C 3 Tuscany (SI) mix

D 4 Tuscany (SI) mix

E 5 Basilicata (PZ)

Coratina

F 6 Basilicata (PZ)

Coratina

G 7 Basilicata (PZ)

Coratina

Frantoio Leccino Correggiolo Frantoio Leccino Correggiolo

CryoCryo TraditionalTraditional

Cryogenolives (ww)Cryogenolives (ww) 02 02 00

Temperature of olivesTemperature of olives (degC)(degC) ~-2~-2 115115

Temperature of pasteTemperature of paste (degC)(degC) ~240~240 ~240~240

Time of MalaxationTime of Malaxation (s)(s) 24002400 24002400

Time of ExtractionTime of Extraction (s)(s) 49004900 43004300

Water addedolivesWater addedolives ()() 8585 9393

Main operating variables adopted Main operating variables adopted during the experimental runs during the experimental runs

Total OIL entrance(kg of crushed fruits x of oil inside the olives)

= Total OIL output

(kg of the olive residues x of oil inside the olive residues)

+EXTRACTED OIL

Total OIL entrance(kg of crushed fruits x of oil inside the olives)

= Total OIL output

(kg of the olive residues x of oil inside the olive residues)

+EXTRACTED OIL

MASS BALANCE during extraction MASS BALANCE during extraction processprocess

In order to evaluate the effect induced by the addition of cryogen on the oil extraction yield

the Extractability Index Variation (EIV) was determined as the percentage of the variation of oil extractability using CO2s compared with the same parameter obtained by a traditional

extraction process

In order to evaluate the effect induced by the addition of cryogen on the oil extraction yield

the Extractability Index Variation (EIV) was determined as the percentage of the variation of oil extractability using CO2s compared with the same parameter obtained by a traditional

extraction process EIV = (EC-ET)ET EIV = (EC-ET)ET 100 100EIV = (EC-ET)ET EIV = (EC-ET)ET 100 100

Results and Results and discussiondiscussion

Results and Results and discussiondiscussion

Oil extraction Oil extraction yield yield

preliminary preliminary resultsresults

Oil extraction yield Oil extraction yield preliminary preliminary resultsresults

Oil extraction yield Oil extraction yield preliminary preliminary resultsresults

Run EC ET

1A 858 825

2B 855 772

3C 912 827

4D 841 748

5E 808 793

6F 736 689

7G 844 774

The direct addition of cryogen to the olives during pre-milling phase could induce a general increase in the oil extraction yield ranging from 2 to

124

The direct addition of cryogen to the olives during pre-milling phase could induce a general increase in the oil extraction yield ranging from 2 to

124

[(EC-ET)ET]10040 108 103 124 19 68 90

[(EC-ET)ET]10040 108 103 124 19 68 90

Preliminary results about oil extraction Preliminary results about oil extraction yield yield discussion Idiscussion I

Preliminary results about oil extraction Preliminary results about oil extraction yield yield discussion Idiscussion I

The number of the experimental runs carried out until now is quite reduced

The number of the experimental runs carried out until now is quite reduced

BUTBUT

The results appear very encouraging and the new method seems very suitable for olive oil extraction

The results appear very encouraging and the new method seems very suitable for olive oil extraction

During the next crop season we will increase the number of experimental runs adopting several combinations of the working parameters (ie amount of cryogenamount of olives fruit ripening stage etc)

During the next crop season we will increase the number of experimental runs adopting several combinations of the working parameters (ie amount of cryogenamount of olives fruit ripening stage etc)

Preliminary results about oil extraction Preliminary results about oil extraction yield yield discussion IIdiscussion II

Preliminary results about oil extraction Preliminary results about oil extraction yield yield discussion IIdiscussion II

If necessary this method allows to move up the olive harvest time in order to greatly reduce the damages due to the third fly attack of Bactrocera oleae that can induce a significant loss in oil production (up to 60) as well as a decrease in oil quality

If necessary this method allows to move up the olive harvest time in order to greatly reduce the damages due to the third fly attack of Bactrocera oleae that can induce a significant loss in oil production (up to 60) as well as a decrease in oil quality

Water content

inside the fruit

Water content

inside the fruit

CELLULAR CRASH

We need 08 kg of CO2s to lower 100 kg of olives temperature by 1degC

Cost of 1 kg of CO2s= euro050 $ 037

Cost to turn down the average temperature of 100

kg of olives by 10degC(15degC 5degC )

08kgdegC x 10degC x 037 $kg=

3 $

Considering an average oil yield of 15

The addition cost for a kg of extravirgin olive oil is

3 $100 kg olives x 15100kg oilkg olives

lt 02$kg oil

Oil elemental Oil elemental profile profile

preliminary preliminary resultsresults

ICP-AES and ICP-MS techniques are particularly advantageous for the application in the definition of the elemental profiles of olive oil since they allow simultaneous multi-elemental analysis and are characterized by wide linear ranges and (especially ICP-MS) very low Detection Limits

Main analytical issues are related to the hard organic content of the oil matrix which requires appropriate sample pre-treatments Microwave-assisted digestion permitted to obtain a complete dissolution of olive oil samples but resulted in the obtainment of highly acidic solutions not directly analyzable by ICP-MS with a consequent reduction of sensitivity (due to the preliminary 110 dilution of the mineralized olive oil)

ETV

LA

Preliminary results about oil elemental Preliminary results about oil elemental profileprofile

Preliminary results about oil elemental Preliminary results about oil elemental profileprofile

Preliminary results show a rather homogeneous elemental content among all the analyzed samples of olive oil

For all elements experimental concentrations fall within the ranges reported in literature In respect to these ranges analyzed samples show a high content of B S and Si while Fe Na Pb Ba Cr and Cu contents are quite low

Samples of olive oil obtained by the traditionalldquo process show - in general - a higher content of Ca Cr Mg Si (except those originating from Basilicata) and Zn compared to those obtained by the addition of ldquocarbonic snowldquo

0

20

40

60

80

100

120

140

B Ca Fe Na S Si

mgk

g

000

050

100

150

200

250

300

350

400

450

500

Al K Mg P Zn

mgk

g

0

500

1000

1500

2000

2500

3000

3500

Co Cr Cu Ni Pb

microgk

g

0

2

4

6

8

10

12

14

16

Ce Er Eu Gd La Nd Pr Sm Y Yb

microgk

g

0

100

200

300

400

500

600

700

800

As Ba Cd Li Mn Rb Sb Sc Se Sr Th Ti V

microgk

g

4000 25000

0

20

40

60

80

100

120

140

160

Ca

Na

Si

concentration range obtained from literature [2]

experimental concentration range ICP-AESDetection LimitICP-MSDetection Limit - Normal Sensitivity modeICP-MSDetection Limit - High Sensitivitymode

S B Yasar E K Baran M Alkan Metal determinations in olive oil In Olive Oil ndash Constituents Quality Health Properties and Bioconversions Ed by Boskou Dimitrios 5 89-108 2012

Preliminary results about oil elemental Preliminary results about oil elemental profileprofile

Preliminary results about oil elemental Preliminary results about oil elemental profileprofile

For any further details about the second part of the research you can contact our colleagues in ENEA

claudiazoanieneait giovannazappaeneait

For any further details about the second part of the research you can contact our colleagues in ENEA

claudiazoanieneait giovannazappaeneait

ReferencesReferencesReferencesReferences

The Utilization of Solid Carbon Dioxide in the Production of Extravirgin Olive Oil

Sanmartin C Zinnai A Venturi F Andrich G Proceedings of EFFOST 2011 9-11 November 2011 Berlino

(D)

Analytical methods for olive oil elemental profile and influence of carbonic snow addition in the extraction

phase C Zoani G Zappa A Zinnai F Venturi C Sanmartin

11th Euro Fed Lipid Congress ndash Antalya (Turkey) 27-30 October 2013

Preliminary results on the influence of carbonic snow addition during the olive processing oil extraction yield

and elemental profile C Zoani G Zappa F Venturi C Sanmartin G Andrich and

A ZinnaiJournal of Nutrition and Food Sciences 4 277 (2014)

doi 1041722155-96001000277

The Utilization of Solid Carbon Dioxide in the Production of Extravirgin Olive Oil

Sanmartin C Zinnai A Venturi F Andrich G Proceedings of EFFOST 2011 9-11 November 2011 Berlino

(D)

Analytical methods for olive oil elemental profile and influence of carbonic snow addition in the extraction

phase C Zoani G Zappa A Zinnai F Venturi C Sanmartin

11th Euro Fed Lipid Congress ndash Antalya (Turkey) 27-30 October 2013

Preliminary results on the influence of carbonic snow addition during the olive processing oil extraction yield

and elemental profile C Zoani G Zappa F Venturi C Sanmartin G Andrich and

A ZinnaiJournal of Nutrition and Food Sciences 4 277 (2014)

doi 1041722155-96001000277

Research in progresshellipResearch in progresshellip

Thank you for your attention

Thank you for your attention

research supported by

It will be possible to apply matrix modification procedures (eg solvent extraction ndash also ultrasound assisted - addition of organic solvents or emulsification) or to employ systems for direct oil sample introduction in torch (eg Flow Injection Analysis systems)

We are conducting experimental tests for evaluating the possibility to employ a Laser Ablation system or an ElectroThermal Vaporization system for direct sample introduction in ICP-AES and ICP-MS

ETV

LA

Future developmentsFuture developmentsFuture developmentsFuture developments

Determination of oil elemental profile sample pre-treatment

High PressureMicrowave Digestion

Milestone 1200 Mega

05 golive oil

Mineralized oil sample

(final V = 25 ml)

2 ml H2O2 + 6 ml HNO3

Different mixtures testedH2O2 30vv (1 divide 2 ml)+ HNO3 699vv (2 divide

6 ml)

Total dissoluti

on

high-purity water

(gt 18 MΩ)

time Power Pressure

1 min 250 WFree

pressure race

1 min 0 W

5 min 400 W

5 min 650 W

Vent = 5 min

TQ mineralized

olive oil solution

Varian Vista MPX(axial configuration

simultaneous 112 Mpixel CCD detector)

study of spectral interferencesstudy of spectral interferences

preliminary qualitative analysis72 elements

preliminary qualitative analysis72 elements

quantitative analysisquantitative analysis

Gas flows optimization based on signal-to-background ratio (SB)

Auxiliary flow (lmin)

Nebulizer flow(lmin)

10 15 09 10 11 12

SBMg 3296 11720 13948 17998 19921 18412Mn 0128 0197 0245 0312 0303 0294Na 1827 1940 1827 3187 6121 4371

Zn - 213857 nm more sensitive but interfered by Fe

Zn - 206200 nm - less sensitive but without interferences

Analytical wavelengths (nm)

Al - 396152 nm K - 766491 nm Rb - 780026 nm

As - 188980 nm Li - 670783 nm S - 181972 nm

B - 249772 nm Mg - 279553 nm Sb - 206834 nm

Ba - 455403 nm Mn - 257610 nm Si - 251611 nm

Ca - 396847 nm Na - 589592 nm Sr - 407771 nm

Cr - 267716 nm Ni - 231604 nm Ti - 334941 nm

Cu - 327395 nm P - 213618 nm V - 311837 nm

Fe - 238204 nm Pb - 220353 nm Zn ndash 206200 nm

Instrumental conditions

RF Frequency 40 MHz (free running air-cooled)

RF Power 12 kW

Gas (plasma auxiliary nebulizer) Argon

Plasma flow 150 lmin

Auxiliary flow 15 lmin

Nebulizer flow 110 lmin

Replicates 5

Replicate read time 5 s

Operating parameters for ICP-AES quantitative analysis

ICP-AES Analysis

Bruker Aurora M90 (90 degree ion mirror ion optics Collision Reaction Interface)110 diluted

mineralized olive oil solution

Tuning with a 5 microgl Be Mg Co In Ba Ce Ti Pb and Th solution for

sensitivity and resolution optimization and mass calibration

Tuning with a 5 microgl Be Mg Co In Ba Ce Ti Pb and Th solution for

sensitivity and resolution optimization and mass calibration

Check of the level of oxide ions by the CeO+Ce+ ratio lt 2

Check of the level of oxide ions by the CeO+Ce+ ratio lt 2

Monitoring of double charged ions by the signal 137Ba++137Ba+ lt 3

Monitoring of double charged ions by the signal 137Ba++137Ba+ lt 3

CheckCorrection of isobaric interferences examination of more isotopes of the same element(eg Rb85 Rb 87 Sr88Sr87 Nd142 Nd146 Nd144 Se77 Se78 Sn147 Sm148 Sm152 Gd157 Gd154 Er166 Er168 Yb170 Yb172) application of correction equations with respect to isotopes of other elements potentially interfering (eg Nd142 corrected by analyzing Ce140 Nd144 by Sm147 Sm152 by Gd157 Rb87 by Sr88 ) use of the Collision Reaction Interface ndash CRI (for As and Se)

CheckCorrection of isobaric interferences examination of more isotopes of the same element(eg Rb85 Rb 87 Sr88Sr87 Nd142 Nd146 Nd144 Se77 Se78 Sn147 Sm148 Sm152 Gd157 Gd154 Er166 Er168 Yb170 Yb172) application of correction equations with respect to isotopes of other elements potentially interfering (eg Nd142 corrected by analyzing Ce140 Nd144 by Sm147 Sm152 by Gd157 Rb87 by Sr88 ) use of the Collision Reaction Interface ndash CRI (for As and Se)

Working rangesbull005 divide 5 microgl - As Cd Ce Er Eu Gd La Mn Nd Pb Pr Rb Sb Sc Se Sm Sr Th V Y Ybbull01 divide 10 microgl - Co Cr Cu Mg Ni

Working rangesbull005 divide 5 microgl - As Cd Ce Er Eu Gd La Mn Nd Pb Pr Rb Sb Sc Se Sm Sr Th V Y Ybbull01 divide 10 microgl - Co Cr Cu Mg Ni

External calibration5 standard solutions + blankCurve Fit LinearWeighted Fit NoCorrelation coefficientsR gt 09999

Normal Sensitivity Mode (without CRI) High Sensitivity Mode As and Se ndash Normal mode with CRI

ICP-MS Analysis

• Slide 1
• Slide 2
• Slide 3
• Slide 4
• Slide 5
• Slide 6
• Slide 7
• Slide 8
• Slide 9
• Slide 10
• Slide 11
• Slide 12
• Slide 13
• Slide 14
• Slide 15
• Slide 16
• Slide 17
• Slide 18
• Slide 19
• Slide 20
• Slide 21
• Slide 22
• Slide 23
• Slide 24
• Slide 25
• Slide 26
• Slide 27
• Slide 28
• Slide 29
• Slide 30
• Slide 31
• Slide 32
• Slide 33
• Slide 34
• Slide 35

Materials and methodsMaterials and methodsMaterials and methodsMaterials and methods

OIL

1

2

3

4

7

20-30 kg of olivesh

5

The olive crusher utilized Oliomio Baby reg The olive crusher utilized Oliomio Baby reg (TEM)(TEM)

6

Water

CO2(s)

ldquomass cryogenrdquordquomass of fruitsrdquo 02

Wet olive residues

Knife crusher

Horizontal continuous

malaxer 2-phase decanter

Circulation of the thermal fluid

Circulation of the thermal fluid

Addition of cryogen

Addition of cryogen

Thermal probes Thermal probes

Olives Olives

The study were conducted on samples of olive The study were conducted on samples of olive oil produced from monovarietal and oil produced from monovarietal and

polyvarietal (polyvarietal (mixmix) olives collected in two ) olives collected in two different Italian regions (from Tuscany and different Italian regions (from Tuscany and

Basilicata) during the same season Basilicata) during the same season

The study were conducted on samples of olive The study were conducted on samples of olive oil produced from monovarietal and oil produced from monovarietal and

polyvarietal (polyvarietal (mixmix) olives collected in two ) olives collected in two different Italian regions (from Tuscany and different Italian regions (from Tuscany and

Basilicata) during the same season Basilicata) during the same season

The olive fruits utilized in each experimental The olive fruits utilized in each experimental runs (runs ( 60 kg) were preliminary and suitably 60 kg) were preliminary and suitably mixed to ensure homogeneous feeds Each mixed to ensure homogeneous feeds Each sample was split in two fractions (30 kg)sample was split in two fractions (30 kg)

The olive fruits utilized in each experimental The olive fruits utilized in each experimental runs (runs ( 60 kg) were preliminary and suitably 60 kg) were preliminary and suitably mixed to ensure homogeneous feeds Each mixed to ensure homogeneous feeds Each sample was split in two fractions (30 kg)sample was split in two fractions (30 kg)

Traditional extraction

process

Traditional extraction

process

Addition of CO2s

Addition of CO2s

Origin and cultivar of the raw matter Origin and cultivar of the raw matter utilizedutilized

Origin and cultivar of the raw matter Origin and cultivar of the raw matter utilizedutilized

Sample ID Geographical

Cultivar

Traditional

Cryo origin

A 1 Tuscany (GR)

Frantoio

B 2 Tuscany (SI) mix

C 3 Tuscany (SI) mix

D 4 Tuscany (SI) mix

E 5 Basilicata (PZ)

Coratina

F 6 Basilicata (PZ)

Coratina

G 7 Basilicata (PZ)

Coratina

Frantoio Leccino Correggiolo Frantoio Leccino Correggiolo

CryoCryo TraditionalTraditional

Cryogenolives (ww)Cryogenolives (ww) 02 02 00

Temperature of olivesTemperature of olives (degC)(degC) ~-2~-2 115115

Temperature of pasteTemperature of paste (degC)(degC) ~240~240 ~240~240

Time of MalaxationTime of Malaxation (s)(s) 24002400 24002400

Time of ExtractionTime of Extraction (s)(s) 49004900 43004300

Water addedolivesWater addedolives ()() 8585 9393

Main operating variables adopted Main operating variables adopted during the experimental runs during the experimental runs

Total OIL entrance(kg of crushed fruits x of oil inside the olives)

= Total OIL output

(kg of the olive residues x of oil inside the olive residues)

+EXTRACTED OIL

Total OIL entrance(kg of crushed fruits x of oil inside the olives)

= Total OIL output

(kg of the olive residues x of oil inside the olive residues)

+EXTRACTED OIL

MASS BALANCE during extraction MASS BALANCE during extraction processprocess

In order to evaluate the effect induced by the addition of cryogen on the oil extraction yield

the Extractability Index Variation (EIV) was determined as the percentage of the variation of oil extractability using CO2s compared with the same parameter obtained by a traditional

extraction process

In order to evaluate the effect induced by the addition of cryogen on the oil extraction yield

the Extractability Index Variation (EIV) was determined as the percentage of the variation of oil extractability using CO2s compared with the same parameter obtained by a traditional

extraction process EIV = (EC-ET)ET EIV = (EC-ET)ET 100 100EIV = (EC-ET)ET EIV = (EC-ET)ET 100 100

Results and Results and discussiondiscussion

Results and Results and discussiondiscussion

Oil extraction Oil extraction yield yield

preliminary preliminary resultsresults

Oil extraction yield Oil extraction yield preliminary preliminary resultsresults

Oil extraction yield Oil extraction yield preliminary preliminary resultsresults

Run EC ET

1A 858 825

2B 855 772

3C 912 827

4D 841 748

5E 808 793

6F 736 689

7G 844 774

The direct addition of cryogen to the olives during pre-milling phase could induce a general increase in the oil extraction yield ranging from 2 to

124

The direct addition of cryogen to the olives during pre-milling phase could induce a general increase in the oil extraction yield ranging from 2 to

124

[(EC-ET)ET]10040 108 103 124 19 68 90

[(EC-ET)ET]10040 108 103 124 19 68 90

Preliminary results about oil extraction Preliminary results about oil extraction yield yield discussion Idiscussion I

Preliminary results about oil extraction Preliminary results about oil extraction yield yield discussion Idiscussion I

The number of the experimental runs carried out until now is quite reduced

The number of the experimental runs carried out until now is quite reduced

BUTBUT

The results appear very encouraging and the new method seems very suitable for olive oil extraction

The results appear very encouraging and the new method seems very suitable for olive oil extraction

During the next crop season we will increase the number of experimental runs adopting several combinations of the working parameters (ie amount of cryogenamount of olives fruit ripening stage etc)

During the next crop season we will increase the number of experimental runs adopting several combinations of the working parameters (ie amount of cryogenamount of olives fruit ripening stage etc)

Preliminary results about oil extraction Preliminary results about oil extraction yield yield discussion IIdiscussion II

Preliminary results about oil extraction Preliminary results about oil extraction yield yield discussion IIdiscussion II

If necessary this method allows to move up the olive harvest time in order to greatly reduce the damages due to the third fly attack of Bactrocera oleae that can induce a significant loss in oil production (up to 60) as well as a decrease in oil quality

If necessary this method allows to move up the olive harvest time in order to greatly reduce the damages due to the third fly attack of Bactrocera oleae that can induce a significant loss in oil production (up to 60) as well as a decrease in oil quality

Water content

inside the fruit

Water content

inside the fruit

CELLULAR CRASH

We need 08 kg of CO2s to lower 100 kg of olives temperature by 1degC

Cost of 1 kg of CO2s= euro050 $ 037

Cost to turn down the average temperature of 100

kg of olives by 10degC(15degC 5degC )

08kgdegC x 10degC x 037 $kg=

3 $

Considering an average oil yield of 15

The addition cost for a kg of extravirgin olive oil is

3 $100 kg olives x 15100kg oilkg olives

lt 02$kg oil

Oil elemental Oil elemental profile profile

preliminary preliminary resultsresults

ICP-AES and ICP-MS techniques are particularly advantageous for the application in the definition of the elemental profiles of olive oil since they allow simultaneous multi-elemental analysis and are characterized by wide linear ranges and (especially ICP-MS) very low Detection Limits

Main analytical issues are related to the hard organic content of the oil matrix which requires appropriate sample pre-treatments Microwave-assisted digestion permitted to obtain a complete dissolution of olive oil samples but resulted in the obtainment of highly acidic solutions not directly analyzable by ICP-MS with a consequent reduction of sensitivity (due to the preliminary 110 dilution of the mineralized olive oil)

ETV

LA

Preliminary results about oil elemental Preliminary results about oil elemental profileprofile

Preliminary results about oil elemental Preliminary results about oil elemental profileprofile

Preliminary results show a rather homogeneous elemental content among all the analyzed samples of olive oil

For all elements experimental concentrations fall within the ranges reported in literature In respect to these ranges analyzed samples show a high content of B S and Si while Fe Na Pb Ba Cr and Cu contents are quite low

Samples of olive oil obtained by the traditionalldquo process show - in general - a higher content of Ca Cr Mg Si (except those originating from Basilicata) and Zn compared to those obtained by the addition of ldquocarbonic snowldquo

0

20

40

60

80

100

120

140

B Ca Fe Na S Si

mgk

g

000

050

100

150

200

250

300

350

400

450

500

Al K Mg P Zn

mgk

g

0

500

1000

1500

2000

2500

3000

3500

Co Cr Cu Ni Pb

microgk

g

0

2

4

6

8

10

12

14

16

Ce Er Eu Gd La Nd Pr Sm Y Yb

microgk

g

0

100

200

300

400

500

600

700

800

As Ba Cd Li Mn Rb Sb Sc Se Sr Th Ti V

microgk

g

4000 25000

0

20

40

60

80

100

120

140

160

Ca

Na

Si

concentration range obtained from literature [2]

experimental concentration range ICP-AESDetection LimitICP-MSDetection Limit - Normal Sensitivity modeICP-MSDetection Limit - High Sensitivitymode

S B Yasar E K Baran M Alkan Metal determinations in olive oil In Olive Oil ndash Constituents Quality Health Properties and Bioconversions Ed by Boskou Dimitrios 5 89-108 2012

Preliminary results about oil elemental Preliminary results about oil elemental profileprofile

Preliminary results about oil elemental Preliminary results about oil elemental profileprofile

For any further details about the second part of the research you can contact our colleagues in ENEA

claudiazoanieneait giovannazappaeneait

For any further details about the second part of the research you can contact our colleagues in ENEA

claudiazoanieneait giovannazappaeneait

ReferencesReferencesReferencesReferences

The Utilization of Solid Carbon Dioxide in the Production of Extravirgin Olive Oil

Sanmartin C Zinnai A Venturi F Andrich G Proceedings of EFFOST 2011 9-11 November 2011 Berlino

(D)

Analytical methods for olive oil elemental profile and influence of carbonic snow addition in the extraction

phase C Zoani G Zappa A Zinnai F Venturi C Sanmartin

11th Euro Fed Lipid Congress ndash Antalya (Turkey) 27-30 October 2013

Preliminary results on the influence of carbonic snow addition during the olive processing oil extraction yield

and elemental profile C Zoani G Zappa F Venturi C Sanmartin G Andrich and

A ZinnaiJournal of Nutrition and Food Sciences 4 277 (2014)

doi 1041722155-96001000277

The Utilization of Solid Carbon Dioxide in the Production of Extravirgin Olive Oil

Sanmartin C Zinnai A Venturi F Andrich G Proceedings of EFFOST 2011 9-11 November 2011 Berlino

(D)

Analytical methods for olive oil elemental profile and influence of carbonic snow addition in the extraction

phase C Zoani G Zappa A Zinnai F Venturi C Sanmartin

11th Euro Fed Lipid Congress ndash Antalya (Turkey) 27-30 October 2013

Preliminary results on the influence of carbonic snow addition during the olive processing oil extraction yield

and elemental profile C Zoani G Zappa F Venturi C Sanmartin G Andrich and

A ZinnaiJournal of Nutrition and Food Sciences 4 277 (2014)

doi 1041722155-96001000277

Research in progresshellipResearch in progresshellip

Thank you for your attention

Thank you for your attention

research supported by

It will be possible to apply matrix modification procedures (eg solvent extraction ndash also ultrasound assisted - addition of organic solvents or emulsification) or to employ systems for direct oil sample introduction in torch (eg Flow Injection Analysis systems)

We are conducting experimental tests for evaluating the possibility to employ a Laser Ablation system or an ElectroThermal Vaporization system for direct sample introduction in ICP-AES and ICP-MS

ETV

LA

Future developmentsFuture developmentsFuture developmentsFuture developments

Determination of oil elemental profile sample pre-treatment

High PressureMicrowave Digestion

Milestone 1200 Mega

05 golive oil

Mineralized oil sample

(final V = 25 ml)

2 ml H2O2 + 6 ml HNO3

Different mixtures testedH2O2 30vv (1 divide 2 ml)+ HNO3 699vv (2 divide

6 ml)

Total dissoluti

on

high-purity water

(gt 18 MΩ)

time Power Pressure

1 min 250 WFree

pressure race

1 min 0 W

5 min 400 W

5 min 650 W

Vent = 5 min

TQ mineralized

olive oil solution

Varian Vista MPX(axial configuration

simultaneous 112 Mpixel CCD detector)

study of spectral interferencesstudy of spectral interferences

preliminary qualitative analysis72 elements

preliminary qualitative analysis72 elements

quantitative analysisquantitative analysis

Gas flows optimization based on signal-to-background ratio (SB)

Auxiliary flow (lmin)

Nebulizer flow(lmin)

10 15 09 10 11 12

SBMg 3296 11720 13948 17998 19921 18412Mn 0128 0197 0245 0312 0303 0294Na 1827 1940 1827 3187 6121 4371

Zn - 213857 nm more sensitive but interfered by Fe

Zn - 206200 nm - less sensitive but without interferences

Analytical wavelengths (nm)

Al - 396152 nm K - 766491 nm Rb - 780026 nm

As - 188980 nm Li - 670783 nm S - 181972 nm

B - 249772 nm Mg - 279553 nm Sb - 206834 nm

Ba - 455403 nm Mn - 257610 nm Si - 251611 nm

Ca - 396847 nm Na - 589592 nm Sr - 407771 nm

Cr - 267716 nm Ni - 231604 nm Ti - 334941 nm

Cu - 327395 nm P - 213618 nm V - 311837 nm

Fe - 238204 nm Pb - 220353 nm Zn ndash 206200 nm

Instrumental conditions

RF Frequency 40 MHz (free running air-cooled)

RF Power 12 kW

Gas (plasma auxiliary nebulizer) Argon

Plasma flow 150 lmin

Auxiliary flow 15 lmin

Nebulizer flow 110 lmin

Replicates 5

Replicate read time 5 s

Operating parameters for ICP-AES quantitative analysis

ICP-AES Analysis

Bruker Aurora M90 (90 degree ion mirror ion optics Collision Reaction Interface)110 diluted

mineralized olive oil solution

Tuning with a 5 microgl Be Mg Co In Ba Ce Ti Pb and Th solution for

sensitivity and resolution optimization and mass calibration

Tuning with a 5 microgl Be Mg Co In Ba Ce Ti Pb and Th solution for

sensitivity and resolution optimization and mass calibration

Check of the level of oxide ions by the CeO+Ce+ ratio lt 2

Check of the level of oxide ions by the CeO+Ce+ ratio lt 2

Monitoring of double charged ions by the signal 137Ba++137Ba+ lt 3

Monitoring of double charged ions by the signal 137Ba++137Ba+ lt 3

CheckCorrection of isobaric interferences examination of more isotopes of the same element(eg Rb85 Rb 87 Sr88Sr87 Nd142 Nd146 Nd144 Se77 Se78 Sn147 Sm148 Sm152 Gd157 Gd154 Er166 Er168 Yb170 Yb172) application of correction equations with respect to isotopes of other elements potentially interfering (eg Nd142 corrected by analyzing Ce140 Nd144 by Sm147 Sm152 by Gd157 Rb87 by Sr88 ) use of the Collision Reaction Interface ndash CRI (for As and Se)

CheckCorrection of isobaric interferences examination of more isotopes of the same element(eg Rb85 Rb 87 Sr88Sr87 Nd142 Nd146 Nd144 Se77 Se78 Sn147 Sm148 Sm152 Gd157 Gd154 Er166 Er168 Yb170 Yb172) application of correction equations with respect to isotopes of other elements potentially interfering (eg Nd142 corrected by analyzing Ce140 Nd144 by Sm147 Sm152 by Gd157 Rb87 by Sr88 ) use of the Collision Reaction Interface ndash CRI (for As and Se)

Working rangesbull005 divide 5 microgl - As Cd Ce Er Eu Gd La Mn Nd Pb Pr Rb Sb Sc Se Sm Sr Th V Y Ybbull01 divide 10 microgl - Co Cr Cu Mg Ni

Working rangesbull005 divide 5 microgl - As Cd Ce Er Eu Gd La Mn Nd Pb Pr Rb Sb Sc Se Sm Sr Th V Y Ybbull01 divide 10 microgl - Co Cr Cu Mg Ni

External calibration5 standard solutions + blankCurve Fit LinearWeighted Fit NoCorrelation coefficientsR gt 09999

Normal Sensitivity Mode (without CRI) High Sensitivity Mode As and Se ndash Normal mode with CRI

ICP-MS Analysis

• Slide 1
• Slide 2
• Slide 3
• Slide 4
• Slide 5
• Slide 6
• Slide 7
• Slide 8
• Slide 9
• Slide 10
• Slide 11
• Slide 12
• Slide 13
• Slide 14
• Slide 15
• Slide 16
• Slide 17
• Slide 18
• Slide 19
• Slide 20
• Slide 21
• Slide 22
• Slide 23
• Slide 24
• Slide 25
• Slide 26
• Slide 27
• Slide 28
• Slide 29
• Slide 30
• Slide 31
• Slide 32
• Slide 33
• Slide 34
• Slide 35

OIL

1

2

3

4

7

20-30 kg of olivesh

5

The olive crusher utilized Oliomio Baby reg The olive crusher utilized Oliomio Baby reg (TEM)(TEM)

6

Water

CO2(s)

ldquomass cryogenrdquordquomass of fruitsrdquo 02

Wet olive residues

Knife crusher

Horizontal continuous

malaxer 2-phase decanter

Circulation of the thermal fluid

Circulation of the thermal fluid

Addition of cryogen

Addition of cryogen

Thermal probes Thermal probes

Olives Olives

The study were conducted on samples of olive The study were conducted on samples of olive oil produced from monovarietal and oil produced from monovarietal and

polyvarietal (polyvarietal (mixmix) olives collected in two ) olives collected in two different Italian regions (from Tuscany and different Italian regions (from Tuscany and

Basilicata) during the same season Basilicata) during the same season

The study were conducted on samples of olive The study were conducted on samples of olive oil produced from monovarietal and oil produced from monovarietal and

polyvarietal (polyvarietal (mixmix) olives collected in two ) olives collected in two different Italian regions (from Tuscany and different Italian regions (from Tuscany and

Basilicata) during the same season Basilicata) during the same season

The olive fruits utilized in each experimental The olive fruits utilized in each experimental runs (runs ( 60 kg) were preliminary and suitably 60 kg) were preliminary and suitably mixed to ensure homogeneous feeds Each mixed to ensure homogeneous feeds Each sample was split in two fractions (30 kg)sample was split in two fractions (30 kg)

The olive fruits utilized in each experimental The olive fruits utilized in each experimental runs (runs ( 60 kg) were preliminary and suitably 60 kg) were preliminary and suitably mixed to ensure homogeneous feeds Each mixed to ensure homogeneous feeds Each sample was split in two fractions (30 kg)sample was split in two fractions (30 kg)

Traditional extraction

process

Traditional extraction

process

Addition of CO2s

Addition of CO2s

Origin and cultivar of the raw matter Origin and cultivar of the raw matter utilizedutilized

Origin and cultivar of the raw matter Origin and cultivar of the raw matter utilizedutilized

Sample ID Geographical

Cultivar

Traditional

Cryo origin

A 1 Tuscany (GR)

Frantoio

B 2 Tuscany (SI) mix

C 3 Tuscany (SI) mix

D 4 Tuscany (SI) mix

E 5 Basilicata (PZ)

Coratina

F 6 Basilicata (PZ)

Coratina

G 7 Basilicata (PZ)

Coratina

Frantoio Leccino Correggiolo Frantoio Leccino Correggiolo

CryoCryo TraditionalTraditional

Cryogenolives (ww)Cryogenolives (ww) 02 02 00

Temperature of olivesTemperature of olives (degC)(degC) ~-2~-2 115115

Temperature of pasteTemperature of paste (degC)(degC) ~240~240 ~240~240

Time of MalaxationTime of Malaxation (s)(s) 24002400 24002400

Time of ExtractionTime of Extraction (s)(s) 49004900 43004300

Water addedolivesWater addedolives ()() 8585 9393

Main operating variables adopted Main operating variables adopted during the experimental runs during the experimental runs

Total OIL entrance(kg of crushed fruits x of oil inside the olives)

= Total OIL output

(kg of the olive residues x of oil inside the olive residues)

+EXTRACTED OIL

Total OIL entrance(kg of crushed fruits x of oil inside the olives)

= Total OIL output

(kg of the olive residues x of oil inside the olive residues)

+EXTRACTED OIL

MASS BALANCE during extraction MASS BALANCE during extraction processprocess

In order to evaluate the effect induced by the addition of cryogen on the oil extraction yield

the Extractability Index Variation (EIV) was determined as the percentage of the variation of oil extractability using CO2s compared with the same parameter obtained by a traditional

extraction process

In order to evaluate the effect induced by the addition of cryogen on the oil extraction yield

the Extractability Index Variation (EIV) was determined as the percentage of the variation of oil extractability using CO2s compared with the same parameter obtained by a traditional

extraction process EIV = (EC-ET)ET EIV = (EC-ET)ET 100 100EIV = (EC-ET)ET EIV = (EC-ET)ET 100 100

Results and Results and discussiondiscussion

Results and Results and discussiondiscussion

Oil extraction Oil extraction yield yield

preliminary preliminary resultsresults

Oil extraction yield Oil extraction yield preliminary preliminary resultsresults

Oil extraction yield Oil extraction yield preliminary preliminary resultsresults

Run EC ET

1A 858 825

2B 855 772

3C 912 827

4D 841 748

5E 808 793

6F 736 689

7G 844 774

The direct addition of cryogen to the olives during pre-milling phase could induce a general increase in the oil extraction yield ranging from 2 to

124

The direct addition of cryogen to the olives during pre-milling phase could induce a general increase in the oil extraction yield ranging from 2 to

124

[(EC-ET)ET]10040 108 103 124 19 68 90

[(EC-ET)ET]10040 108 103 124 19 68 90

Preliminary results about oil extraction Preliminary results about oil extraction yield yield discussion Idiscussion I

Preliminary results about oil extraction Preliminary results about oil extraction yield yield discussion Idiscussion I

The number of the experimental runs carried out until now is quite reduced

The number of the experimental runs carried out until now is quite reduced

BUTBUT

The results appear very encouraging and the new method seems very suitable for olive oil extraction

The results appear very encouraging and the new method seems very suitable for olive oil extraction

During the next crop season we will increase the number of experimental runs adopting several combinations of the working parameters (ie amount of cryogenamount of olives fruit ripening stage etc)

During the next crop season we will increase the number of experimental runs adopting several combinations of the working parameters (ie amount of cryogenamount of olives fruit ripening stage etc)

Preliminary results about oil extraction Preliminary results about oil extraction yield yield discussion IIdiscussion II

Preliminary results about oil extraction Preliminary results about oil extraction yield yield discussion IIdiscussion II

If necessary this method allows to move up the olive harvest time in order to greatly reduce the damages due to the third fly attack of Bactrocera oleae that can induce a significant loss in oil production (up to 60) as well as a decrease in oil quality

If necessary this method allows to move up the olive harvest time in order to greatly reduce the damages due to the third fly attack of Bactrocera oleae that can induce a significant loss in oil production (up to 60) as well as a decrease in oil quality

Water content

inside the fruit

Water content

inside the fruit

CELLULAR CRASH

We need 08 kg of CO2s to lower 100 kg of olives temperature by 1degC

Cost of 1 kg of CO2s= euro050 $ 037

Cost to turn down the average temperature of 100

kg of olives by 10degC(15degC 5degC )

08kgdegC x 10degC x 037 $kg=

3 $

Considering an average oil yield of 15

The addition cost for a kg of extravirgin olive oil is

3 $100 kg olives x 15100kg oilkg olives

lt 02$kg oil

Oil elemental Oil elemental profile profile

preliminary preliminary resultsresults

ICP-AES and ICP-MS techniques are particularly advantageous for the application in the definition of the elemental profiles of olive oil since they allow simultaneous multi-elemental analysis and are characterized by wide linear ranges and (especially ICP-MS) very low Detection Limits

Main analytical issues are related to the hard organic content of the oil matrix which requires appropriate sample pre-treatments Microwave-assisted digestion permitted to obtain a complete dissolution of olive oil samples but resulted in the obtainment of highly acidic solutions not directly analyzable by ICP-MS with a consequent reduction of sensitivity (due to the preliminary 110 dilution of the mineralized olive oil)

ETV

LA

Preliminary results about oil elemental Preliminary results about oil elemental profileprofile

Preliminary results about oil elemental Preliminary results about oil elemental profileprofile

Preliminary results show a rather homogeneous elemental content among all the analyzed samples of olive oil

For all elements experimental concentrations fall within the ranges reported in literature In respect to these ranges analyzed samples show a high content of B S and Si while Fe Na Pb Ba Cr and Cu contents are quite low

Samples of olive oil obtained by the traditionalldquo process show - in general - a higher content of Ca Cr Mg Si (except those originating from Basilicata) and Zn compared to those obtained by the addition of ldquocarbonic snowldquo

0

20

40

60

80

100

120

140

B Ca Fe Na S Si

mgk

g

000

050

100

150

200

250

300

350

400

450

500

Al K Mg P Zn

mgk

g

0

500

1000

1500

2000

2500

3000

3500

Co Cr Cu Ni Pb

microgk

g

0

2

4

6

8

10

12

14

16

Ce Er Eu Gd La Nd Pr Sm Y Yb

microgk

g

0

100

200

300

400

500

600

700

800

As Ba Cd Li Mn Rb Sb Sc Se Sr Th Ti V

microgk

g

4000 25000

0

20

40

60

80

100

120

140

160

Ca

Na

Si

concentration range obtained from literature [2]

experimental concentration range ICP-AESDetection LimitICP-MSDetection Limit - Normal Sensitivity modeICP-MSDetection Limit - High Sensitivitymode

S B Yasar E K Baran M Alkan Metal determinations in olive oil In Olive Oil ndash Constituents Quality Health Properties and Bioconversions Ed by Boskou Dimitrios 5 89-108 2012

Preliminary results about oil elemental Preliminary results about oil elemental profileprofile

Preliminary results about oil elemental Preliminary results about oil elemental profileprofile

For any further details about the second part of the research you can contact our colleagues in ENEA

claudiazoanieneait giovannazappaeneait

For any further details about the second part of the research you can contact our colleagues in ENEA

claudiazoanieneait giovannazappaeneait

ReferencesReferencesReferencesReferences

The Utilization of Solid Carbon Dioxide in the Production of Extravirgin Olive Oil

Sanmartin C Zinnai A Venturi F Andrich G Proceedings of EFFOST 2011 9-11 November 2011 Berlino

(D)

Analytical methods for olive oil elemental profile and influence of carbonic snow addition in the extraction

phase C Zoani G Zappa A Zinnai F Venturi C Sanmartin

11th Euro Fed Lipid Congress ndash Antalya (Turkey) 27-30 October 2013

Preliminary results on the influence of carbonic snow addition during the olive processing oil extraction yield

and elemental profile C Zoani G Zappa F Venturi C Sanmartin G Andrich and

A ZinnaiJournal of Nutrition and Food Sciences 4 277 (2014)

doi 1041722155-96001000277

The Utilization of Solid Carbon Dioxide in the Production of Extravirgin Olive Oil

Sanmartin C Zinnai A Venturi F Andrich G Proceedings of EFFOST 2011 9-11 November 2011 Berlino

(D)

Analytical methods for olive oil elemental profile and influence of carbonic snow addition in the extraction

phase C Zoani G Zappa A Zinnai F Venturi C Sanmartin

11th Euro Fed Lipid Congress ndash Antalya (Turkey) 27-30 October 2013

Preliminary results on the influence of carbonic snow addition during the olive processing oil extraction yield

and elemental profile C Zoani G Zappa F Venturi C Sanmartin G Andrich and

A ZinnaiJournal of Nutrition and Food Sciences 4 277 (2014)

doi 1041722155-96001000277

Research in progresshellipResearch in progresshellip

Thank you for your attention

Thank you for your attention

research supported by

It will be possible to apply matrix modification procedures (eg solvent extraction ndash also ultrasound assisted - addition of organic solvents or emulsification) or to employ systems for direct oil sample introduction in torch (eg Flow Injection Analysis systems)

We are conducting experimental tests for evaluating the possibility to employ a Laser Ablation system or an ElectroThermal Vaporization system for direct sample introduction in ICP-AES and ICP-MS

ETV

LA

Future developmentsFuture developmentsFuture developmentsFuture developments

Determination of oil elemental profile sample pre-treatment

High PressureMicrowave Digestion

Milestone 1200 Mega

05 golive oil

Mineralized oil sample

(final V = 25 ml)

2 ml H2O2 + 6 ml HNO3

Different mixtures testedH2O2 30vv (1 divide 2 ml)+ HNO3 699vv (2 divide

6 ml)

Total dissoluti

on

high-purity water

(gt 18 MΩ)

time Power Pressure

1 min 250 WFree

pressure race

1 min 0 W

5 min 400 W

5 min 650 W

Vent = 5 min

TQ mineralized

olive oil solution

Varian Vista MPX(axial configuration

simultaneous 112 Mpixel CCD detector)

study of spectral interferencesstudy of spectral interferences

preliminary qualitative analysis72 elements

preliminary qualitative analysis72 elements

quantitative analysisquantitative analysis

Gas flows optimization based on signal-to-background ratio (SB)

Auxiliary flow (lmin)

Nebulizer flow(lmin)

10 15 09 10 11 12

SBMg 3296 11720 13948 17998 19921 18412Mn 0128 0197 0245 0312 0303 0294Na 1827 1940 1827 3187 6121 4371

Zn - 213857 nm more sensitive but interfered by Fe

Zn - 206200 nm - less sensitive but without interferences

Analytical wavelengths (nm)

Al - 396152 nm K - 766491 nm Rb - 780026 nm

As - 188980 nm Li - 670783 nm S - 181972 nm

B - 249772 nm Mg - 279553 nm Sb - 206834 nm

Ba - 455403 nm Mn - 257610 nm Si - 251611 nm

Ca - 396847 nm Na - 589592 nm Sr - 407771 nm

Cr - 267716 nm Ni - 231604 nm Ti - 334941 nm

Cu - 327395 nm P - 213618 nm V - 311837 nm

Fe - 238204 nm Pb - 220353 nm Zn ndash 206200 nm

Instrumental conditions

RF Frequency 40 MHz (free running air-cooled)

RF Power 12 kW

Gas (plasma auxiliary nebulizer) Argon

Plasma flow 150 lmin

Auxiliary flow 15 lmin

Nebulizer flow 110 lmin

Replicates 5

Replicate read time 5 s

Operating parameters for ICP-AES quantitative analysis

ICP-AES Analysis

Bruker Aurora M90 (90 degree ion mirror ion optics Collision Reaction Interface)110 diluted

mineralized olive oil solution

Tuning with a 5 microgl Be Mg Co In Ba Ce Ti Pb and Th solution for

sensitivity and resolution optimization and mass calibration

Tuning with a 5 microgl Be Mg Co In Ba Ce Ti Pb and Th solution for

sensitivity and resolution optimization and mass calibration

Check of the level of oxide ions by the CeO+Ce+ ratio lt 2

Check of the level of oxide ions by the CeO+Ce+ ratio lt 2

Monitoring of double charged ions by the signal 137Ba++137Ba+ lt 3

Monitoring of double charged ions by the signal 137Ba++137Ba+ lt 3

CheckCorrection of isobaric interferences examination of more isotopes of the same element(eg Rb85 Rb 87 Sr88Sr87 Nd142 Nd146 Nd144 Se77 Se78 Sn147 Sm148 Sm152 Gd157 Gd154 Er166 Er168 Yb170 Yb172) application of correction equations with respect to isotopes of other elements potentially interfering (eg Nd142 corrected by analyzing Ce140 Nd144 by Sm147 Sm152 by Gd157 Rb87 by Sr88 ) use of the Collision Reaction Interface ndash CRI (for As and Se)

CheckCorrection of isobaric interferences examination of more isotopes of the same element(eg Rb85 Rb 87 Sr88Sr87 Nd142 Nd146 Nd144 Se77 Se78 Sn147 Sm148 Sm152 Gd157 Gd154 Er166 Er168 Yb170 Yb172) application of correction equations with respect to isotopes of other elements potentially interfering (eg Nd142 corrected by analyzing Ce140 Nd144 by Sm147 Sm152 by Gd157 Rb87 by Sr88 ) use of the Collision Reaction Interface ndash CRI (for As and Se)

Working rangesbull005 divide 5 microgl - As Cd Ce Er Eu Gd La Mn Nd Pb Pr Rb Sb Sc Se Sm Sr Th V Y Ybbull01 divide 10 microgl - Co Cr Cu Mg Ni

Working rangesbull005 divide 5 microgl - As Cd Ce Er Eu Gd La Mn Nd Pb Pr Rb Sb Sc Se Sm Sr Th V Y Ybbull01 divide 10 microgl - Co Cr Cu Mg Ni

External calibration5 standard solutions + blankCurve Fit LinearWeighted Fit NoCorrelation coefficientsR gt 09999

Normal Sensitivity Mode (without CRI) High Sensitivity Mode As and Se ndash Normal mode with CRI

ICP-MS Analysis

• Slide 1
• Slide 2
• Slide 3
• Slide 4
• Slide 5
• Slide 6
• Slide 7
• Slide 8
• Slide 9
• Slide 10
• Slide 11
• Slide 12
• Slide 13
• Slide 14
• Slide 15
• Slide 16
• Slide 17
• Slide 18
• Slide 19
• Slide 20
• Slide 21
• Slide 22
• Slide 23
• Slide 24
• Slide 25
• Slide 26
• Slide 27
• Slide 28
• Slide 29
• Slide 30
• Slide 31
• Slide 32
• Slide 33
• Slide 34
• Slide 35

Circulation of the thermal fluid

Circulation of the thermal fluid

Addition of cryogen

Addition of cryogen

Thermal probes Thermal probes

Olives Olives

The study were conducted on samples of olive The study were conducted on samples of olive oil produced from monovarietal and oil produced from monovarietal and

polyvarietal (polyvarietal (mixmix) olives collected in two ) olives collected in two different Italian regions (from Tuscany and different Italian regions (from Tuscany and

Basilicata) during the same season Basilicata) during the same season

The study were conducted on samples of olive The study were conducted on samples of olive oil produced from monovarietal and oil produced from monovarietal and

polyvarietal (polyvarietal (mixmix) olives collected in two ) olives collected in two different Italian regions (from Tuscany and different Italian regions (from Tuscany and

Basilicata) during the same season Basilicata) during the same season

The olive fruits utilized in each experimental The olive fruits utilized in each experimental runs (runs ( 60 kg) were preliminary and suitably 60 kg) were preliminary and suitably mixed to ensure homogeneous feeds Each mixed to ensure homogeneous feeds Each sample was split in two fractions (30 kg)sample was split in two fractions (30 kg)

The olive fruits utilized in each experimental The olive fruits utilized in each experimental runs (runs ( 60 kg) were preliminary and suitably 60 kg) were preliminary and suitably mixed to ensure homogeneous feeds Each mixed to ensure homogeneous feeds Each sample was split in two fractions (30 kg)sample was split in two fractions (30 kg)

Traditional extraction

process

Traditional extraction

process

Addition of CO2s

Addition of CO2s

Origin and cultivar of the raw matter Origin and cultivar of the raw matter utilizedutilized

Origin and cultivar of the raw matter Origin and cultivar of the raw matter utilizedutilized

Sample ID Geographical

Cultivar

Traditional

Cryo origin

A 1 Tuscany (GR)

Frantoio

B 2 Tuscany (SI) mix

C 3 Tuscany (SI) mix

D 4 Tuscany (SI) mix

E 5 Basilicata (PZ)

Coratina

F 6 Basilicata (PZ)

Coratina

G 7 Basilicata (PZ)

Coratina

Frantoio Leccino Correggiolo Frantoio Leccino Correggiolo

CryoCryo TraditionalTraditional

Cryogenolives (ww)Cryogenolives (ww) 02 02 00

Temperature of olivesTemperature of olives (degC)(degC) ~-2~-2 115115

Temperature of pasteTemperature of paste (degC)(degC) ~240~240 ~240~240

Time of MalaxationTime of Malaxation (s)(s) 24002400 24002400

Time of ExtractionTime of Extraction (s)(s) 49004900 43004300

Water addedolivesWater addedolives ()() 8585 9393

Main operating variables adopted Main operating variables adopted during the experimental runs during the experimental runs

Total OIL entrance(kg of crushed fruits x of oil inside the olives)

= Total OIL output

(kg of the olive residues x of oil inside the olive residues)

+EXTRACTED OIL

Total OIL entrance(kg of crushed fruits x of oil inside the olives)

= Total OIL output

(kg of the olive residues x of oil inside the olive residues)

+EXTRACTED OIL

MASS BALANCE during extraction MASS BALANCE during extraction processprocess

In order to evaluate the effect induced by the addition of cryogen on the oil extraction yield

the Extractability Index Variation (EIV) was determined as the percentage of the variation of oil extractability using CO2s compared with the same parameter obtained by a traditional

extraction process

In order to evaluate the effect induced by the addition of cryogen on the oil extraction yield

the Extractability Index Variation (EIV) was determined as the percentage of the variation of oil extractability using CO2s compared with the same parameter obtained by a traditional

extraction process EIV = (EC-ET)ET EIV = (EC-ET)ET 100 100EIV = (EC-ET)ET EIV = (EC-ET)ET 100 100

Results and Results and discussiondiscussion

Results and Results and discussiondiscussion

Oil extraction Oil extraction yield yield

preliminary preliminary resultsresults

Oil extraction yield Oil extraction yield preliminary preliminary resultsresults

Oil extraction yield Oil extraction yield preliminary preliminary resultsresults

Run EC ET

1A 858 825

2B 855 772

3C 912 827

4D 841 748

5E 808 793

6F 736 689

7G 844 774

The direct addition of cryogen to the olives during pre-milling phase could induce a general increase in the oil extraction yield ranging from 2 to

124

The direct addition of cryogen to the olives during pre-milling phase could induce a general increase in the oil extraction yield ranging from 2 to

124

[(EC-ET)ET]10040 108 103 124 19 68 90

[(EC-ET)ET]10040 108 103 124 19 68 90

Preliminary results about oil extraction Preliminary results about oil extraction yield yield discussion Idiscussion I

Preliminary results about oil extraction Preliminary results about oil extraction yield yield discussion Idiscussion I

The number of the experimental runs carried out until now is quite reduced

The number of the experimental runs carried out until now is quite reduced

BUTBUT

The results appear very encouraging and the new method seems very suitable for olive oil extraction

The results appear very encouraging and the new method seems very suitable for olive oil extraction

During the next crop season we will increase the number of experimental runs adopting several combinations of the working parameters (ie amount of cryogenamount of olives fruit ripening stage etc)

During the next crop season we will increase the number of experimental runs adopting several combinations of the working parameters (ie amount of cryogenamount of olives fruit ripening stage etc)

Preliminary results about oil extraction Preliminary results about oil extraction yield yield discussion IIdiscussion II

Preliminary results about oil extraction Preliminary results about oil extraction yield yield discussion IIdiscussion II

If necessary this method allows to move up the olive harvest time in order to greatly reduce the damages due to the third fly attack of Bactrocera oleae that can induce a significant loss in oil production (up to 60) as well as a decrease in oil quality

If necessary this method allows to move up the olive harvest time in order to greatly reduce the damages due to the third fly attack of Bactrocera oleae that can induce a significant loss in oil production (up to 60) as well as a decrease in oil quality

Water content

inside the fruit

Water content

inside the fruit

CELLULAR CRASH

We need 08 kg of CO2s to lower 100 kg of olives temperature by 1degC

Cost of 1 kg of CO2s= euro050 $ 037

Cost to turn down the average temperature of 100

kg of olives by 10degC(15degC 5degC )

08kgdegC x 10degC x 037 $kg=

3 $

Considering an average oil yield of 15

The addition cost for a kg of extravirgin olive oil is

3 $100 kg olives x 15100kg oilkg olives

lt 02$kg oil

Oil elemental Oil elemental profile profile

preliminary preliminary resultsresults

ICP-AES and ICP-MS techniques are particularly advantageous for the application in the definition of the elemental profiles of olive oil since they allow simultaneous multi-elemental analysis and are characterized by wide linear ranges and (especially ICP-MS) very low Detection Limits

Main analytical issues are related to the hard organic content of the oil matrix which requires appropriate sample pre-treatments Microwave-assisted digestion permitted to obtain a complete dissolution of olive oil samples but resulted in the obtainment of highly acidic solutions not directly analyzable by ICP-MS with a consequent reduction of sensitivity (due to the preliminary 110 dilution of the mineralized olive oil)

ETV

LA

Preliminary results about oil elemental Preliminary results about oil elemental profileprofile

Preliminary results about oil elemental Preliminary results about oil elemental profileprofile

Preliminary results show a rather homogeneous elemental content among all the analyzed samples of olive oil

For all elements experimental concentrations fall within the ranges reported in literature In respect to these ranges analyzed samples show a high content of B S and Si while Fe Na Pb Ba Cr and Cu contents are quite low

Samples of olive oil obtained by the traditionalldquo process show - in general - a higher content of Ca Cr Mg Si (except those originating from Basilicata) and Zn compared to those obtained by the addition of ldquocarbonic snowldquo

0

20

40

60

80

100

120

140

B Ca Fe Na S Si

mgk

g

000

050

100

150

200

250

300

350

400

450

500

Al K Mg P Zn

mgk

g

0

500

1000

1500

2000

2500

3000

3500

Co Cr Cu Ni Pb

microgk

g

0

2

4

6

8

10

12

14

16

Ce Er Eu Gd La Nd Pr Sm Y Yb

microgk

g

0

100

200

300

400

500

600

700

800

As Ba Cd Li Mn Rb Sb Sc Se Sr Th Ti V

microgk

g

4000 25000

0

20

40

60

80

100

120

140

160

Ca

Na

Si

concentration range obtained from literature [2]

experimental concentration range ICP-AESDetection LimitICP-MSDetection Limit - Normal Sensitivity modeICP-MSDetection Limit - High Sensitivitymode

S B Yasar E K Baran M Alkan Metal determinations in olive oil In Olive Oil ndash Constituents Quality Health Properties and Bioconversions Ed by Boskou Dimitrios 5 89-108 2012

Preliminary results about oil elemental Preliminary results about oil elemental profileprofile

Preliminary results about oil elemental Preliminary results about oil elemental profileprofile

For any further details about the second part of the research you can contact our colleagues in ENEA

claudiazoanieneait giovannazappaeneait

For any further details about the second part of the research you can contact our colleagues in ENEA

claudiazoanieneait giovannazappaeneait

ReferencesReferencesReferencesReferences

The Utilization of Solid Carbon Dioxide in the Production of Extravirgin Olive Oil

Sanmartin C Zinnai A Venturi F Andrich G Proceedings of EFFOST 2011 9-11 November 2011 Berlino

(D)

Analytical methods for olive oil elemental profile and influence of carbonic snow addition in the extraction

phase C Zoani G Zappa A Zinnai F Venturi C Sanmartin

11th Euro Fed Lipid Congress ndash Antalya (Turkey) 27-30 October 2013

Preliminary results on the influence of carbonic snow addition during the olive processing oil extraction yield

and elemental profile C Zoani G Zappa F Venturi C Sanmartin G Andrich and

A ZinnaiJournal of Nutrition and Food Sciences 4 277 (2014)

doi 1041722155-96001000277

The Utilization of Solid Carbon Dioxide in the Production of Extravirgin Olive Oil

Sanmartin C Zinnai A Venturi F Andrich G Proceedings of EFFOST 2011 9-11 November 2011 Berlino

(D)

Analytical methods for olive oil elemental profile and influence of carbonic snow addition in the extraction

phase C Zoani G Zappa A Zinnai F Venturi C Sanmartin

11th Euro Fed Lipid Congress ndash Antalya (Turkey) 27-30 October 2013

Preliminary results on the influence of carbonic snow addition during the olive processing oil extraction yield

and elemental profile C Zoani G Zappa F Venturi C Sanmartin G Andrich and

A ZinnaiJournal of Nutrition and Food Sciences 4 277 (2014)

doi 1041722155-96001000277

Research in progresshellipResearch in progresshellip

Thank you for your attention

Thank you for your attention

research supported by

It will be possible to apply matrix modification procedures (eg solvent extraction ndash also ultrasound assisted - addition of organic solvents or emulsification) or to employ systems for direct oil sample introduction in torch (eg Flow Injection Analysis systems)

We are conducting experimental tests for evaluating the possibility to employ a Laser Ablation system or an ElectroThermal Vaporization system for direct sample introduction in ICP-AES and ICP-MS

ETV

LA

Future developmentsFuture developmentsFuture developmentsFuture developments

Determination of oil elemental profile sample pre-treatment

High PressureMicrowave Digestion

Milestone 1200 Mega

05 golive oil

Mineralized oil sample

(final V = 25 ml)

2 ml H2O2 + 6 ml HNO3

Different mixtures testedH2O2 30vv (1 divide 2 ml)+ HNO3 699vv (2 divide

6 ml)

Total dissoluti

on

high-purity water

(gt 18 MΩ)

time Power Pressure

1 min 250 WFree

pressure race

1 min 0 W

5 min 400 W

5 min 650 W

Vent = 5 min

TQ mineralized

olive oil solution

Varian Vista MPX(axial configuration

simultaneous 112 Mpixel CCD detector)

study of spectral interferencesstudy of spectral interferences

preliminary qualitative analysis72 elements

preliminary qualitative analysis72 elements

quantitative analysisquantitative analysis

Gas flows optimization based on signal-to-background ratio (SB)

Auxiliary flow (lmin)

Nebulizer flow(lmin)

10 15 09 10 11 12

SBMg 3296 11720 13948 17998 19921 18412Mn 0128 0197 0245 0312 0303 0294Na 1827 1940 1827 3187 6121 4371

Zn - 213857 nm more sensitive but interfered by Fe

Zn - 206200 nm - less sensitive but without interferences

Analytical wavelengths (nm)

Al - 396152 nm K - 766491 nm Rb - 780026 nm

As - 188980 nm Li - 670783 nm S - 181972 nm

B - 249772 nm Mg - 279553 nm Sb - 206834 nm

Ba - 455403 nm Mn - 257610 nm Si - 251611 nm

Ca - 396847 nm Na - 589592 nm Sr - 407771 nm

Cr - 267716 nm Ni - 231604 nm Ti - 334941 nm

Cu - 327395 nm P - 213618 nm V - 311837 nm

Fe - 238204 nm Pb - 220353 nm Zn ndash 206200 nm

Instrumental conditions

RF Frequency 40 MHz (free running air-cooled)

RF Power 12 kW

Gas (plasma auxiliary nebulizer) Argon

Plasma flow 150 lmin

Auxiliary flow 15 lmin

Nebulizer flow 110 lmin

Replicates 5

Replicate read time 5 s

Operating parameters for ICP-AES quantitative analysis

ICP-AES Analysis

Bruker Aurora M90 (90 degree ion mirror ion optics Collision Reaction Interface)110 diluted

mineralized olive oil solution

Tuning with a 5 microgl Be Mg Co In Ba Ce Ti Pb and Th solution for

sensitivity and resolution optimization and mass calibration

Tuning with a 5 microgl Be Mg Co In Ba Ce Ti Pb and Th solution for

sensitivity and resolution optimization and mass calibration

Check of the level of oxide ions by the CeO+Ce+ ratio lt 2

Check of the level of oxide ions by the CeO+Ce+ ratio lt 2

Monitoring of double charged ions by the signal 137Ba++137Ba+ lt 3

Monitoring of double charged ions by the signal 137Ba++137Ba+ lt 3

CheckCorrection of isobaric interferences examination of more isotopes of the same element(eg Rb85 Rb 87 Sr88Sr87 Nd142 Nd146 Nd144 Se77 Se78 Sn147 Sm148 Sm152 Gd157 Gd154 Er166 Er168 Yb170 Yb172) application of correction equations with respect to isotopes of other elements potentially interfering (eg Nd142 corrected by analyzing Ce140 Nd144 by Sm147 Sm152 by Gd157 Rb87 by Sr88 ) use of the Collision Reaction Interface ndash CRI (for As and Se)

CheckCorrection of isobaric interferences examination of more isotopes of the same element(eg Rb85 Rb 87 Sr88Sr87 Nd142 Nd146 Nd144 Se77 Se78 Sn147 Sm148 Sm152 Gd157 Gd154 Er166 Er168 Yb170 Yb172) application of correction equations with respect to isotopes of other elements potentially interfering (eg Nd142 corrected by analyzing Ce140 Nd144 by Sm147 Sm152 by Gd157 Rb87 by Sr88 ) use of the Collision Reaction Interface ndash CRI (for As and Se)

Working rangesbull005 divide 5 microgl - As Cd Ce Er Eu Gd La Mn Nd Pb Pr Rb Sb Sc Se Sm Sr Th V Y Ybbull01 divide 10 microgl - Co Cr Cu Mg Ni

Working rangesbull005 divide 5 microgl - As Cd Ce Er Eu Gd La Mn Nd Pb Pr Rb Sb Sc Se Sm Sr Th V Y Ybbull01 divide 10 microgl - Co Cr Cu Mg Ni

External calibration5 standard solutions + blankCurve Fit LinearWeighted Fit NoCorrelation coefficientsR gt 09999

Normal Sensitivity Mode (without CRI) High Sensitivity Mode As and Se ndash Normal mode with CRI

ICP-MS Analysis

• Slide 1
• Slide 2
• Slide 3
• Slide 4
• Slide 5
• Slide 6
• Slide 7
• Slide 8
• Slide 9
• Slide 10
• Slide 11
• Slide 12
• Slide 13
• Slide 14
• Slide 15
• Slide 16
• Slide 17
• Slide 18
• Slide 19
• Slide 20
• Slide 21
• Slide 22
• Slide 23
• Slide 24
• Slide 25
• Slide 26
• Slide 27
• Slide 28
• Slide 29
• Slide 30
• Slide 31
• Slide 32
• Slide 33
• Slide 34
• Slide 35

The study were conducted on samples of olive The study were conducted on samples of olive oil produced from monovarietal and oil produced from monovarietal and

polyvarietal (polyvarietal (mixmix) olives collected in two ) olives collected in two different Italian regions (from Tuscany and different Italian regions (from Tuscany and

Basilicata) during the same season Basilicata) during the same season

The study were conducted on samples of olive The study were conducted on samples of olive oil produced from monovarietal and oil produced from monovarietal and

polyvarietal (polyvarietal (mixmix) olives collected in two ) olives collected in two different Italian regions (from Tuscany and different Italian regions (from Tuscany and

Basilicata) during the same season Basilicata) during the same season

The olive fruits utilized in each experimental The olive fruits utilized in each experimental runs (runs ( 60 kg) were preliminary and suitably 60 kg) were preliminary and suitably mixed to ensure homogeneous feeds Each mixed to ensure homogeneous feeds Each sample was split in two fractions (30 kg)sample was split in two fractions (30 kg)

The olive fruits utilized in each experimental The olive fruits utilized in each experimental runs (runs ( 60 kg) were preliminary and suitably 60 kg) were preliminary and suitably mixed to ensure homogeneous feeds Each mixed to ensure homogeneous feeds Each sample was split in two fractions (30 kg)sample was split in two fractions (30 kg)

Traditional extraction

process

Traditional extraction

process

Addition of CO2s

Addition of CO2s

Origin and cultivar of the raw matter Origin and cultivar of the raw matter utilizedutilized

Origin and cultivar of the raw matter Origin and cultivar of the raw matter utilizedutilized

Sample ID Geographical

Cultivar

Traditional

Cryo origin

A 1 Tuscany (GR)

Frantoio

B 2 Tuscany (SI) mix

C 3 Tuscany (SI) mix

D 4 Tuscany (SI) mix

E 5 Basilicata (PZ)

Coratina

F 6 Basilicata (PZ)

Coratina

G 7 Basilicata (PZ)

Coratina

Frantoio Leccino Correggiolo Frantoio Leccino Correggiolo

CryoCryo TraditionalTraditional

Cryogenolives (ww)Cryogenolives (ww) 02 02 00

Temperature of olivesTemperature of olives (degC)(degC) ~-2~-2 115115

Temperature of pasteTemperature of paste (degC)(degC) ~240~240 ~240~240

Time of MalaxationTime of Malaxation (s)(s) 24002400 24002400

Time of ExtractionTime of Extraction (s)(s) 49004900 43004300

Water addedolivesWater addedolives ()() 8585 9393

Main operating variables adopted Main operating variables adopted during the experimental runs during the experimental runs

Total OIL entrance(kg of crushed fruits x of oil inside the olives)

= Total OIL output

(kg of the olive residues x of oil inside the olive residues)

+EXTRACTED OIL

Total OIL entrance(kg of crushed fruits x of oil inside the olives)

= Total OIL output

(kg of the olive residues x of oil inside the olive residues)

+EXTRACTED OIL

MASS BALANCE during extraction MASS BALANCE during extraction processprocess

In order to evaluate the effect induced by the addition of cryogen on the oil extraction yield

the Extractability Index Variation (EIV) was determined as the percentage of the variation of oil extractability using CO2s compared with the same parameter obtained by a traditional

extraction process

In order to evaluate the effect induced by the addition of cryogen on the oil extraction yield

the Extractability Index Variation (EIV) was determined as the percentage of the variation of oil extractability using CO2s compared with the same parameter obtained by a traditional

extraction process EIV = (EC-ET)ET EIV = (EC-ET)ET 100 100EIV = (EC-ET)ET EIV = (EC-ET)ET 100 100

Results and Results and discussiondiscussion

Results and Results and discussiondiscussion

Oil extraction Oil extraction yield yield

preliminary preliminary resultsresults

Oil extraction yield Oil extraction yield preliminary preliminary resultsresults

Oil extraction yield Oil extraction yield preliminary preliminary resultsresults

Run EC ET

1A 858 825

2B 855 772

3C 912 827

4D 841 748

5E 808 793

6F 736 689

7G 844 774

The direct addition of cryogen to the olives during pre-milling phase could induce a general increase in the oil extraction yield ranging from 2 to

124

The direct addition of cryogen to the olives during pre-milling phase could induce a general increase in the oil extraction yield ranging from 2 to

124

[(EC-ET)ET]10040 108 103 124 19 68 90

[(EC-ET)ET]10040 108 103 124 19 68 90

Preliminary results about oil extraction Preliminary results about oil extraction yield yield discussion Idiscussion I

Preliminary results about oil extraction Preliminary results about oil extraction yield yield discussion Idiscussion I

The number of the experimental runs carried out until now is quite reduced

The number of the experimental runs carried out until now is quite reduced

BUTBUT

The results appear very encouraging and the new method seems very suitable for olive oil extraction

The results appear very encouraging and the new method seems very suitable for olive oil extraction

During the next crop season we will increase the number of experimental runs adopting several combinations of the working parameters (ie amount of cryogenamount of olives fruit ripening stage etc)

During the next crop season we will increase the number of experimental runs adopting several combinations of the working parameters (ie amount of cryogenamount of olives fruit ripening stage etc)

Preliminary results about oil extraction Preliminary results about oil extraction yield yield discussion IIdiscussion II

Preliminary results about oil extraction Preliminary results about oil extraction yield yield discussion IIdiscussion II

If necessary this method allows to move up the olive harvest time in order to greatly reduce the damages due to the third fly attack of Bactrocera oleae that can induce a significant loss in oil production (up to 60) as well as a decrease in oil quality

If necessary this method allows to move up the olive harvest time in order to greatly reduce the damages due to the third fly attack of Bactrocera oleae that can induce a significant loss in oil production (up to 60) as well as a decrease in oil quality

Water content

inside the fruit

Water content

inside the fruit

CELLULAR CRASH

We need 08 kg of CO2s to lower 100 kg of olives temperature by 1degC

Cost of 1 kg of CO2s= euro050 $ 037

Cost to turn down the average temperature of 100

kg of olives by 10degC(15degC 5degC )

08kgdegC x 10degC x 037 $kg=

3 $

Considering an average oil yield of 15

The addition cost for a kg of extravirgin olive oil is

3 $100 kg olives x 15100kg oilkg olives

lt 02$kg oil

Oil elemental Oil elemental profile profile

preliminary preliminary resultsresults

ICP-AES and ICP-MS techniques are particularly advantageous for the application in the definition of the elemental profiles of olive oil since they allow simultaneous multi-elemental analysis and are characterized by wide linear ranges and (especially ICP-MS) very low Detection Limits

Main analytical issues are related to the hard organic content of the oil matrix which requires appropriate sample pre-treatments Microwave-assisted digestion permitted to obtain a complete dissolution of olive oil samples but resulted in the obtainment of highly acidic solutions not directly analyzable by ICP-MS with a consequent reduction of sensitivity (due to the preliminary 110 dilution of the mineralized olive oil)

ETV

LA

Preliminary results about oil elemental Preliminary results about oil elemental profileprofile

Preliminary results about oil elemental Preliminary results about oil elemental profileprofile

Preliminary results show a rather homogeneous elemental content among all the analyzed samples of olive oil

For all elements experimental concentrations fall within the ranges reported in literature In respect to these ranges analyzed samples show a high content of B S and Si while Fe Na Pb Ba Cr and Cu contents are quite low

Samples of olive oil obtained by the traditionalldquo process show - in general - a higher content of Ca Cr Mg Si (except those originating from Basilicata) and Zn compared to those obtained by the addition of ldquocarbonic snowldquo

0

20

40

60

80

100

120

140

B Ca Fe Na S Si

mgk

g

000

050

100

150

200

250

300

350

400

450

500

Al K Mg P Zn

mgk

g

0

500

1000

1500

2000

2500

3000

3500

Co Cr Cu Ni Pb

microgk

g

0

2

4

6

8

10

12

14

16

Ce Er Eu Gd La Nd Pr Sm Y Yb

microgk

g

0

100

200

300

400

500

600

700

800

As Ba Cd Li Mn Rb Sb Sc Se Sr Th Ti V

microgk

g

4000 25000

0

20

40

60

80

100

120

140

160

Ca

Na

Si

concentration range obtained from literature [2]

experimental concentration range ICP-AESDetection LimitICP-MSDetection Limit - Normal Sensitivity modeICP-MSDetection Limit - High Sensitivitymode

S B Yasar E K Baran M Alkan Metal determinations in olive oil In Olive Oil ndash Constituents Quality Health Properties and Bioconversions Ed by Boskou Dimitrios 5 89-108 2012

Preliminary results about oil elemental Preliminary results about oil elemental profileprofile

Preliminary results about oil elemental Preliminary results about oil elemental profileprofile

For any further details about the second part of the research you can contact our colleagues in ENEA

claudiazoanieneait giovannazappaeneait

For any further details about the second part of the research you can contact our colleagues in ENEA

claudiazoanieneait giovannazappaeneait

ReferencesReferencesReferencesReferences

The Utilization of Solid Carbon Dioxide in the Production of Extravirgin Olive Oil

Sanmartin C Zinnai A Venturi F Andrich G Proceedings of EFFOST 2011 9-11 November 2011 Berlino

(D)

Analytical methods for olive oil elemental profile and influence of carbonic snow addition in the extraction

phase C Zoani G Zappa A Zinnai F Venturi C Sanmartin

11th Euro Fed Lipid Congress ndash Antalya (Turkey) 27-30 October 2013

Preliminary results on the influence of carbonic snow addition during the olive processing oil extraction yield

and elemental profile C Zoani G Zappa F Venturi C Sanmartin G Andrich and

A ZinnaiJournal of Nutrition and Food Sciences 4 277 (2014)

doi 1041722155-96001000277

The Utilization of Solid Carbon Dioxide in the Production of Extravirgin Olive Oil

Sanmartin C Zinnai A Venturi F Andrich G Proceedings of EFFOST 2011 9-11 November 2011 Berlino

(D)

Analytical methods for olive oil elemental profile and influence of carbonic snow addition in the extraction

phase C Zoani G Zappa A Zinnai F Venturi C Sanmartin

11th Euro Fed Lipid Congress ndash Antalya (Turkey) 27-30 October 2013

Preliminary results on the influence of carbonic snow addition during the olive processing oil extraction yield

and elemental profile C Zoani G Zappa F Venturi C Sanmartin G Andrich and

A ZinnaiJournal of Nutrition and Food Sciences 4 277 (2014)

doi 1041722155-96001000277

Research in progresshellipResearch in progresshellip

Thank you for your attention

Thank you for your attention

research supported by

It will be possible to apply matrix modification procedures (eg solvent extraction ndash also ultrasound assisted - addition of organic solvents or emulsification) or to employ systems for direct oil sample introduction in torch (eg Flow Injection Analysis systems)

We are conducting experimental tests for evaluating the possibility to employ a Laser Ablation system or an ElectroThermal Vaporization system for direct sample introduction in ICP-AES and ICP-MS

ETV

LA

Future developmentsFuture developmentsFuture developmentsFuture developments

Determination of oil elemental profile sample pre-treatment

High PressureMicrowave Digestion

Milestone 1200 Mega

05 golive oil

Mineralized oil sample

(final V = 25 ml)

2 ml H2O2 + 6 ml HNO3

Different mixtures testedH2O2 30vv (1 divide 2 ml)+ HNO3 699vv (2 divide

6 ml)

Total dissoluti

on

high-purity water

(gt 18 MΩ)

time Power Pressure

1 min 250 WFree

pressure race

1 min 0 W

5 min 400 W

5 min 650 W

Vent = 5 min

TQ mineralized

olive oil solution

Varian Vista MPX(axial configuration

simultaneous 112 Mpixel CCD detector)

study of spectral interferencesstudy of spectral interferences

preliminary qualitative analysis72 elements

preliminary qualitative analysis72 elements

quantitative analysisquantitative analysis

Gas flows optimization based on signal-to-background ratio (SB)

Auxiliary flow (lmin)

Nebulizer flow(lmin)

10 15 09 10 11 12

SBMg 3296 11720 13948 17998 19921 18412Mn 0128 0197 0245 0312 0303 0294Na 1827 1940 1827 3187 6121 4371

Zn - 213857 nm more sensitive but interfered by Fe

Zn - 206200 nm - less sensitive but without interferences

Analytical wavelengths (nm)

Al - 396152 nm K - 766491 nm Rb - 780026 nm

As - 188980 nm Li - 670783 nm S - 181972 nm

B - 249772 nm Mg - 279553 nm Sb - 206834 nm

Ba - 455403 nm Mn - 257610 nm Si - 251611 nm

Ca - 396847 nm Na - 589592 nm Sr - 407771 nm

Cr - 267716 nm Ni - 231604 nm Ti - 334941 nm

Cu - 327395 nm P - 213618 nm V - 311837 nm

Fe - 238204 nm Pb - 220353 nm Zn ndash 206200 nm

Instrumental conditions

RF Frequency 40 MHz (free running air-cooled)

RF Power 12 kW

Gas (plasma auxiliary nebulizer) Argon

Plasma flow 150 lmin

Auxiliary flow 15 lmin

Nebulizer flow 110 lmin

Replicates 5

Replicate read time 5 s

Operating parameters for ICP-AES quantitative analysis

ICP-AES Analysis

Bruker Aurora M90 (90 degree ion mirror ion optics Collision Reaction Interface)110 diluted

mineralized olive oil solution

Tuning with a 5 microgl Be Mg Co In Ba Ce Ti Pb and Th solution for

sensitivity and resolution optimization and mass calibration

Tuning with a 5 microgl Be Mg Co In Ba Ce Ti Pb and Th solution for

sensitivity and resolution optimization and mass calibration

Check of the level of oxide ions by the CeO+Ce+ ratio lt 2

Check of the level of oxide ions by the CeO+Ce+ ratio lt 2

Monitoring of double charged ions by the signal 137Ba++137Ba+ lt 3

Monitoring of double charged ions by the signal 137Ba++137Ba+ lt 3

CheckCorrection of isobaric interferences examination of more isotopes of the same element(eg Rb85 Rb 87 Sr88Sr87 Nd142 Nd146 Nd144 Se77 Se78 Sn147 Sm148 Sm152 Gd157 Gd154 Er166 Er168 Yb170 Yb172) application of correction equations with respect to isotopes of other elements potentially interfering (eg Nd142 corrected by analyzing Ce140 Nd144 by Sm147 Sm152 by Gd157 Rb87 by Sr88 ) use of the Collision Reaction Interface ndash CRI (for As and Se)

CheckCorrection of isobaric interferences examination of more isotopes of the same element(eg Rb85 Rb 87 Sr88Sr87 Nd142 Nd146 Nd144 Se77 Se78 Sn147 Sm148 Sm152 Gd157 Gd154 Er166 Er168 Yb170 Yb172) application of correction equations with respect to isotopes of other elements potentially interfering (eg Nd142 corrected by analyzing Ce140 Nd144 by Sm147 Sm152 by Gd157 Rb87 by Sr88 ) use of the Collision Reaction Interface ndash CRI (for As and Se)

Working rangesbull005 divide 5 microgl - As Cd Ce Er Eu Gd La Mn Nd Pb Pr Rb Sb Sc Se Sm Sr Th V Y Ybbull01 divide 10 microgl - Co Cr Cu Mg Ni

Working rangesbull005 divide 5 microgl - As Cd Ce Er Eu Gd La Mn Nd Pb Pr Rb Sb Sc Se Sm Sr Th V Y Ybbull01 divide 10 microgl - Co Cr Cu Mg Ni

External calibration5 standard solutions + blankCurve Fit LinearWeighted Fit NoCorrelation coefficientsR gt 09999

Normal Sensitivity Mode (without CRI) High Sensitivity Mode As and Se ndash Normal mode with CRI

ICP-MS Analysis

• Slide 1
• Slide 2
• Slide 3
• Slide 4
• Slide 5
• Slide 6
• Slide 7
• Slide 8
• Slide 9
• Slide 10
• Slide 11
• Slide 12
• Slide 13
• Slide 14
• Slide 15
• Slide 16
• Slide 17
• Slide 18
• Slide 19
• Slide 20
• Slide 21
• Slide 22
• Slide 23
• Slide 24
• Slide 25
• Slide 26
• Slide 27
• Slide 28
• Slide 29
• Slide 30
• Slide 31
• Slide 32
• Slide 33
• Slide 34
• Slide 35

Origin and cultivar of the raw matter Origin and cultivar of the raw matter utilizedutilized

Origin and cultivar of the raw matter Origin and cultivar of the raw matter utilizedutilized

Sample ID Geographical

Cultivar

Traditional

Cryo origin

A 1 Tuscany (GR)

Frantoio

B 2 Tuscany (SI) mix

C 3 Tuscany (SI) mix

D 4 Tuscany (SI) mix

E 5 Basilicata (PZ)

Coratina

F 6 Basilicata (PZ)

Coratina

G 7 Basilicata (PZ)

Coratina

Frantoio Leccino Correggiolo Frantoio Leccino Correggiolo

CryoCryo TraditionalTraditional

Cryogenolives (ww)Cryogenolives (ww) 02 02 00

Temperature of olivesTemperature of olives (degC)(degC) ~-2~-2 115115

Temperature of pasteTemperature of paste (degC)(degC) ~240~240 ~240~240

Time of MalaxationTime of Malaxation (s)(s) 24002400 24002400

Time of ExtractionTime of Extraction (s)(s) 49004900 43004300

Water addedolivesWater addedolives ()() 8585 9393

Main operating variables adopted Main operating variables adopted during the experimental runs during the experimental runs

Total OIL entrance(kg of crushed fruits x of oil inside the olives)

= Total OIL output

(kg of the olive residues x of oil inside the olive residues)

+EXTRACTED OIL

Total OIL entrance(kg of crushed fruits x of oil inside the olives)

= Total OIL output

(kg of the olive residues x of oil inside the olive residues)

+EXTRACTED OIL

MASS BALANCE during extraction MASS BALANCE during extraction processprocess

In order to evaluate the effect induced by the addition of cryogen on the oil extraction yield

the Extractability Index Variation (EIV) was determined as the percentage of the variation of oil extractability using CO2s compared with the same parameter obtained by a traditional

extraction process

In order to evaluate the effect induced by the addition of cryogen on the oil extraction yield

the Extractability Index Variation (EIV) was determined as the percentage of the variation of oil extractability using CO2s compared with the same parameter obtained by a traditional

extraction process EIV = (EC-ET)ET EIV = (EC-ET)ET 100 100EIV = (EC-ET)ET EIV = (EC-ET)ET 100 100

Results and Results and discussiondiscussion

Results and Results and discussiondiscussion

Oil extraction Oil extraction yield yield

preliminary preliminary resultsresults

Oil extraction yield Oil extraction yield preliminary preliminary resultsresults

Oil extraction yield Oil extraction yield preliminary preliminary resultsresults

Run EC ET

1A 858 825

2B 855 772

3C 912 827

4D 841 748

5E 808 793

6F 736 689

7G 844 774

The direct addition of cryogen to the olives during pre-milling phase could induce a general increase in the oil extraction yield ranging from 2 to

124

The direct addition of cryogen to the olives during pre-milling phase could induce a general increase in the oil extraction yield ranging from 2 to

124

[(EC-ET)ET]10040 108 103 124 19 68 90

[(EC-ET)ET]10040 108 103 124 19 68 90

Preliminary results about oil extraction Preliminary results about oil extraction yield yield discussion Idiscussion I

Preliminary results about oil extraction Preliminary results about oil extraction yield yield discussion Idiscussion I

The number of the experimental runs carried out until now is quite reduced

The number of the experimental runs carried out until now is quite reduced

BUTBUT

The results appear very encouraging and the new method seems very suitable for olive oil extraction

The results appear very encouraging and the new method seems very suitable for olive oil extraction

During the next crop season we will increase the number of experimental runs adopting several combinations of the working parameters (ie amount of cryogenamount of olives fruit ripening stage etc)

During the next crop season we will increase the number of experimental runs adopting several combinations of the working parameters (ie amount of cryogenamount of olives fruit ripening stage etc)

Preliminary results about oil extraction Preliminary results about oil extraction yield yield discussion IIdiscussion II

Preliminary results about oil extraction Preliminary results about oil extraction yield yield discussion IIdiscussion II

If necessary this method allows to move up the olive harvest time in order to greatly reduce the damages due to the third fly attack of Bactrocera oleae that can induce a significant loss in oil production (up to 60) as well as a decrease in oil quality

If necessary this method allows to move up the olive harvest time in order to greatly reduce the damages due to the third fly attack of Bactrocera oleae that can induce a significant loss in oil production (up to 60) as well as a decrease in oil quality

Water content

inside the fruit

Water content

inside the fruit

CELLULAR CRASH

We need 08 kg of CO2s to lower 100 kg of olives temperature by 1degC

Cost of 1 kg of CO2s= euro050 $ 037

Cost to turn down the average temperature of 100

kg of olives by 10degC(15degC 5degC )

08kgdegC x 10degC x 037 $kg=

3 $

Considering an average oil yield of 15

The addition cost for a kg of extravirgin olive oil is

3 $100 kg olives x 15100kg oilkg olives

lt 02$kg oil

Oil elemental Oil elemental profile profile

preliminary preliminary resultsresults

ICP-AES and ICP-MS techniques are particularly advantageous for the application in the definition of the elemental profiles of olive oil since they allow simultaneous multi-elemental analysis and are characterized by wide linear ranges and (especially ICP-MS) very low Detection Limits

Main analytical issues are related to the hard organic content of the oil matrix which requires appropriate sample pre-treatments Microwave-assisted digestion permitted to obtain a complete dissolution of olive oil samples but resulted in the obtainment of highly acidic solutions not directly analyzable by ICP-MS with a consequent reduction of sensitivity (due to the preliminary 110 dilution of the mineralized olive oil)

ETV

LA

Preliminary results about oil elemental Preliminary results about oil elemental profileprofile

Preliminary results about oil elemental Preliminary results about oil elemental profileprofile

Preliminary results show a rather homogeneous elemental content among all the analyzed samples of olive oil

For all elements experimental concentrations fall within the ranges reported in literature In respect to these ranges analyzed samples show a high content of B S and Si while Fe Na Pb Ba Cr and Cu contents are quite low

Samples of olive oil obtained by the traditionalldquo process show - in general - a higher content of Ca Cr Mg Si (except those originating from Basilicata) and Zn compared to those obtained by the addition of ldquocarbonic snowldquo

0

20

40

60

80

100

120

140

B Ca Fe Na S Si

mgk

g

000

050

100

150

200

250

300

350

400

450

500

Al K Mg P Zn

mgk

g

0

500

1000

1500

2000

2500

3000

3500

Co Cr Cu Ni Pb

microgk

g

0

2

4

6

8

10

12

14

16

Ce Er Eu Gd La Nd Pr Sm Y Yb

microgk

g

0

100

200

300

400

500

600

700

800

As Ba Cd Li Mn Rb Sb Sc Se Sr Th Ti V

microgk

g

4000 25000

0

20

40

60

80

100

120

140

160

Ca

Na

Si

concentration range obtained from literature [2]

experimental concentration range ICP-AESDetection LimitICP-MSDetection Limit - Normal Sensitivity modeICP-MSDetection Limit - High Sensitivitymode

S B Yasar E K Baran M Alkan Metal determinations in olive oil In Olive Oil ndash Constituents Quality Health Properties and Bioconversions Ed by Boskou Dimitrios 5 89-108 2012

Preliminary results about oil elemental Preliminary results about oil elemental profileprofile

Preliminary results about oil elemental Preliminary results about oil elemental profileprofile

For any further details about the second part of the research you can contact our colleagues in ENEA

claudiazoanieneait giovannazappaeneait

For any further details about the second part of the research you can contact our colleagues in ENEA

claudiazoanieneait giovannazappaeneait

ReferencesReferencesReferencesReferences

The Utilization of Solid Carbon Dioxide in the Production of Extravirgin Olive Oil

Sanmartin C Zinnai A Venturi F Andrich G Proceedings of EFFOST 2011 9-11 November 2011 Berlino

(D)

Analytical methods for olive oil elemental profile and influence of carbonic snow addition in the extraction

phase C Zoani G Zappa A Zinnai F Venturi C Sanmartin

11th Euro Fed Lipid Congress ndash Antalya (Turkey) 27-30 October 2013

Preliminary results on the influence of carbonic snow addition during the olive processing oil extraction yield

and elemental profile C Zoani G Zappa F Venturi C Sanmartin G Andrich and

A ZinnaiJournal of Nutrition and Food Sciences 4 277 (2014)

doi 1041722155-96001000277

The Utilization of Solid Carbon Dioxide in the Production of Extravirgin Olive Oil

Sanmartin C Zinnai A Venturi F Andrich G Proceedings of EFFOST 2011 9-11 November 2011 Berlino

(D)

Analytical methods for olive oil elemental profile and influence of carbonic snow addition in the extraction

phase C Zoani G Zappa A Zinnai F Venturi C Sanmartin

11th Euro Fed Lipid Congress ndash Antalya (Turkey) 27-30 October 2013

Preliminary results on the influence of carbonic snow addition during the olive processing oil extraction yield

and elemental profile C Zoani G Zappa F Venturi C Sanmartin G Andrich and

A ZinnaiJournal of Nutrition and Food Sciences 4 277 (2014)

doi 1041722155-96001000277

Research in progresshellipResearch in progresshellip

Thank you for your attention

Thank you for your attention

research supported by

It will be possible to apply matrix modification procedures (eg solvent extraction ndash also ultrasound assisted - addition of organic solvents or emulsification) or to employ systems for direct oil sample introduction in torch (eg Flow Injection Analysis systems)

We are conducting experimental tests for evaluating the possibility to employ a Laser Ablation system or an ElectroThermal Vaporization system for direct sample introduction in ICP-AES and ICP-MS

ETV

LA

Future developmentsFuture developmentsFuture developmentsFuture developments

Determination of oil elemental profile sample pre-treatment

High PressureMicrowave Digestion

Milestone 1200 Mega

05 golive oil

Mineralized oil sample

(final V = 25 ml)

2 ml H2O2 + 6 ml HNO3

Different mixtures testedH2O2 30vv (1 divide 2 ml)+ HNO3 699vv (2 divide

6 ml)

Total dissoluti

on

high-purity water

(gt 18 MΩ)

time Power Pressure

1 min 250 WFree

pressure race

1 min 0 W

5 min 400 W

5 min 650 W

Vent = 5 min

TQ mineralized

olive oil solution

Varian Vista MPX(axial configuration

simultaneous 112 Mpixel CCD detector)

study of spectral interferencesstudy of spectral interferences

preliminary qualitative analysis72 elements

preliminary qualitative analysis72 elements

quantitative analysisquantitative analysis

Gas flows optimization based on signal-to-background ratio (SB)

Auxiliary flow (lmin)

Nebulizer flow(lmin)

10 15 09 10 11 12

SBMg 3296 11720 13948 17998 19921 18412Mn 0128 0197 0245 0312 0303 0294Na 1827 1940 1827 3187 6121 4371

Zn - 213857 nm more sensitive but interfered by Fe

Zn - 206200 nm - less sensitive but without interferences

Analytical wavelengths (nm)

Al - 396152 nm K - 766491 nm Rb - 780026 nm

As - 188980 nm Li - 670783 nm S - 181972 nm

B - 249772 nm Mg - 279553 nm Sb - 206834 nm

Ba - 455403 nm Mn - 257610 nm Si - 251611 nm

Ca - 396847 nm Na - 589592 nm Sr - 407771 nm

Cr - 267716 nm Ni - 231604 nm Ti - 334941 nm

Cu - 327395 nm P - 213618 nm V - 311837 nm

Fe - 238204 nm Pb - 220353 nm Zn ndash 206200 nm

Instrumental conditions

RF Frequency 40 MHz (free running air-cooled)

RF Power 12 kW

Gas (plasma auxiliary nebulizer) Argon

Plasma flow 150 lmin

Auxiliary flow 15 lmin

Nebulizer flow 110 lmin

Replicates 5

Replicate read time 5 s

Operating parameters for ICP-AES quantitative analysis

ICP-AES Analysis

Bruker Aurora M90 (90 degree ion mirror ion optics Collision Reaction Interface)110 diluted

mineralized olive oil solution

Tuning with a 5 microgl Be Mg Co In Ba Ce Ti Pb and Th solution for

sensitivity and resolution optimization and mass calibration

Tuning with a 5 microgl Be Mg Co In Ba Ce Ti Pb and Th solution for

sensitivity and resolution optimization and mass calibration

Check of the level of oxide ions by the CeO+Ce+ ratio lt 2

Check of the level of oxide ions by the CeO+Ce+ ratio lt 2

Monitoring of double charged ions by the signal 137Ba++137Ba+ lt 3

Monitoring of double charged ions by the signal 137Ba++137Ba+ lt 3

CheckCorrection of isobaric interferences examination of more isotopes of the same element(eg Rb85 Rb 87 Sr88Sr87 Nd142 Nd146 Nd144 Se77 Se78 Sn147 Sm148 Sm152 Gd157 Gd154 Er166 Er168 Yb170 Yb172) application of correction equations with respect to isotopes of other elements potentially interfering (eg Nd142 corrected by analyzing Ce140 Nd144 by Sm147 Sm152 by Gd157 Rb87 by Sr88 ) use of the Collision Reaction Interface ndash CRI (for As and Se)

CheckCorrection of isobaric interferences examination of more isotopes of the same element(eg Rb85 Rb 87 Sr88Sr87 Nd142 Nd146 Nd144 Se77 Se78 Sn147 Sm148 Sm152 Gd157 Gd154 Er166 Er168 Yb170 Yb172) application of correction equations with respect to isotopes of other elements potentially interfering (eg Nd142 corrected by analyzing Ce140 Nd144 by Sm147 Sm152 by Gd157 Rb87 by Sr88 ) use of the Collision Reaction Interface ndash CRI (for As and Se)

Working rangesbull005 divide 5 microgl - As Cd Ce Er Eu Gd La Mn Nd Pb Pr Rb Sb Sc Se Sm Sr Th V Y Ybbull01 divide 10 microgl - Co Cr Cu Mg Ni

Working rangesbull005 divide 5 microgl - As Cd Ce Er Eu Gd La Mn Nd Pb Pr Rb Sb Sc Se Sm Sr Th V Y Ybbull01 divide 10 microgl - Co Cr Cu Mg Ni

External calibration5 standard solutions + blankCurve Fit LinearWeighted Fit NoCorrelation coefficientsR gt 09999

Normal Sensitivity Mode (without CRI) High Sensitivity Mode As and Se ndash Normal mode with CRI

ICP-MS Analysis

• Slide 1
• Slide 2
• Slide 3
• Slide 4
• Slide 5
• Slide 6
• Slide 7
• Slide 8
• Slide 9
• Slide 10
• Slide 11
• Slide 12
• Slide 13
• Slide 14
• Slide 15
• Slide 16
• Slide 17
• Slide 18
• Slide 19
• Slide 20
• Slide 21
• Slide 22
• Slide 23
• Slide 24
• Slide 25
• Slide 26
• Slide 27
• Slide 28
• Slide 29
• Slide 30
• Slide 31
• Slide 32
• Slide 33
• Slide 34
• Slide 35

CryoCryo TraditionalTraditional

Cryogenolives (ww)Cryogenolives (ww) 02 02 00

Temperature of olivesTemperature of olives (degC)(degC) ~-2~-2 115115

Temperature of pasteTemperature of paste (degC)(degC) ~240~240 ~240~240

Time of MalaxationTime of Malaxation (s)(s) 24002400 24002400

Time of ExtractionTime of Extraction (s)(s) 49004900 43004300

Water addedolivesWater addedolives ()() 8585 9393

Main operating variables adopted Main operating variables adopted during the experimental runs during the experimental runs

Total OIL entrance(kg of crushed fruits x of oil inside the olives)

= Total OIL output

(kg of the olive residues x of oil inside the olive residues)

+EXTRACTED OIL

Total OIL entrance(kg of crushed fruits x of oil inside the olives)

= Total OIL output

(kg of the olive residues x of oil inside the olive residues)

+EXTRACTED OIL

MASS BALANCE during extraction MASS BALANCE during extraction processprocess

In order to evaluate the effect induced by the addition of cryogen on the oil extraction yield

the Extractability Index Variation (EIV) was determined as the percentage of the variation of oil extractability using CO2s compared with the same parameter obtained by a traditional

extraction process

In order to evaluate the effect induced by the addition of cryogen on the oil extraction yield

the Extractability Index Variation (EIV) was determined as the percentage of the variation of oil extractability using CO2s compared with the same parameter obtained by a traditional

extraction process EIV = (EC-ET)ET EIV = (EC-ET)ET 100 100EIV = (EC-ET)ET EIV = (EC-ET)ET 100 100

Results and Results and discussiondiscussion

Results and Results and discussiondiscussion

Oil extraction Oil extraction yield yield

preliminary preliminary resultsresults

Oil extraction yield Oil extraction yield preliminary preliminary resultsresults

Oil extraction yield Oil extraction yield preliminary preliminary resultsresults

Run EC ET

1A 858 825

2B 855 772

3C 912 827

4D 841 748

5E 808 793

6F 736 689

7G 844 774

The direct addition of cryogen to the olives during pre-milling phase could induce a general increase in the oil extraction yield ranging from 2 to

124

The direct addition of cryogen to the olives during pre-milling phase could induce a general increase in the oil extraction yield ranging from 2 to

124

[(EC-ET)ET]10040 108 103 124 19 68 90

[(EC-ET)ET]10040 108 103 124 19 68 90

Preliminary results about oil extraction Preliminary results about oil extraction yield yield discussion Idiscussion I

Preliminary results about oil extraction Preliminary results about oil extraction yield yield discussion Idiscussion I

The number of the experimental runs carried out until now is quite reduced

The number of the experimental runs carried out until now is quite reduced

BUTBUT

The results appear very encouraging and the new method seems very suitable for olive oil extraction

The results appear very encouraging and the new method seems very suitable for olive oil extraction

During the next crop season we will increase the number of experimental runs adopting several combinations of the working parameters (ie amount of cryogenamount of olives fruit ripening stage etc)

During the next crop season we will increase the number of experimental runs adopting several combinations of the working parameters (ie amount of cryogenamount of olives fruit ripening stage etc)

Preliminary results about oil extraction Preliminary results about oil extraction yield yield discussion IIdiscussion II

Preliminary results about oil extraction Preliminary results about oil extraction yield yield discussion IIdiscussion II

If necessary this method allows to move up the olive harvest time in order to greatly reduce the damages due to the third fly attack of Bactrocera oleae that can induce a significant loss in oil production (up to 60) as well as a decrease in oil quality

If necessary this method allows to move up the olive harvest time in order to greatly reduce the damages due to the third fly attack of Bactrocera oleae that can induce a significant loss in oil production (up to 60) as well as a decrease in oil quality

Water content

inside the fruit

Water content

inside the fruit

CELLULAR CRASH

We need 08 kg of CO2s to lower 100 kg of olives temperature by 1degC

Cost of 1 kg of CO2s= euro050 $ 037

Cost to turn down the average temperature of 100

kg of olives by 10degC(15degC 5degC )

08kgdegC x 10degC x 037 $kg=

3 $

Considering an average oil yield of 15

The addition cost for a kg of extravirgin olive oil is

3 $100 kg olives x 15100kg oilkg olives

lt 02$kg oil

Oil elemental Oil elemental profile profile

preliminary preliminary resultsresults

ICP-AES and ICP-MS techniques are particularly advantageous for the application in the definition of the elemental profiles of olive oil since they allow simultaneous multi-elemental analysis and are characterized by wide linear ranges and (especially ICP-MS) very low Detection Limits

Main analytical issues are related to the hard organic content of the oil matrix which requires appropriate sample pre-treatments Microwave-assisted digestion permitted to obtain a complete dissolution of olive oil samples but resulted in the obtainment of highly acidic solutions not directly analyzable by ICP-MS with a consequent reduction of sensitivity (due to the preliminary 110 dilution of the mineralized olive oil)

ETV

LA

Preliminary results about oil elemental Preliminary results about oil elemental profileprofile

Preliminary results about oil elemental Preliminary results about oil elemental profileprofile

Preliminary results show a rather homogeneous elemental content among all the analyzed samples of olive oil

For all elements experimental concentrations fall within the ranges reported in literature In respect to these ranges analyzed samples show a high content of B S and Si while Fe Na Pb Ba Cr and Cu contents are quite low

Samples of olive oil obtained by the traditionalldquo process show - in general - a higher content of Ca Cr Mg Si (except those originating from Basilicata) and Zn compared to those obtained by the addition of ldquocarbonic snowldquo

0

20

40

60

80

100

120

140

B Ca Fe Na S Si

mgk

g

000

050

100

150

200

250

300

350

400

450

500

Al K Mg P Zn

mgk

g

0

500

1000

1500

2000

2500

3000

3500

Co Cr Cu Ni Pb

microgk

g

0

2

4

6

8

10

12

14

16

Ce Er Eu Gd La Nd Pr Sm Y Yb

microgk

g

0

100

200

300

400

500

600

700

800

As Ba Cd Li Mn Rb Sb Sc Se Sr Th Ti V

microgk

g

4000 25000

0

20

40

60

80

100

120

140

160

Ca

Na

Si

concentration range obtained from literature [2]

experimental concentration range ICP-AESDetection LimitICP-MSDetection Limit - Normal Sensitivity modeICP-MSDetection Limit - High Sensitivitymode

S B Yasar E K Baran M Alkan Metal determinations in olive oil In Olive Oil ndash Constituents Quality Health Properties and Bioconversions Ed by Boskou Dimitrios 5 89-108 2012

Preliminary results about oil elemental Preliminary results about oil elemental profileprofile

Preliminary results about oil elemental Preliminary results about oil elemental profileprofile

For any further details about the second part of the research you can contact our colleagues in ENEA

claudiazoanieneait giovannazappaeneait

For any further details about the second part of the research you can contact our colleagues in ENEA

claudiazoanieneait giovannazappaeneait

ReferencesReferencesReferencesReferences

The Utilization of Solid Carbon Dioxide in the Production of Extravirgin Olive Oil

Sanmartin C Zinnai A Venturi F Andrich G Proceedings of EFFOST 2011 9-11 November 2011 Berlino

(D)

Analytical methods for olive oil elemental profile and influence of carbonic snow addition in the extraction

phase C Zoani G Zappa A Zinnai F Venturi C Sanmartin

11th Euro Fed Lipid Congress ndash Antalya (Turkey) 27-30 October 2013

Preliminary results on the influence of carbonic snow addition during the olive processing oil extraction yield

and elemental profile C Zoani G Zappa F Venturi C Sanmartin G Andrich and

A ZinnaiJournal of Nutrition and Food Sciences 4 277 (2014)

doi 1041722155-96001000277

The Utilization of Solid Carbon Dioxide in the Production of Extravirgin Olive Oil

Sanmartin C Zinnai A Venturi F Andrich G Proceedings of EFFOST 2011 9-11 November 2011 Berlino

(D)

Analytical methods for olive oil elemental profile and influence of carbonic snow addition in the extraction

phase C Zoani G Zappa A Zinnai F Venturi C Sanmartin

11th Euro Fed Lipid Congress ndash Antalya (Turkey) 27-30 October 2013

Preliminary results on the influence of carbonic snow addition during the olive processing oil extraction yield

and elemental profile C Zoani G Zappa F Venturi C Sanmartin G Andrich and

A ZinnaiJournal of Nutrition and Food Sciences 4 277 (2014)

doi 1041722155-96001000277

Research in progresshellipResearch in progresshellip

Thank you for your attention

Thank you for your attention

research supported by

It will be possible to apply matrix modification procedures (eg solvent extraction ndash also ultrasound assisted - addition of organic solvents or emulsification) or to employ systems for direct oil sample introduction in torch (eg Flow Injection Analysis systems)

We are conducting experimental tests for evaluating the possibility to employ a Laser Ablation system or an ElectroThermal Vaporization system for direct sample introduction in ICP-AES and ICP-MS

ETV

LA

Future developmentsFuture developmentsFuture developmentsFuture developments

Determination of oil elemental profile sample pre-treatment

High PressureMicrowave Digestion

Milestone 1200 Mega

05 golive oil

Mineralized oil sample

(final V = 25 ml)

2 ml H2O2 + 6 ml HNO3

Different mixtures testedH2O2 30vv (1 divide 2 ml)+ HNO3 699vv (2 divide

6 ml)

Total dissoluti

on

high-purity water

(gt 18 MΩ)

time Power Pressure

1 min 250 WFree

pressure race

1 min 0 W

5 min 400 W

5 min 650 W

Vent = 5 min

TQ mineralized

olive oil solution

Varian Vista MPX(axial configuration

simultaneous 112 Mpixel CCD detector)

study of spectral interferencesstudy of spectral interferences

preliminary qualitative analysis72 elements

preliminary qualitative analysis72 elements

quantitative analysisquantitative analysis

Gas flows optimization based on signal-to-background ratio (SB)

Auxiliary flow (lmin)

Nebulizer flow(lmin)

10 15 09 10 11 12

SBMg 3296 11720 13948 17998 19921 18412Mn 0128 0197 0245 0312 0303 0294Na 1827 1940 1827 3187 6121 4371

Zn - 213857 nm more sensitive but interfered by Fe

Zn - 206200 nm - less sensitive but without interferences

Analytical wavelengths (nm)

Al - 396152 nm K - 766491 nm Rb - 780026 nm

As - 188980 nm Li - 670783 nm S - 181972 nm

B - 249772 nm Mg - 279553 nm Sb - 206834 nm

Ba - 455403 nm Mn - 257610 nm Si - 251611 nm

Ca - 396847 nm Na - 589592 nm Sr - 407771 nm

Cr - 267716 nm Ni - 231604 nm Ti - 334941 nm

Cu - 327395 nm P - 213618 nm V - 311837 nm

Fe - 238204 nm Pb - 220353 nm Zn ndash 206200 nm

Instrumental conditions

RF Frequency 40 MHz (free running air-cooled)

RF Power 12 kW

Gas (plasma auxiliary nebulizer) Argon

Plasma flow 150 lmin

Auxiliary flow 15 lmin

Nebulizer flow 110 lmin

Replicates 5

Replicate read time 5 s

Operating parameters for ICP-AES quantitative analysis

ICP-AES Analysis

Bruker Aurora M90 (90 degree ion mirror ion optics Collision Reaction Interface)110 diluted

mineralized olive oil solution

Tuning with a 5 microgl Be Mg Co In Ba Ce Ti Pb and Th solution for

sensitivity and resolution optimization and mass calibration

Tuning with a 5 microgl Be Mg Co In Ba Ce Ti Pb and Th solution for

sensitivity and resolution optimization and mass calibration

Check of the level of oxide ions by the CeO+Ce+ ratio lt 2

Check of the level of oxide ions by the CeO+Ce+ ratio lt 2

Monitoring of double charged ions by the signal 137Ba++137Ba+ lt 3

Monitoring of double charged ions by the signal 137Ba++137Ba+ lt 3

CheckCorrection of isobaric interferences examination of more isotopes of the same element(eg Rb85 Rb 87 Sr88Sr87 Nd142 Nd146 Nd144 Se77 Se78 Sn147 Sm148 Sm152 Gd157 Gd154 Er166 Er168 Yb170 Yb172) application of correction equations with respect to isotopes of other elements potentially interfering (eg Nd142 corrected by analyzing Ce140 Nd144 by Sm147 Sm152 by Gd157 Rb87 by Sr88 ) use of the Collision Reaction Interface ndash CRI (for As and Se)

CheckCorrection of isobaric interferences examination of more isotopes of the same element(eg Rb85 Rb 87 Sr88Sr87 Nd142 Nd146 Nd144 Se77 Se78 Sn147 Sm148 Sm152 Gd157 Gd154 Er166 Er168 Yb170 Yb172) application of correction equations with respect to isotopes of other elements potentially interfering (eg Nd142 corrected by analyzing Ce140 Nd144 by Sm147 Sm152 by Gd157 Rb87 by Sr88 ) use of the Collision Reaction Interface ndash CRI (for As and Se)

Working rangesbull005 divide 5 microgl - As Cd Ce Er Eu Gd La Mn Nd Pb Pr Rb Sb Sc Se Sm Sr Th V Y Ybbull01 divide 10 microgl - Co Cr Cu Mg Ni

Working rangesbull005 divide 5 microgl - As Cd Ce Er Eu Gd La Mn Nd Pb Pr Rb Sb Sc Se Sm Sr Th V Y Ybbull01 divide 10 microgl - Co Cr Cu Mg Ni

External calibration5 standard solutions + blankCurve Fit LinearWeighted Fit NoCorrelation coefficientsR gt 09999

Normal Sensitivity Mode (without CRI) High Sensitivity Mode As and Se ndash Normal mode with CRI

ICP-MS Analysis

• Slide 1
• Slide 2
• Slide 3
• Slide 4
• Slide 5
• Slide 6
• Slide 7
• Slide 8
• Slide 9
• Slide 10
• Slide 11
• Slide 12
• Slide 13
• Slide 14
• Slide 15
• Slide 16
• Slide 17
• Slide 18
• Slide 19
• Slide 20
• Slide 21
• Slide 22
• Slide 23
• Slide 24
• Slide 25
• Slide 26
• Slide 27
• Slide 28
• Slide 29
• Slide 30
• Slide 31
• Slide 32
• Slide 33
• Slide 34
• Slide 35

Total OIL entrance(kg of crushed fruits x of oil inside the olives)

= Total OIL output

(kg of the olive residues x of oil inside the olive residues)

+EXTRACTED OIL

Total OIL entrance(kg of crushed fruits x of oil inside the olives)

= Total OIL output

(kg of the olive residues x of oil inside the olive residues)

+EXTRACTED OIL

MASS BALANCE during extraction MASS BALANCE during extraction processprocess

In order to evaluate the effect induced by the addition of cryogen on the oil extraction yield

the Extractability Index Variation (EIV) was determined as the percentage of the variation of oil extractability using CO2s compared with the same parameter obtained by a traditional

extraction process

In order to evaluate the effect induced by the addition of cryogen on the oil extraction yield

the Extractability Index Variation (EIV) was determined as the percentage of the variation of oil extractability using CO2s compared with the same parameter obtained by a traditional

extraction process EIV = (EC-ET)ET EIV = (EC-ET)ET 100 100EIV = (EC-ET)ET EIV = (EC-ET)ET 100 100

Results and Results and discussiondiscussion

Results and Results and discussiondiscussion

Oil extraction Oil extraction yield yield

preliminary preliminary resultsresults

Oil extraction yield Oil extraction yield preliminary preliminary resultsresults

Oil extraction yield Oil extraction yield preliminary preliminary resultsresults

Run EC ET

1A 858 825

2B 855 772

3C 912 827

4D 841 748

5E 808 793

6F 736 689

7G 844 774

The direct addition of cryogen to the olives during pre-milling phase could induce a general increase in the oil extraction yield ranging from 2 to

124

The direct addition of cryogen to the olives during pre-milling phase could induce a general increase in the oil extraction yield ranging from 2 to

124

[(EC-ET)ET]10040 108 103 124 19 68 90

[(EC-ET)ET]10040 108 103 124 19 68 90

Preliminary results about oil extraction Preliminary results about oil extraction yield yield discussion Idiscussion I

Preliminary results about oil extraction Preliminary results about oil extraction yield yield discussion Idiscussion I

The number of the experimental runs carried out until now is quite reduced

The number of the experimental runs carried out until now is quite reduced

BUTBUT

The results appear very encouraging and the new method seems very suitable for olive oil extraction

The results appear very encouraging and the new method seems very suitable for olive oil extraction

During the next crop season we will increase the number of experimental runs adopting several combinations of the working parameters (ie amount of cryogenamount of olives fruit ripening stage etc)

During the next crop season we will increase the number of experimental runs adopting several combinations of the working parameters (ie amount of cryogenamount of olives fruit ripening stage etc)

Preliminary results about oil extraction Preliminary results about oil extraction yield yield discussion IIdiscussion II

Preliminary results about oil extraction Preliminary results about oil extraction yield yield discussion IIdiscussion II

If necessary this method allows to move up the olive harvest time in order to greatly reduce the damages due to the third fly attack of Bactrocera oleae that can induce a significant loss in oil production (up to 60) as well as a decrease in oil quality

If necessary this method allows to move up the olive harvest time in order to greatly reduce the damages due to the third fly attack of Bactrocera oleae that can induce a significant loss in oil production (up to 60) as well as a decrease in oil quality

Water content

inside the fruit

Water content

inside the fruit

CELLULAR CRASH

We need 08 kg of CO2s to lower 100 kg of olives temperature by 1degC

Cost of 1 kg of CO2s= euro050 $ 037

Cost to turn down the average temperature of 100

kg of olives by 10degC(15degC 5degC )

08kgdegC x 10degC x 037 $kg=

3 $

Considering an average oil yield of 15

The addition cost for a kg of extravirgin olive oil is

3 $100 kg olives x 15100kg oilkg olives

lt 02$kg oil

Oil elemental Oil elemental profile profile

preliminary preliminary resultsresults

ICP-AES and ICP-MS techniques are particularly advantageous for the application in the definition of the elemental profiles of olive oil since they allow simultaneous multi-elemental analysis and are characterized by wide linear ranges and (especially ICP-MS) very low Detection Limits

Main analytical issues are related to the hard organic content of the oil matrix which requires appropriate sample pre-treatments Microwave-assisted digestion permitted to obtain a complete dissolution of olive oil samples but resulted in the obtainment of highly acidic solutions not directly analyzable by ICP-MS with a consequent reduction of sensitivity (due to the preliminary 110 dilution of the mineralized olive oil)

ETV

LA

Preliminary results about oil elemental Preliminary results about oil elemental profileprofile

Preliminary results about oil elemental Preliminary results about oil elemental profileprofile

Preliminary results show a rather homogeneous elemental content among all the analyzed samples of olive oil

For all elements experimental concentrations fall within the ranges reported in literature In respect to these ranges analyzed samples show a high content of B S and Si while Fe Na Pb Ba Cr and Cu contents are quite low

Samples of olive oil obtained by the traditionalldquo process show - in general - a higher content of Ca Cr Mg Si (except those originating from Basilicata) and Zn compared to those obtained by the addition of ldquocarbonic snowldquo

0

20

40

60

80

100

120

140

B Ca Fe Na S Si

mgk

g

000

050

100

150

200

250

300

350

400

450

500

Al K Mg P Zn

mgk

g

0

500

1000

1500

2000

2500

3000

3500

Co Cr Cu Ni Pb

microgk

g

0

2

4

6

8

10

12

14

16

Ce Er Eu Gd La Nd Pr Sm Y Yb

microgk

g

0

100

200

300

400

500

600

700

800

As Ba Cd Li Mn Rb Sb Sc Se Sr Th Ti V

microgk

g

4000 25000

0

20

40

60

80

100

120

140

160

Ca

Na

Si

concentration range obtained from literature [2]

experimental concentration range ICP-AESDetection LimitICP-MSDetection Limit - Normal Sensitivity modeICP-MSDetection Limit - High Sensitivitymode

S B Yasar E K Baran M Alkan Metal determinations in olive oil In Olive Oil ndash Constituents Quality Health Properties and Bioconversions Ed by Boskou Dimitrios 5 89-108 2012

Preliminary results about oil elemental Preliminary results about oil elemental profileprofile

Preliminary results about oil elemental Preliminary results about oil elemental profileprofile

For any further details about the second part of the research you can contact our colleagues in ENEA

claudiazoanieneait giovannazappaeneait

For any further details about the second part of the research you can contact our colleagues in ENEA

claudiazoanieneait giovannazappaeneait

ReferencesReferencesReferencesReferences

The Utilization of Solid Carbon Dioxide in the Production of Extravirgin Olive Oil

Sanmartin C Zinnai A Venturi F Andrich G Proceedings of EFFOST 2011 9-11 November 2011 Berlino

(D)

Analytical methods for olive oil elemental profile and influence of carbonic snow addition in the extraction

phase C Zoani G Zappa A Zinnai F Venturi C Sanmartin

11th Euro Fed Lipid Congress ndash Antalya (Turkey) 27-30 October 2013

Preliminary results on the influence of carbonic snow addition during the olive processing oil extraction yield

and elemental profile C Zoani G Zappa F Venturi C Sanmartin G Andrich and

A ZinnaiJournal of Nutrition and Food Sciences 4 277 (2014)

doi 1041722155-96001000277

The Utilization of Solid Carbon Dioxide in the Production of Extravirgin Olive Oil

Sanmartin C Zinnai A Venturi F Andrich G Proceedings of EFFOST 2011 9-11 November 2011 Berlino

(D)

Analytical methods for olive oil elemental profile and influence of carbonic snow addition in the extraction

phase C Zoani G Zappa A Zinnai F Venturi C Sanmartin

11th Euro Fed Lipid Congress ndash Antalya (Turkey) 27-30 October 2013

Preliminary results on the influence of carbonic snow addition during the olive processing oil extraction yield

and elemental profile C Zoani G Zappa F Venturi C Sanmartin G Andrich and

A ZinnaiJournal of Nutrition and Food Sciences 4 277 (2014)

doi 1041722155-96001000277

Research in progresshellipResearch in progresshellip

Thank you for your attention

Thank you for your attention

research supported by

It will be possible to apply matrix modification procedures (eg solvent extraction ndash also ultrasound assisted - addition of organic solvents or emulsification) or to employ systems for direct oil sample introduction in torch (eg Flow Injection Analysis systems)

We are conducting experimental tests for evaluating the possibility to employ a Laser Ablation system or an ElectroThermal Vaporization system for direct sample introduction in ICP-AES and ICP-MS

ETV

LA

Future developmentsFuture developmentsFuture developmentsFuture developments

Determination of oil elemental profile sample pre-treatment

High PressureMicrowave Digestion

Milestone 1200 Mega

05 golive oil

Mineralized oil sample

(final V = 25 ml)

2 ml H2O2 + 6 ml HNO3

Different mixtures testedH2O2 30vv (1 divide 2 ml)+ HNO3 699vv (2 divide

6 ml)

Total dissoluti

on

high-purity water

(gt 18 MΩ)

time Power Pressure

1 min 250 WFree

pressure race

1 min 0 W

5 min 400 W

5 min 650 W

Vent = 5 min

TQ mineralized

olive oil solution

Varian Vista MPX(axial configuration

simultaneous 112 Mpixel CCD detector)

study of spectral interferencesstudy of spectral interferences

preliminary qualitative analysis72 elements

preliminary qualitative analysis72 elements

quantitative analysisquantitative analysis

Gas flows optimization based on signal-to-background ratio (SB)

Auxiliary flow (lmin)

Nebulizer flow(lmin)

10 15 09 10 11 12

SBMg 3296 11720 13948 17998 19921 18412Mn 0128 0197 0245 0312 0303 0294Na 1827 1940 1827 3187 6121 4371

Zn - 213857 nm more sensitive but interfered by Fe

Zn - 206200 nm - less sensitive but without interferences

Analytical wavelengths (nm)

Al - 396152 nm K - 766491 nm Rb - 780026 nm

As - 188980 nm Li - 670783 nm S - 181972 nm

B - 249772 nm Mg - 279553 nm Sb - 206834 nm

Ba - 455403 nm Mn - 257610 nm Si - 251611 nm

Ca - 396847 nm Na - 589592 nm Sr - 407771 nm

Cr - 267716 nm Ni - 231604 nm Ti - 334941 nm

Cu - 327395 nm P - 213618 nm V - 311837 nm

Fe - 238204 nm Pb - 220353 nm Zn ndash 206200 nm

Instrumental conditions

RF Frequency 40 MHz (free running air-cooled)

RF Power 12 kW

Gas (plasma auxiliary nebulizer) Argon

Plasma flow 150 lmin

Auxiliary flow 15 lmin

Nebulizer flow 110 lmin

Replicates 5

Replicate read time 5 s

Operating parameters for ICP-AES quantitative analysis

ICP-AES Analysis

Bruker Aurora M90 (90 degree ion mirror ion optics Collision Reaction Interface)110 diluted

mineralized olive oil solution

Tuning with a 5 microgl Be Mg Co In Ba Ce Ti Pb and Th solution for

sensitivity and resolution optimization and mass calibration

Tuning with a 5 microgl Be Mg Co In Ba Ce Ti Pb and Th solution for

sensitivity and resolution optimization and mass calibration

Check of the level of oxide ions by the CeO+Ce+ ratio lt 2

Check of the level of oxide ions by the CeO+Ce+ ratio lt 2

Monitoring of double charged ions by the signal 137Ba++137Ba+ lt 3

Monitoring of double charged ions by the signal 137Ba++137Ba+ lt 3

CheckCorrection of isobaric interferences examination of more isotopes of the same element(eg Rb85 Rb 87 Sr88Sr87 Nd142 Nd146 Nd144 Se77 Se78 Sn147 Sm148 Sm152 Gd157 Gd154 Er166 Er168 Yb170 Yb172) application of correction equations with respect to isotopes of other elements potentially interfering (eg Nd142 corrected by analyzing Ce140 Nd144 by Sm147 Sm152 by Gd157 Rb87 by Sr88 ) use of the Collision Reaction Interface ndash CRI (for As and Se)

CheckCorrection of isobaric interferences examination of more isotopes of the same element(eg Rb85 Rb 87 Sr88Sr87 Nd142 Nd146 Nd144 Se77 Se78 Sn147 Sm148 Sm152 Gd157 Gd154 Er166 Er168 Yb170 Yb172) application of correction equations with respect to isotopes of other elements potentially interfering (eg Nd142 corrected by analyzing Ce140 Nd144 by Sm147 Sm152 by Gd157 Rb87 by Sr88 ) use of the Collision Reaction Interface ndash CRI (for As and Se)

Working rangesbull005 divide 5 microgl - As Cd Ce Er Eu Gd La Mn Nd Pb Pr Rb Sb Sc Se Sm Sr Th V Y Ybbull01 divide 10 microgl - Co Cr Cu Mg Ni

Working rangesbull005 divide 5 microgl - As Cd Ce Er Eu Gd La Mn Nd Pb Pr Rb Sb Sc Se Sm Sr Th V Y Ybbull01 divide 10 microgl - Co Cr Cu Mg Ni

External calibration5 standard solutions + blankCurve Fit LinearWeighted Fit NoCorrelation coefficientsR gt 09999

Normal Sensitivity Mode (without CRI) High Sensitivity Mode As and Se ndash Normal mode with CRI

ICP-MS Analysis

• Slide 1
• Slide 2
• Slide 3
• Slide 4
• Slide 5
• Slide 6
• Slide 7
• Slide 8
• Slide 9
• Slide 10
• Slide 11
• Slide 12
• Slide 13
• Slide 14
• Slide 15
• Slide 16
• Slide 17
• Slide 18
• Slide 19
• Slide 20
• Slide 21
• Slide 22
• Slide 23
• Slide 24
• Slide 25
• Slide 26
• Slide 27
• Slide 28
• Slide 29
• Slide 30
• Slide 31
• Slide 32
• Slide 33
• Slide 34
• Slide 35

In order to evaluate the effect induced by the addition of cryogen on the oil extraction yield

the Extractability Index Variation (EIV) was determined as the percentage of the variation of oil extractability using CO2s compared with the same parameter obtained by a traditional

extraction process

In order to evaluate the effect induced by the addition of cryogen on the oil extraction yield

the Extractability Index Variation (EIV) was determined as the percentage of the variation of oil extractability using CO2s compared with the same parameter obtained by a traditional

extraction process EIV = (EC-ET)ET EIV = (EC-ET)ET 100 100EIV = (EC-ET)ET EIV = (EC-ET)ET 100 100

Results and Results and discussiondiscussion

Results and Results and discussiondiscussion

Oil extraction Oil extraction yield yield

preliminary preliminary resultsresults

Oil extraction yield Oil extraction yield preliminary preliminary resultsresults

Oil extraction yield Oil extraction yield preliminary preliminary resultsresults

Run EC ET

1A 858 825

2B 855 772

3C 912 827

4D 841 748

5E 808 793

6F 736 689

7G 844 774

The direct addition of cryogen to the olives during pre-milling phase could induce a general increase in the oil extraction yield ranging from 2 to

124

The direct addition of cryogen to the olives during pre-milling phase could induce a general increase in the oil extraction yield ranging from 2 to

124

[(EC-ET)ET]10040 108 103 124 19 68 90

[(EC-ET)ET]10040 108 103 124 19 68 90

Preliminary results about oil extraction Preliminary results about oil extraction yield yield discussion Idiscussion I

Preliminary results about oil extraction Preliminary results about oil extraction yield yield discussion Idiscussion I

The number of the experimental runs carried out until now is quite reduced

The number of the experimental runs carried out until now is quite reduced

BUTBUT

The results appear very encouraging and the new method seems very suitable for olive oil extraction

The results appear very encouraging and the new method seems very suitable for olive oil extraction

During the next crop season we will increase the number of experimental runs adopting several combinations of the working parameters (ie amount of cryogenamount of olives fruit ripening stage etc)

During the next crop season we will increase the number of experimental runs adopting several combinations of the working parameters (ie amount of cryogenamount of olives fruit ripening stage etc)

Preliminary results about oil extraction Preliminary results about oil extraction yield yield discussion IIdiscussion II

Preliminary results about oil extraction Preliminary results about oil extraction yield yield discussion IIdiscussion II

If necessary this method allows to move up the olive harvest time in order to greatly reduce the damages due to the third fly attack of Bactrocera oleae that can induce a significant loss in oil production (up to 60) as well as a decrease in oil quality

If necessary this method allows to move up the olive harvest time in order to greatly reduce the damages due to the third fly attack of Bactrocera oleae that can induce a significant loss in oil production (up to 60) as well as a decrease in oil quality

Water content

inside the fruit

Water content

inside the fruit

CELLULAR CRASH

We need 08 kg of CO2s to lower 100 kg of olives temperature by 1degC

Cost of 1 kg of CO2s= euro050 $ 037

Cost to turn down the average temperature of 100

kg of olives by 10degC(15degC 5degC )

08kgdegC x 10degC x 037 $kg=

3 $

Considering an average oil yield of 15

The addition cost for a kg of extravirgin olive oil is

3 $100 kg olives x 15100kg oilkg olives

lt 02$kg oil

Oil elemental Oil elemental profile profile

preliminary preliminary resultsresults

ICP-AES and ICP-MS techniques are particularly advantageous for the application in the definition of the elemental profiles of olive oil since they allow simultaneous multi-elemental analysis and are characterized by wide linear ranges and (especially ICP-MS) very low Detection Limits

Main analytical issues are related to the hard organic content of the oil matrix which requires appropriate sample pre-treatments Microwave-assisted digestion permitted to obtain a complete dissolution of olive oil samples but resulted in the obtainment of highly acidic solutions not directly analyzable by ICP-MS with a consequent reduction of sensitivity (due to the preliminary 110 dilution of the mineralized olive oil)

ETV

LA

Preliminary results about oil elemental Preliminary results about oil elemental profileprofile

Preliminary results about oil elemental Preliminary results about oil elemental profileprofile

Preliminary results show a rather homogeneous elemental content among all the analyzed samples of olive oil

For all elements experimental concentrations fall within the ranges reported in literature In respect to these ranges analyzed samples show a high content of B S and Si while Fe Na Pb Ba Cr and Cu contents are quite low

Samples of olive oil obtained by the traditionalldquo process show - in general - a higher content of Ca Cr Mg Si (except those originating from Basilicata) and Zn compared to those obtained by the addition of ldquocarbonic snowldquo

0

20

40

60

80

100

120

140

B Ca Fe Na S Si

mgk

g

000

050

100

150

200

250

300

350

400

450

500

Al K Mg P Zn

mgk

g

0

500

1000

1500

2000

2500

3000

3500

Co Cr Cu Ni Pb

microgk

g

0

2

4

6

8

10

12

14

16

Ce Er Eu Gd La Nd Pr Sm Y Yb

microgk

g

0

100

200

300

400

500

600

700

800

As Ba Cd Li Mn Rb Sb Sc Se Sr Th Ti V

microgk

g

4000 25000

0

20

40

60

80

100

120

140

160

Ca

Na

Si

concentration range obtained from literature [2]

experimental concentration range ICP-AESDetection LimitICP-MSDetection Limit - Normal Sensitivity modeICP-MSDetection Limit - High Sensitivitymode

S B Yasar E K Baran M Alkan Metal determinations in olive oil In Olive Oil ndash Constituents Quality Health Properties and Bioconversions Ed by Boskou Dimitrios 5 89-108 2012

Preliminary results about oil elemental Preliminary results about oil elemental profileprofile

Preliminary results about oil elemental Preliminary results about oil elemental profileprofile

For any further details about the second part of the research you can contact our colleagues in ENEA

claudiazoanieneait giovannazappaeneait

For any further details about the second part of the research you can contact our colleagues in ENEA

claudiazoanieneait giovannazappaeneait

ReferencesReferencesReferencesReferences

The Utilization of Solid Carbon Dioxide in the Production of Extravirgin Olive Oil

Sanmartin C Zinnai A Venturi F Andrich G Proceedings of EFFOST 2011 9-11 November 2011 Berlino

(D)

Analytical methods for olive oil elemental profile and influence of carbonic snow addition in the extraction

phase C Zoani G Zappa A Zinnai F Venturi C Sanmartin

11th Euro Fed Lipid Congress ndash Antalya (Turkey) 27-30 October 2013

Preliminary results on the influence of carbonic snow addition during the olive processing oil extraction yield

and elemental profile C Zoani G Zappa F Venturi C Sanmartin G Andrich and

A ZinnaiJournal of Nutrition and Food Sciences 4 277 (2014)

doi 1041722155-96001000277

The Utilization of Solid Carbon Dioxide in the Production of Extravirgin Olive Oil

Sanmartin C Zinnai A Venturi F Andrich G Proceedings of EFFOST 2011 9-11 November 2011 Berlino

(D)

Analytical methods for olive oil elemental profile and influence of carbonic snow addition in the extraction

phase C Zoani G Zappa A Zinnai F Venturi C Sanmartin

11th Euro Fed Lipid Congress ndash Antalya (Turkey) 27-30 October 2013

Preliminary results on the influence of carbonic snow addition during the olive processing oil extraction yield

and elemental profile C Zoani G Zappa F Venturi C Sanmartin G Andrich and

A ZinnaiJournal of Nutrition and Food Sciences 4 277 (2014)

doi 1041722155-96001000277

Research in progresshellipResearch in progresshellip

Thank you for your attention

Thank you for your attention

research supported by

It will be possible to apply matrix modification procedures (eg solvent extraction ndash also ultrasound assisted - addition of organic solvents or emulsification) or to employ systems for direct oil sample introduction in torch (eg Flow Injection Analysis systems)

We are conducting experimental tests for evaluating the possibility to employ a Laser Ablation system or an ElectroThermal Vaporization system for direct sample introduction in ICP-AES and ICP-MS

ETV

LA

Future developmentsFuture developmentsFuture developmentsFuture developments

Determination of oil elemental profile sample pre-treatment

High PressureMicrowave Digestion

Milestone 1200 Mega

05 golive oil

Mineralized oil sample

(final V = 25 ml)

2 ml H2O2 + 6 ml HNO3

Different mixtures testedH2O2 30vv (1 divide 2 ml)+ HNO3 699vv (2 divide

6 ml)

Total dissoluti

on

high-purity water

(gt 18 MΩ)

time Power Pressure

1 min 250 WFree

pressure race

1 min 0 W

5 min 400 W

5 min 650 W

Vent = 5 min

TQ mineralized

olive oil solution

Varian Vista MPX(axial configuration

simultaneous 112 Mpixel CCD detector)

study of spectral interferencesstudy of spectral interferences

preliminary qualitative analysis72 elements

preliminary qualitative analysis72 elements

quantitative analysisquantitative analysis

Gas flows optimization based on signal-to-background ratio (SB)

Auxiliary flow (lmin)

Nebulizer flow(lmin)

10 15 09 10 11 12

SBMg 3296 11720 13948 17998 19921 18412Mn 0128 0197 0245 0312 0303 0294Na 1827 1940 1827 3187 6121 4371

Zn - 213857 nm more sensitive but interfered by Fe

Zn - 206200 nm - less sensitive but without interferences

Analytical wavelengths (nm)

Al - 396152 nm K - 766491 nm Rb - 780026 nm

As - 188980 nm Li - 670783 nm S - 181972 nm

B - 249772 nm Mg - 279553 nm Sb - 206834 nm

Ba - 455403 nm Mn - 257610 nm Si - 251611 nm

Ca - 396847 nm Na - 589592 nm Sr - 407771 nm

Cr - 267716 nm Ni - 231604 nm Ti - 334941 nm

Cu - 327395 nm P - 213618 nm V - 311837 nm

Fe - 238204 nm Pb - 220353 nm Zn ndash 206200 nm

Instrumental conditions

RF Frequency 40 MHz (free running air-cooled)

RF Power 12 kW

Gas (plasma auxiliary nebulizer) Argon

Plasma flow 150 lmin

Auxiliary flow 15 lmin

Nebulizer flow 110 lmin

Replicates 5

Replicate read time 5 s

Operating parameters for ICP-AES quantitative analysis

ICP-AES Analysis

Bruker Aurora M90 (90 degree ion mirror ion optics Collision Reaction Interface)110 diluted

mineralized olive oil solution

Tuning with a 5 microgl Be Mg Co In Ba Ce Ti Pb and Th solution for

sensitivity and resolution optimization and mass calibration

Tuning with a 5 microgl Be Mg Co In Ba Ce Ti Pb and Th solution for

sensitivity and resolution optimization and mass calibration

Check of the level of oxide ions by the CeO+Ce+ ratio lt 2

Check of the level of oxide ions by the CeO+Ce+ ratio lt 2

Monitoring of double charged ions by the signal 137Ba++137Ba+ lt 3

Monitoring of double charged ions by the signal 137Ba++137Ba+ lt 3

CheckCorrection of isobaric interferences examination of more isotopes of the same element(eg Rb85 Rb 87 Sr88Sr87 Nd142 Nd146 Nd144 Se77 Se78 Sn147 Sm148 Sm152 Gd157 Gd154 Er166 Er168 Yb170 Yb172) application of correction equations with respect to isotopes of other elements potentially interfering (eg Nd142 corrected by analyzing Ce140 Nd144 by Sm147 Sm152 by Gd157 Rb87 by Sr88 ) use of the Collision Reaction Interface ndash CRI (for As and Se)

CheckCorrection of isobaric interferences examination of more isotopes of the same element(eg Rb85 Rb 87 Sr88Sr87 Nd142 Nd146 Nd144 Se77 Se78 Sn147 Sm148 Sm152 Gd157 Gd154 Er166 Er168 Yb170 Yb172) application of correction equations with respect to isotopes of other elements potentially interfering (eg Nd142 corrected by analyzing Ce140 Nd144 by Sm147 Sm152 by Gd157 Rb87 by Sr88 ) use of the Collision Reaction Interface ndash CRI (for As and Se)

Working rangesbull005 divide 5 microgl - As Cd Ce Er Eu Gd La Mn Nd Pb Pr Rb Sb Sc Se Sm Sr Th V Y Ybbull01 divide 10 microgl - Co Cr Cu Mg Ni

Working rangesbull005 divide 5 microgl - As Cd Ce Er Eu Gd La Mn Nd Pb Pr Rb Sb Sc Se Sm Sr Th V Y Ybbull01 divide 10 microgl - Co Cr Cu Mg Ni

External calibration5 standard solutions + blankCurve Fit LinearWeighted Fit NoCorrelation coefficientsR gt 09999

Normal Sensitivity Mode (without CRI) High Sensitivity Mode As and Se ndash Normal mode with CRI

ICP-MS Analysis

• Slide 1
• Slide 2
• Slide 3
• Slide 4
• Slide 5
• Slide 6
• Slide 7
• Slide 8
• Slide 9
• Slide 10
• Slide 11
• Slide 12
• Slide 13
• Slide 14
• Slide 15
• Slide 16
• Slide 17
• Slide 18
• Slide 19
• Slide 20
• Slide 21
• Slide 22
• Slide 23
• Slide 24
• Slide 25
• Slide 26
• Slide 27
• Slide 28
• Slide 29
• Slide 30
• Slide 31
• Slide 32
• Slide 33
• Slide 34
• Slide 35

Results and Results and discussiondiscussion

Results and Results and discussiondiscussion

Oil extraction Oil extraction yield yield

preliminary preliminary resultsresults

Oil extraction yield Oil extraction yield preliminary preliminary resultsresults

Oil extraction yield Oil extraction yield preliminary preliminary resultsresults

Run EC ET

1A 858 825

2B 855 772

3C 912 827

4D 841 748

5E 808 793

6F 736 689

7G 844 774

The direct addition of cryogen to the olives during pre-milling phase could induce a general increase in the oil extraction yield ranging from 2 to

124

The direct addition of cryogen to the olives during pre-milling phase could induce a general increase in the oil extraction yield ranging from 2 to

124

[(EC-ET)ET]10040 108 103 124 19 68 90

[(EC-ET)ET]10040 108 103 124 19 68 90

Preliminary results about oil extraction Preliminary results about oil extraction yield yield discussion Idiscussion I

Preliminary results about oil extraction Preliminary results about oil extraction yield yield discussion Idiscussion I

The number of the experimental runs carried out until now is quite reduced

The number of the experimental runs carried out until now is quite reduced

BUTBUT

The results appear very encouraging and the new method seems very suitable for olive oil extraction

The results appear very encouraging and the new method seems very suitable for olive oil extraction

During the next crop season we will increase the number of experimental runs adopting several combinations of the working parameters (ie amount of cryogenamount of olives fruit ripening stage etc)

During the next crop season we will increase the number of experimental runs adopting several combinations of the working parameters (ie amount of cryogenamount of olives fruit ripening stage etc)

Preliminary results about oil extraction Preliminary results about oil extraction yield yield discussion IIdiscussion II

Preliminary results about oil extraction Preliminary results about oil extraction yield yield discussion IIdiscussion II

If necessary this method allows to move up the olive harvest time in order to greatly reduce the damages due to the third fly attack of Bactrocera oleae that can induce a significant loss in oil production (up to 60) as well as a decrease in oil quality

If necessary this method allows to move up the olive harvest time in order to greatly reduce the damages due to the third fly attack of Bactrocera oleae that can induce a significant loss in oil production (up to 60) as well as a decrease in oil quality

Water content

inside the fruit

Water content

inside the fruit

CELLULAR CRASH

We need 08 kg of CO2s to lower 100 kg of olives temperature by 1degC

Cost of 1 kg of CO2s= euro050 $ 037

Cost to turn down the average temperature of 100

kg of olives by 10degC(15degC 5degC )

08kgdegC x 10degC x 037 $kg=

3 $

Considering an average oil yield of 15

The addition cost for a kg of extravirgin olive oil is

3 $100 kg olives x 15100kg oilkg olives

lt 02$kg oil

Oil elemental Oil elemental profile profile

preliminary preliminary resultsresults

ICP-AES and ICP-MS techniques are particularly advantageous for the application in the definition of the elemental profiles of olive oil since they allow simultaneous multi-elemental analysis and are characterized by wide linear ranges and (especially ICP-MS) very low Detection Limits

Main analytical issues are related to the hard organic content of the oil matrix which requires appropriate sample pre-treatments Microwave-assisted digestion permitted to obtain a complete dissolution of olive oil samples but resulted in the obtainment of highly acidic solutions not directly analyzable by ICP-MS with a consequent reduction of sensitivity (due to the preliminary 110 dilution of the mineralized olive oil)

ETV

LA

Preliminary results about oil elemental Preliminary results about oil elemental profileprofile

Preliminary results about oil elemental Preliminary results about oil elemental profileprofile

Preliminary results show a rather homogeneous elemental content among all the analyzed samples of olive oil

For all elements experimental concentrations fall within the ranges reported in literature In respect to these ranges analyzed samples show a high content of B S and Si while Fe Na Pb Ba Cr and Cu contents are quite low

Samples of olive oil obtained by the traditionalldquo process show - in general - a higher content of Ca Cr Mg Si (except those originating from Basilicata) and Zn compared to those obtained by the addition of ldquocarbonic snowldquo

0

20

40

60

80

100

120

140

B Ca Fe Na S Si

mgk

g

000

050

100

150

200

250

300

350

400

450

500

Al K Mg P Zn

mgk

g

0

500

1000

1500

2000

2500

3000

3500

Co Cr Cu Ni Pb

microgk

g

0

2

4

6

8

10

12

14

16

Ce Er Eu Gd La Nd Pr Sm Y Yb

microgk

g

0

100

200

300

400

500

600

700

800

As Ba Cd Li Mn Rb Sb Sc Se Sr Th Ti V

microgk

g

4000 25000

0

20

40

60

80

100

120

140

160

Ca

Na

Si

concentration range obtained from literature [2]

experimental concentration range ICP-AESDetection LimitICP-MSDetection Limit - Normal Sensitivity modeICP-MSDetection Limit - High Sensitivitymode

S B Yasar E K Baran M Alkan Metal determinations in olive oil In Olive Oil ndash Constituents Quality Health Properties and Bioconversions Ed by Boskou Dimitrios 5 89-108 2012

Preliminary results about oil elemental Preliminary results about oil elemental profileprofile

Preliminary results about oil elemental Preliminary results about oil elemental profileprofile

For any further details about the second part of the research you can contact our colleagues in ENEA

claudiazoanieneait giovannazappaeneait

For any further details about the second part of the research you can contact our colleagues in ENEA

claudiazoanieneait giovannazappaeneait

ReferencesReferencesReferencesReferences

The Utilization of Solid Carbon Dioxide in the Production of Extravirgin Olive Oil

Sanmartin C Zinnai A Venturi F Andrich G Proceedings of EFFOST 2011 9-11 November 2011 Berlino

(D)

Analytical methods for olive oil elemental profile and influence of carbonic snow addition in the extraction

phase C Zoani G Zappa A Zinnai F Venturi C Sanmartin

11th Euro Fed Lipid Congress ndash Antalya (Turkey) 27-30 October 2013

Preliminary results on the influence of carbonic snow addition during the olive processing oil extraction yield

and elemental profile C Zoani G Zappa F Venturi C Sanmartin G Andrich and

A ZinnaiJournal of Nutrition and Food Sciences 4 277 (2014)

doi 1041722155-96001000277

The Utilization of Solid Carbon Dioxide in the Production of Extravirgin Olive Oil

Sanmartin C Zinnai A Venturi F Andrich G Proceedings of EFFOST 2011 9-11 November 2011 Berlino

(D)

Analytical methods for olive oil elemental profile and influence of carbonic snow addition in the extraction

phase C Zoani G Zappa A Zinnai F Venturi C Sanmartin

11th Euro Fed Lipid Congress ndash Antalya (Turkey) 27-30 October 2013

Preliminary results on the influence of carbonic snow addition during the olive processing oil extraction yield

and elemental profile C Zoani G Zappa F Venturi C Sanmartin G Andrich and

A ZinnaiJournal of Nutrition and Food Sciences 4 277 (2014)

doi 1041722155-96001000277

Research in progresshellipResearch in progresshellip

Thank you for your attention

Thank you for your attention

research supported by

It will be possible to apply matrix modification procedures (eg solvent extraction ndash also ultrasound assisted - addition of organic solvents or emulsification) or to employ systems for direct oil sample introduction in torch (eg Flow Injection Analysis systems)

We are conducting experimental tests for evaluating the possibility to employ a Laser Ablation system or an ElectroThermal Vaporization system for direct sample introduction in ICP-AES and ICP-MS

ETV

LA

Future developmentsFuture developmentsFuture developmentsFuture developments

Determination of oil elemental profile sample pre-treatment

High PressureMicrowave Digestion

Milestone 1200 Mega

05 golive oil

Mineralized oil sample

(final V = 25 ml)

2 ml H2O2 + 6 ml HNO3

Different mixtures testedH2O2 30vv (1 divide 2 ml)+ HNO3 699vv (2 divide

6 ml)

Total dissoluti

on

high-purity water

(gt 18 MΩ)

time Power Pressure

1 min 250 WFree

pressure race

1 min 0 W

5 min 400 W

5 min 650 W

Vent = 5 min

TQ mineralized

olive oil solution

Varian Vista MPX(axial configuration

simultaneous 112 Mpixel CCD detector)

study of spectral interferencesstudy of spectral interferences

preliminary qualitative analysis72 elements

preliminary qualitative analysis72 elements

quantitative analysisquantitative analysis

Gas flows optimization based on signal-to-background ratio (SB)

Auxiliary flow (lmin)

Nebulizer flow(lmin)

10 15 09 10 11 12

SBMg 3296 11720 13948 17998 19921 18412Mn 0128 0197 0245 0312 0303 0294Na 1827 1940 1827 3187 6121 4371

Zn - 213857 nm more sensitive but interfered by Fe

Zn - 206200 nm - less sensitive but without interferences

Analytical wavelengths (nm)

Al - 396152 nm K - 766491 nm Rb - 780026 nm

As - 188980 nm Li - 670783 nm S - 181972 nm

B - 249772 nm Mg - 279553 nm Sb - 206834 nm

Ba - 455403 nm Mn - 257610 nm Si - 251611 nm

Ca - 396847 nm Na - 589592 nm Sr - 407771 nm

Cr - 267716 nm Ni - 231604 nm Ti - 334941 nm

Cu - 327395 nm P - 213618 nm V - 311837 nm

Fe - 238204 nm Pb - 220353 nm Zn ndash 206200 nm

Instrumental conditions

RF Frequency 40 MHz (free running air-cooled)

RF Power 12 kW

Gas (plasma auxiliary nebulizer) Argon

Plasma flow 150 lmin

Auxiliary flow 15 lmin

Nebulizer flow 110 lmin

Replicates 5

Replicate read time 5 s

Operating parameters for ICP-AES quantitative analysis

ICP-AES Analysis

Bruker Aurora M90 (90 degree ion mirror ion optics Collision Reaction Interface)110 diluted

mineralized olive oil solution

Tuning with a 5 microgl Be Mg Co In Ba Ce Ti Pb and Th solution for

sensitivity and resolution optimization and mass calibration

Tuning with a 5 microgl Be Mg Co In Ba Ce Ti Pb and Th solution for

sensitivity and resolution optimization and mass calibration

Check of the level of oxide ions by the CeO+Ce+ ratio lt 2

Check of the level of oxide ions by the CeO+Ce+ ratio lt 2

Monitoring of double charged ions by the signal 137Ba++137Ba+ lt 3

Monitoring of double charged ions by the signal 137Ba++137Ba+ lt 3

CheckCorrection of isobaric interferences examination of more isotopes of the same element(eg Rb85 Rb 87 Sr88Sr87 Nd142 Nd146 Nd144 Se77 Se78 Sn147 Sm148 Sm152 Gd157 Gd154 Er166 Er168 Yb170 Yb172) application of correction equations with respect to isotopes of other elements potentially interfering (eg Nd142 corrected by analyzing Ce140 Nd144 by Sm147 Sm152 by Gd157 Rb87 by Sr88 ) use of the Collision Reaction Interface ndash CRI (for As and Se)

CheckCorrection of isobaric interferences examination of more isotopes of the same element(eg Rb85 Rb 87 Sr88Sr87 Nd142 Nd146 Nd144 Se77 Se78 Sn147 Sm148 Sm152 Gd157 Gd154 Er166 Er168 Yb170 Yb172) application of correction equations with respect to isotopes of other elements potentially interfering (eg Nd142 corrected by analyzing Ce140 Nd144 by Sm147 Sm152 by Gd157 Rb87 by Sr88 ) use of the Collision Reaction Interface ndash CRI (for As and Se)

Working rangesbull005 divide 5 microgl - As Cd Ce Er Eu Gd La Mn Nd Pb Pr Rb Sb Sc Se Sm Sr Th V Y Ybbull01 divide 10 microgl - Co Cr Cu Mg Ni

Working rangesbull005 divide 5 microgl - As Cd Ce Er Eu Gd La Mn Nd Pb Pr Rb Sb Sc Se Sm Sr Th V Y Ybbull01 divide 10 microgl - Co Cr Cu Mg Ni

External calibration5 standard solutions + blankCurve Fit LinearWeighted Fit NoCorrelation coefficientsR gt 09999

Normal Sensitivity Mode (without CRI) High Sensitivity Mode As and Se ndash Normal mode with CRI

ICP-MS Analysis

• Slide 1
• Slide 2
• Slide 3
• Slide 4
• Slide 5
• Slide 6
• Slide 7
• Slide 8
• Slide 9
• Slide 10
• Slide 11
• Slide 12
• Slide 13
• Slide 14
• Slide 15
• Slide 16
• Slide 17
• Slide 18
• Slide 19
• Slide 20
• Slide 21
• Slide 22
• Slide 23
• Slide 24
• Slide 25
• Slide 26
• Slide 27
• Slide 28
• Slide 29
• Slide 30
• Slide 31
• Slide 32
• Slide 33
• Slide 34
• Slide 35

Oil extraction Oil extraction yield yield

preliminary preliminary resultsresults

Oil extraction yield Oil extraction yield preliminary preliminary resultsresults

Oil extraction yield Oil extraction yield preliminary preliminary resultsresults

Run EC ET

1A 858 825

2B 855 772

3C 912 827

4D 841 748

5E 808 793

6F 736 689

7G 844 774

The direct addition of cryogen to the olives during pre-milling phase could induce a general increase in the oil extraction yield ranging from 2 to

124

The direct addition of cryogen to the olives during pre-milling phase could induce a general increase in the oil extraction yield ranging from 2 to

124

[(EC-ET)ET]10040 108 103 124 19 68 90

[(EC-ET)ET]10040 108 103 124 19 68 90

Preliminary results about oil extraction Preliminary results about oil extraction yield yield discussion Idiscussion I

Preliminary results about oil extraction Preliminary results about oil extraction yield yield discussion Idiscussion I

The number of the experimental runs carried out until now is quite reduced

The number of the experimental runs carried out until now is quite reduced

BUTBUT

The results appear very encouraging and the new method seems very suitable for olive oil extraction

The results appear very encouraging and the new method seems very suitable for olive oil extraction

During the next crop season we will increase the number of experimental runs adopting several combinations of the working parameters (ie amount of cryogenamount of olives fruit ripening stage etc)

During the next crop season we will increase the number of experimental runs adopting several combinations of the working parameters (ie amount of cryogenamount of olives fruit ripening stage etc)

Preliminary results about oil extraction Preliminary results about oil extraction yield yield discussion IIdiscussion II

Preliminary results about oil extraction Preliminary results about oil extraction yield yield discussion IIdiscussion II

If necessary this method allows to move up the olive harvest time in order to greatly reduce the damages due to the third fly attack of Bactrocera oleae that can induce a significant loss in oil production (up to 60) as well as a decrease in oil quality

If necessary this method allows to move up the olive harvest time in order to greatly reduce the damages due to the third fly attack of Bactrocera oleae that can induce a significant loss in oil production (up to 60) as well as a decrease in oil quality

Water content

inside the fruit

Water content

inside the fruit

CELLULAR CRASH

We need 08 kg of CO2s to lower 100 kg of olives temperature by 1degC

Cost of 1 kg of CO2s= euro050 $ 037

Cost to turn down the average temperature of 100

kg of olives by 10degC(15degC 5degC )

08kgdegC x 10degC x 037 $kg=

3 $

Considering an average oil yield of 15

The addition cost for a kg of extravirgin olive oil is

3 $100 kg olives x 15100kg oilkg olives

lt 02$kg oil

Oil elemental Oil elemental profile profile

preliminary preliminary resultsresults

ICP-AES and ICP-MS techniques are particularly advantageous for the application in the definition of the elemental profiles of olive oil since they allow simultaneous multi-elemental analysis and are characterized by wide linear ranges and (especially ICP-MS) very low Detection Limits

Main analytical issues are related to the hard organic content of the oil matrix which requires appropriate sample pre-treatments Microwave-assisted digestion permitted to obtain a complete dissolution of olive oil samples but resulted in the obtainment of highly acidic solutions not directly analyzable by ICP-MS with a consequent reduction of sensitivity (due to the preliminary 110 dilution of the mineralized olive oil)

ETV

LA

Preliminary results about oil elemental Preliminary results about oil elemental profileprofile

Preliminary results about oil elemental Preliminary results about oil elemental profileprofile

Preliminary results show a rather homogeneous elemental content among all the analyzed samples of olive oil

For all elements experimental concentrations fall within the ranges reported in literature In respect to these ranges analyzed samples show a high content of B S and Si while Fe Na Pb Ba Cr and Cu contents are quite low

Samples of olive oil obtained by the traditionalldquo process show - in general - a higher content of Ca Cr Mg Si (except those originating from Basilicata) and Zn compared to those obtained by the addition of ldquocarbonic snowldquo

0

20

40

60

80

100

120

140

B Ca Fe Na S Si

mgk

g

000

050

100

150

200

250

300

350

400

450

500

Al K Mg P Zn

mgk

g

0

500

1000

1500

2000

2500

3000

3500

Co Cr Cu Ni Pb

microgk

g

0

2

4

6

8

10

12

14

16

Ce Er Eu Gd La Nd Pr Sm Y Yb

microgk

g

0

100

200

300

400

500

600

700

800

As Ba Cd Li Mn Rb Sb Sc Se Sr Th Ti V

microgk

g

4000 25000

0

20

40

60

80

100

120

140

160

Ca

Na

Si

concentration range obtained from literature [2]

experimental concentration range ICP-AESDetection LimitICP-MSDetection Limit - Normal Sensitivity modeICP-MSDetection Limit - High Sensitivitymode

S B Yasar E K Baran M Alkan Metal determinations in olive oil In Olive Oil ndash Constituents Quality Health Properties and Bioconversions Ed by Boskou Dimitrios 5 89-108 2012

Preliminary results about oil elemental Preliminary results about oil elemental profileprofile

Preliminary results about oil elemental Preliminary results about oil elemental profileprofile

For any further details about the second part of the research you can contact our colleagues in ENEA

claudiazoanieneait giovannazappaeneait

For any further details about the second part of the research you can contact our colleagues in ENEA

claudiazoanieneait giovannazappaeneait

ReferencesReferencesReferencesReferences

The Utilization of Solid Carbon Dioxide in the Production of Extravirgin Olive Oil

Sanmartin C Zinnai A Venturi F Andrich G Proceedings of EFFOST 2011 9-11 November 2011 Berlino

(D)

Analytical methods for olive oil elemental profile and influence of carbonic snow addition in the extraction

phase C Zoani G Zappa A Zinnai F Venturi C Sanmartin

11th Euro Fed Lipid Congress ndash Antalya (Turkey) 27-30 October 2013

Preliminary results on the influence of carbonic snow addition during the olive processing oil extraction yield

and elemental profile C Zoani G Zappa F Venturi C Sanmartin G Andrich and

A ZinnaiJournal of Nutrition and Food Sciences 4 277 (2014)

doi 1041722155-96001000277

The Utilization of Solid Carbon Dioxide in the Production of Extravirgin Olive Oil

Sanmartin C Zinnai A Venturi F Andrich G Proceedings of EFFOST 2011 9-11 November 2011 Berlino

(D)

Analytical methods for olive oil elemental profile and influence of carbonic snow addition in the extraction

phase C Zoani G Zappa A Zinnai F Venturi C Sanmartin

11th Euro Fed Lipid Congress ndash Antalya (Turkey) 27-30 October 2013

Preliminary results on the influence of carbonic snow addition during the olive processing oil extraction yield

and elemental profile C Zoani G Zappa F Venturi C Sanmartin G Andrich and

A ZinnaiJournal of Nutrition and Food Sciences 4 277 (2014)

doi 1041722155-96001000277

Research in progresshellipResearch in progresshellip

Thank you for your attention

Thank you for your attention

research supported by

It will be possible to apply matrix modification procedures (eg solvent extraction ndash also ultrasound assisted - addition of organic solvents or emulsification) or to employ systems for direct oil sample introduction in torch (eg Flow Injection Analysis systems)

We are conducting experimental tests for evaluating the possibility to employ a Laser Ablation system or an ElectroThermal Vaporization system for direct sample introduction in ICP-AES and ICP-MS

ETV

LA

Future developmentsFuture developmentsFuture developmentsFuture developments

Determination of oil elemental profile sample pre-treatment

High PressureMicrowave Digestion

Milestone 1200 Mega

05 golive oil

Mineralized oil sample

(final V = 25 ml)

2 ml H2O2 + 6 ml HNO3

Different mixtures testedH2O2 30vv (1 divide 2 ml)+ HNO3 699vv (2 divide

6 ml)

Total dissoluti

on

high-purity water

(gt 18 MΩ)

time Power Pressure

1 min 250 WFree

pressure race

1 min 0 W

5 min 400 W

5 min 650 W

Vent = 5 min

TQ mineralized

olive oil solution

Varian Vista MPX(axial configuration

simultaneous 112 Mpixel CCD detector)

study of spectral interferencesstudy of spectral interferences

preliminary qualitative analysis72 elements

preliminary qualitative analysis72 elements

quantitative analysisquantitative analysis

Gas flows optimization based on signal-to-background ratio (SB)

Auxiliary flow (lmin)

Nebulizer flow(lmin)

10 15 09 10 11 12

SBMg 3296 11720 13948 17998 19921 18412Mn 0128 0197 0245 0312 0303 0294Na 1827 1940 1827 3187 6121 4371

Zn - 213857 nm more sensitive but interfered by Fe

Zn - 206200 nm - less sensitive but without interferences

Analytical wavelengths (nm)

Al - 396152 nm K - 766491 nm Rb - 780026 nm

As - 188980 nm Li - 670783 nm S - 181972 nm

B - 249772 nm Mg - 279553 nm Sb - 206834 nm

Ba - 455403 nm Mn - 257610 nm Si - 251611 nm

Ca - 396847 nm Na - 589592 nm Sr - 407771 nm

Cr - 267716 nm Ni - 231604 nm Ti - 334941 nm

Cu - 327395 nm P - 213618 nm V - 311837 nm

Fe - 238204 nm Pb - 220353 nm Zn ndash 206200 nm

Instrumental conditions

RF Frequency 40 MHz (free running air-cooled)

RF Power 12 kW

Gas (plasma auxiliary nebulizer) Argon

Plasma flow 150 lmin

Auxiliary flow 15 lmin

Nebulizer flow 110 lmin

Replicates 5

Replicate read time 5 s

Operating parameters for ICP-AES quantitative analysis

ICP-AES Analysis

Bruker Aurora M90 (90 degree ion mirror ion optics Collision Reaction Interface)110 diluted

mineralized olive oil solution

Tuning with a 5 microgl Be Mg Co In Ba Ce Ti Pb and Th solution for

sensitivity and resolution optimization and mass calibration

Tuning with a 5 microgl Be Mg Co In Ba Ce Ti Pb and Th solution for

sensitivity and resolution optimization and mass calibration

Check of the level of oxide ions by the CeO+Ce+ ratio lt 2

Check of the level of oxide ions by the CeO+Ce+ ratio lt 2

Monitoring of double charged ions by the signal 137Ba++137Ba+ lt 3

Monitoring of double charged ions by the signal 137Ba++137Ba+ lt 3

CheckCorrection of isobaric interferences examination of more isotopes of the same element(eg Rb85 Rb 87 Sr88Sr87 Nd142 Nd146 Nd144 Se77 Se78 Sn147 Sm148 Sm152 Gd157 Gd154 Er166 Er168 Yb170 Yb172) application of correction equations with respect to isotopes of other elements potentially interfering (eg Nd142 corrected by analyzing Ce140 Nd144 by Sm147 Sm152 by Gd157 Rb87 by Sr88 ) use of the Collision Reaction Interface ndash CRI (for As and Se)

CheckCorrection of isobaric interferences examination of more isotopes of the same element(eg Rb85 Rb 87 Sr88Sr87 Nd142 Nd146 Nd144 Se77 Se78 Sn147 Sm148 Sm152 Gd157 Gd154 Er166 Er168 Yb170 Yb172) application of correction equations with respect to isotopes of other elements potentially interfering (eg Nd142 corrected by analyzing Ce140 Nd144 by Sm147 Sm152 by Gd157 Rb87 by Sr88 ) use of the Collision Reaction Interface ndash CRI (for As and Se)

Working rangesbull005 divide 5 microgl - As Cd Ce Er Eu Gd La Mn Nd Pb Pr Rb Sb Sc Se Sm Sr Th V Y Ybbull01 divide 10 microgl - Co Cr Cu Mg Ni

Working rangesbull005 divide 5 microgl - As Cd Ce Er Eu Gd La Mn Nd Pb Pr Rb Sb Sc Se Sm Sr Th V Y Ybbull01 divide 10 microgl - Co Cr Cu Mg Ni

External calibration5 standard solutions + blankCurve Fit LinearWeighted Fit NoCorrelation coefficientsR gt 09999

Normal Sensitivity Mode (without CRI) High Sensitivity Mode As and Se ndash Normal mode with CRI

ICP-MS Analysis

• Slide 1
• Slide 2
• Slide 3
• Slide 4
• Slide 5
• Slide 6
• Slide 7
• Slide 8
• Slide 9
• Slide 10
• Slide 11
• Slide 12
• Slide 13
• Slide 14
• Slide 15
• Slide 16
• Slide 17
• Slide 18
• Slide 19
• Slide 20
• Slide 21
• Slide 22
• Slide 23
• Slide 24
• Slide 25
• Slide 26
• Slide 27
• Slide 28
• Slide 29
• Slide 30
• Slide 31
• Slide 32
• Slide 33
• Slide 34
• Slide 35

Oil extraction yield Oil extraction yield preliminary preliminary resultsresults

Oil extraction yield Oil extraction yield preliminary preliminary resultsresults

Run EC ET

1A 858 825

2B 855 772

3C 912 827

4D 841 748

5E 808 793

6F 736 689

7G 844 774

The direct addition of cryogen to the olives during pre-milling phase could induce a general increase in the oil extraction yield ranging from 2 to

124

The direct addition of cryogen to the olives during pre-milling phase could induce a general increase in the oil extraction yield ranging from 2 to

124

[(EC-ET)ET]10040 108 103 124 19 68 90

[(EC-ET)ET]10040 108 103 124 19 68 90

Preliminary results about oil extraction Preliminary results about oil extraction yield yield discussion Idiscussion I

Preliminary results about oil extraction Preliminary results about oil extraction yield yield discussion Idiscussion I

The number of the experimental runs carried out until now is quite reduced

The number of the experimental runs carried out until now is quite reduced

BUTBUT

The results appear very encouraging and the new method seems very suitable for olive oil extraction

The results appear very encouraging and the new method seems very suitable for olive oil extraction

During the next crop season we will increase the number of experimental runs adopting several combinations of the working parameters (ie amount of cryogenamount of olives fruit ripening stage etc)

During the next crop season we will increase the number of experimental runs adopting several combinations of the working parameters (ie amount of cryogenamount of olives fruit ripening stage etc)

Preliminary results about oil extraction Preliminary results about oil extraction yield yield discussion IIdiscussion II

Preliminary results about oil extraction Preliminary results about oil extraction yield yield discussion IIdiscussion II

If necessary this method allows to move up the olive harvest time in order to greatly reduce the damages due to the third fly attack of Bactrocera oleae that can induce a significant loss in oil production (up to 60) as well as a decrease in oil quality

If necessary this method allows to move up the olive harvest time in order to greatly reduce the damages due to the third fly attack of Bactrocera oleae that can induce a significant loss in oil production (up to 60) as well as a decrease in oil quality

Water content

inside the fruit

Water content

inside the fruit

CELLULAR CRASH

We need 08 kg of CO2s to lower 100 kg of olives temperature by 1degC

Cost of 1 kg of CO2s= euro050 $ 037

Cost to turn down the average temperature of 100

kg of olives by 10degC(15degC 5degC )

08kgdegC x 10degC x 037 $kg=

3 $

Considering an average oil yield of 15

The addition cost for a kg of extravirgin olive oil is

3 $100 kg olives x 15100kg oilkg olives

lt 02$kg oil

Oil elemental Oil elemental profile profile

preliminary preliminary resultsresults

ICP-AES and ICP-MS techniques are particularly advantageous for the application in the definition of the elemental profiles of olive oil since they allow simultaneous multi-elemental analysis and are characterized by wide linear ranges and (especially ICP-MS) very low Detection Limits

Main analytical issues are related to the hard organic content of the oil matrix which requires appropriate sample pre-treatments Microwave-assisted digestion permitted to obtain a complete dissolution of olive oil samples but resulted in the obtainment of highly acidic solutions not directly analyzable by ICP-MS with a consequent reduction of sensitivity (due to the preliminary 110 dilution of the mineralized olive oil)

ETV

LA

Preliminary results about oil elemental Preliminary results about oil elemental profileprofile

Preliminary results about oil elemental Preliminary results about oil elemental profileprofile

Preliminary results show a rather homogeneous elemental content among all the analyzed samples of olive oil

For all elements experimental concentrations fall within the ranges reported in literature In respect to these ranges analyzed samples show a high content of B S and Si while Fe Na Pb Ba Cr and Cu contents are quite low

Samples of olive oil obtained by the traditionalldquo process show - in general - a higher content of Ca Cr Mg Si (except those originating from Basilicata) and Zn compared to those obtained by the addition of ldquocarbonic snowldquo

0

20

40

60

80

100

120

140

B Ca Fe Na S Si

mgk

g

000

050

100

150

200

250

300

350

400

450

500

Al K Mg P Zn

mgk

g

0

500

1000

1500

2000

2500

3000

3500

Co Cr Cu Ni Pb

microgk

g

0

2

4

6

8

10

12

14

16

Ce Er Eu Gd La Nd Pr Sm Y Yb

microgk

g

0

100

200

300

400

500

600

700

800

As Ba Cd Li Mn Rb Sb Sc Se Sr Th Ti V

microgk

g

4000 25000

0

20

40

60

80

100

120

140

160

Ca

Na

Si

concentration range obtained from literature [2]

experimental concentration range ICP-AESDetection LimitICP-MSDetection Limit - Normal Sensitivity modeICP-MSDetection Limit - High Sensitivitymode

S B Yasar E K Baran M Alkan Metal determinations in olive oil In Olive Oil ndash Constituents Quality Health Properties and Bioconversions Ed by Boskou Dimitrios 5 89-108 2012

Preliminary results about oil elemental Preliminary results about oil elemental profileprofile

Preliminary results about oil elemental Preliminary results about oil elemental profileprofile

For any further details about the second part of the research you can contact our colleagues in ENEA

claudiazoanieneait giovannazappaeneait

For any further details about the second part of the research you can contact our colleagues in ENEA

claudiazoanieneait giovannazappaeneait

ReferencesReferencesReferencesReferences

The Utilization of Solid Carbon Dioxide in the Production of Extravirgin Olive Oil

Sanmartin C Zinnai A Venturi F Andrich G Proceedings of EFFOST 2011 9-11 November 2011 Berlino

(D)

Analytical methods for olive oil elemental profile and influence of carbonic snow addition in the extraction

phase C Zoani G Zappa A Zinnai F Venturi C Sanmartin

11th Euro Fed Lipid Congress ndash Antalya (Turkey) 27-30 October 2013

Preliminary results on the influence of carbonic snow addition during the olive processing oil extraction yield

and elemental profile C Zoani G Zappa F Venturi C Sanmartin G Andrich and

A ZinnaiJournal of Nutrition and Food Sciences 4 277 (2014)

doi 1041722155-96001000277

The Utilization of Solid Carbon Dioxide in the Production of Extravirgin Olive Oil

Sanmartin C Zinnai A Venturi F Andrich G Proceedings of EFFOST 2011 9-11 November 2011 Berlino

(D)

Analytical methods for olive oil elemental profile and influence of carbonic snow addition in the extraction

phase C Zoani G Zappa A Zinnai F Venturi C Sanmartin

11th Euro Fed Lipid Congress ndash Antalya (Turkey) 27-30 October 2013

Preliminary results on the influence of carbonic snow addition during the olive processing oil extraction yield

and elemental profile C Zoani G Zappa F Venturi C Sanmartin G Andrich and

A ZinnaiJournal of Nutrition and Food Sciences 4 277 (2014)

doi 1041722155-96001000277

Research in progresshellipResearch in progresshellip

Thank you for your attention

Thank you for your attention

research supported by

It will be possible to apply matrix modification procedures (eg solvent extraction ndash also ultrasound assisted - addition of organic solvents or emulsification) or to employ systems for direct oil sample introduction in torch (eg Flow Injection Analysis systems)

We are conducting experimental tests for evaluating the possibility to employ a Laser Ablation system or an ElectroThermal Vaporization system for direct sample introduction in ICP-AES and ICP-MS

ETV

LA

Future developmentsFuture developmentsFuture developmentsFuture developments

Determination of oil elemental profile sample pre-treatment

High PressureMicrowave Digestion

Milestone 1200 Mega

05 golive oil

Mineralized oil sample

(final V = 25 ml)

2 ml H2O2 + 6 ml HNO3

Different mixtures testedH2O2 30vv (1 divide 2 ml)+ HNO3 699vv (2 divide

6 ml)

Total dissoluti

on

high-purity water

(gt 18 MΩ)

time Power Pressure

1 min 250 WFree

pressure race

1 min 0 W

5 min 400 W

5 min 650 W

Vent = 5 min

TQ mineralized

olive oil solution

Varian Vista MPX(axial configuration

simultaneous 112 Mpixel CCD detector)

study of spectral interferencesstudy of spectral interferences

preliminary qualitative analysis72 elements

preliminary qualitative analysis72 elements

quantitative analysisquantitative analysis

Gas flows optimization based on signal-to-background ratio (SB)

Auxiliary flow (lmin)

Nebulizer flow(lmin)

10 15 09 10 11 12

SBMg 3296 11720 13948 17998 19921 18412Mn 0128 0197 0245 0312 0303 0294Na 1827 1940 1827 3187 6121 4371

Zn - 213857 nm more sensitive but interfered by Fe

Zn - 206200 nm - less sensitive but without interferences

Analytical wavelengths (nm)

Al - 396152 nm K - 766491 nm Rb - 780026 nm

As - 188980 nm Li - 670783 nm S - 181972 nm

B - 249772 nm Mg - 279553 nm Sb - 206834 nm

Ba - 455403 nm Mn - 257610 nm Si - 251611 nm

Ca - 396847 nm Na - 589592 nm Sr - 407771 nm

Cr - 267716 nm Ni - 231604 nm Ti - 334941 nm

Cu - 327395 nm P - 213618 nm V - 311837 nm

Fe - 238204 nm Pb - 220353 nm Zn ndash 206200 nm

Instrumental conditions

RF Frequency 40 MHz (free running air-cooled)

RF Power 12 kW

Gas (plasma auxiliary nebulizer) Argon

Plasma flow 150 lmin

Auxiliary flow 15 lmin

Nebulizer flow 110 lmin

Replicates 5

Replicate read time 5 s

Operating parameters for ICP-AES quantitative analysis

ICP-AES Analysis

Bruker Aurora M90 (90 degree ion mirror ion optics Collision Reaction Interface)110 diluted

mineralized olive oil solution

Tuning with a 5 microgl Be Mg Co In Ba Ce Ti Pb and Th solution for

sensitivity and resolution optimization and mass calibration

Tuning with a 5 microgl Be Mg Co In Ba Ce Ti Pb and Th solution for

sensitivity and resolution optimization and mass calibration

Check of the level of oxide ions by the CeO+Ce+ ratio lt 2

Check of the level of oxide ions by the CeO+Ce+ ratio lt 2

Monitoring of double charged ions by the signal 137Ba++137Ba+ lt 3

Monitoring of double charged ions by the signal 137Ba++137Ba+ lt 3

CheckCorrection of isobaric interferences examination of more isotopes of the same element(eg Rb85 Rb 87 Sr88Sr87 Nd142 Nd146 Nd144 Se77 Se78 Sn147 Sm148 Sm152 Gd157 Gd154 Er166 Er168 Yb170 Yb172) application of correction equations with respect to isotopes of other elements potentially interfering (eg Nd142 corrected by analyzing Ce140 Nd144 by Sm147 Sm152 by Gd157 Rb87 by Sr88 ) use of the Collision Reaction Interface ndash CRI (for As and Se)

CheckCorrection of isobaric interferences examination of more isotopes of the same element(eg Rb85 Rb 87 Sr88Sr87 Nd142 Nd146 Nd144 Se77 Se78 Sn147 Sm148 Sm152 Gd157 Gd154 Er166 Er168 Yb170 Yb172) application of correction equations with respect to isotopes of other elements potentially interfering (eg Nd142 corrected by analyzing Ce140 Nd144 by Sm147 Sm152 by Gd157 Rb87 by Sr88 ) use of the Collision Reaction Interface ndash CRI (for As and Se)

Working rangesbull005 divide 5 microgl - As Cd Ce Er Eu Gd La Mn Nd Pb Pr Rb Sb Sc Se Sm Sr Th V Y Ybbull01 divide 10 microgl - Co Cr Cu Mg Ni

Working rangesbull005 divide 5 microgl - As Cd Ce Er Eu Gd La Mn Nd Pb Pr Rb Sb Sc Se Sm Sr Th V Y Ybbull01 divide 10 microgl - Co Cr Cu Mg Ni

External calibration5 standard solutions + blankCurve Fit LinearWeighted Fit NoCorrelation coefficientsR gt 09999

Normal Sensitivity Mode (without CRI) High Sensitivity Mode As and Se ndash Normal mode with CRI

ICP-MS Analysis

• Slide 1
• Slide 2
• Slide 3
• Slide 4
• Slide 5
• Slide 6
• Slide 7
• Slide 8
• Slide 9
• Slide 10
• Slide 11
• Slide 12
• Slide 13
• Slide 14
• Slide 15
• Slide 16
• Slide 17
• Slide 18
• Slide 19
• Slide 20
• Slide 21
• Slide 22
• Slide 23
• Slide 24
• Slide 25
• Slide 26
• Slide 27
• Slide 28
• Slide 29
• Slide 30
• Slide 31
• Slide 32
• Slide 33
• Slide 34
• Slide 35

Preliminary results about oil extraction Preliminary results about oil extraction yield yield discussion Idiscussion I

Preliminary results about oil extraction Preliminary results about oil extraction yield yield discussion Idiscussion I

The number of the experimental runs carried out until now is quite reduced

The number of the experimental runs carried out until now is quite reduced

BUTBUT

The results appear very encouraging and the new method seems very suitable for olive oil extraction

The results appear very encouraging and the new method seems very suitable for olive oil extraction

During the next crop season we will increase the number of experimental runs adopting several combinations of the working parameters (ie amount of cryogenamount of olives fruit ripening stage etc)

During the next crop season we will increase the number of experimental runs adopting several combinations of the working parameters (ie amount of cryogenamount of olives fruit ripening stage etc)

Preliminary results about oil extraction Preliminary results about oil extraction yield yield discussion IIdiscussion II

Preliminary results about oil extraction Preliminary results about oil extraction yield yield discussion IIdiscussion II

If necessary this method allows to move up the olive harvest time in order to greatly reduce the damages due to the third fly attack of Bactrocera oleae that can induce a significant loss in oil production (up to 60) as well as a decrease in oil quality

If necessary this method allows to move up the olive harvest time in order to greatly reduce the damages due to the third fly attack of Bactrocera oleae that can induce a significant loss in oil production (up to 60) as well as a decrease in oil quality

Water content

inside the fruit

Water content

inside the fruit

CELLULAR CRASH

We need 08 kg of CO2s to lower 100 kg of olives temperature by 1degC

Cost of 1 kg of CO2s= euro050 $ 037

Cost to turn down the average temperature of 100

kg of olives by 10degC(15degC 5degC )

08kgdegC x 10degC x 037 $kg=

3 $

Considering an average oil yield of 15

The addition cost for a kg of extravirgin olive oil is

3 $100 kg olives x 15100kg oilkg olives

lt 02$kg oil

Oil elemental Oil elemental profile profile

preliminary preliminary resultsresults

ICP-AES and ICP-MS techniques are particularly advantageous for the application in the definition of the elemental profiles of olive oil since they allow simultaneous multi-elemental analysis and are characterized by wide linear ranges and (especially ICP-MS) very low Detection Limits

Main analytical issues are related to the hard organic content of the oil matrix which requires appropriate sample pre-treatments Microwave-assisted digestion permitted to obtain a complete dissolution of olive oil samples but resulted in the obtainment of highly acidic solutions not directly analyzable by ICP-MS with a consequent reduction of sensitivity (due to the preliminary 110 dilution of the mineralized olive oil)

ETV

LA

Preliminary results about oil elemental Preliminary results about oil elemental profileprofile

Preliminary results about oil elemental Preliminary results about oil elemental profileprofile

Preliminary results show a rather homogeneous elemental content among all the analyzed samples of olive oil

For all elements experimental concentrations fall within the ranges reported in literature In respect to these ranges analyzed samples show a high content of B S and Si while Fe Na Pb Ba Cr and Cu contents are quite low

Samples of olive oil obtained by the traditionalldquo process show - in general - a higher content of Ca Cr Mg Si (except those originating from Basilicata) and Zn compared to those obtained by the addition of ldquocarbonic snowldquo

0

20

40

60

80

100

120

140

B Ca Fe Na S Si

mgk

g

000

050

100

150

200

250

300

350

400

450

500

Al K Mg P Zn

mgk

g

0

500

1000

1500

2000

2500

3000

3500

Co Cr Cu Ni Pb

microgk

g

0

2

4

6

8

10

12

14

16

Ce Er Eu Gd La Nd Pr Sm Y Yb

microgk

g

0

100

200

300

400

500

600

700

800

As Ba Cd Li Mn Rb Sb Sc Se Sr Th Ti V

microgk

g

4000 25000

0

20

40

60

80

100

120

140

160

Ca

Na

Si

concentration range obtained from literature [2]

experimental concentration range ICP-AESDetection LimitICP-MSDetection Limit - Normal Sensitivity modeICP-MSDetection Limit - High Sensitivitymode

S B Yasar E K Baran M Alkan Metal determinations in olive oil In Olive Oil ndash Constituents Quality Health Properties and Bioconversions Ed by Boskou Dimitrios 5 89-108 2012

Preliminary results about oil elemental Preliminary results about oil elemental profileprofile

Preliminary results about oil elemental Preliminary results about oil elemental profileprofile

For any further details about the second part of the research you can contact our colleagues in ENEA

claudiazoanieneait giovannazappaeneait

For any further details about the second part of the research you can contact our colleagues in ENEA

claudiazoanieneait giovannazappaeneait

ReferencesReferencesReferencesReferences

The Utilization of Solid Carbon Dioxide in the Production of Extravirgin Olive Oil

Sanmartin C Zinnai A Venturi F Andrich G Proceedings of EFFOST 2011 9-11 November 2011 Berlino

(D)

Analytical methods for olive oil elemental profile and influence of carbonic snow addition in the extraction

phase C Zoani G Zappa A Zinnai F Venturi C Sanmartin

11th Euro Fed Lipid Congress ndash Antalya (Turkey) 27-30 October 2013

Preliminary results on the influence of carbonic snow addition during the olive processing oil extraction yield

and elemental profile C Zoani G Zappa F Venturi C Sanmartin G Andrich and

A ZinnaiJournal of Nutrition and Food Sciences 4 277 (2014)

doi 1041722155-96001000277

The Utilization of Solid Carbon Dioxide in the Production of Extravirgin Olive Oil

Sanmartin C Zinnai A Venturi F Andrich G Proceedings of EFFOST 2011 9-11 November 2011 Berlino

(D)

Analytical methods for olive oil elemental profile and influence of carbonic snow addition in the extraction

phase C Zoani G Zappa A Zinnai F Venturi C Sanmartin

11th Euro Fed Lipid Congress ndash Antalya (Turkey) 27-30 October 2013

Preliminary results on the influence of carbonic snow addition during the olive processing oil extraction yield

and elemental profile C Zoani G Zappa F Venturi C Sanmartin G Andrich and

A ZinnaiJournal of Nutrition and Food Sciences 4 277 (2014)

doi 1041722155-96001000277

Research in progresshellipResearch in progresshellip

Thank you for your attention

Thank you for your attention

research supported by

It will be possible to apply matrix modification procedures (eg solvent extraction ndash also ultrasound assisted - addition of organic solvents or emulsification) or to employ systems for direct oil sample introduction in torch (eg Flow Injection Analysis systems)

We are conducting experimental tests for evaluating the possibility to employ a Laser Ablation system or an ElectroThermal Vaporization system for direct sample introduction in ICP-AES and ICP-MS

ETV

LA

Future developmentsFuture developmentsFuture developmentsFuture developments

Determination of oil elemental profile sample pre-treatment

High PressureMicrowave Digestion

Milestone 1200 Mega

05 golive oil

Mineralized oil sample

(final V = 25 ml)

2 ml H2O2 + 6 ml HNO3

Different mixtures testedH2O2 30vv (1 divide 2 ml)+ HNO3 699vv (2 divide

6 ml)

Total dissoluti

on

high-purity water

(gt 18 MΩ)

time Power Pressure

1 min 250 WFree

pressure race

1 min 0 W

5 min 400 W

5 min 650 W

Vent = 5 min

TQ mineralized

olive oil solution

Varian Vista MPX(axial configuration

simultaneous 112 Mpixel CCD detector)

study of spectral interferencesstudy of spectral interferences

preliminary qualitative analysis72 elements

preliminary qualitative analysis72 elements

quantitative analysisquantitative analysis

Gas flows optimization based on signal-to-background ratio (SB)

Auxiliary flow (lmin)

Nebulizer flow(lmin)

10 15 09 10 11 12

SBMg 3296 11720 13948 17998 19921 18412Mn 0128 0197 0245 0312 0303 0294Na 1827 1940 1827 3187 6121 4371

Zn - 213857 nm more sensitive but interfered by Fe

Zn - 206200 nm - less sensitive but without interferences

Analytical wavelengths (nm)

Al - 396152 nm K - 766491 nm Rb - 780026 nm

As - 188980 nm Li - 670783 nm S - 181972 nm

B - 249772 nm Mg - 279553 nm Sb - 206834 nm

Ba - 455403 nm Mn - 257610 nm Si - 251611 nm

Ca - 396847 nm Na - 589592 nm Sr - 407771 nm

Cr - 267716 nm Ni - 231604 nm Ti - 334941 nm

Cu - 327395 nm P - 213618 nm V - 311837 nm

Fe - 238204 nm Pb - 220353 nm Zn ndash 206200 nm

Instrumental conditions

RF Frequency 40 MHz (free running air-cooled)

RF Power 12 kW

Gas (plasma auxiliary nebulizer) Argon

Plasma flow 150 lmin

Auxiliary flow 15 lmin

Nebulizer flow 110 lmin

Replicates 5

Replicate read time 5 s

Operating parameters for ICP-AES quantitative analysis

ICP-AES Analysis

Bruker Aurora M90 (90 degree ion mirror ion optics Collision Reaction Interface)110 diluted

mineralized olive oil solution

Tuning with a 5 microgl Be Mg Co In Ba Ce Ti Pb and Th solution for

sensitivity and resolution optimization and mass calibration

Tuning with a 5 microgl Be Mg Co In Ba Ce Ti Pb and Th solution for

sensitivity and resolution optimization and mass calibration

Check of the level of oxide ions by the CeO+Ce+ ratio lt 2

Check of the level of oxide ions by the CeO+Ce+ ratio lt 2

Monitoring of double charged ions by the signal 137Ba++137Ba+ lt 3

Monitoring of double charged ions by the signal 137Ba++137Ba+ lt 3

CheckCorrection of isobaric interferences examination of more isotopes of the same element(eg Rb85 Rb 87 Sr88Sr87 Nd142 Nd146 Nd144 Se77 Se78 Sn147 Sm148 Sm152 Gd157 Gd154 Er166 Er168 Yb170 Yb172) application of correction equations with respect to isotopes of other elements potentially interfering (eg Nd142 corrected by analyzing Ce140 Nd144 by Sm147 Sm152 by Gd157 Rb87 by Sr88 ) use of the Collision Reaction Interface ndash CRI (for As and Se)

CheckCorrection of isobaric interferences examination of more isotopes of the same element(eg Rb85 Rb 87 Sr88Sr87 Nd142 Nd146 Nd144 Se77 Se78 Sn147 Sm148 Sm152 Gd157 Gd154 Er166 Er168 Yb170 Yb172) application of correction equations with respect to isotopes of other elements potentially interfering (eg Nd142 corrected by analyzing Ce140 Nd144 by Sm147 Sm152 by Gd157 Rb87 by Sr88 ) use of the Collision Reaction Interface ndash CRI (for As and Se)

Working rangesbull005 divide 5 microgl - As Cd Ce Er Eu Gd La Mn Nd Pb Pr Rb Sb Sc Se Sm Sr Th V Y Ybbull01 divide 10 microgl - Co Cr Cu Mg Ni

Working rangesbull005 divide 5 microgl - As Cd Ce Er Eu Gd La Mn Nd Pb Pr Rb Sb Sc Se Sm Sr Th V Y Ybbull01 divide 10 microgl - Co Cr Cu Mg Ni

External calibration5 standard solutions + blankCurve Fit LinearWeighted Fit NoCorrelation coefficientsR gt 09999

Normal Sensitivity Mode (without CRI) High Sensitivity Mode As and Se ndash Normal mode with CRI

ICP-MS Analysis

• Slide 1
• Slide 2
• Slide 3
• Slide 4
• Slide 5
• Slide 6
• Slide 7
• Slide 8
• Slide 9
• Slide 10
• Slide 11
• Slide 12
• Slide 13
• Slide 14
• Slide 15
• Slide 16
• Slide 17
• Slide 18
• Slide 19
• Slide 20
• Slide 21
• Slide 22
• Slide 23
• Slide 24
• Slide 25
• Slide 26
• Slide 27
• Slide 28
• Slide 29
• Slide 30
• Slide 31
• Slide 32
• Slide 33
• Slide 34
• Slide 35

Preliminary results about oil extraction Preliminary results about oil extraction yield yield discussion IIdiscussion II

Preliminary results about oil extraction Preliminary results about oil extraction yield yield discussion IIdiscussion II

If necessary this method allows to move up the olive harvest time in order to greatly reduce the damages due to the third fly attack of Bactrocera oleae that can induce a significant loss in oil production (up to 60) as well as a decrease in oil quality

If necessary this method allows to move up the olive harvest time in order to greatly reduce the damages due to the third fly attack of Bactrocera oleae that can induce a significant loss in oil production (up to 60) as well as a decrease in oil quality

Water content

inside the fruit

Water content

inside the fruit

CELLULAR CRASH

We need 08 kg of CO2s to lower 100 kg of olives temperature by 1degC

Cost of 1 kg of CO2s= euro050 $ 037

Cost to turn down the average temperature of 100

kg of olives by 10degC(15degC 5degC )

08kgdegC x 10degC x 037 $kg=

3 $

Considering an average oil yield of 15

The addition cost for a kg of extravirgin olive oil is

3 $100 kg olives x 15100kg oilkg olives

lt 02$kg oil

Oil elemental Oil elemental profile profile

preliminary preliminary resultsresults

ICP-AES and ICP-MS techniques are particularly advantageous for the application in the definition of the elemental profiles of olive oil since they allow simultaneous multi-elemental analysis and are characterized by wide linear ranges and (especially ICP-MS) very low Detection Limits

Main analytical issues are related to the hard organic content of the oil matrix which requires appropriate sample pre-treatments Microwave-assisted digestion permitted to obtain a complete dissolution of olive oil samples but resulted in the obtainment of highly acidic solutions not directly analyzable by ICP-MS with a consequent reduction of sensitivity (due to the preliminary 110 dilution of the mineralized olive oil)

ETV

LA

Preliminary results about oil elemental Preliminary results about oil elemental profileprofile

Preliminary results about oil elemental Preliminary results about oil elemental profileprofile

Preliminary results show a rather homogeneous elemental content among all the analyzed samples of olive oil

For all elements experimental concentrations fall within the ranges reported in literature In respect to these ranges analyzed samples show a high content of B S and Si while Fe Na Pb Ba Cr and Cu contents are quite low

Samples of olive oil obtained by the traditionalldquo process show - in general - a higher content of Ca Cr Mg Si (except those originating from Basilicata) and Zn compared to those obtained by the addition of ldquocarbonic snowldquo

0

20

40

60

80

100

120

140

B Ca Fe Na S Si

mgk

g

000

050

100

150

200

250

300

350

400

450

500

Al K Mg P Zn

mgk

g

0

500

1000

1500

2000

2500

3000

3500

Co Cr Cu Ni Pb

microgk

g

0

2

4

6

8

10

12

14

16

Ce Er Eu Gd La Nd Pr Sm Y Yb

microgk

g

0

100

200

300

400

500

600

700

800

As Ba Cd Li Mn Rb Sb Sc Se Sr Th Ti V

microgk

g

4000 25000

0

20

40

60

80

100

120

140

160

Ca

Na

Si

concentration range obtained from literature [2]

experimental concentration range ICP-AESDetection LimitICP-MSDetection Limit - Normal Sensitivity modeICP-MSDetection Limit - High Sensitivitymode

S B Yasar E K Baran M Alkan Metal determinations in olive oil In Olive Oil ndash Constituents Quality Health Properties and Bioconversions Ed by Boskou Dimitrios 5 89-108 2012

Preliminary results about oil elemental Preliminary results about oil elemental profileprofile

Preliminary results about oil elemental Preliminary results about oil elemental profileprofile

For any further details about the second part of the research you can contact our colleagues in ENEA

claudiazoanieneait giovannazappaeneait

For any further details about the second part of the research you can contact our colleagues in ENEA

claudiazoanieneait giovannazappaeneait

ReferencesReferencesReferencesReferences

The Utilization of Solid Carbon Dioxide in the Production of Extravirgin Olive Oil

Sanmartin C Zinnai A Venturi F Andrich G Proceedings of EFFOST 2011 9-11 November 2011 Berlino

(D)

Analytical methods for olive oil elemental profile and influence of carbonic snow addition in the extraction

phase C Zoani G Zappa A Zinnai F Venturi C Sanmartin

11th Euro Fed Lipid Congress ndash Antalya (Turkey) 27-30 October 2013

Preliminary results on the influence of carbonic snow addition during the olive processing oil extraction yield

and elemental profile C Zoani G Zappa F Venturi C Sanmartin G Andrich and

A ZinnaiJournal of Nutrition and Food Sciences 4 277 (2014)

doi 1041722155-96001000277

The Utilization of Solid Carbon Dioxide in the Production of Extravirgin Olive Oil

Sanmartin C Zinnai A Venturi F Andrich G Proceedings of EFFOST 2011 9-11 November 2011 Berlino

(D)

Analytical methods for olive oil elemental profile and influence of carbonic snow addition in the extraction

phase C Zoani G Zappa A Zinnai F Venturi C Sanmartin

11th Euro Fed Lipid Congress ndash Antalya (Turkey) 27-30 October 2013

Preliminary results on the influence of carbonic snow addition during the olive processing oil extraction yield

and elemental profile C Zoani G Zappa F Venturi C Sanmartin G Andrich and

A ZinnaiJournal of Nutrition and Food Sciences 4 277 (2014)

doi 1041722155-96001000277

Research in progresshellipResearch in progresshellip

Thank you for your attention

Thank you for your attention

research supported by

It will be possible to apply matrix modification procedures (eg solvent extraction ndash also ultrasound assisted - addition of organic solvents or emulsification) or to employ systems for direct oil sample introduction in torch (eg Flow Injection Analysis systems)

We are conducting experimental tests for evaluating the possibility to employ a Laser Ablation system or an ElectroThermal Vaporization system for direct sample introduction in ICP-AES and ICP-MS

ETV

LA

Future developmentsFuture developmentsFuture developmentsFuture developments

Determination of oil elemental profile sample pre-treatment

High PressureMicrowave Digestion

Milestone 1200 Mega

05 golive oil

Mineralized oil sample

(final V = 25 ml)

2 ml H2O2 + 6 ml HNO3

Different mixtures testedH2O2 30vv (1 divide 2 ml)+ HNO3 699vv (2 divide

6 ml)

Total dissoluti

on

high-purity water

(gt 18 MΩ)

time Power Pressure

1 min 250 WFree

pressure race

1 min 0 W

5 min 400 W

5 min 650 W

Vent = 5 min

TQ mineralized

olive oil solution

Varian Vista MPX(axial configuration

simultaneous 112 Mpixel CCD detector)

study of spectral interferencesstudy of spectral interferences

preliminary qualitative analysis72 elements

preliminary qualitative analysis72 elements

quantitative analysisquantitative analysis

Gas flows optimization based on signal-to-background ratio (SB)

Auxiliary flow (lmin)

Nebulizer flow(lmin)

10 15 09 10 11 12

SBMg 3296 11720 13948 17998 19921 18412Mn 0128 0197 0245 0312 0303 0294Na 1827 1940 1827 3187 6121 4371

Zn - 213857 nm more sensitive but interfered by Fe

Zn - 206200 nm - less sensitive but without interferences

Analytical wavelengths (nm)

Al - 396152 nm K - 766491 nm Rb - 780026 nm

As - 188980 nm Li - 670783 nm S - 181972 nm

B - 249772 nm Mg - 279553 nm Sb - 206834 nm

Ba - 455403 nm Mn - 257610 nm Si - 251611 nm

Ca - 396847 nm Na - 589592 nm Sr - 407771 nm

Cr - 267716 nm Ni - 231604 nm Ti - 334941 nm

Cu - 327395 nm P - 213618 nm V - 311837 nm

Fe - 238204 nm Pb - 220353 nm Zn ndash 206200 nm

Instrumental conditions

RF Frequency 40 MHz (free running air-cooled)

RF Power 12 kW

Gas (plasma auxiliary nebulizer) Argon

Plasma flow 150 lmin

Auxiliary flow 15 lmin

Nebulizer flow 110 lmin

Replicates 5

Replicate read time 5 s

Operating parameters for ICP-AES quantitative analysis

ICP-AES Analysis

Bruker Aurora M90 (90 degree ion mirror ion optics Collision Reaction Interface)110 diluted

mineralized olive oil solution

Tuning with a 5 microgl Be Mg Co In Ba Ce Ti Pb and Th solution for

sensitivity and resolution optimization and mass calibration

Tuning with a 5 microgl Be Mg Co In Ba Ce Ti Pb and Th solution for

sensitivity and resolution optimization and mass calibration

Check of the level of oxide ions by the CeO+Ce+ ratio lt 2

Check of the level of oxide ions by the CeO+Ce+ ratio lt 2

Monitoring of double charged ions by the signal 137Ba++137Ba+ lt 3

Monitoring of double charged ions by the signal 137Ba++137Ba+ lt 3

CheckCorrection of isobaric interferences examination of more isotopes of the same element(eg Rb85 Rb 87 Sr88Sr87 Nd142 Nd146 Nd144 Se77 Se78 Sn147 Sm148 Sm152 Gd157 Gd154 Er166 Er168 Yb170 Yb172) application of correction equations with respect to isotopes of other elements potentially interfering (eg Nd142 corrected by analyzing Ce140 Nd144 by Sm147 Sm152 by Gd157 Rb87 by Sr88 ) use of the Collision Reaction Interface ndash CRI (for As and Se)

CheckCorrection of isobaric interferences examination of more isotopes of the same element(eg Rb85 Rb 87 Sr88Sr87 Nd142 Nd146 Nd144 Se77 Se78 Sn147 Sm148 Sm152 Gd157 Gd154 Er166 Er168 Yb170 Yb172) application of correction equations with respect to isotopes of other elements potentially interfering (eg Nd142 corrected by analyzing Ce140 Nd144 by Sm147 Sm152 by Gd157 Rb87 by Sr88 ) use of the Collision Reaction Interface ndash CRI (for As and Se)

Working rangesbull005 divide 5 microgl - As Cd Ce Er Eu Gd La Mn Nd Pb Pr Rb Sb Sc Se Sm Sr Th V Y Ybbull01 divide 10 microgl - Co Cr Cu Mg Ni

Working rangesbull005 divide 5 microgl - As Cd Ce Er Eu Gd La Mn Nd Pb Pr Rb Sb Sc Se Sm Sr Th V Y Ybbull01 divide 10 microgl - Co Cr Cu Mg Ni

External calibration5 standard solutions + blankCurve Fit LinearWeighted Fit NoCorrelation coefficientsR gt 09999

Normal Sensitivity Mode (without CRI) High Sensitivity Mode As and Se ndash Normal mode with CRI

ICP-MS Analysis

• Slide 1
• Slide 2
• Slide 3
• Slide 4
• Slide 5
• Slide 6
• Slide 7
• Slide 8
• Slide 9
• Slide 10
• Slide 11
• Slide 12
• Slide 13
• Slide 14
• Slide 15
• Slide 16
• Slide 17
• Slide 18
• Slide 19
• Slide 20
• Slide 21
• Slide 22
• Slide 23
• Slide 24
• Slide 25
• Slide 26
• Slide 27
• Slide 28
• Slide 29
• Slide 30
• Slide 31
• Slide 32
• Slide 33
• Slide 34
• Slide 35

We need 08 kg of CO2s to lower 100 kg of olives temperature by 1degC

Cost of 1 kg of CO2s= euro050 $ 037

Cost to turn down the average temperature of 100

kg of olives by 10degC(15degC 5degC )

08kgdegC x 10degC x 037 $kg=

3 $

Considering an average oil yield of 15

The addition cost for a kg of extravirgin olive oil is

3 $100 kg olives x 15100kg oilkg olives

lt 02$kg oil

Oil elemental Oil elemental profile profile

preliminary preliminary resultsresults

ICP-AES and ICP-MS techniques are particularly advantageous for the application in the definition of the elemental profiles of olive oil since they allow simultaneous multi-elemental analysis and are characterized by wide linear ranges and (especially ICP-MS) very low Detection Limits

Main analytical issues are related to the hard organic content of the oil matrix which requires appropriate sample pre-treatments Microwave-assisted digestion permitted to obtain a complete dissolution of olive oil samples but resulted in the obtainment of highly acidic solutions not directly analyzable by ICP-MS with a consequent reduction of sensitivity (due to the preliminary 110 dilution of the mineralized olive oil)

ETV

LA

Preliminary results about oil elemental Preliminary results about oil elemental profileprofile

Preliminary results about oil elemental Preliminary results about oil elemental profileprofile

Preliminary results show a rather homogeneous elemental content among all the analyzed samples of olive oil

For all elements experimental concentrations fall within the ranges reported in literature In respect to these ranges analyzed samples show a high content of B S and Si while Fe Na Pb Ba Cr and Cu contents are quite low

Samples of olive oil obtained by the traditionalldquo process show - in general - a higher content of Ca Cr Mg Si (except those originating from Basilicata) and Zn compared to those obtained by the addition of ldquocarbonic snowldquo

0

20

40

60

80

100

120

140

B Ca Fe Na S Si

mgk

g

000

050

100

150

200

250

300

350

400

450

500

Al K Mg P Zn

mgk

g

0

500

1000

1500

2000

2500

3000

3500

Co Cr Cu Ni Pb

microgk

g

0

2

4

6

8

10

12

14

16

Ce Er Eu Gd La Nd Pr Sm Y Yb

microgk

g

0

100

200

300

400

500

600

700

800

As Ba Cd Li Mn Rb Sb Sc Se Sr Th Ti V

microgk

g

4000 25000

0

20

40

60

80

100

120

140

160

Ca

Na

Si

concentration range obtained from literature [2]

experimental concentration range ICP-AESDetection LimitICP-MSDetection Limit - Normal Sensitivity modeICP-MSDetection Limit - High Sensitivitymode

S B Yasar E K Baran M Alkan Metal determinations in olive oil In Olive Oil ndash Constituents Quality Health Properties and Bioconversions Ed by Boskou Dimitrios 5 89-108 2012

Preliminary results about oil elemental Preliminary results about oil elemental profileprofile

Preliminary results about oil elemental Preliminary results about oil elemental profileprofile

For any further details about the second part of the research you can contact our colleagues in ENEA

claudiazoanieneait giovannazappaeneait

For any further details about the second part of the research you can contact our colleagues in ENEA

claudiazoanieneait giovannazappaeneait

ReferencesReferencesReferencesReferences

The Utilization of Solid Carbon Dioxide in the Production of Extravirgin Olive Oil

Sanmartin C Zinnai A Venturi F Andrich G Proceedings of EFFOST 2011 9-11 November 2011 Berlino

(D)

Analytical methods for olive oil elemental profile and influence of carbonic snow addition in the extraction

phase C Zoani G Zappa A Zinnai F Venturi C Sanmartin

11th Euro Fed Lipid Congress ndash Antalya (Turkey) 27-30 October 2013

Preliminary results on the influence of carbonic snow addition during the olive processing oil extraction yield

and elemental profile C Zoani G Zappa F Venturi C Sanmartin G Andrich and

A ZinnaiJournal of Nutrition and Food Sciences 4 277 (2014)

doi 1041722155-96001000277

The Utilization of Solid Carbon Dioxide in the Production of Extravirgin Olive Oil

Sanmartin C Zinnai A Venturi F Andrich G Proceedings of EFFOST 2011 9-11 November 2011 Berlino

(D)

Analytical methods for olive oil elemental profile and influence of carbonic snow addition in the extraction

phase C Zoani G Zappa A Zinnai F Venturi C Sanmartin

11th Euro Fed Lipid Congress ndash Antalya (Turkey) 27-30 October 2013

Preliminary results on the influence of carbonic snow addition during the olive processing oil extraction yield

and elemental profile C Zoani G Zappa F Venturi C Sanmartin G Andrich and

A ZinnaiJournal of Nutrition and Food Sciences 4 277 (2014)

doi 1041722155-96001000277

Research in progresshellipResearch in progresshellip

Thank you for your attention

Thank you for your attention

research supported by

It will be possible to apply matrix modification procedures (eg solvent extraction ndash also ultrasound assisted - addition of organic solvents or emulsification) or to employ systems for direct oil sample introduction in torch (eg Flow Injection Analysis systems)

We are conducting experimental tests for evaluating the possibility to employ a Laser Ablation system or an ElectroThermal Vaporization system for direct sample introduction in ICP-AES and ICP-MS

ETV

LA

Future developmentsFuture developmentsFuture developmentsFuture developments

Determination of oil elemental profile sample pre-treatment

High PressureMicrowave Digestion

Milestone 1200 Mega

05 golive oil

Mineralized oil sample

(final V = 25 ml)

2 ml H2O2 + 6 ml HNO3

Different mixtures testedH2O2 30vv (1 divide 2 ml)+ HNO3 699vv (2 divide

6 ml)

Total dissoluti

on

high-purity water

(gt 18 MΩ)

time Power Pressure

1 min 250 WFree

pressure race

1 min 0 W

5 min 400 W

5 min 650 W

Vent = 5 min

TQ mineralized

olive oil solution

Varian Vista MPX(axial configuration

simultaneous 112 Mpixel CCD detector)

study of spectral interferencesstudy of spectral interferences

preliminary qualitative analysis72 elements

preliminary qualitative analysis72 elements

quantitative analysisquantitative analysis

Gas flows optimization based on signal-to-background ratio (SB)

Auxiliary flow (lmin)

Nebulizer flow(lmin)

10 15 09 10 11 12

SBMg 3296 11720 13948 17998 19921 18412Mn 0128 0197 0245 0312 0303 0294Na 1827 1940 1827 3187 6121 4371

Zn - 213857 nm more sensitive but interfered by Fe

Zn - 206200 nm - less sensitive but without interferences

Analytical wavelengths (nm)

Al - 396152 nm K - 766491 nm Rb - 780026 nm

As - 188980 nm Li - 670783 nm S - 181972 nm

B - 249772 nm Mg - 279553 nm Sb - 206834 nm

Ba - 455403 nm Mn - 257610 nm Si - 251611 nm

Ca - 396847 nm Na - 589592 nm Sr - 407771 nm

Cr - 267716 nm Ni - 231604 nm Ti - 334941 nm

Cu - 327395 nm P - 213618 nm V - 311837 nm

Fe - 238204 nm Pb - 220353 nm Zn ndash 206200 nm

Instrumental conditions

RF Frequency 40 MHz (free running air-cooled)

RF Power 12 kW

Gas (plasma auxiliary nebulizer) Argon

Plasma flow 150 lmin

Auxiliary flow 15 lmin

Nebulizer flow 110 lmin

Replicates 5

Replicate read time 5 s

Operating parameters for ICP-AES quantitative analysis

ICP-AES Analysis

Bruker Aurora M90 (90 degree ion mirror ion optics Collision Reaction Interface)110 diluted

mineralized olive oil solution

Tuning with a 5 microgl Be Mg Co In Ba Ce Ti Pb and Th solution for

sensitivity and resolution optimization and mass calibration

Tuning with a 5 microgl Be Mg Co In Ba Ce Ti Pb and Th solution for

sensitivity and resolution optimization and mass calibration

Check of the level of oxide ions by the CeO+Ce+ ratio lt 2

Check of the level of oxide ions by the CeO+Ce+ ratio lt 2

Monitoring of double charged ions by the signal 137Ba++137Ba+ lt 3

Monitoring of double charged ions by the signal 137Ba++137Ba+ lt 3

CheckCorrection of isobaric interferences examination of more isotopes of the same element(eg Rb85 Rb 87 Sr88Sr87 Nd142 Nd146 Nd144 Se77 Se78 Sn147 Sm148 Sm152 Gd157 Gd154 Er166 Er168 Yb170 Yb172) application of correction equations with respect to isotopes of other elements potentially interfering (eg Nd142 corrected by analyzing Ce140 Nd144 by Sm147 Sm152 by Gd157 Rb87 by Sr88 ) use of the Collision Reaction Interface ndash CRI (for As and Se)

CheckCorrection of isobaric interferences examination of more isotopes of the same element(eg Rb85 Rb 87 Sr88Sr87 Nd142 Nd146 Nd144 Se77 Se78 Sn147 Sm148 Sm152 Gd157 Gd154 Er166 Er168 Yb170 Yb172) application of correction equations with respect to isotopes of other elements potentially interfering (eg Nd142 corrected by analyzing Ce140 Nd144 by Sm147 Sm152 by Gd157 Rb87 by Sr88 ) use of the Collision Reaction Interface ndash CRI (for As and Se)

Working rangesbull005 divide 5 microgl - As Cd Ce Er Eu Gd La Mn Nd Pb Pr Rb Sb Sc Se Sm Sr Th V Y Ybbull01 divide 10 microgl - Co Cr Cu Mg Ni

Working rangesbull005 divide 5 microgl - As Cd Ce Er Eu Gd La Mn Nd Pb Pr Rb Sb Sc Se Sm Sr Th V Y Ybbull01 divide 10 microgl - Co Cr Cu Mg Ni

External calibration5 standard solutions + blankCurve Fit LinearWeighted Fit NoCorrelation coefficientsR gt 09999

Normal Sensitivity Mode (without CRI) High Sensitivity Mode As and Se ndash Normal mode with CRI

ICP-MS Analysis

• Slide 1
• Slide 2
• Slide 3
• Slide 4
• Slide 5
• Slide 6
• Slide 7
• Slide 8
• Slide 9
• Slide 10
• Slide 11
• Slide 12
• Slide 13
• Slide 14
• Slide 15
• Slide 16
• Slide 17
• Slide 18
• Slide 19
• Slide 20
• Slide 21
• Slide 22
• Slide 23
• Slide 24
• Slide 25
• Slide 26
• Slide 27
• Slide 28
• Slide 29
• Slide 30
• Slide 31
• Slide 32
• Slide 33
• Slide 34
• Slide 35

Oil elemental Oil elemental profile profile

preliminary preliminary resultsresults

ICP-AES and ICP-MS techniques are particularly advantageous for the application in the definition of the elemental profiles of olive oil since they allow simultaneous multi-elemental analysis and are characterized by wide linear ranges and (especially ICP-MS) very low Detection Limits

Main analytical issues are related to the hard organic content of the oil matrix which requires appropriate sample pre-treatments Microwave-assisted digestion permitted to obtain a complete dissolution of olive oil samples but resulted in the obtainment of highly acidic solutions not directly analyzable by ICP-MS with a consequent reduction of sensitivity (due to the preliminary 110 dilution of the mineralized olive oil)

ETV

LA

Preliminary results about oil elemental Preliminary results about oil elemental profileprofile

Preliminary results about oil elemental Preliminary results about oil elemental profileprofile

Preliminary results show a rather homogeneous elemental content among all the analyzed samples of olive oil

For all elements experimental concentrations fall within the ranges reported in literature In respect to these ranges analyzed samples show a high content of B S and Si while Fe Na Pb Ba Cr and Cu contents are quite low

Samples of olive oil obtained by the traditionalldquo process show - in general - a higher content of Ca Cr Mg Si (except those originating from Basilicata) and Zn compared to those obtained by the addition of ldquocarbonic snowldquo

0

20

40

60

80

100

120

140

B Ca Fe Na S Si

mgk

g

000

050

100

150

200

250

300

350

400

450

500

Al K Mg P Zn

mgk

g

0

500

1000

1500

2000

2500

3000

3500

Co Cr Cu Ni Pb

microgk

g

0

2

4

6

8

10

12

14

16

Ce Er Eu Gd La Nd Pr Sm Y Yb

microgk

g

0

100

200

300

400

500

600

700

800

As Ba Cd Li Mn Rb Sb Sc Se Sr Th Ti V

microgk

g

4000 25000

0

20

40

60

80

100

120

140

160

Ca

Na

Si

concentration range obtained from literature [2]

experimental concentration range ICP-AESDetection LimitICP-MSDetection Limit - Normal Sensitivity modeICP-MSDetection Limit - High Sensitivitymode

S B Yasar E K Baran M Alkan Metal determinations in olive oil In Olive Oil ndash Constituents Quality Health Properties and Bioconversions Ed by Boskou Dimitrios 5 89-108 2012

Preliminary results about oil elemental Preliminary results about oil elemental profileprofile

Preliminary results about oil elemental Preliminary results about oil elemental profileprofile

For any further details about the second part of the research you can contact our colleagues in ENEA

claudiazoanieneait giovannazappaeneait

For any further details about the second part of the research you can contact our colleagues in ENEA

claudiazoanieneait giovannazappaeneait

ReferencesReferencesReferencesReferences

The Utilization of Solid Carbon Dioxide in the Production of Extravirgin Olive Oil

Sanmartin C Zinnai A Venturi F Andrich G Proceedings of EFFOST 2011 9-11 November 2011 Berlino

(D)

Analytical methods for olive oil elemental profile and influence of carbonic snow addition in the extraction

phase C Zoani G Zappa A Zinnai F Venturi C Sanmartin

11th Euro Fed Lipid Congress ndash Antalya (Turkey) 27-30 October 2013

Preliminary results on the influence of carbonic snow addition during the olive processing oil extraction yield

and elemental profile C Zoani G Zappa F Venturi C Sanmartin G Andrich and

A ZinnaiJournal of Nutrition and Food Sciences 4 277 (2014)

doi 1041722155-96001000277

The Utilization of Solid Carbon Dioxide in the Production of Extravirgin Olive Oil

Sanmartin C Zinnai A Venturi F Andrich G Proceedings of EFFOST 2011 9-11 November 2011 Berlino

(D)

Analytical methods for olive oil elemental profile and influence of carbonic snow addition in the extraction

phase C Zoani G Zappa A Zinnai F Venturi C Sanmartin

11th Euro Fed Lipid Congress ndash Antalya (Turkey) 27-30 October 2013

Preliminary results on the influence of carbonic snow addition during the olive processing oil extraction yield

and elemental profile C Zoani G Zappa F Venturi C Sanmartin G Andrich and

A ZinnaiJournal of Nutrition and Food Sciences 4 277 (2014)

doi 1041722155-96001000277

Research in progresshellipResearch in progresshellip

Thank you for your attention

Thank you for your attention

research supported by

It will be possible to apply matrix modification procedures (eg solvent extraction ndash also ultrasound assisted - addition of organic solvents or emulsification) or to employ systems for direct oil sample introduction in torch (eg Flow Injection Analysis systems)

We are conducting experimental tests for evaluating the possibility to employ a Laser Ablation system or an ElectroThermal Vaporization system for direct sample introduction in ICP-AES and ICP-MS

ETV

LA

Future developmentsFuture developmentsFuture developmentsFuture developments

Determination of oil elemental profile sample pre-treatment

High PressureMicrowave Digestion

Milestone 1200 Mega

05 golive oil

Mineralized oil sample

(final V = 25 ml)

2 ml H2O2 + 6 ml HNO3

Different mixtures testedH2O2 30vv (1 divide 2 ml)+ HNO3 699vv (2 divide

6 ml)

Total dissoluti

on

high-purity water

(gt 18 MΩ)

time Power Pressure

1 min 250 WFree

pressure race

1 min 0 W

5 min 400 W

5 min 650 W

Vent = 5 min

TQ mineralized

olive oil solution

Varian Vista MPX(axial configuration

simultaneous 112 Mpixel CCD detector)

study of spectral interferencesstudy of spectral interferences

preliminary qualitative analysis72 elements

preliminary qualitative analysis72 elements

quantitative analysisquantitative analysis

Gas flows optimization based on signal-to-background ratio (SB)

Auxiliary flow (lmin)

Nebulizer flow(lmin)

10 15 09 10 11 12

SBMg 3296 11720 13948 17998 19921 18412Mn 0128 0197 0245 0312 0303 0294Na 1827 1940 1827 3187 6121 4371

Zn - 213857 nm more sensitive but interfered by Fe

Zn - 206200 nm - less sensitive but without interferences

Analytical wavelengths (nm)

Al - 396152 nm K - 766491 nm Rb - 780026 nm

As - 188980 nm Li - 670783 nm S - 181972 nm

B - 249772 nm Mg - 279553 nm Sb - 206834 nm

Ba - 455403 nm Mn - 257610 nm Si - 251611 nm

Ca - 396847 nm Na - 589592 nm Sr - 407771 nm

Cr - 267716 nm Ni - 231604 nm Ti - 334941 nm

Cu - 327395 nm P - 213618 nm V - 311837 nm

Fe - 238204 nm Pb - 220353 nm Zn ndash 206200 nm

Instrumental conditions

RF Frequency 40 MHz (free running air-cooled)

RF Power 12 kW

Gas (plasma auxiliary nebulizer) Argon

Plasma flow 150 lmin

Auxiliary flow 15 lmin

Nebulizer flow 110 lmin

Replicates 5

Replicate read time 5 s

Operating parameters for ICP-AES quantitative analysis

ICP-AES Analysis

Bruker Aurora M90 (90 degree ion mirror ion optics Collision Reaction Interface)110 diluted

mineralized olive oil solution

Tuning with a 5 microgl Be Mg Co In Ba Ce Ti Pb and Th solution for

sensitivity and resolution optimization and mass calibration

Tuning with a 5 microgl Be Mg Co In Ba Ce Ti Pb and Th solution for

sensitivity and resolution optimization and mass calibration

Check of the level of oxide ions by the CeO+Ce+ ratio lt 2

Check of the level of oxide ions by the CeO+Ce+ ratio lt 2

Monitoring of double charged ions by the signal 137Ba++137Ba+ lt 3

Monitoring of double charged ions by the signal 137Ba++137Ba+ lt 3

CheckCorrection of isobaric interferences examination of more isotopes of the same element(eg Rb85 Rb 87 Sr88Sr87 Nd142 Nd146 Nd144 Se77 Se78 Sn147 Sm148 Sm152 Gd157 Gd154 Er166 Er168 Yb170 Yb172) application of correction equations with respect to isotopes of other elements potentially interfering (eg Nd142 corrected by analyzing Ce140 Nd144 by Sm147 Sm152 by Gd157 Rb87 by Sr88 ) use of the Collision Reaction Interface ndash CRI (for As and Se)

CheckCorrection of isobaric interferences examination of more isotopes of the same element(eg Rb85 Rb 87 Sr88Sr87 Nd142 Nd146 Nd144 Se77 Se78 Sn147 Sm148 Sm152 Gd157 Gd154 Er166 Er168 Yb170 Yb172) application of correction equations with respect to isotopes of other elements potentially interfering (eg Nd142 corrected by analyzing Ce140 Nd144 by Sm147 Sm152 by Gd157 Rb87 by Sr88 ) use of the Collision Reaction Interface ndash CRI (for As and Se)

Working rangesbull005 divide 5 microgl - As Cd Ce Er Eu Gd La Mn Nd Pb Pr Rb Sb Sc Se Sm Sr Th V Y Ybbull01 divide 10 microgl - Co Cr Cu Mg Ni

Working rangesbull005 divide 5 microgl - As Cd Ce Er Eu Gd La Mn Nd Pb Pr Rb Sb Sc Se Sm Sr Th V Y Ybbull01 divide 10 microgl - Co Cr Cu Mg Ni

External calibration5 standard solutions + blankCurve Fit LinearWeighted Fit NoCorrelation coefficientsR gt 09999

Normal Sensitivity Mode (without CRI) High Sensitivity Mode As and Se ndash Normal mode with CRI

ICP-MS Analysis

• Slide 1
• Slide 2
• Slide 3
• Slide 4
• Slide 5
• Slide 6
• Slide 7
• Slide 8
• Slide 9
• Slide 10
• Slide 11
• Slide 12
• Slide 13
• Slide 14
• Slide 15
• Slide 16
• Slide 17
• Slide 18
• Slide 19
• Slide 20
• Slide 21
• Slide 22
• Slide 23
• Slide 24
• Slide 25
• Slide 26
• Slide 27
• Slide 28
• Slide 29
• Slide 30
• Slide 31
• Slide 32
• Slide 33
• Slide 34
• Slide 35

ICP-AES and ICP-MS techniques are particularly advantageous for the application in the definition of the elemental profiles of olive oil since they allow simultaneous multi-elemental analysis and are characterized by wide linear ranges and (especially ICP-MS) very low Detection Limits

Main analytical issues are related to the hard organic content of the oil matrix which requires appropriate sample pre-treatments Microwave-assisted digestion permitted to obtain a complete dissolution of olive oil samples but resulted in the obtainment of highly acidic solutions not directly analyzable by ICP-MS with a consequent reduction of sensitivity (due to the preliminary 110 dilution of the mineralized olive oil)

ETV

LA

Preliminary results about oil elemental Preliminary results about oil elemental profileprofile

Preliminary results about oil elemental Preliminary results about oil elemental profileprofile

Preliminary results show a rather homogeneous elemental content among all the analyzed samples of olive oil

For all elements experimental concentrations fall within the ranges reported in literature In respect to these ranges analyzed samples show a high content of B S and Si while Fe Na Pb Ba Cr and Cu contents are quite low

Samples of olive oil obtained by the traditionalldquo process show - in general - a higher content of Ca Cr Mg Si (except those originating from Basilicata) and Zn compared to those obtained by the addition of ldquocarbonic snowldquo

0

20

40

60

80

100

120

140

B Ca Fe Na S Si

mgk

g

000

050

100

150

200

250

300

350

400

450

500

Al K Mg P Zn

mgk

g

0

500

1000

1500

2000

2500

3000

3500

Co Cr Cu Ni Pb

microgk

g

0

2

4

6

8

10

12

14

16

Ce Er Eu Gd La Nd Pr Sm Y Yb

microgk

g

0

100

200

300

400

500

600

700

800

As Ba Cd Li Mn Rb Sb Sc Se Sr Th Ti V

microgk

g

4000 25000

0

20

40

60

80

100

120

140

160

Ca

Na

Si

concentration range obtained from literature [2]

experimental concentration range ICP-AESDetection LimitICP-MSDetection Limit - Normal Sensitivity modeICP-MSDetection Limit - High Sensitivitymode

S B Yasar E K Baran M Alkan Metal determinations in olive oil In Olive Oil ndash Constituents Quality Health Properties and Bioconversions Ed by Boskou Dimitrios 5 89-108 2012

Preliminary results about oil elemental Preliminary results about oil elemental profileprofile

Preliminary results about oil elemental Preliminary results about oil elemental profileprofile

For any further details about the second part of the research you can contact our colleagues in ENEA

claudiazoanieneait giovannazappaeneait

For any further details about the second part of the research you can contact our colleagues in ENEA

claudiazoanieneait giovannazappaeneait

ReferencesReferencesReferencesReferences

The Utilization of Solid Carbon Dioxide in the Production of Extravirgin Olive Oil

Sanmartin C Zinnai A Venturi F Andrich G Proceedings of EFFOST 2011 9-11 November 2011 Berlino

(D)

Analytical methods for olive oil elemental profile and influence of carbonic snow addition in the extraction

phase C Zoani G Zappa A Zinnai F Venturi C Sanmartin

11th Euro Fed Lipid Congress ndash Antalya (Turkey) 27-30 October 2013

Preliminary results on the influence of carbonic snow addition during the olive processing oil extraction yield

and elemental profile C Zoani G Zappa F Venturi C Sanmartin G Andrich and

A ZinnaiJournal of Nutrition and Food Sciences 4 277 (2014)

doi 1041722155-96001000277

The Utilization of Solid Carbon Dioxide in the Production of Extravirgin Olive Oil

Sanmartin C Zinnai A Venturi F Andrich G Proceedings of EFFOST 2011 9-11 November 2011 Berlino

(D)

Analytical methods for olive oil elemental profile and influence of carbonic snow addition in the extraction

phase C Zoani G Zappa A Zinnai F Venturi C Sanmartin

11th Euro Fed Lipid Congress ndash Antalya (Turkey) 27-30 October 2013

Preliminary results on the influence of carbonic snow addition during the olive processing oil extraction yield

and elemental profile C Zoani G Zappa F Venturi C Sanmartin G Andrich and

A ZinnaiJournal of Nutrition and Food Sciences 4 277 (2014)

doi 1041722155-96001000277

Research in progresshellipResearch in progresshellip

Thank you for your attention

Thank you for your attention

research supported by

It will be possible to apply matrix modification procedures (eg solvent extraction ndash also ultrasound assisted - addition of organic solvents or emulsification) or to employ systems for direct oil sample introduction in torch (eg Flow Injection Analysis systems)

We are conducting experimental tests for evaluating the possibility to employ a Laser Ablation system or an ElectroThermal Vaporization system for direct sample introduction in ICP-AES and ICP-MS

ETV

LA

Future developmentsFuture developmentsFuture developmentsFuture developments

Determination of oil elemental profile sample pre-treatment

High PressureMicrowave Digestion

Milestone 1200 Mega

05 golive oil

Mineralized oil sample

(final V = 25 ml)

2 ml H2O2 + 6 ml HNO3

Different mixtures testedH2O2 30vv (1 divide 2 ml)+ HNO3 699vv (2 divide

6 ml)

Total dissoluti

on

high-purity water

(gt 18 MΩ)

time Power Pressure

1 min 250 WFree

pressure race

1 min 0 W

5 min 400 W

5 min 650 W

Vent = 5 min

TQ mineralized

olive oil solution

Varian Vista MPX(axial configuration

simultaneous 112 Mpixel CCD detector)

study of spectral interferencesstudy of spectral interferences

preliminary qualitative analysis72 elements

preliminary qualitative analysis72 elements

quantitative analysisquantitative analysis

Gas flows optimization based on signal-to-background ratio (SB)

Auxiliary flow (lmin)

Nebulizer flow(lmin)

10 15 09 10 11 12

SBMg 3296 11720 13948 17998 19921 18412Mn 0128 0197 0245 0312 0303 0294Na 1827 1940 1827 3187 6121 4371

Zn - 213857 nm more sensitive but interfered by Fe

Zn - 206200 nm - less sensitive but without interferences

Analytical wavelengths (nm)

Al - 396152 nm K - 766491 nm Rb - 780026 nm

As - 188980 nm Li - 670783 nm S - 181972 nm

B - 249772 nm Mg - 279553 nm Sb - 206834 nm

Ba - 455403 nm Mn - 257610 nm Si - 251611 nm

Ca - 396847 nm Na - 589592 nm Sr - 407771 nm

Cr - 267716 nm Ni - 231604 nm Ti - 334941 nm

Cu - 327395 nm P - 213618 nm V - 311837 nm

Fe - 238204 nm Pb - 220353 nm Zn ndash 206200 nm

Instrumental conditions

RF Frequency 40 MHz (free running air-cooled)

RF Power 12 kW

Gas (plasma auxiliary nebulizer) Argon

Plasma flow 150 lmin

Auxiliary flow 15 lmin

Nebulizer flow 110 lmin

Replicates 5

Replicate read time 5 s

Operating parameters for ICP-AES quantitative analysis

ICP-AES Analysis

Bruker Aurora M90 (90 degree ion mirror ion optics Collision Reaction Interface)110 diluted

mineralized olive oil solution

Tuning with a 5 microgl Be Mg Co In Ba Ce Ti Pb and Th solution for

sensitivity and resolution optimization and mass calibration

Tuning with a 5 microgl Be Mg Co In Ba Ce Ti Pb and Th solution for

sensitivity and resolution optimization and mass calibration

Check of the level of oxide ions by the CeO+Ce+ ratio lt 2

Check of the level of oxide ions by the CeO+Ce+ ratio lt 2

Monitoring of double charged ions by the signal 137Ba++137Ba+ lt 3

Monitoring of double charged ions by the signal 137Ba++137Ba+ lt 3

CheckCorrection of isobaric interferences examination of more isotopes of the same element(eg Rb85 Rb 87 Sr88Sr87 Nd142 Nd146 Nd144 Se77 Se78 Sn147 Sm148 Sm152 Gd157 Gd154 Er166 Er168 Yb170 Yb172) application of correction equations with respect to isotopes of other elements potentially interfering (eg Nd142 corrected by analyzing Ce140 Nd144 by Sm147 Sm152 by Gd157 Rb87 by Sr88 ) use of the Collision Reaction Interface ndash CRI (for As and Se)

CheckCorrection of isobaric interferences examination of more isotopes of the same element(eg Rb85 Rb 87 Sr88Sr87 Nd142 Nd146 Nd144 Se77 Se78 Sn147 Sm148 Sm152 Gd157 Gd154 Er166 Er168 Yb170 Yb172) application of correction equations with respect to isotopes of other elements potentially interfering (eg Nd142 corrected by analyzing Ce140 Nd144 by Sm147 Sm152 by Gd157 Rb87 by Sr88 ) use of the Collision Reaction Interface ndash CRI (for As and Se)

Working rangesbull005 divide 5 microgl - As Cd Ce Er Eu Gd La Mn Nd Pb Pr Rb Sb Sc Se Sm Sr Th V Y Ybbull01 divide 10 microgl - Co Cr Cu Mg Ni

Working rangesbull005 divide 5 microgl - As Cd Ce Er Eu Gd La Mn Nd Pb Pr Rb Sb Sc Se Sm Sr Th V Y Ybbull01 divide 10 microgl - Co Cr Cu Mg Ni

External calibration5 standard solutions + blankCurve Fit LinearWeighted Fit NoCorrelation coefficientsR gt 09999

Normal Sensitivity Mode (without CRI) High Sensitivity Mode As and Se ndash Normal mode with CRI

ICP-MS Analysis

• Slide 1
• Slide 2
• Slide 3
• Slide 4
• Slide 5
• Slide 6
• Slide 7
• Slide 8
• Slide 9
• Slide 10
• Slide 11
• Slide 12
• Slide 13
• Slide 14
• Slide 15
• Slide 16
• Slide 17
• Slide 18
• Slide 19
• Slide 20
• Slide 21
• Slide 22
• Slide 23
• Slide 24
• Slide 25
• Slide 26
• Slide 27
• Slide 28
• Slide 29
• Slide 30
• Slide 31
• Slide 32
• Slide 33
• Slide 34
• Slide 35

Preliminary results show a rather homogeneous elemental content among all the analyzed samples of olive oil

For all elements experimental concentrations fall within the ranges reported in literature In respect to these ranges analyzed samples show a high content of B S and Si while Fe Na Pb Ba Cr and Cu contents are quite low

Samples of olive oil obtained by the traditionalldquo process show - in general - a higher content of Ca Cr Mg Si (except those originating from Basilicata) and Zn compared to those obtained by the addition of ldquocarbonic snowldquo

0

20

40

60

80

100

120

140

B Ca Fe Na S Si

mgk

g

000

050

100

150

200

250

300

350

400

450

500

Al K Mg P Zn

mgk

g

0

500

1000

1500

2000

2500

3000

3500

Co Cr Cu Ni Pb

microgk

g

0

2

4

6

8

10

12

14

16

Ce Er Eu Gd La Nd Pr Sm Y Yb

microgk

g

0

100

200

300

400

500

600

700

800

As Ba Cd Li Mn Rb Sb Sc Se Sr Th Ti V

microgk

g

4000 25000

0

20

40

60

80

100

120

140

160

Ca

Na

Si

concentration range obtained from literature [2]

experimental concentration range ICP-AESDetection LimitICP-MSDetection Limit - Normal Sensitivity modeICP-MSDetection Limit - High Sensitivitymode

S B Yasar E K Baran M Alkan Metal determinations in olive oil In Olive Oil ndash Constituents Quality Health Properties and Bioconversions Ed by Boskou Dimitrios 5 89-108 2012

Preliminary results about oil elemental Preliminary results about oil elemental profileprofile

Preliminary results about oil elemental Preliminary results about oil elemental profileprofile

For any further details about the second part of the research you can contact our colleagues in ENEA

claudiazoanieneait giovannazappaeneait

For any further details about the second part of the research you can contact our colleagues in ENEA

claudiazoanieneait giovannazappaeneait

ReferencesReferencesReferencesReferences

The Utilization of Solid Carbon Dioxide in the Production of Extravirgin Olive Oil

Sanmartin C Zinnai A Venturi F Andrich G Proceedings of EFFOST 2011 9-11 November 2011 Berlino

(D)

Analytical methods for olive oil elemental profile and influence of carbonic snow addition in the extraction

phase C Zoani G Zappa A Zinnai F Venturi C Sanmartin

11th Euro Fed Lipid Congress ndash Antalya (Turkey) 27-30 October 2013

Preliminary results on the influence of carbonic snow addition during the olive processing oil extraction yield

and elemental profile C Zoani G Zappa F Venturi C Sanmartin G Andrich and

A ZinnaiJournal of Nutrition and Food Sciences 4 277 (2014)

doi 1041722155-96001000277

The Utilization of Solid Carbon Dioxide in the Production of Extravirgin Olive Oil

Sanmartin C Zinnai A Venturi F Andrich G Proceedings of EFFOST 2011 9-11 November 2011 Berlino

(D)

Analytical methods for olive oil elemental profile and influence of carbonic snow addition in the extraction

phase C Zoani G Zappa A Zinnai F Venturi C Sanmartin

11th Euro Fed Lipid Congress ndash Antalya (Turkey) 27-30 October 2013

Preliminary results on the influence of carbonic snow addition during the olive processing oil extraction yield

and elemental profile C Zoani G Zappa F Venturi C Sanmartin G Andrich and

A ZinnaiJournal of Nutrition and Food Sciences 4 277 (2014)

doi 1041722155-96001000277

Research in progresshellipResearch in progresshellip

Thank you for your attention

Thank you for your attention

research supported by

It will be possible to apply matrix modification procedures (eg solvent extraction ndash also ultrasound assisted - addition of organic solvents or emulsification) or to employ systems for direct oil sample introduction in torch (eg Flow Injection Analysis systems)

We are conducting experimental tests for evaluating the possibility to employ a Laser Ablation system or an ElectroThermal Vaporization system for direct sample introduction in ICP-AES and ICP-MS

ETV

LA

Future developmentsFuture developmentsFuture developmentsFuture developments

Determination of oil elemental profile sample pre-treatment

High PressureMicrowave Digestion

Milestone 1200 Mega

05 golive oil

Mineralized oil sample

(final V = 25 ml)

2 ml H2O2 + 6 ml HNO3

Different mixtures testedH2O2 30vv (1 divide 2 ml)+ HNO3 699vv (2 divide

6 ml)

Total dissoluti

on

high-purity water

(gt 18 MΩ)

time Power Pressure

1 min 250 WFree

pressure race

1 min 0 W

5 min 400 W

5 min 650 W

Vent = 5 min

TQ mineralized

olive oil solution

Varian Vista MPX(axial configuration

simultaneous 112 Mpixel CCD detector)

study of spectral interferencesstudy of spectral interferences

preliminary qualitative analysis72 elements

preliminary qualitative analysis72 elements

quantitative analysisquantitative analysis

Gas flows optimization based on signal-to-background ratio (SB)

Auxiliary flow (lmin)

Nebulizer flow(lmin)

10 15 09 10 11 12

SBMg 3296 11720 13948 17998 19921 18412Mn 0128 0197 0245 0312 0303 0294Na 1827 1940 1827 3187 6121 4371

Zn - 213857 nm more sensitive but interfered by Fe

Zn - 206200 nm - less sensitive but without interferences

Analytical wavelengths (nm)

Al - 396152 nm K - 766491 nm Rb - 780026 nm

As - 188980 nm Li - 670783 nm S - 181972 nm

B - 249772 nm Mg - 279553 nm Sb - 206834 nm

Ba - 455403 nm Mn - 257610 nm Si - 251611 nm

Ca - 396847 nm Na - 589592 nm Sr - 407771 nm

Cr - 267716 nm Ni - 231604 nm Ti - 334941 nm

Cu - 327395 nm P - 213618 nm V - 311837 nm

Fe - 238204 nm Pb - 220353 nm Zn ndash 206200 nm

Instrumental conditions

RF Frequency 40 MHz (free running air-cooled)

RF Power 12 kW

Gas (plasma auxiliary nebulizer) Argon

Plasma flow 150 lmin

Auxiliary flow 15 lmin

Nebulizer flow 110 lmin

Replicates 5

Replicate read time 5 s

Operating parameters for ICP-AES quantitative analysis

ICP-AES Analysis

Bruker Aurora M90 (90 degree ion mirror ion optics Collision Reaction Interface)110 diluted

mineralized olive oil solution

Tuning with a 5 microgl Be Mg Co In Ba Ce Ti Pb and Th solution for

sensitivity and resolution optimization and mass calibration

Tuning with a 5 microgl Be Mg Co In Ba Ce Ti Pb and Th solution for

sensitivity and resolution optimization and mass calibration

Check of the level of oxide ions by the CeO+Ce+ ratio lt 2

Check of the level of oxide ions by the CeO+Ce+ ratio lt 2

Monitoring of double charged ions by the signal 137Ba++137Ba+ lt 3

Monitoring of double charged ions by the signal 137Ba++137Ba+ lt 3

CheckCorrection of isobaric interferences examination of more isotopes of the same element(eg Rb85 Rb 87 Sr88Sr87 Nd142 Nd146 Nd144 Se77 Se78 Sn147 Sm148 Sm152 Gd157 Gd154 Er166 Er168 Yb170 Yb172) application of correction equations with respect to isotopes of other elements potentially interfering (eg Nd142 corrected by analyzing Ce140 Nd144 by Sm147 Sm152 by Gd157 Rb87 by Sr88 ) use of the Collision Reaction Interface ndash CRI (for As and Se)

CheckCorrection of isobaric interferences examination of more isotopes of the same element(eg Rb85 Rb 87 Sr88Sr87 Nd142 Nd146 Nd144 Se77 Se78 Sn147 Sm148 Sm152 Gd157 Gd154 Er166 Er168 Yb170 Yb172) application of correction equations with respect to isotopes of other elements potentially interfering (eg Nd142 corrected by analyzing Ce140 Nd144 by Sm147 Sm152 by Gd157 Rb87 by Sr88 ) use of the Collision Reaction Interface ndash CRI (for As and Se)

Working rangesbull005 divide 5 microgl - As Cd Ce Er Eu Gd La Mn Nd Pb Pr Rb Sb Sc Se Sm Sr Th V Y Ybbull01 divide 10 microgl - Co Cr Cu Mg Ni

Working rangesbull005 divide 5 microgl - As Cd Ce Er Eu Gd La Mn Nd Pb Pr Rb Sb Sc Se Sm Sr Th V Y Ybbull01 divide 10 microgl - Co Cr Cu Mg Ni

External calibration5 standard solutions + blankCurve Fit LinearWeighted Fit NoCorrelation coefficientsR gt 09999

Normal Sensitivity Mode (without CRI) High Sensitivity Mode As and Se ndash Normal mode with CRI

ICP-MS Analysis

• Slide 1
• Slide 2
• Slide 3
• Slide 4
• Slide 5
• Slide 6
• Slide 7
• Slide 8
• Slide 9
• Slide 10
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• Slide 33
• Slide 34
• Slide 35

For any further details about the second part of the research you can contact our colleagues in ENEA

claudiazoanieneait giovannazappaeneait

For any further details about the second part of the research you can contact our colleagues in ENEA

claudiazoanieneait giovannazappaeneait

ReferencesReferencesReferencesReferences

The Utilization of Solid Carbon Dioxide in the Production of Extravirgin Olive Oil

Sanmartin C Zinnai A Venturi F Andrich G Proceedings of EFFOST 2011 9-11 November 2011 Berlino

(D)

Analytical methods for olive oil elemental profile and influence of carbonic snow addition in the extraction

phase C Zoani G Zappa A Zinnai F Venturi C Sanmartin

11th Euro Fed Lipid Congress ndash Antalya (Turkey) 27-30 October 2013

Preliminary results on the influence of carbonic snow addition during the olive processing oil extraction yield

and elemental profile C Zoani G Zappa F Venturi C Sanmartin G Andrich and

A ZinnaiJournal of Nutrition and Food Sciences 4 277 (2014)

doi 1041722155-96001000277

The Utilization of Solid Carbon Dioxide in the Production of Extravirgin Olive Oil

Sanmartin C Zinnai A Venturi F Andrich G Proceedings of EFFOST 2011 9-11 November 2011 Berlino

(D)

Analytical methods for olive oil elemental profile and influence of carbonic snow addition in the extraction

phase C Zoani G Zappa A Zinnai F Venturi C Sanmartin

11th Euro Fed Lipid Congress ndash Antalya (Turkey) 27-30 October 2013

Preliminary results on the influence of carbonic snow addition during the olive processing oil extraction yield

and elemental profile C Zoani G Zappa F Venturi C Sanmartin G Andrich and

A ZinnaiJournal of Nutrition and Food Sciences 4 277 (2014)

doi 1041722155-96001000277

Research in progresshellipResearch in progresshellip

Thank you for your attention

Thank you for your attention

research supported by

It will be possible to apply matrix modification procedures (eg solvent extraction ndash also ultrasound assisted - addition of organic solvents or emulsification) or to employ systems for direct oil sample introduction in torch (eg Flow Injection Analysis systems)

We are conducting experimental tests for evaluating the possibility to employ a Laser Ablation system or an ElectroThermal Vaporization system for direct sample introduction in ICP-AES and ICP-MS

ETV

LA

Future developmentsFuture developmentsFuture developmentsFuture developments

Determination of oil elemental profile sample pre-treatment

High PressureMicrowave Digestion

Milestone 1200 Mega

05 golive oil

Mineralized oil sample

(final V = 25 ml)

2 ml H2O2 + 6 ml HNO3

Different mixtures testedH2O2 30vv (1 divide 2 ml)+ HNO3 699vv (2 divide

6 ml)

Total dissoluti

on

high-purity water

(gt 18 MΩ)

time Power Pressure

1 min 250 WFree

pressure race

1 min 0 W

5 min 400 W

5 min 650 W

Vent = 5 min

TQ mineralized

olive oil solution

Varian Vista MPX(axial configuration

simultaneous 112 Mpixel CCD detector)

study of spectral interferencesstudy of spectral interferences

preliminary qualitative analysis72 elements

preliminary qualitative analysis72 elements

quantitative analysisquantitative analysis

Gas flows optimization based on signal-to-background ratio (SB)

Auxiliary flow (lmin)

Nebulizer flow(lmin)

10 15 09 10 11 12

SBMg 3296 11720 13948 17998 19921 18412Mn 0128 0197 0245 0312 0303 0294Na 1827 1940 1827 3187 6121 4371

Zn - 213857 nm more sensitive but interfered by Fe

Zn - 206200 nm - less sensitive but without interferences

Analytical wavelengths (nm)

Al - 396152 nm K - 766491 nm Rb - 780026 nm

As - 188980 nm Li - 670783 nm S - 181972 nm

B - 249772 nm Mg - 279553 nm Sb - 206834 nm

Ba - 455403 nm Mn - 257610 nm Si - 251611 nm

Ca - 396847 nm Na - 589592 nm Sr - 407771 nm

Cr - 267716 nm Ni - 231604 nm Ti - 334941 nm

Cu - 327395 nm P - 213618 nm V - 311837 nm

Fe - 238204 nm Pb - 220353 nm Zn ndash 206200 nm

Instrumental conditions

RF Frequency 40 MHz (free running air-cooled)

RF Power 12 kW

Gas (plasma auxiliary nebulizer) Argon

Plasma flow 150 lmin

Auxiliary flow 15 lmin

Nebulizer flow 110 lmin

Replicates 5

Replicate read time 5 s

Operating parameters for ICP-AES quantitative analysis

ICP-AES Analysis

Bruker Aurora M90 (90 degree ion mirror ion optics Collision Reaction Interface)110 diluted

mineralized olive oil solution

Tuning with a 5 microgl Be Mg Co In Ba Ce Ti Pb and Th solution for

sensitivity and resolution optimization and mass calibration

Tuning with a 5 microgl Be Mg Co In Ba Ce Ti Pb and Th solution for

sensitivity and resolution optimization and mass calibration

Check of the level of oxide ions by the CeO+Ce+ ratio lt 2

Check of the level of oxide ions by the CeO+Ce+ ratio lt 2

Monitoring of double charged ions by the signal 137Ba++137Ba+ lt 3

Monitoring of double charged ions by the signal 137Ba++137Ba+ lt 3

CheckCorrection of isobaric interferences examination of more isotopes of the same element(eg Rb85 Rb 87 Sr88Sr87 Nd142 Nd146 Nd144 Se77 Se78 Sn147 Sm148 Sm152 Gd157 Gd154 Er166 Er168 Yb170 Yb172) application of correction equations with respect to isotopes of other elements potentially interfering (eg Nd142 corrected by analyzing Ce140 Nd144 by Sm147 Sm152 by Gd157 Rb87 by Sr88 ) use of the Collision Reaction Interface ndash CRI (for As and Se)

CheckCorrection of isobaric interferences examination of more isotopes of the same element(eg Rb85 Rb 87 Sr88Sr87 Nd142 Nd146 Nd144 Se77 Se78 Sn147 Sm148 Sm152 Gd157 Gd154 Er166 Er168 Yb170 Yb172) application of correction equations with respect to isotopes of other elements potentially interfering (eg Nd142 corrected by analyzing Ce140 Nd144 by Sm147 Sm152 by Gd157 Rb87 by Sr88 ) use of the Collision Reaction Interface ndash CRI (for As and Se)

Working rangesbull005 divide 5 microgl - As Cd Ce Er Eu Gd La Mn Nd Pb Pr Rb Sb Sc Se Sm Sr Th V Y Ybbull01 divide 10 microgl - Co Cr Cu Mg Ni

Working rangesbull005 divide 5 microgl - As Cd Ce Er Eu Gd La Mn Nd Pb Pr Rb Sb Sc Se Sm Sr Th V Y Ybbull01 divide 10 microgl - Co Cr Cu Mg Ni

External calibration5 standard solutions + blankCurve Fit LinearWeighted Fit NoCorrelation coefficientsR gt 09999

Normal Sensitivity Mode (without CRI) High Sensitivity Mode As and Se ndash Normal mode with CRI

ICP-MS Analysis

• Slide 1
• Slide 2
• Slide 3
• Slide 4
• Slide 5
• Slide 6
• Slide 7
• Slide 8
• Slide 9
• Slide 10
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• Slide 27
• Slide 28
• Slide 29
• Slide 30
• Slide 31
• Slide 32
• Slide 33
• Slide 34
• Slide 35

ReferencesReferencesReferencesReferences

The Utilization of Solid Carbon Dioxide in the Production of Extravirgin Olive Oil

Sanmartin C Zinnai A Venturi F Andrich G Proceedings of EFFOST 2011 9-11 November 2011 Berlino

(D)

Analytical methods for olive oil elemental profile and influence of carbonic snow addition in the extraction

phase C Zoani G Zappa A Zinnai F Venturi C Sanmartin

11th Euro Fed Lipid Congress ndash Antalya (Turkey) 27-30 October 2013

Preliminary results on the influence of carbonic snow addition during the olive processing oil extraction yield

and elemental profile C Zoani G Zappa F Venturi C Sanmartin G Andrich and

A ZinnaiJournal of Nutrition and Food Sciences 4 277 (2014)

doi 1041722155-96001000277

The Utilization of Solid Carbon Dioxide in the Production of Extravirgin Olive Oil

Sanmartin C Zinnai A Venturi F Andrich G Proceedings of EFFOST 2011 9-11 November 2011 Berlino

(D)

Analytical methods for olive oil elemental profile and influence of carbonic snow addition in the extraction

phase C Zoani G Zappa A Zinnai F Venturi C Sanmartin

11th Euro Fed Lipid Congress ndash Antalya (Turkey) 27-30 October 2013

Preliminary results on the influence of carbonic snow addition during the olive processing oil extraction yield

and elemental profile C Zoani G Zappa F Venturi C Sanmartin G Andrich and

A ZinnaiJournal of Nutrition and Food Sciences 4 277 (2014)

doi 1041722155-96001000277

Research in progresshellipResearch in progresshellip

Thank you for your attention

Thank you for your attention

research supported by

It will be possible to apply matrix modification procedures (eg solvent extraction ndash also ultrasound assisted - addition of organic solvents or emulsification) or to employ systems for direct oil sample introduction in torch (eg Flow Injection Analysis systems)

We are conducting experimental tests for evaluating the possibility to employ a Laser Ablation system or an ElectroThermal Vaporization system for direct sample introduction in ICP-AES and ICP-MS

ETV

LA

Future developmentsFuture developmentsFuture developmentsFuture developments

Determination of oil elemental profile sample pre-treatment

High PressureMicrowave Digestion

Milestone 1200 Mega

05 golive oil

Mineralized oil sample

(final V = 25 ml)

2 ml H2O2 + 6 ml HNO3

Different mixtures testedH2O2 30vv (1 divide 2 ml)+ HNO3 699vv (2 divide

6 ml)

Total dissoluti

on

high-purity water

(gt 18 MΩ)

time Power Pressure

1 min 250 WFree

pressure race

1 min 0 W

5 min 400 W

5 min 650 W

Vent = 5 min

TQ mineralized

olive oil solution

Varian Vista MPX(axial configuration

simultaneous 112 Mpixel CCD detector)

study of spectral interferencesstudy of spectral interferences

preliminary qualitative analysis72 elements

preliminary qualitative analysis72 elements

quantitative analysisquantitative analysis

Gas flows optimization based on signal-to-background ratio (SB)

Auxiliary flow (lmin)

Nebulizer flow(lmin)

10 15 09 10 11 12

SBMg 3296 11720 13948 17998 19921 18412Mn 0128 0197 0245 0312 0303 0294Na 1827 1940 1827 3187 6121 4371

Zn - 213857 nm more sensitive but interfered by Fe

Zn - 206200 nm - less sensitive but without interferences

Analytical wavelengths (nm)

Al - 396152 nm K - 766491 nm Rb - 780026 nm

As - 188980 nm Li - 670783 nm S - 181972 nm

B - 249772 nm Mg - 279553 nm Sb - 206834 nm

Ba - 455403 nm Mn - 257610 nm Si - 251611 nm

Ca - 396847 nm Na - 589592 nm Sr - 407771 nm

Cr - 267716 nm Ni - 231604 nm Ti - 334941 nm

Cu - 327395 nm P - 213618 nm V - 311837 nm

Fe - 238204 nm Pb - 220353 nm Zn ndash 206200 nm

Instrumental conditions

RF Frequency 40 MHz (free running air-cooled)

RF Power 12 kW

Gas (plasma auxiliary nebulizer) Argon

Plasma flow 150 lmin

Auxiliary flow 15 lmin

Nebulizer flow 110 lmin

Replicates 5

Replicate read time 5 s

Operating parameters for ICP-AES quantitative analysis

ICP-AES Analysis

Bruker Aurora M90 (90 degree ion mirror ion optics Collision Reaction Interface)110 diluted

mineralized olive oil solution

Tuning with a 5 microgl Be Mg Co In Ba Ce Ti Pb and Th solution for

sensitivity and resolution optimization and mass calibration

Tuning with a 5 microgl Be Mg Co In Ba Ce Ti Pb and Th solution for

sensitivity and resolution optimization and mass calibration

Check of the level of oxide ions by the CeO+Ce+ ratio lt 2

Check of the level of oxide ions by the CeO+Ce+ ratio lt 2

Monitoring of double charged ions by the signal 137Ba++137Ba+ lt 3

Monitoring of double charged ions by the signal 137Ba++137Ba+ lt 3

CheckCorrection of isobaric interferences examination of more isotopes of the same element(eg Rb85 Rb 87 Sr88Sr87 Nd142 Nd146 Nd144 Se77 Se78 Sn147 Sm148 Sm152 Gd157 Gd154 Er166 Er168 Yb170 Yb172) application of correction equations with respect to isotopes of other elements potentially interfering (eg Nd142 corrected by analyzing Ce140 Nd144 by Sm147 Sm152 by Gd157 Rb87 by Sr88 ) use of the Collision Reaction Interface ndash CRI (for As and Se)

CheckCorrection of isobaric interferences examination of more isotopes of the same element(eg Rb85 Rb 87 Sr88Sr87 Nd142 Nd146 Nd144 Se77 Se78 Sn147 Sm148 Sm152 Gd157 Gd154 Er166 Er168 Yb170 Yb172) application of correction equations with respect to isotopes of other elements potentially interfering (eg Nd142 corrected by analyzing Ce140 Nd144 by Sm147 Sm152 by Gd157 Rb87 by Sr88 ) use of the Collision Reaction Interface ndash CRI (for As and Se)

Working rangesbull005 divide 5 microgl - As Cd Ce Er Eu Gd La Mn Nd Pb Pr Rb Sb Sc Se Sm Sr Th V Y Ybbull01 divide 10 microgl - Co Cr Cu Mg Ni

Working rangesbull005 divide 5 microgl - As Cd Ce Er Eu Gd La Mn Nd Pb Pr Rb Sb Sc Se Sm Sr Th V Y Ybbull01 divide 10 microgl - Co Cr Cu Mg Ni

External calibration5 standard solutions + blankCurve Fit LinearWeighted Fit NoCorrelation coefficientsR gt 09999

Normal Sensitivity Mode (without CRI) High Sensitivity Mode As and Se ndash Normal mode with CRI

ICP-MS Analysis

• Slide 1
• Slide 2
• Slide 3
• Slide 4
• Slide 5
• Slide 6
• Slide 7
• Slide 8
• Slide 9
• Slide 10
• Slide 11
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• Slide 26
• Slide 27
• Slide 28
• Slide 29
• Slide 30
• Slide 31
• Slide 32
• Slide 33
• Slide 34
• Slide 35

Research in progresshellipResearch in progresshellip

Thank you for your attention

Thank you for your attention

research supported by

It will be possible to apply matrix modification procedures (eg solvent extraction ndash also ultrasound assisted - addition of organic solvents or emulsification) or to employ systems for direct oil sample introduction in torch (eg Flow Injection Analysis systems)

We are conducting experimental tests for evaluating the possibility to employ a Laser Ablation system or an ElectroThermal Vaporization system for direct sample introduction in ICP-AES and ICP-MS

ETV

LA

Future developmentsFuture developmentsFuture developmentsFuture developments

Determination of oil elemental profile sample pre-treatment

High PressureMicrowave Digestion

Milestone 1200 Mega

05 golive oil

Mineralized oil sample

(final V = 25 ml)

2 ml H2O2 + 6 ml HNO3

Different mixtures testedH2O2 30vv (1 divide 2 ml)+ HNO3 699vv (2 divide

6 ml)

Total dissoluti

on

high-purity water

(gt 18 MΩ)

time Power Pressure

1 min 250 WFree

pressure race

1 min 0 W

5 min 400 W

5 min 650 W

Vent = 5 min

TQ mineralized

olive oil solution

Varian Vista MPX(axial configuration

simultaneous 112 Mpixel CCD detector)

study of spectral interferencesstudy of spectral interferences

preliminary qualitative analysis72 elements

preliminary qualitative analysis72 elements

quantitative analysisquantitative analysis

Gas flows optimization based on signal-to-background ratio (SB)

Auxiliary flow (lmin)

Nebulizer flow(lmin)

10 15 09 10 11 12

SBMg 3296 11720 13948 17998 19921 18412Mn 0128 0197 0245 0312 0303 0294Na 1827 1940 1827 3187 6121 4371

Zn - 213857 nm more sensitive but interfered by Fe

Zn - 206200 nm - less sensitive but without interferences

Analytical wavelengths (nm)

Al - 396152 nm K - 766491 nm Rb - 780026 nm

As - 188980 nm Li - 670783 nm S - 181972 nm

B - 249772 nm Mg - 279553 nm Sb - 206834 nm

Ba - 455403 nm Mn - 257610 nm Si - 251611 nm

Ca - 396847 nm Na - 589592 nm Sr - 407771 nm

Cr - 267716 nm Ni - 231604 nm Ti - 334941 nm

Cu - 327395 nm P - 213618 nm V - 311837 nm

Fe - 238204 nm Pb - 220353 nm Zn ndash 206200 nm

Instrumental conditions

RF Frequency 40 MHz (free running air-cooled)

RF Power 12 kW

Gas (plasma auxiliary nebulizer) Argon

Plasma flow 150 lmin

Auxiliary flow 15 lmin

Nebulizer flow 110 lmin

Replicates 5

Replicate read time 5 s

Operating parameters for ICP-AES quantitative analysis

ICP-AES Analysis

Bruker Aurora M90 (90 degree ion mirror ion optics Collision Reaction Interface)110 diluted

mineralized olive oil solution

Tuning with a 5 microgl Be Mg Co In Ba Ce Ti Pb and Th solution for

sensitivity and resolution optimization and mass calibration

Tuning with a 5 microgl Be Mg Co In Ba Ce Ti Pb and Th solution for

sensitivity and resolution optimization and mass calibration

Check of the level of oxide ions by the CeO+Ce+ ratio lt 2

Check of the level of oxide ions by the CeO+Ce+ ratio lt 2

Monitoring of double charged ions by the signal 137Ba++137Ba+ lt 3

Monitoring of double charged ions by the signal 137Ba++137Ba+ lt 3

CheckCorrection of isobaric interferences examination of more isotopes of the same element(eg Rb85 Rb 87 Sr88Sr87 Nd142 Nd146 Nd144 Se77 Se78 Sn147 Sm148 Sm152 Gd157 Gd154 Er166 Er168 Yb170 Yb172) application of correction equations with respect to isotopes of other elements potentially interfering (eg Nd142 corrected by analyzing Ce140 Nd144 by Sm147 Sm152 by Gd157 Rb87 by Sr88 ) use of the Collision Reaction Interface ndash CRI (for As and Se)

CheckCorrection of isobaric interferences examination of more isotopes of the same element(eg Rb85 Rb 87 Sr88Sr87 Nd142 Nd146 Nd144 Se77 Se78 Sn147 Sm148 Sm152 Gd157 Gd154 Er166 Er168 Yb170 Yb172) application of correction equations with respect to isotopes of other elements potentially interfering (eg Nd142 corrected by analyzing Ce140 Nd144 by Sm147 Sm152 by Gd157 Rb87 by Sr88 ) use of the Collision Reaction Interface ndash CRI (for As and Se)

Working rangesbull005 divide 5 microgl - As Cd Ce Er Eu Gd La Mn Nd Pb Pr Rb Sb Sc Se Sm Sr Th V Y Ybbull01 divide 10 microgl - Co Cr Cu Mg Ni

Working rangesbull005 divide 5 microgl - As Cd Ce Er Eu Gd La Mn Nd Pb Pr Rb Sb Sc Se Sm Sr Th V Y Ybbull01 divide 10 microgl - Co Cr Cu Mg Ni

External calibration5 standard solutions + blankCurve Fit LinearWeighted Fit NoCorrelation coefficientsR gt 09999

Normal Sensitivity Mode (without CRI) High Sensitivity Mode As and Se ndash Normal mode with CRI

ICP-MS Analysis

• Slide 1
• Slide 2
• Slide 3
• Slide 4
• Slide 5
• Slide 6
• Slide 7
• Slide 8
• Slide 9
• Slide 10
• Slide 11
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• Slide 13
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• Slide 15
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• Slide 22
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• Slide 24
• Slide 25
• Slide 26
• Slide 27
• Slide 28
• Slide 29
• Slide 30
• Slide 31
• Slide 32
• Slide 33
• Slide 34
• Slide 35

It will be possible to apply matrix modification procedures (eg solvent extraction ndash also ultrasound assisted - addition of organic solvents or emulsification) or to employ systems for direct oil sample introduction in torch (eg Flow Injection Analysis systems)

We are conducting experimental tests for evaluating the possibility to employ a Laser Ablation system or an ElectroThermal Vaporization system for direct sample introduction in ICP-AES and ICP-MS

ETV

LA

Future developmentsFuture developmentsFuture developmentsFuture developments

Determination of oil elemental profile sample pre-treatment

High PressureMicrowave Digestion

Milestone 1200 Mega

05 golive oil

Mineralized oil sample

(final V = 25 ml)

2 ml H2O2 + 6 ml HNO3

Different mixtures testedH2O2 30vv (1 divide 2 ml)+ HNO3 699vv (2 divide

6 ml)

Total dissoluti

on

high-purity water

(gt 18 MΩ)

time Power Pressure

1 min 250 WFree

pressure race

1 min 0 W

5 min 400 W

5 min 650 W

Vent = 5 min

TQ mineralized

olive oil solution

Varian Vista MPX(axial configuration

simultaneous 112 Mpixel CCD detector)

study of spectral interferencesstudy of spectral interferences

preliminary qualitative analysis72 elements

preliminary qualitative analysis72 elements

quantitative analysisquantitative analysis

Gas flows optimization based on signal-to-background ratio (SB)

Auxiliary flow (lmin)

Nebulizer flow(lmin)

10 15 09 10 11 12

SBMg 3296 11720 13948 17998 19921 18412Mn 0128 0197 0245 0312 0303 0294Na 1827 1940 1827 3187 6121 4371

Zn - 213857 nm more sensitive but interfered by Fe

Zn - 206200 nm - less sensitive but without interferences

Analytical wavelengths (nm)

Al - 396152 nm K - 766491 nm Rb - 780026 nm

As - 188980 nm Li - 670783 nm S - 181972 nm

B - 249772 nm Mg - 279553 nm Sb - 206834 nm

Ba - 455403 nm Mn - 257610 nm Si - 251611 nm

Ca - 396847 nm Na - 589592 nm Sr - 407771 nm

Cr - 267716 nm Ni - 231604 nm Ti - 334941 nm

Cu - 327395 nm P - 213618 nm V - 311837 nm

Fe - 238204 nm Pb - 220353 nm Zn ndash 206200 nm

Instrumental conditions

RF Frequency 40 MHz (free running air-cooled)

RF Power 12 kW

Gas (plasma auxiliary nebulizer) Argon

Plasma flow 150 lmin

Auxiliary flow 15 lmin

Nebulizer flow 110 lmin

Replicates 5

Replicate read time 5 s

Operating parameters for ICP-AES quantitative analysis

ICP-AES Analysis

Bruker Aurora M90 (90 degree ion mirror ion optics Collision Reaction Interface)110 diluted

mineralized olive oil solution

Tuning with a 5 microgl Be Mg Co In Ba Ce Ti Pb and Th solution for

sensitivity and resolution optimization and mass calibration

Tuning with a 5 microgl Be Mg Co In Ba Ce Ti Pb and Th solution for

sensitivity and resolution optimization and mass calibration

Check of the level of oxide ions by the CeO+Ce+ ratio lt 2

Check of the level of oxide ions by the CeO+Ce+ ratio lt 2

Monitoring of double charged ions by the signal 137Ba++137Ba+ lt 3

Monitoring of double charged ions by the signal 137Ba++137Ba+ lt 3

CheckCorrection of isobaric interferences examination of more isotopes of the same element(eg Rb85 Rb 87 Sr88Sr87 Nd142 Nd146 Nd144 Se77 Se78 Sn147 Sm148 Sm152 Gd157 Gd154 Er166 Er168 Yb170 Yb172) application of correction equations with respect to isotopes of other elements potentially interfering (eg Nd142 corrected by analyzing Ce140 Nd144 by Sm147 Sm152 by Gd157 Rb87 by Sr88 ) use of the Collision Reaction Interface ndash CRI (for As and Se)

CheckCorrection of isobaric interferences examination of more isotopes of the same element(eg Rb85 Rb 87 Sr88Sr87 Nd142 Nd146 Nd144 Se77 Se78 Sn147 Sm148 Sm152 Gd157 Gd154 Er166 Er168 Yb170 Yb172) application of correction equations with respect to isotopes of other elements potentially interfering (eg Nd142 corrected by analyzing Ce140 Nd144 by Sm147 Sm152 by Gd157 Rb87 by Sr88 ) use of the Collision Reaction Interface ndash CRI (for As and Se)

Working rangesbull005 divide 5 microgl - As Cd Ce Er Eu Gd La Mn Nd Pb Pr Rb Sb Sc Se Sm Sr Th V Y Ybbull01 divide 10 microgl - Co Cr Cu Mg Ni

Working rangesbull005 divide 5 microgl - As Cd Ce Er Eu Gd La Mn Nd Pb Pr Rb Sb Sc Se Sm Sr Th V Y Ybbull01 divide 10 microgl - Co Cr Cu Mg Ni

External calibration5 standard solutions + blankCurve Fit LinearWeighted Fit NoCorrelation coefficientsR gt 09999

Normal Sensitivity Mode (without CRI) High Sensitivity Mode As and Se ndash Normal mode with CRI

ICP-MS Analysis

• Slide 1
• Slide 2
• Slide 3
• Slide 4
• Slide 5
• Slide 6
• Slide 7
• Slide 8
• Slide 9
• Slide 10
• Slide 11
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• Slide 26
• Slide 27
• Slide 28
• Slide 29
• Slide 30
• Slide 31
• Slide 32
• Slide 33
• Slide 34
• Slide 35

Determination of oil elemental profile sample pre-treatment

High PressureMicrowave Digestion

Milestone 1200 Mega

05 golive oil

Mineralized oil sample

(final V = 25 ml)

2 ml H2O2 + 6 ml HNO3

Different mixtures testedH2O2 30vv (1 divide 2 ml)+ HNO3 699vv (2 divide

6 ml)

Total dissoluti

on

high-purity water

(gt 18 MΩ)

time Power Pressure

1 min 250 WFree

pressure race

1 min 0 W

5 min 400 W

5 min 650 W

Vent = 5 min

TQ mineralized

olive oil solution

Varian Vista MPX(axial configuration

simultaneous 112 Mpixel CCD detector)

study of spectral interferencesstudy of spectral interferences

preliminary qualitative analysis72 elements

preliminary qualitative analysis72 elements

quantitative analysisquantitative analysis

Gas flows optimization based on signal-to-background ratio (SB)

Auxiliary flow (lmin)

Nebulizer flow(lmin)

10 15 09 10 11 12

SBMg 3296 11720 13948 17998 19921 18412Mn 0128 0197 0245 0312 0303 0294Na 1827 1940 1827 3187 6121 4371

Zn - 213857 nm more sensitive but interfered by Fe

Zn - 206200 nm - less sensitive but without interferences

Analytical wavelengths (nm)

Al - 396152 nm K - 766491 nm Rb - 780026 nm

As - 188980 nm Li - 670783 nm S - 181972 nm

B - 249772 nm Mg - 279553 nm Sb - 206834 nm

Ba - 455403 nm Mn - 257610 nm Si - 251611 nm

Ca - 396847 nm Na - 589592 nm Sr - 407771 nm

Cr - 267716 nm Ni - 231604 nm Ti - 334941 nm

Cu - 327395 nm P - 213618 nm V - 311837 nm

Fe - 238204 nm Pb - 220353 nm Zn ndash 206200 nm

Instrumental conditions

RF Frequency 40 MHz (free running air-cooled)

RF Power 12 kW

Gas (plasma auxiliary nebulizer) Argon

Plasma flow 150 lmin

Auxiliary flow 15 lmin

Nebulizer flow 110 lmin

Replicates 5

Replicate read time 5 s

Operating parameters for ICP-AES quantitative analysis

ICP-AES Analysis

Bruker Aurora M90 (90 degree ion mirror ion optics Collision Reaction Interface)110 diluted

mineralized olive oil solution

Tuning with a 5 microgl Be Mg Co In Ba Ce Ti Pb and Th solution for

sensitivity and resolution optimization and mass calibration

Tuning with a 5 microgl Be Mg Co In Ba Ce Ti Pb and Th solution for

sensitivity and resolution optimization and mass calibration

Check of the level of oxide ions by the CeO+Ce+ ratio lt 2

Check of the level of oxide ions by the CeO+Ce+ ratio lt 2

Monitoring of double charged ions by the signal 137Ba++137Ba+ lt 3

Monitoring of double charged ions by the signal 137Ba++137Ba+ lt 3

CheckCorrection of isobaric interferences examination of more isotopes of the same element(eg Rb85 Rb 87 Sr88Sr87 Nd142 Nd146 Nd144 Se77 Se78 Sn147 Sm148 Sm152 Gd157 Gd154 Er166 Er168 Yb170 Yb172) application of correction equations with respect to isotopes of other elements potentially interfering (eg Nd142 corrected by analyzing Ce140 Nd144 by Sm147 Sm152 by Gd157 Rb87 by Sr88 ) use of the Collision Reaction Interface ndash CRI (for As and Se)

CheckCorrection of isobaric interferences examination of more isotopes of the same element(eg Rb85 Rb 87 Sr88Sr87 Nd142 Nd146 Nd144 Se77 Se78 Sn147 Sm148 Sm152 Gd157 Gd154 Er166 Er168 Yb170 Yb172) application of correction equations with respect to isotopes of other elements potentially interfering (eg Nd142 corrected by analyzing Ce140 Nd144 by Sm147 Sm152 by Gd157 Rb87 by Sr88 ) use of the Collision Reaction Interface ndash CRI (for As and Se)

Working rangesbull005 divide 5 microgl - As Cd Ce Er Eu Gd La Mn Nd Pb Pr Rb Sb Sc Se Sm Sr Th V Y Ybbull01 divide 10 microgl - Co Cr Cu Mg Ni

Working rangesbull005 divide 5 microgl - As Cd Ce Er Eu Gd La Mn Nd Pb Pr Rb Sb Sc Se Sm Sr Th V Y Ybbull01 divide 10 microgl - Co Cr Cu Mg Ni

External calibration5 standard solutions + blankCurve Fit LinearWeighted Fit NoCorrelation coefficientsR gt 09999

Normal Sensitivity Mode (without CRI) High Sensitivity Mode As and Se ndash Normal mode with CRI

ICP-MS Analysis

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TQ mineralized

olive oil solution

Varian Vista MPX(axial configuration

simultaneous 112 Mpixel CCD detector)

study of spectral interferencesstudy of spectral interferences

preliminary qualitative analysis72 elements

preliminary qualitative analysis72 elements

quantitative analysisquantitative analysis

Gas flows optimization based on signal-to-background ratio (SB)

Auxiliary flow (lmin)

Nebulizer flow(lmin)

10 15 09 10 11 12

SBMg 3296 11720 13948 17998 19921 18412Mn 0128 0197 0245 0312 0303 0294Na 1827 1940 1827 3187 6121 4371

Zn - 213857 nm more sensitive but interfered by Fe

Zn - 206200 nm - less sensitive but without interferences

Analytical wavelengths (nm)

Al - 396152 nm K - 766491 nm Rb - 780026 nm

As - 188980 nm Li - 670783 nm S - 181972 nm

B - 249772 nm Mg - 279553 nm Sb - 206834 nm

Ba - 455403 nm Mn - 257610 nm Si - 251611 nm

Ca - 396847 nm Na - 589592 nm Sr - 407771 nm

Cr - 267716 nm Ni - 231604 nm Ti - 334941 nm

Cu - 327395 nm P - 213618 nm V - 311837 nm

Fe - 238204 nm Pb - 220353 nm Zn ndash 206200 nm

Instrumental conditions

RF Frequency 40 MHz (free running air-cooled)

RF Power 12 kW

Gas (plasma auxiliary nebulizer) Argon

Plasma flow 150 lmin

Auxiliary flow 15 lmin

Nebulizer flow 110 lmin

Replicates 5

Replicate read time 5 s

Operating parameters for ICP-AES quantitative analysis

ICP-AES Analysis

Bruker Aurora M90 (90 degree ion mirror ion optics Collision Reaction Interface)110 diluted

mineralized olive oil solution

Tuning with a 5 microgl Be Mg Co In Ba Ce Ti Pb and Th solution for

sensitivity and resolution optimization and mass calibration

Tuning with a 5 microgl Be Mg Co In Ba Ce Ti Pb and Th solution for

sensitivity and resolution optimization and mass calibration

Check of the level of oxide ions by the CeO+Ce+ ratio lt 2

Check of the level of oxide ions by the CeO+Ce+ ratio lt 2

Monitoring of double charged ions by the signal 137Ba++137Ba+ lt 3

Monitoring of double charged ions by the signal 137Ba++137Ba+ lt 3

CheckCorrection of isobaric interferences examination of more isotopes of the same element(eg Rb85 Rb 87 Sr88Sr87 Nd142 Nd146 Nd144 Se77 Se78 Sn147 Sm148 Sm152 Gd157 Gd154 Er166 Er168 Yb170 Yb172) application of correction equations with respect to isotopes of other elements potentially interfering (eg Nd142 corrected by analyzing Ce140 Nd144 by Sm147 Sm152 by Gd157 Rb87 by Sr88 ) use of the Collision Reaction Interface ndash CRI (for As and Se)

CheckCorrection of isobaric interferences examination of more isotopes of the same element(eg Rb85 Rb 87 Sr88Sr87 Nd142 Nd146 Nd144 Se77 Se78 Sn147 Sm148 Sm152 Gd157 Gd154 Er166 Er168 Yb170 Yb172) application of correction equations with respect to isotopes of other elements potentially interfering (eg Nd142 corrected by analyzing Ce140 Nd144 by Sm147 Sm152 by Gd157 Rb87 by Sr88 ) use of the Collision Reaction Interface ndash CRI (for As and Se)

Working rangesbull005 divide 5 microgl - As Cd Ce Er Eu Gd La Mn Nd Pb Pr Rb Sb Sc Se Sm Sr Th V Y Ybbull01 divide 10 microgl - Co Cr Cu Mg Ni

Working rangesbull005 divide 5 microgl - As Cd Ce Er Eu Gd La Mn Nd Pb Pr Rb Sb Sc Se Sm Sr Th V Y Ybbull01 divide 10 microgl - Co Cr Cu Mg Ni

External calibration5 standard solutions + blankCurve Fit LinearWeighted Fit NoCorrelation coefficientsR gt 09999

Normal Sensitivity Mode (without CRI) High Sensitivity Mode As and Se ndash Normal mode with CRI

ICP-MS Analysis

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Bruker Aurora M90 (90 degree ion mirror ion optics Collision Reaction Interface)110 diluted

mineralized olive oil solution

Tuning with a 5 microgl Be Mg Co In Ba Ce Ti Pb and Th solution for

sensitivity and resolution optimization and mass calibration

Tuning with a 5 microgl Be Mg Co In Ba Ce Ti Pb and Th solution for

sensitivity and resolution optimization and mass calibration

Check of the level of oxide ions by the CeO+Ce+ ratio lt 2

Check of the level of oxide ions by the CeO+Ce+ ratio lt 2

Monitoring of double charged ions by the signal 137Ba++137Ba+ lt 3

Monitoring of double charged ions by the signal 137Ba++137Ba+ lt 3

CheckCorrection of isobaric interferences examination of more isotopes of the same element(eg Rb85 Rb 87 Sr88Sr87 Nd142 Nd146 Nd144 Se77 Se78 Sn147 Sm148 Sm152 Gd157 Gd154 Er166 Er168 Yb170 Yb172) application of correction equations with respect to isotopes of other elements potentially interfering (eg Nd142 corrected by analyzing Ce140 Nd144 by Sm147 Sm152 by Gd157 Rb87 by Sr88 ) use of the Collision Reaction Interface ndash CRI (for As and Se)

CheckCorrection of isobaric interferences examination of more isotopes of the same element(eg Rb85 Rb 87 Sr88Sr87 Nd142 Nd146 Nd144 Se77 Se78 Sn147 Sm148 Sm152 Gd157 Gd154 Er166 Er168 Yb170 Yb172) application of correction equations with respect to isotopes of other elements potentially interfering (eg Nd142 corrected by analyzing Ce140 Nd144 by Sm147 Sm152 by Gd157 Rb87 by Sr88 ) use of the Collision Reaction Interface ndash CRI (for As and Se)

Working rangesbull005 divide 5 microgl - As Cd Ce Er Eu Gd La Mn Nd Pb Pr Rb Sb Sc Se Sm Sr Th V Y Ybbull01 divide 10 microgl - Co Cr Cu Mg Ni

Working rangesbull005 divide 5 microgl - As Cd Ce Er Eu Gd La Mn Nd Pb Pr Rb Sb Sc Se Sm Sr Th V Y Ybbull01 divide 10 microgl - Co Cr Cu Mg Ni

External calibration5 standard solutions + blankCurve Fit LinearWeighted Fit NoCorrelation coefficientsR gt 09999

Normal Sensitivity Mode (without CRI) High Sensitivity Mode As and Se ndash Normal mode with CRI

ICP-MS Analysis

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