discussion paper on the evaluation of distribution of ... · on the evaluation of distribution of...
TRANSCRIPT
Amadeo R. Fernández-AlbaCRL-FV
Beijing (CHINA)20-25/04/2009
Beijing (CHINA)20-25/04/2009
DISCUSSION PAPERON THE EVALUATION OF DISTRIBUTION
OF PESTICIDE RESIDUESAFTER PRIMARY PROCESS
IN CITRUS FRUIT, POME FRUIT, OILSEEDS AND WINE GRAPES
EU Community Reference Laboratory for PesticideResidues in Fruits and Vegetables
Amadeo R. Fernández-AlbaCRL-FV
Beijing (CHINA)20-25/04/2009
Beijing (CHINA)20-25/04/2009
OECD GUIDELINE FOR THE TESTING OF CHEMICALSMagnitude of the Pesticide Residues in Processed Commodities
OECD/OCDE508 Adopted:3 October 2008
PURPOSE
2. Studies on the magnitude of residues in processed commodities provide data on the transfer of residues to different processed commodities from the raw agricultural commodity (RAC). Studies on the magnitude of residues are conducted in order to quantify levels of residues in processed commodities and to provide the distribution of residues (active ingredient, and/or metabolites, degradation products) in various processed products resulting from the processing of a commodity. This information about dilution and concentration of residues and the estimation of processing factors (the ratio of residue levels in processed commodities to those in the raw agricultural commodity) is used to:
• conduct refined dietary exposure assessments with primary processed products to assess consumer safety; • provide results on residues in commodities that may be used as animal feedstuffs and thus to allow a more
realistic calculation of the dietary burden of livestock; • establish MRLs for processed commodities; and • monitor compliance with the RAC MRL.
8. The processing factor (Pf) that originates only from residues of the same single compound in the RAC is calculated as follows:
residue level in the RAC or commodity to be processed
residue level in processed commodityPf=
14. Important conclusions concerning the behaviour of the active ingredient and/or metabolites during processing can be drawn from the distribution coefficients for n-octanol/water, hydrolysis stability, heat stability and solubility behaviour. For example, when the log Pow is greater than three, it can be assumed that the residue will likely be concentrated in oil or solids like meal, whereas high water solubility indicates that residues may be expected in juices. For example: the extremely high potential concentration factors for citrus oil (Pf = 1000) and mint oil (Pf = 330) should be considered.
Amadeo R. Fernández-AlbaCRL-FV
Beijing (CHINA)20-25/04/2009
Beijing (CHINA)20-25/04/2009
OECD GUIDANCE DOCUMENT ON MAGNITUDEOF PESTICIDE RESIDUES IN PROCESSED COMMODITIES
ENV/JM/MONO(2008)2329 Jul 2008
The mean processing factor for tomato paste, 2.6, may be used for both monitoring (enforcement) and dietary exposure assessment considerations.
3.10.22Paste
-0.07Tomato (RAC)2
2.00.48Paste
-0.24Tomato (RAC)1
PfThiacloprid(mg/kg)CommodityStudy Number
Thiacloprid: Pkow = 1.26; water solubility= 185 mg/L
Amadeo R. Fernández-AlbaCRL-FV
Beijing (CHINA)20-25/04/2009
Beijing (CHINA)20-25/04/2009
Further Consideration of Processing as Related to the Establishment of MRLs for Processed Foods: Recommendations
on Principles and PracticesPrepared by the USA and the EC
1. Processing studies should be mandatory for a short list of commodities (about 16 at that time). Proposed MRLs for the relevant raw agricultural commodities may not advance to Step 8 without processing studies deemed acceptable by the JMPR.
2. CXLs or processing factors should be established for those processed commodities where a significant increase (>1.3 times) of residue of concern occurs from the RAC to the processed commodity. It should be decided in advance for which commodities and for which processing factors, they will be established
3. CXLs or processing factors should be established for processed commodities where a significant decrease in residue occurs from RAC to processed commodity and the processing factor must be considered in order to achieve a satisfactory dietary exposure assessment. It should be decided in advance for which commodities and for which processing factors they will be established
4. A limited number of generic default processing factors should be established for some predefined common processes, such as dehydration. These would be useful for risk assessment purposes.
1. Mandatory Processing StudiesThe need for a processing study is based on a consideration of the 5 factors above. A series of large industrial scale processes are listed, and studies are usually considered essential for these processes. These processes include the preparation of:
• fruit juice (and byproducts)• alcoholic beverages (such as fermentation, malting, brewing, distillation)• vegetable juices• oils• milling fractions• silage (livestock only)• sugar
Amadeo R. Fernández-AlbaCRL-FV
Beijing (CHINA)20-25/04/2009
Beijing (CHINA)20-25/04/2009
Commodities with Established Dehydration Factors
792.9%13%Chili pepper, dryVO 444 Peppers chili
1092.9%9%Sweet pepper, dry VO 445 Peppers Sweet
1485%6.1%Tomato, sun driedVO 448 Tomato
4.673%16%Fruit, dried FP 230 Pear
4.969%14%Fruit, driedFS 240 Apricot
4.068%17%Fruit, driedFP 226 Apple
3.570%20%PrunesFS 0014 Plums
4.386%20%HayGrass
4.785%18%Fruit, driedFB 0269 Grapes
3.474%22%Fruit, driedFT 0297 Figs
Theoretical processing factor
Dry matter in dried product
Dry matter content in RACProcessed productRaw agricultural commodity
Further Consideration of Processing as Related to the Establishment of MRLs for Processed Foods: Recommendations
on Principles and PracticesPrepared by the EC and the USA
Amadeo R. Fernández-AlbaCRL-FV
Beijing (CHINA)20-25/04/2009
Beijing (CHINA)20-25/04/2009
APPLE JUICE
Amadeo R. Fernández-AlbaCRL-FV
Beijing (CHINA)20-25/04/2009
Beijing (CHINA)20-25/04/2009
ORANGE JUICE
Amadeo R. Fernández-AlbaCRL-FV
Beijing (CHINA)20-25/04/2009
Beijing (CHINA)20-25/04/2009
GRA GRAPE WINE
Amadeo R. Fernández-AlbaCRL-FV
Beijing (CHINA)20-25/04/2009
Beijing (CHINA)20-25/04/2009
1000 g Orange1 mg pesticide1 mg/kg
670 g Wet Pomace (67%)0.96 mg pesticide (96%)1.43 mg/kg
330 g Juice (33%)0.03 mg pesticide (3%)0.09 mg/kg
250 g Peel (25%)0.81 mg pesticide (81%)3.24 mg/kg
420 g Pulp (42%)0.13 mg pesticide (13%)0.31 mg/kg
Thiabendazole Distribution
Amadeo R. Fernández-AlbaCRL-FV
Beijing (CHINA)20-25/04/2009
Beijing (CHINA)20-25/04/2009
1.430.96670Wet
Pomace
Juice
Orange
ThiabendazolepKow=2.4
Peel
Pulp
3.24
0.31
0.09
1
PesticideConcentration
(mg/kg)
0.8125081
0.1342013
96
0.033303
11000100
Pesticide Mass(mg)
Mass(g)
PesticideDistribution
%
Amadeo R. Fernández-AlbaCRL-FV
Beijing (CHINA)20-25/04/2009
Beijing (CHINA)20-25/04/2009
EXPERIMENTAL
Amadeo R. Fernández-AlbaCRL-FV
Beijing (CHINA)20-25/04/2009
Beijing (CHINA)20-25/04/2009
PESTICIDES USED
Amadeo R. Fernández-AlbaCRL-FV
Beijing (CHINA)20-25/04/2009
Beijing (CHINA)20-25/04/2009
Acetamiprid Azoxystrobin Carbaryl Carbendazim
Fenhexamid
Fenoxycarb
Ciprodinil
Dimethoate
Imidacloprid
ImazalilMyclobutanil
OmethoatePirimicarb
Pyrimethanil
Amadeo R. Fernández-AlbaCRL-FV
Beijing (CHINA)20-25/04/2009
Beijing (CHINA)20-25/04/2009
Tebufenozide Metalaxyl
Iprodione
Thiabendazol
ThiaclopridTriadimefon
Triadimenol
Endosulfan sulfate Difenoconazole
α-Cypermethrinβ-Cyfluthrin
α-Endosulfan
β-Endosulfan
Chlorpyrifos
Diflufenican
Amadeo R. Fernández-AlbaCRL-FV
Beijing (CHINA)20-25/04/2009
Beijing (CHINA)20-25/04/2009
MCPA
Methidathion
OxyfluorfenPenconazole
Phosmet Prochloraz
Procymidone
Terbuthylazine Thiophanate-methyl
Dimethomorph
Diuron
Fluquinconazole
Fluroxypyr Kresoxim-methyl
Malathion
Amadeo R. Fernández-AlbaCRL-FV
Beijing (CHINA)20-25/04/2009
Beijing (CHINA)20-25/04/2009
3,82Imazalil
4Ciprodynil
3,72Penconazole
3,4Kresoxim methyl
3,14Procymidone
2,7Dimethomorf
2,5Azoxystrobin
2,39Thiabendazol
1,85Carbaril
1,51Carbendazima
0,8Acetamiprid
0,7Dimethoate
0,57Imidacloprid
Log KowPesticide
Grapes
Amadeo R. Fernández-AlbaCRL-FV
Beijing (CHINA)20-25/04/2009
Beijing (CHINA)20-25/04/2009
Olives
6.6
5.9
4.9
4.79
4.74
4.70
4.47
4.2
3.21
2.95
2.85
2.75
2.2
-0.71
Log Kow
α-Cypermethrin
β-Cyfluthrin
Diflufenican
β-Endosulfan
α-Endosulfan
Chlorpyriphos
Oxyfluorfen
Difenoconazole
Terbuthylazine
Phosmet
Diuron
Malathion
Methidathion
MCPA
Pesticide
Amadeo R. Fernández-AlbaCRL-FV
Beijing (CHINA)20-25/04/2009
Beijing (CHINA)20-25/04/2009
3.08, 3.28Triadimenol3.0Iprodione
2.94Myclobutanil
3.51Fenhexamid3.24Fluquinconazole3.11Triadimefon
Apple and Orange
4.64.254.07
2.842.52.4
1.851.751.71.5
1.260.8
-0.740.7
Log Kow
ImazalilTebufenozideFenoxicarb
PyrimethanilAzoxystrobinThiabendazoleCarbarilMetalaxylPirimicarbCarbendazimThiaclopridAcetamipridOmethoateDimethoate
Pesticide
Amadeo R. Fernández-AlbaCRL-FV
Beijing (CHINA)20-25/04/2009
Beijing (CHINA)20-25/04/2009
Malathion
Methidathion Phosmet
Chlorpyrifos
1452.75Malathion1.404.70Chlorpyrifos
2002.20Methidathion252.95Phosmet
Sw (mg/L)pKowPesticide
Olives
Amadeo R. Fernández-AlbaCRL-FV
Beijing (CHINA)20-25/04/2009
Beijing (CHINA)20-25/04/2009
134Ciprodinil
Sw (mg/L)Log KowPesticida238000.7Dimetoato
Sw (mg/L)Log KowPesticida
6100.57Imidacloprid
Sw (mg/L)Log KowPesticida
Amadeo R. Fernández-AlbaCRL-FV
Beijing (CHINA)20-25/04/2009
Beijing (CHINA)20-25/04/2009
0.5Included0.21550cc/hl (25% p/v)Triadimenol0.5Not included0.21550cc/hl (25% p/v)Triadimefon3Included0.3140.025-0.03% (48% p/v)Thiacloprid2Included5Not applicable0.15-0.2% (60% p/v)Thiabendazol2Not included1Not applicable0.075% (24% p/v)Tebunofenozide8Included5280.75-1 l/haPyrimethanil50Included270.1% (50% p/p)Pirimicarb
Not included0.02Omethoate6Not included0.5280.04-0.05% (12.5% p/v)Myclobutanil
Not included1Metalaxil75Included5210.15-0.23% (50%p/v)Iprodione4Included230125 cc/hl (34% p/v)Imazalil15Not included1210.2-0.3% (25% p/p)Fenoxycarb
Included0.05FenhexamidIncluded0.02Dimethoate
3Included0.21560g/hl (50% p/v)Carbendazim1.7Not included0.057100-200g/hl (85% p/v)Carbaryl
Included0.05Azoxystrobin7Included0.1 1425-35% (20% p/p)Acetamiprid
Dose in fruit(mg/kg)
estimation
Status underDirective
91/414/EEC
MRL (mg/kg)Reg. (EC)
No 396/2005
ElapsingTime (days)
RecommendedDose
Apple
Amadeo R. Fernández-AlbaCRL-FV
Beijing (CHINA)20-25/04/2009
Beijing (CHINA)20-25/04/2009
1016 g
332 g (33%) 675 g (67%)
JuiceJuice processingprocessingImazalilImazalil
ThiophanateThiophanate methylmethylThiabendazoleThiabendazole
ProchlorazProchloraz
Solid Residue
Amadeo R. Fernández-AlbaCRL-FV
Beijing (CHINA)20-25/04/2009
Beijing (CHINA)20-25/04/2009
1630 g
389 g (24%) 1241 g (76%)
PostharvestPostharvest treatmenttreatmentImazalilImazalil
ThiophanateThiophanate methylmethylThiabendazolThiabendazol
ProchlorazProchlorazaprox.1 aprox.1 ppmppm
Amadeo R. Fernández-AlbaCRL-FV
Beijing (CHINA)20-25/04/2009
Beijing (CHINA)20-25/04/2009
Grape
IntroductionIntroduction•• Wine Wine processprocess
Destemmer/crusher Crushed
Stems
80 mg/L SO20.5 L fermented must
Maceration (Fermentation)
10 days
Pressing
Grape Pomace
Must Fermentation10 days
Sediment
Wine
Amadeo R. Fernández-AlbaCRL-FV
Beijing (CHINA)20-25/04/2009
Beijing (CHINA)20-25/04/2009
Wine
BentoniteGelatine
LeesClarifiedWine
5 L
IntroductionIntroduction•• Wine Wine processprocess
Amadeo R. Fernández-AlbaCRL-FV
Beijing (CHINA)20-25/04/2009
Beijing (CHINA)20-25/04/2009Grape
Crushed
Pressing
Grape pomace
Wine
Must
Sediment
Clarified wine
80 mg/L SO2
0.5 L fermented must
Fermentartion10 days
Fermentation10 days
Bentonite and gelatin
Stems
Lees
Crushed
Crushedafter fermentation
Grape pomace
Must
Sediment
Wine
Lees
Clarified wine
Grape
5 replicates and a blank
3 analysis of each
IntroductionIntroduction•• Wine Wine processprocess
Amadeo R. Fernández-AlbaCRL-FV
Beijing (CHINA)20-25/04/2009
Beijing (CHINA)20-25/04/2009
•• PesticidasPesticidasAzoxystrobin
Carbendazima
Ciprodynil
Dimethomorf
Imazalil
Kresoxim methyl
Penconazole
Procymidone
Thiabendazol
Acetamiprid
Carbaril
Dimethoate
Imidacloprid
Insecticidas
Fungicidas
IntroducciIntroduccióónn
Amadeo R. Fernández-AlbaCRL-FV
Beijing (CHINA)20-25/04/2009
Beijing (CHINA)20-25/04/2009
Mass balance
Grape Crushed
Grape pomace
Wine
Must
Sediment
150 kg 105 kg
12 L
4 L
16 L
5 kg
21 kg
21 kg
21 kg
21 kg
21 kg
IntroductionIntroduction•• Wine Wine processprocess
Amadeo R. Fernández-AlbaCRL-FV
Beijing (CHINA)20-25/04/2009
Beijing (CHINA)20-25/04/2009
Olive Paste100mL of water are
added
30 min. stirringCentrifuge it for 1 min
Olive Pomace
Gravity decantation
15 min. centrifuge at 3500rpm
SupernatantOlive Oil
Olive Oil Process
The rest is the Alpechin
Amadeo R. Fernández-AlbaCRL-FV
Beijing (CHINA)20-25/04/2009
Beijing (CHINA)20-25/04/2009
Yields obtainedVolume obtained (mL) x densty (g/mL)
% of Juice(Oil/Wine) =Initial Weight (g)
Pomace (30%)Pomace (50%)
Peel(12%-25%) Pulp(30%-42%)
Pomace (65-70%)
%
35-63%Orange
40-50%Apple55-70%Wine
15-20%Olive oil% JuiceRAC
Amadeo R. Fernández-AlbaCRL-FV
Beijing (CHINA)20-25/04/2009
Beijing (CHINA)20-25/04/2009
0%
20%
40%
60%
80%
100%
AcetamipridAzo
xystr
obinCarbaryl
CarbendazimDim
ethoateFe
nhexamid
Fenoxy
carb
Fluquinconazo
leIm
azalil
IprodioneMetalaxil
Myclobutanil
OmethoatePir
imicarb
Tebun
ofenozide
Thiabendazo
lTh
iaclopridTria
dimefon
Triadim
enol
%
Apple Apple Pomace JUICE
•• PesticidePesticide distributiondistribution %%
ResultsResults onon ApplesApples
Amadeo R. Fernández-AlbaCRL-FV
Beijing (CHINA)20-25/04/2009
Beijing (CHINA)20-25/04/2009
ResultsResults•• Real Real samplessamples analisysanalisys
0102030405060708090
100
Imazalil-Doncella Thiabendazole-Delicious
Thiabendazole-GrannySmith
AppleSolid residueJuice
Amadeo R. Fernández-AlbaCRL-FV
Beijing (CHINA)20-25/04/2009
Beijing (CHINA)20-25/04/2009
Pesticides in Pome Fruit Juicing
0
20
40
60
80
100
120
-1 0 1 2 3 4 5pKow
Pest
icid
e %
in P
omac
eApple Juicing
Amadeo R. Fernández-AlbaCRL-FV
Beijing (CHINA)20-25/04/2009
Beijing (CHINA)20-25/04/2009
Pesticides in Pome Fruit Juicing
0
20
40
60
80
100
120
-1 0 1 2 3 4 5pKow
Pest
icid
e %
in P
omac
eApple Juicing
Omethoate
Dimethoate
Acetamiprid
Thiacloprid
Carbendazim
MetalaxylCarbaryl
PirimicarbIprodione
TriadimefonTriadimenol
Imazalil
Fenoxycarb
Tebufenozide
Thia
bend
azol
Azo
xyst
robi
n
Myc
lobu
tani
l
Fluq
uinc
onaz
ole
Fenh
exam
id
Amadeo R. Fernández-AlbaCRL-FV
Beijing (CHINA)20-25/04/2009
Beijing (CHINA)20-25/04/2009
Pesticides in Pome Fruit Juicing
0
5
10
15
20
25
30
35
-1 0 1 2 3 4 5pKow
Pest
icid
e%
in J
uice
Apple Juicing
Omethoate Dimethoate
Acetamiprid
Thiacloprid
Carbendazim
Metalaxyl
Carbaryl
Pirimicarb
Thiabendazol
Azoxystrobin
Iprodione
Triadimefon
Myclobutanil
Fluq
uinc
onaz
ole
Fenh
exam
id
Imazalil
Fenoxycarb
Tebufenozide
Triadimenol
Amadeo R. Fernández-AlbaCRL-FV
Beijing (CHINA)20-25/04/2009
Beijing (CHINA)20-25/04/2009
•• PesticidePesticide distributiondistribution--concentrationconcentrationResultsResults
0
100
200
300
400
500
600
700μg/K
Ace
tam
iprid
Azo
xyst
robi
n
Car
bary
l
Car
bend
azim
Dim
etho
ate
Fenh
exam
id
Feno
xyca
rb
Fluq
uinc
onaz
ole
Imaz
alil
Ipro
dion
e
Met
alax
il
Myc
lobu
tani
l
Om
etho
ate
Piri
mic
arb
Tebu
nofe
nozi
de
Thia
bend
azol
Thia
clop
rid
Tria
dim
efon
Tria
dim
enol
Apple Juice Pomace
Amadeo R. Fernández-AlbaCRL-FV
Beijing (CHINA)20-25/04/2009
Beijing (CHINA)20-25/04/2009
8400 mg/L1.75Metalaxil2700 mg/L1.70Pirimicarb
8 mg/L1.50Carbendazim
184 mg/L1.26ThiaclopridWater solubilityLog KowPesticide
Amadeo R. Fernández-AlbaCRL-FV
Beijing (CHINA)20-25/04/2009
Beijing (CHINA)20-25/04/2009
•• PesticidePesticide distributiondistribution
ResultsResults onon OrangesOranges JuiceJuice
0102030405060708090
100
Imazalil
Thiabendazole
Tiofanato metil
CarbendazimaProchloraz
Orange Solid residueJuice
Amadeo R. Fernández-AlbaCRL-FV
Beijing (CHINA)20-25/04/2009
Beijing (CHINA)20-25/04/2009
Pesticides in Orange Juicing
50
60
70
80
90
100
0 1 2 3 4 5
pKow
Pest
icid
e %
in P
omac
e
Carbendazim
Thiabendazol Imazalil
ProchlorazThiophanate methyl
Amadeo R. Fernández-AlbaCRL-FV
Beijing (CHINA)20-25/04/2009
Beijing (CHINA)20-25/04/2009
Pesticides in Orange Juicing
0
1
2
3
4
5
0 1 2 3 4 5
pKow
Pest
icid
e %
in J
uice
Carbendazim
Thiophanate methyl
Thiabendazol
Imazalil
Prochloraz
Amadeo R. Fernández-AlbaCRL-FV
Beijing (CHINA)20-25/04/2009
Beijing (CHINA)20-25/04/2009
Orange Orange -- ConcentrationConcentration ((μμgg//kgkg))
0
500
1000
1500
2000
2500
3000
Orange (ppb) Pulp (ppb) Skin (ppb)
Imazalil
3 hours
24 hours
4 days
7 days
0
500
1000
1500
2000
2500
Orange (ppb) Pulp (ppb) Skin (ppb)
Thiabendazole
3 hours
24 hours
4 days
7 days
0
1000
2000
3000
4000
Orange (ppb) Pulp (ppb) Skin (ppb)
Prochloraz
3 hours24 hours4 days7 days
Amadeo R. Fernández-AlbaCRL-FV
Beijing (CHINA)20-25/04/2009
Beijing (CHINA)20-25/04/2009
ResultsResults
Orange Orange -- ConcentrationConcentration ((μμgg//kgkg))
0
200
400
600
800
Orange (ppb) Pulp (ppb) Skin (ppb)
Thiophanate methyl
3 hours24 hours4 days7 days
0
100
200
300
400
Orange (ppb) Pulp (ppb) Skin (ppb)
Carbendazim
3 hours24 hours4 days7 days
Amadeo R. Fernández-AlbaCRL-FV
Beijing (CHINA)20-25/04/2009
Beijing (CHINA)20-25/04/2009
•• Real Real samplessamples analisysanalisys
373510955Imazalil
-189Carbendazim
Pomace(µg/kg)
Peel(µg/kg)
Orange(µg/kg)Pesticide
ResultsResults
Amadeo R. Fernández-AlbaCRL-FV
Beijing (CHINA)20-25/04/2009
Beijing (CHINA)20-25/04/2009
ResultsResults onon WineWine•• DistributionDistribution of of pesticidespesticides (% (% mgmg))
0
20
40
60
80
100
120
Acetam
iprid
Azoxy
strob
inCarba
rilCarbe
ndazim
Ciprodyn
ilDim
ethoa
teDim
ethom
orfIm
azalil
Imidac
loprid
Kresox
im m
ethyl
Penco
nazo
leProc
ymido
neThia
benda
zole
grapeswinegrape pomace
Amadeo R. Fernández-AlbaCRL-FV
Beijing (CHINA)20-25/04/2009
Beijing (CHINA)20-25/04/2009
ResultsResults
•• DistributionDistribution of of pesticidespesticides ((mgmg))
0102030405060708090
Ace
tam
iprid
Azo
xyst
robi
n
Car
baril
Car
bend
azim
Cip
rody
nil
Dim
etho
ate
Dim
etho
mor
f
Imaz
alil
Imid
aclo
prid
Kre
soxi
mm
ethy
l
Pen
cona
zole
Pro
cym
idon
e
Thia
bend
azol
e
grapeswine
Amadeo R. Fernández-AlbaCRL-FV
Beijing (CHINA)20-25/04/2009
Beijing (CHINA)20-25/04/2009
ResultsResults
•• DistributionDistribution of of pesticidespesticides ((mgmg))
0102030405060708090
Ace
tam
iprid
Azo
xyst
robi
n
Car
baril
Car
bend
azim
Cip
rody
nil
Dim
etho
ate
Dim
etho
mor
f
Imaz
alil
Imid
aclo
prid
Kre
soxi
mm
ethy
lP
enco
nazo
le
Pro
cym
idon
e
Thia
bend
azol
e
grapesgrapes pomace
Amadeo R. Fernández-AlbaCRL-FV
Beijing (CHINA)20-25/04/2009
Beijing (CHINA)20-25/04/2009
Grape Pomace
0
10
20
30
40
50
60
70
80
0 0,5 1 1,5 2 2,5 3 3,5 4 4,5
pKow
% P
estic
ide
Amadeo R. Fernández-AlbaCRL-FV
Beijing (CHINA)20-25/04/2009
Beijing (CHINA)20-25/04/2009
Grape Pomace
Imidacloprid
DimethoateAcetamiprid
Carbaril Imazalil
Carbendazim
Thiabendazole
Azoxystrobin
Dimethomorf
Procymidone
Kresoxim methyl
Penconazole
Ciprodynil
0
10
20
30
40
50
60
70
80
0 0,5 1 1,5 2 2,5 3 3,5 4 4,5
pKow
% P
estic
ide
Losses in the Crushed Process
Losses in the Maceration Process
Amadeo R. Fernández-AlbaCRL-FV
Beijing (CHINA)20-25/04/2009
Beijing (CHINA)20-25/04/2009
Wine
0
10
20
30
40
50
60
0 0,5 1 1,5 2 2,5 3 3,5 4 4,5
pKow
% P
estic
ide
Amadeo R. Fernández-AlbaCRL-FV
Beijing (CHINA)20-25/04/2009
Beijing (CHINA)20-25/04/2009
Wine
Dimethoate
Acetamiprid
Carbaril
ImidaclopridCarbendazim
Thiabendazole
Azoxystrobin
Dimethomorf
Procymidone
Kresoxim methyl
PenconazoleImazalil
Ciprodynil0
10
20
30
40
50
60
0 0,5 1 1,5 2 2,5 3 3,5 4 4,5
pKow
% P
estic
ide
Amadeo R. Fernández-AlbaCRL-FV
Beijing (CHINA)20-25/04/2009
Beijing (CHINA)20-25/04/2009
ResultsResults
•• DistributionDistribution of of pesticidespesticides ((μμgg//KgKg))
0
500
1000
1500
2000
2500
3000A
ceta
mip
rid
Azo
xyst
robi
n
Car
baril
Car
bend
azim
a
Cip
rody
nil
Dim
etho
ate
Dim
etho
mor
f
Imaz
alil
Imid
aclo
prid
Kre
soxi
mm
ethy
l
Pen
cona
zole
Pro
cym
idon
e
Thia
bend
azol
GrapesWine
Amadeo R. Fernández-AlbaCRL-FV
Beijing (CHINA)20-25/04/2009
Beijing (CHINA)20-25/04/2009
ResultsResults
•• DistributionDistribution of of pesticidespesticides ((μμgg//KgKg))
0
500
1000
1500
2000
2500
3000
Acet
amip
rid
Azox
ystro
bin
Car
baril
Car
bend
azim
Cip
rody
nil
Dim
etho
ate
Dim
etho
mor
f
Imaz
alil
Imid
aclo
prid
Kres
oxim
met
hyl
Penc
onaz
ole
Proc
ymid
one
Thia
bend
azol
e
grapesgrape pomace
Amadeo R. Fernández-AlbaCRL-FV
Beijing (CHINA)20-25/04/2009
Beijing (CHINA)20-25/04/2009
Pesticide % in Olive Oil
0
10
20
30
40
50
60
70
-2,0
00
-1,0
00
0,00
0
1,00
0
2,00
0
3,00
0
4,00
0
5,00
0
6,00
0
7,00
0
pKow
Pest
icid
e %
Partially removed to the water
MCPA
PhosmetMalathion
Diuron Chlorpyrifos
alfa-EndosulfanTerbuthylazine
DifenoconazoleDiflufenican
beta-EndosulfanOxyfluorfen
sulfate-Endosulfan
beta-Cyfluthrin
alfa-Cypermethrin
Results on Olive Oil
Amadeo R. Fernández-AlbaCRL-FV
Beijing (CHINA)20-25/04/2009
Beijing (CHINA)20-25/04/2009
273.9MCPA145Malation36.4Diuron25Phosmet8.5Terbuthylazine15Difenoconazole
>0.33sulfo-Endosulfan0.116Oxyfluorfen
1.4Chlorpyrifos0.32alfa-Endosulfan0.33beta-Endosulfan0.05Diflufenicam
0.0012beta-Cyfluthrin0.004alfa-Cypermethrin
SolubilityPesticide
Amadeo R. Fernández-AlbaCRL-FV
Beijing (CHINA)20-25/04/2009
Beijing (CHINA)20-25/04/2009
Pesticide % in Olive Pomace
05
101520253035404550
-2,0
00
-1,0
00
0,00
0
1,00
0
2,00
0
3,00
0
4,00
0
5,00
0
6,00
0
7,00
0
pKow
Pest
icid
e %
Removed to the water
MCPAPhosmet
Malathion Diuron
Chlorpyrifosalfa-EndosulfanTerbuthylazine
Difenoconazole
Diflufenicanbeta-EndosulfanOxyfluorfen
sulfate-Endosulfan
beta-Cyfluthrin
alfa-Cypermethrin
Amadeo R. Fernández-AlbaCRL-FV
Beijing (CHINA)20-25/04/2009
Beijing (CHINA)20-25/04/2009
Olive Oil Concentration
0,00
0,50
1,00
1,50
2,00
2,50
alfa
-Cyp
erm
ethr
in
beta
-Cyf
luth
rin
Difl
ufen
ican
beta
-End
osul
fan
alfa
-End
osul
fan
Chl
orpy
rifo
s
Oxy
fluor
fen
sulfa
te-E
ndos
ulfa
n
Dife
noco
nazo
le
Terb
uthy
lazi
ne
Phos
met
Diu
ron
Mal
athi
on
MC
PA
mg/
Kg
Paste Olive Pomace Olive Oil
Amadeo R. Fernández-AlbaCRL-FV
Beijing (CHINA)20-25/04/2009
Beijing (CHINA)20-25/04/2009
Pesticide % * 5,5
0
50
100
150
200
250
300
350
400
-2,0
00
-1,0
00
0,00
0
1,00
0
2,00
0
3,00
0
4,00
0
5,00
0
6,00
0
7,00
0
pKow
Pest
icid
e %
130MCPA
PhosmetMalathion
Diuron Chlorpyrifos
alfa-EndosulfanTerbuthylazine
DifenoconazoleDiflufenican
beta-EndosulfanOxyfluorfen
sulfate-Endosulfan
beta-Cyfluthrin
alfa-Cypermethrin
Amadeo R. Fernández-AlbaCRL-FV
Beijing (CHINA)20-25/04/2009
Beijing (CHINA)20-25/04/2009
Pesticides in Soya
FungicidesInsecticides
PropiconazolZetametrinaMalathion
TetraconazolTriflumuronLufenuron
EpoxiconazolTefubonizideFlufenuxuron
CiproconazolImidaclopridFipronil
AzoxystrbinTiodicarbEndosulfan
IprodioneThiametoxamDiflubenzuron
TiodicarbTeflubenzuronDiazinon
FludioxinilSpinosadDeltametrina
FlutriafolPropenofosClorpirifosmetil
TebuconazolDifeconazolPirimifos metilClorpirifos
PyraclostrobinCarboxinNovaluronCialotrina
MyclobutanilMetalaxilMetxiofenocideCipermetrina
Kresoxim metilCarbendazimMetomilCartap
FlusilazolCaptanMetiocarbAlfametrina
Amadeo R. Fernández-AlbaCRL-FV
Beijing (CHINA)20-25/04/2009
Beijing (CHINA)20-25/04/2009
- The factors affecting the concentration or dilution of pesticide residues in the PPF are various depending on; (i) pesticide (ii) process applied, (ii) commodity and (iv) degradation processes involved.
- In the apple and orange juicing processes studied a dilution was the general effect. It means PF lower than 1. In general PF of 20-30% are common but lower values were also detected (in especial in the case of orange juice).
- For wine production, with yields of around 70%, the PF are in general close to 0.5. Higher values up to 1 are obtained with pesticideswith low Kow and high water solubility. Only in a few cases, fermentation processes have a significant effect in pesticide degradation.
-The low yield obtained for olive oil production lead to an important concentration of the pesticide residues with PF from 2 to almost 6.
-An acceptable linear trend of the Log Kow versus pesticide distributionis noticed. It can be used as a rough estimation of the residue distribution. That behavior could be used for risk assessment purposes.
Amadeo R. Fernández-AlbaCRL-FV
Beijing (CHINA)20-25/04/2009
Beijing (CHINA)20-25/04/2009
-Further evaluations should be considered for setting MRLson processed commodities in specific cases.
-Furthermore studies on the most frequent transformation productsare needed in setting those MRLs.