application of green sample preparation techniques for the

Analytica Vietnam , 17-19.04.2013, Ho Chi Minh City

AApplicationpplication of green sampleof green sample preparation preparation techniques for the isolation, preconcentration techniques for the isolation, preconcentration

and gas chromatographic determination and gas chromatographic determination of organic environmental pollutantsof organic environmental pollutants

Marcinkowski Łukasz1, Spietelun Agata1, Kloskowski Adam1, Namieśnik Jacek2

1Department of Physical Chemistry, Chemical Faculty 2Department of Analytical Chemistry, Chemical Faculty

Gdańsk University of Technology, 80-233 Gdansk, 11/12 G. Narutowicza St., Poland

*[email protected]

1


accurately monitoring the state of the environmentand the processes taking place in it

determining an wide range of analytes, often presentin trace and ultratrace amounts in sample matriceswith complex or variable compositions

need to introduce to analytical practice newmethodologies and equipment in order to complywith the principles of sustainable developmentand green chemistry

FURTHERFURTHER CHALLENGES CHALLENGES OF ANALYTICAL CHEMISTRYOF ANALYTICAL CHEMISTRY

2

2003

1997

1996

1995

1993

1991

1987

Office of Pollution Prevention and Toxicslaunched a research grants program called Alternative Synthetic Pathways for Pollution Prevention

Paul Anastas coined the term GREEN CHEMISTRY

an annual award was established for achievements in the application of GREEN CHEMISTRY principles

IUPAC Working Party on Green Chemistryfounded

the GREEN CHEMISTRY INSTITUTE (EPA) came into being in the USA. It fosters contacts between governmental agencies and industrial corporations on the one hand, and university research centres on the other

the first international GREEN CHEMISTRY symposium took place

the first national conference devoted to GREEN CHEMISTRY took place in Poland – EkoChemTech’03

GREEN CHEMISTRYGREEN CHEMISTRY (SHORT(SHORT HISTORY)HISTORY)

Our Common Future, also known as the Brundtland Report, from the United Nations World Commission on Environment and Development (WCED) was published

Green Chemistry Program was inaugurated by the US EPA

Analytica Vietnam , 17-19.04.2013, Ho Chi Minh City3

GREEN CHEMISTRY

1. Prevent waste

2. Maximize atom economy

3. Less hazardouschemical syntheses

4. Safer chemicals andproducts

5. Safer solvents andreaction conditions

6. Increase energyefficiency

7. Use renewablefeedstocks

8. Avoid chemicalderivatives

9. Use catalysts

10. Design chemicalsand products to degardeafter use

12. Minimize potential for accidents11. Analyze in real time to

prevent pollution

PRINCIPLES of GREEN CHEMISTRY(P.T. Anastas, J. Warner, Green Chemistry.Theory and Practice,

Oxford University Press,New York, 1998, p. 30)

PRINCIPLES of GREEN CHEMICAL TECHNOLOGY(N. Winterton, Green Chem., 3 (2001) G73)

PRINCIPLES of GREEN CHEMICAL ENGINEERING(P.T. Anastas, J.B. Zimmerman, Environ. Sci.Technol., 37 (2003) 94A-101A.)

Analytica Vietnam , 17-19.04.2013, Ho Chi Minh City 4

GREEN CHEMISTRY

GREEN ANALYTICAL CHEMISTRY-GAC

‘The use of analytical chemistry techniques and methodologies that reduce or eliminate solvents, reagents, preservatives, and other

chemicals that are hazardous to human health or the environment and that also may enable faster and more energy efficient analyses

without compromising required performance criteria’

H. K. Lawrence, Green Analytical Methodology Curriculumhttp://www.chemistshelpingchemists.org/GreenAnalyticalMethodologyCurriculum.ppt#257,2,Curriculum

‘Green chemistry, is the invention, design and application of chemical products and processes to reduce or to eliminate the use and

generation of hazardous substances’

P. T. Anastas, J. C. Warner, Green Chemistry: Theory and Praktice. Oxford Science Publications, Oxford (1998)


THE COMPONENTS OF GREEN ANALYSIS


A. Gałuszka, Z.M. Migaszewski, J. Namieśnik Twelve principles of green analytical chemistry –SIGNIFICANCE of green analytical practices. Trends Anal. Chem. Submitted.

6

THE PRINCIPLES OF GAC EXPRESSED ASTHE MNEMONIC SIGNIFICANCE


A. Gałuszka, Z.M. Migaszewski, J. Namieśnik Twelve principles of green analytical chemistry –SIGNIFICANCE of green analytical practices. Trends Anal. Chem. Submitted.

— select direct analytical technique— integrate analytical processes and operations— generate as little waste as possible and treat it properly— never waste energy— implement automation and miniaturization of methods— favor reagents obtained from renewable source— increase safety for operator— carry out in-situ measurements— avoid derivatization— note that the sample number and size should be minimal— choose multi-analyte or multi-parameter metod— eliminate or replace toxic reagents

7


1974 Development of flow injection analysis - FIA

1974 Development of purge-and-trap technique - PT

1976 Development of solid phase extraction - SPE

1978 Development of cloud point extraction - CPE

1985 Development of microwave-assisted extraction - MAE Development of supercritical fluid extraction - SFE

1987 The concept of ecological chemistry (H. Malissa)The concept of sustainable development

1990 Development of solid-phase microextraction - SPMEDevelopment of micro total analysis system - µTAS

1993 Development of molecularly imprinted solid-phase extraction - MIMSPE

1995 The concept of environmentally friendly analytical chemistry (M. de la Guardia, J. Ruzicka)

1996 Development of presurized solvent extraction - PSE Development of liquid phase micro extraction - LPME Development of single drop microextration -SDME

1999 The concept of green chemistry (P.T. Anastas)The concept of clean analytical method ( M. de la Guardia)The concept of green analytical chemistry ( J. Namieśnik)

Development of stir bar sorptive extraction- SBSE

MILESTONES IN MILESTONES IN GREEN GREEN ANALYTICAL ANALYTICAL CHEMISTRYCHEMISTRY


NEW EXTRACTION MEDIA NEW EXTRACTION MEDIA GREEN SOLVENTSGREEN SOLVENTS

Parameter Supercritical CO2 Superheated H2OAnalyte solubility can be changed 10-100 times 50-1000000 times

Extractable analytes polar constituents non-polarconstituents

Easily extractable analytes non-polar constituents polar constituents

Analyte reactivity low low-average

Analyte preconcentration (after extraction) usually easy variable level of

difficulty

Selectivity of extraction of analytes of different polarity average good

Selectivity of extraction from samples with a given matrix

composition (e.g. soils)good poor

Range of analyte polarity(ε) 1-2 10-80


NEW EXTRACTION MEDIA NEW EXTRACTION MEDIA GREEN SOLVENTSGREEN SOLVENTS

IONIC LIQUIDS IONIC LIQUIDS –– SOLVENTS OF THE 21SOLVENTS OF THE 21STST CENTURY

• at room temperature these salts are liquids;

• dissolve organic and inorganic compounds;

• thermally stable;

• high viscosity;

• hydrofobic/hydrophilic;

• non-volatile (very low vapour pressure at 25°C);

• high electrical conductance

INTERESTING AND PROMISING INTERESTING AND PROMISING PROPERTIESPROPERTIES OF IONIC LIQUIDSOF IONIC LIQUIDS

THEORETICAL NUMBER OF COMBINATIONS CATION-ANION

IS EQUAL 1012

So far known is about 1500 IONIC LIQUIDS.

commercially available just 500.


SOLVENTSOLVENT--FREEFREE SAMPLE SAMPLE PREPARATION TECHNIQUESPREPARATION TECHNIQUES

preconcentration of the analytes to a level above the limit of detection of the measuring/monitoring instrument

isolating the analytes from the original sample matrix and/or matrix simplification

removal of interferents and elimination of sample constituents being strongly adsorbed in the chromatographic column and thus accelerating its consumption

Sample preparation - most critical step of the whole analytical protocoleNO SAMPLE PRETREATMENT BEFORE ANALYSIS NECESSARY

AN IDEAL SOLUTION BUTBUT only a limited number of such techniques!


Application of streamof inert gas as extractant

Supercritical Fluid Extraction

SOLVENT‐FREE SAMPLE PREPARATION TECHNIQUES

Static Headspace analysis (S-HS)Dynamic Headspace (D-HS)Cryotrapping (CT)

Solid phase extractiontechniques with thermal

desorption

Membrane extractiontechniques

Virtually no solventextraction techniques


SINGLE DROP MICROEXTRACTIONSINGLE DROP MICROEXTRACTION((SDMESDME))

High selectivityLow detection limitsSimple, fast, and easyMinimal sample preparationCan be automated with commercially available equipmentPossible application for trace water analysis

Ethylene glycol

ButylacetateDiisopropyl ether

Tolueneo -Xylene1-Octanol

n -Octaneiso-Octane

Cyclohexanen -Hexadecane

n -DecaneTetradecane

DI-SDME HS-SDMEn -Hexane n -Octane

EXTRACTING SOLVENTS FOR SDME

IL-SDMEBMIM PF 6

HMIM PF 6

OMIM PF6

HMIM NTf 2

G. Liu, P.K. Dasgupta, Anal. Chem. 68 (1996) 1817

Drop volume

1 – 8μL


CONTINOUS FLOW

LLLME

SDME SDME ModesModes ofof operationoperation

H.F. Wu, J.H. Yen, C.C. Chin, Anal. Chem., 78 (2006) 1707M. Ma, F.F. Cantwell, Anal. Chem.,

70 (1998), p. 3912

W. Liu, H.K. Lee, Anal. Chem., 72 (2000), 4462 L. Xu, C. Basheer, H.K. Lee. J. Chromatog. A, 1152 (2007), 184

T. Sikanen, S. Pedersen-Bjergaard, H. Jensen, R. Kostiainen, K. E. Rasmussen, T. Kotiaho,

Anal. Chim. Acta 658 (2010) 133

DROP-TO-DROP DMD-LPME


SOLIDIFICATION OF FLOATING ORGANIC SOLIDIFICATION OF FLOATING ORGANIC DROP MICROEXTRACTION (SFOD/SFOME) DROP MICROEXTRACTION (SFOD/SFOME)

Physical and chemical properties of solvents for SFOME:

• immiscible with water• low volatility• low density• able to extract analytes

2-Dodecanol

n-Hexadecane

Common used solvents in SFOMEOrganic solvent Melting point (oC)

1,10-Dichlorodecane

13-15

22-24

17-18

18

14-16

1-Undecanol

1-Dodecanol

M.R.K. Zanjani, Y. Yamini, S. Shariati, J.Å . Jönsson, Anal. Chim.Acta, 585 (2007) 286


Fig. D. Han, K. H. Row, Microchim. Acta,176 (2012) 1

HF-LPME may be accomplished in:•three-phase mode (a)•two-phase mode (b)

HOLLOW HOLLOW FFIBERIBER LIQUIDLIQUID--PHASEPHASEMICROEXTRACTION MICROEXTRACTION (HF(HF--LPME)LPME)

Inexpensive, simple, clean-upPossibility of automationCompatible with GC, HPLC, CEHigh versatility and selectivity Headspace/immersion modePossibility of n-situ derivatization

ADVANCES IN ADVANCES IN HFHF--LPMELPME TECHNIQUE:TECHNIQUE:

Hollow Fiber Membrane Liquid–Liquid–LiquidMicroextraction (HFM-LLLME)

dynamic-HF-LPME

Solvent Cooling Assisted Dynamic HF-LPME (SC-DHF-LPME)


ELECTROELECTRO MEMBRANE ISOLATION (EMI) MEMBRANE ISOLATION (EMI) ELECTRO MEMBRANE EXTRACTION (EME)ELECTRO MEMBRANE EXTRACTION (EME)

On chip - EME

M. D. Ramos Payán, H. Jensen, N. J. Petersen, S. H. Hansen, S. Pedersen-Bjergaard, Anal. Chim. Acta, 735 (2012) 46

S. Pedersen-Bjergaard, K.E. Rasmussen, J. Chromatogr., A 1109 (2006) 183.


DISPERSIVE DISPERSIVE LIQUDLIQUD--LIQUIDLIQUIDMICROEXTRACTION MICROEXTRACTION ((DLLDLLME)ME)

Fig. A. V. Herrera-Herrera, M. Asensio-Ramos, J. Hernández-Borges, M. Á. Rodríguez-Delgado, Trends Anal. Chem., 29 (2010) 728

Inexpensive, simple, fastEasy to operatePossibility of automation Enormous contact area between acceptor phase and sampleCompatible with GC, HPLC, CE, UV-vis spectrometryFast extraction kineticsHigh enrichment factor obtained

M. Rezaee, Y. Assadi, M.R.M. Hosseini, E. Aghaee, F. Ahmadi, S. Berijani, J. Chromatogr., A 1116 (2006) 1.


ADVANCES IN DLLME TECHNIQUEADVANCES IN DLLME TECHNIQUE

SOLVENT DEMULSIFICATION DLLME

NEW EXTRACTION SOLVENTS

SOLVENT TERMINATED- DLLME

EXTRACTION SOLVENT LIGHTER THAN WATER

IONIC LIQUID

SPECIAL HOME-MADEEXTRACTION DEVICES

DLLME BASED ON THE SOLIDIFICATION OF A FLOATING ORGANIC DROP

COLD- INDUCED AGGREGATION MICROEXTRACTION (CIAME)

IN SITU SOLVENT-FORMATION MICROEXTRACTION (ISFME)

TEMPERATURE-CONTROLLED IONIC LIQUIDEXHAUSTIVELY DLLME (TILDLME)

SEQUENTIAL INJECTION–DLLME

LOW-DENSITY SOLVENT-BASED SOLVENT DEMULSIFICATION-DLLME

SURFACTANT-ASSISTED DLLME

COACERVATES AND REVERSE MICELLES

ULTRASOUND ASSISTED DLLME

VORTEX-ASSISTED DLLME


Stir Membrane liquid–liquid microextraction(SM-LLME)

M. C. Alcudia-León, R. Lucena, S. Cárdenas, M. Valcárcel, Anal. Chem., 81 (2009) 8957

ROTATING LIQUID PHASE ROTATING LIQUID PHASE EXTRACTION DEVICESEXTRACTION DEVICES

Hollow Fiber Solid-Liquid Phase Microextraction (HF-SLPME)

Z. Es’haghi, M. A.-K. Khooni, T. Heidari, Spectrochim. Acta Part A, 79 (2011) 603

Solvent Bar Microextraction (SBME)

X. Jiang, H. K. Lee, Anal. Chem., 76 (2004) 5591

Dual Solvent Stir Bars Microextraction(DSSBME)

C. Yu, Q. Liu, L. Lan, B. Hu, J. Chromatogr. A, 1188 (2008) 124


ROTATING SOLID PHASE ROTATING SOLID PHASE EXTRACTION DEVICESEXTRACTION DEVICES

N.R. Neng, A.R.M. Silva, J.M.F. Nogueira, J.Chromatogr. A, 1217 (2010) 7303

Modes:•bar adsorptive μ- extraction (BaμE) •multi-spheres adsorptive μ-extraction (MSAμE)

Adsorptive μ-extraction (AμE)Stir cake sorptive extraction (SCSE)

Rotating disk sorbent extraction (RDSE)

Stir rod sorptive extraction (SRSE)

X. Huang, L. Chen, F Lin, D. Yuan, J. Sep. Sci., 34 (2011) 2145

P. Richter, C. Leiva, C. Choque, A. Giordano, B. Sepulveda, J. Chromatogr. A, 1216 (2009) 8598

Y. B. Luo, Q. Ma, Y. Q. Feng, J. Chromatogr. A, 1217 (2010) 3583.


STIR BAR SORTPIVE EXTRACTION STIR BAR SORTPIVE EXTRACTION (SBSE)(SBSE)

AdvancesAdvances inin SBSSBSEE techniquetechnique::

Application of poliurethane foams, PPESK, alkyl-diolsilica RAM, silica materials, molecularly imprinted coatings, monoliths and sol-gel technique to prepare of stir bar coatings

Double-phase stir bar coatings

Rapid, simple, solvent-freeSensitive and effective extractionCompatible with GC, HPLC, CEHeadspace and immersion modesHigh thermal and chemical stability of stir bar coatings

E. Baltussen, H. G. Janssen, P. Sandra, C. A. Cramers, J. High. Resolut. Chromatogr., 20 (1997) 385


MICRO MICRO SOLIDSOLID--PHASEPHASEEXTRACTION (EXTRACTION (µµSPE)SPE)

AdvancesAdvances inin ((µµSPE) SPE) techniquetechnique::

Application of mulberry paper bag, electrospun composite of polyaniline-nylon-6 (PANI-N6),electrospun composite of polypyrrole-polyamide (PP-PA) as sorbent sheet

Inexpensive, simple, clean-upConveniently applicableEasy to be manipulatedCompatible with GC, HPLCHeadspace and immersion modesSufficient sensitivityGood reproducibilityExcellent enrichment

C. Basheer, A. A. Alnedhary,B. S. M. Rao, S. Valliyaveettil, H. K. Lee, Anal. Chem., 78 (2006) 2853



APPLICATION OF NANOPARTICLES APPLICATION OF NANOPARTICLES IN NANOEXTRACTION TECHNIQUESIN NANOEXTRACTION TECHNIQUES

VARIANT I VARIANT II

Solid-phase nanoextraction(SPNE)H. Wang, A. D. Campiglia, Anal. Chem., 80 (2008) 8202

WATER SAMPLE MICRO‐PLANE GLASS WITH Au NPs

SHAKING AND CENTRIFUGATION

COLLECT PRECIPITATE

SOLVENT ADDITION

SHAKING AND CENTRIFUGATION

SUPERNATANT COLLECTION

HPLC LETRESS

H. Wang, A. D. Campiglia, Anal. Chem., 80 (2008) 8202Y. Zhu, S. Zhang, Y. Tang, M. Guo, C. Jin, T. Qi, J Solid State Electrochem, 14 (2010) 1609.

SOLID PHASE MICROEXTRACTION SOLID PHASE MICROEXTRACTION (SPME)(SPME)

1. Plunger2. Barrel3. Injection needle4. Inner needle5. Coated fused silica fiber

simplicity of operationshort extraction and desorption timesolvent-free operationsmall size (convenient for designing portable devices)possibility of full automationdirect linkup with a GCpossibility to in-situ and in-vivo samplingdirect-immerson and headspace mode

C. L. Arthur, J. Pawliszyn, Anal. Chem., 62 (1990) 2145


MILESTONES IN THE MILESTONES IN THE DEVELOPMENT OF SPME DEVELOPMENT OF SPME

HEADSPACE SPME (HS-SPME)

COOLED COATED FIBRE SPME (CCF-SPME)

IN-TUBE SPME

WIRE-IN-TUBE SPMEFIBRE-IN-TUBE SPME

MEMBRANE-SPME (M-SPME)


ADVANCES IN SPME TECHNIQUE

AUTOMATION

NEW EXTRACTION PHASE

NEW DEVICES AND MODIFICATIONS

IONIC LIQUIDS

CARBON NANOTUBES AND GRAPHEN

SILICA MICROSTRUCTURES

MEMBRANE-SPME

LIQUID-LIQUID-SOLIDMICROEXTRACTION

ELECTROSORPTION ENHANCED-SPME


COMMERCIAL SPME COMMERCIAL SPME FIBERSFIBERS

limited choicehigh costpoor selectivity for polar analytespossibility of competing of the matrixcompounds with the analytes for available adsorbent sitesneed to high temperatures to be used to desorb the less volatile compounds

degradation of the analytes promote catalytic breakdown of trapped analytes

ADSORPTIONADSORPTIONartefact formation incomplete desorptionstrong catalytic interactions of trapped analytes with adsorbents

ABSORTIONABSORTIONanalytes are retained by dissolutionmoderate desortion temperatures analyte decomposition can be ruled outnon-specific interactions between analyte and sorbent


LIQUIDLIQUID––LIQUIDLIQUID––SOLIDSOLIDMICROEXTRACTION (LLSME)MICROEXTRACTION (LLSME)

simpleexciting low-cost environment-friendly negligible organic solvent consumption enhanced efficiencyhigh selective and sensitive pretreatment

Y. Hu, Y. Wang, Y. Hu, G. Li, J. Chromatogr. A, 1216 (2009) 8304


ELECTROSORPTION ENHANCED SPME ELECTROSORPTION ENHANCED SPME ((EEEE--SPMESPME))

simple, fast, sensitivegood performance short adsorption timewide linear rangelow detection limithigh recoveries

X. Chai, Y. He, D. Ying, J. Jia, T. Sun, J. Chromatogr. A, 1165 (2007) 26

Q. Li, Y. Ding, D. Yuan, Talanta 85 (2011) 1148

Nanoparticle-coated WE electrodein EE-SPME mode is known as:

ELECTROCHEMICAL SOLID-PHASE NANOEXTRACTION

Y. Zhu, S. Zhang, Y. Tang, M. Guo, C. Jin, T. Qi, J. Solid State Electrochem, 14 (2010) 1609.


MEMBRANEMEMBRANE--SPMESPME ((MM--SPMESPME))

1) silica fiber2) coating of polyethylene glycol (PEG)3) coating of polydimethylsiloxane (PDMS)

Inner coating Outer coatingAbsorbent material PEG PDMSAverage thickness of coating 40-50μm 100-110μmLength of sorbent coating 1cm 1,2 cmThe role of sorbent coating very polar

retaining mediumhydrophobic,

nonpolar membrane

A. Kloskowski, M. Pilarczyk, J. Namieśnik, Anal. Chem., 81 (2009) 7363.


MM--SPME ADVANTAGESSPME ADVANTAGESlow cost of fiber preparation

high thermal stability (PDMS is stable up to 300oC)

short extraction and desorption time

lack of water sorption (due to the presence of hydrophobic membrane)

high affinity to polar analytes

At the extraction temperature PEG of low molecular weight behaves as an immobilised liquid (viscous liquid polymer)

Analytes are retained by dissolution in the sorbent layer

absorption nature of the retentionpartitioning mechanism of the extraction


A. Kloskowski, M. Pilarczyk, J. Namieśnik, Anal. Chem., 81 (2009) 7363

DeterminationDetermination ofof phenolsphenolsusingusing MM--SPMESPME andand GCGC

Compound Linearity range (µg/L) R2

LOD (µg/L)

M-SPME PA

4-Chloro-3-methylphenol 15-1500 0.9953 7 50

2-Chlorophenol 3-300 0.9936 43 530

2,4-Dichlorophenol 3-300 0.9987 15 120

2,4-Dimethylphenol 3-300 0.9921 9 110

2,4-Dinitrophenol 10-1000 0.9963 110 950

2-Methyl-4,6-dinitrophenol 15-1500 0.9898 81 680

2-Nitrophenol 3-300 0.9945 9 60

4-Nitrophenol 15-1500 0.9937 150 1800

Pentachlorophenol 15-1500 0.9914 83 740

2,4,6-Trichlorophenol 10-1000 0.9932 61 440


Compound

R2 LOD (mg/L) RSD (%)

M-SPME DVB/CAR/PDMS M-SPME DVB/CAR

/PDMS M-SPME DVB/CAR/PDMS

chlorobenzene 0.997 0.994 0.031 0.016 11 9p-xylene 0.992 0.986 0.022 0.015 9 6o-xylene 0.986 0.994 0.018 0.014 12 7

isopropylbenzene 0.994 0.995 0.015 0.018 12 8n-propylbenzene 0.998 0.997 0.013 0.017 14 102-chlorotoluene 0.997 0.993 0.016 0.019 8 64-chlorotoluene 0.995 0.995 0.017 0.018 10 6t-butylbenzene 0.997 0.985 0.011 0.021 12 8

sec-butylbenzene 0.987 0.992 0.011 0.021 11 81,3-dichlorobenzene 0.989 0.998 0.017 0.017 14 101,4-dichlorobenzene 0.994 0.987 0.017 0.023 13 71,2-dichlorobenzene 0.986 0.988 0.016 0.028 13 7

DeterminationDetermination ofof VOCsVOCsusingusing MM--SPMESPME andand GCGC


MM--SPMESPME conclusionconclusionpartitioning mechanism of the extraction, which is characterized by significantly higher linearity range when compared to commercial fibre

enabling highly polar sorbents to be used without the risk of dissolving in polar sample matrix

povides opportunity of application of quite new kinds of materials, which due to low melting temperatures or solubility in water have not been taken into consideration so far in this kind of applications

high extraction efficiency of phenols and VOCs obtainable with M-SPME fibres, comparable and better than the extraction efficiency using commercially available fibres

M-SPME combined with determination by GC may become a powerful, environmentally friendly tool for sampling, isolation and preconcentration of organic pollutants

• applicable on the sample preparation step prior to the finalquantitative determination of analytes on the ppb level


EVALUATING THE ENVIRONMENTAL EVALUATING THE ENVIRONMENTAL IIMPACT OF ANALYTICAL PROCEDURESMPACT OF ANALYTICAL PROCEDURES

TOOLS:

Life Cycle Assessment (LCA)1

Eco- Scale2

Eco-Compass3

1 Consoli, F., D. Allen, R. Weston, I. Boustead, J. Fava, W. Franklin, A. Jensen, N. de Oude, R. Parrish, R. Perriman, D. Postlethwaite, B. Quay, J. Séguin and B. Vigon., Guidelines for life cycleassessment: A Code of practice. SETAC, Brussels and Pensacola, 1993.

2 Aken K., L. Strekowski, L. Patiny, EcoScale, a semi-quantitative tool to select an organic preparation based on economical and ecological parameters, Beilstein J. Org. Chem. 2, 3, 2006.

3 Home Sustainability Assessment, http://www.ecocompass.com.au/


A new tool for evaluation of the greenness of analytical methodology

Eco-Scale = 100 – total penalty points

The result is ranked on the following scale:>75 – excellent green analysis>50 – acceptable green analysis<50 – inadequate green analysis

Penalty points are assigned for amount of reagents, hazards (physical, environmental,

health and occupational), energy used and waste generated in the analytical procedure

Gałuszka A., Konieczka P., Migaszewski Z.M., Namieśnik J. 2012. Analytical Eco-Scale for assessing the greenness of analytical procedures.

Trends in Analytical Chemistry 37, 61–72.

ANALYTICAL ANALYTICAL ECOECO--SCALESCALE


REAGENTSSubtotal PP Total PP

Amount<10 mL (g) 1

Amount PP×Hazard

PP

10-100 mL (g) 2>100 mL (g) 3

Hazard (physical, environmental, health)

None 0Less severe hazard 1More severe hazard 2

INSTRUMENTS

Energy

≤0.1 kWh per sample 0

≤1.5 kWh per sample 1

>1.5 kWh per sample 2

Occupational hazardAnalytical process hermetization 0

Emission of vapors and gases to the air 3

Waste

None 0

<1 mL (g) 1

1-10 mL (g) 3

>10 mL (g) 5

RecyclingDegradation PassivationNo treatment

0123

THE PENALTY POINTS (PPS) THE PENALTY POINTS (PPS) TO CALCULATE ANALYTICAL TO CALCULATE ANALYTICAL ECOECO--SCALESCALE


DDEPARTMENT OF ANALYTICAL EPARTMENT OF ANALYTICAL CHEMISTRYCHEMISTRY

CHEMICAL FACULTYCHEMICAL FACULTYGDANSK UNIVERSITY OF TECHNOLOGYGDANSK UNIVERSITY OF TECHNOLOGY

Department of Analytical Chemistry

This lecture can also be found on the homepageof the Department of Analytical Chemistry

http://www.pg.gda.pl/chem/Katedry/Analityczna/analit.html


EUROPEAN MASTER IN QUALITY EUROPEAN MASTER IN QUALITY IN ANALYTICAL LABORATORIESIN ANALYTICAL LABORATORIES-- EMQALEMQAL

http://eacea.ec.europa.eu/erasmus_mundus/Analytica Vietnam , 17-19.04.2013, Ho Chi Minh City 41

MODAS„Production and attestation of new types of reference

materials crucial for achieving European accreditation for polish industrial laboratories ‐

MODAS”

http://www.pg.gda.pl/chem/modas/


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43

MMEMBERS OF MY RESEARCH GROUPEMBERS OF MY RESEARCH GROUP


THANK YOU FOR YOUR ATTENTION!THANK YOU FOR YOUR ATTENTION!


application of green sample preparation techniques for the

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