DISCUSSION PAPER ON THE EVALUATION OF DISTRIBUTION OF ... · ON THE EVALUATION OF DISTRIBUTION OF PESTICIDE RESIDUES AFTER PRIMARY PROCESS IN CITRUS FRUIT, POME FRUIT, OILSEEDS AND

Amadeo R. Fernández-AlbaCRL-FV

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




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.




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




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




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




APPLE JUICE




ORANGE JUICE




GRA GRAPE WINE




OLIVE OIL




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




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

%




EXPERIMENTAL




PESTICIDES USED




Acetamiprid Azoxystrobin Carbaryl Carbendazim

Fenhexamid

Fenoxycarb

Ciprodinil

Dimethoate

Imidacloprid

ImazalilMyclobutanil

OmethoatePirimicarb

Pyrimethanil




Tebufenozide Metalaxyl

Iprodione

Thiabendazol

ThiaclopridTriadimefon

Triadimenol

Endosulfan sulfate Difenoconazole

α-Cypermethrinβ-Cyfluthrin

α-Endosulfan

β-Endosulfan

Chlorpyrifos

Diflufenican




MCPA

Methidathion

OxyfluorfenPenconazole

Phosmet Prochloraz

Procymidone

Terbuthylazine Thiophanate-methyl

Dimethomorph

Diuron

Fluquinconazole

Fluroxypyr Kresoxim-methyl

Malathion




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




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




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




Malathion

Methidathion Phosmet

Chlorpyrifos

1452.75Malathion1.404.70Chlorpyrifos

2002.20Methidathion252.95Phosmet

Sw (mg/L)pKowPesticide

Olives




134Ciprodinil

Sw (mg/L)Log KowPesticida238000.7Dimetoato

Sw (mg/L)Log KowPesticida

6100.57Imidacloprid

Sw (mg/L)Log KowPesticida




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




1016 g

332 g (33%) 675 g (67%)

JuiceJuice processingprocessingImazalilImazalil

ThiophanateThiophanate methylmethylThiabendazoleThiabendazole

ProchlorazProchloraz

Solid Residue




1630 g

389 g (24%) 1241 g (76%)

PostharvestPostharvest treatmenttreatmentImazalilImazalil

ThiophanateThiophanate methylmethylThiabendazolThiabendazol

ProchlorazProchlorazaprox.1 aprox.1 ppmppm




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




Wine

BentoniteGelatine

LeesClarifiedWine

5 L




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





•• PesticidasPesticidasAzoxystrobin

Carbendazima

Ciprodynil

Dimethomorf

Imazalil

Kresoxim methyl

Penconazole

Procymidone

Thiabendazol

Acetamiprid

Carbaril

Dimethoate

Imidacloprid

Insecticidas

Fungicidas

IntroducciIntroduccióónn




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





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




RESULTs




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




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




ResultsResults•• Real Real samplessamples analisysanalisys

0102030405060708090

100

Imazalil-Doncella Thiabendazole-Delicious

Thiabendazole-GrannySmith

AppleSolid residueJuice




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





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





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




•• 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




8400 mg/L1.75Metalaxil2700 mg/L1.70Pirimicarb

8 mg/L1.50Carbendazim

184 mg/L1.26ThiaclopridWater solubilityLog KowPesticide




•• PesticidePesticide distributiondistribution

ResultsResults onon OrangesOranges JuiceJuice

0102030405060708090

100

Imazalil

Thiabendazole

Tiofanato metil

CarbendazimaProchloraz

Orange Solid residueJuice




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




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




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


Thiabendazole

3 hours

24 hours

4 days

7 days

0

1000

2000

3000

4000


Prochloraz

3 hours24 hours4 days7 days




ResultsResults

Orange Orange -- ConcentrationConcentration ((μμgg//kgkg))

0

200

400

600

800


Thiophanate methyl


0

100

200

300

400


Carbendazim





•• Real Real samplessamples analisysanalisys

373510955Imazalil

-189Carbendazim

Pomace(µg/kg)

Peel(µg/kg)

Orange(µg/kg)Pesticide

ResultsResults




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




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




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




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




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




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




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




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




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




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




273.9MCPA145Malation36.4Diuron25Phosmet8.5Terbuthylazine15Difenoconazole

>0.33sulfo-Endosulfan0.116Oxyfluorfen

1.4Chlorpyrifos0.32alfa-Endosulfan0.33beta-Endosulfan0.05Diflufenicam

0.0012beta-Cyfluthrin0.004alfa-Cypermethrin

SolubilityPesticide




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




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




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




Soya




Pesticides in Soya

FungicidesInsecticides

PropiconazolZetametrinaMalathion

TetraconazolTriflumuronLufenuron

EpoxiconazolTefubonizideFlufenuxuron

CiproconazolImidaclopridFipronil

AzoxystrbinTiodicarbEndosulfan

IprodioneThiametoxamDiflubenzuron

TiodicarbTeflubenzuronDiazinon

FludioxinilSpinosadDeltametrina

FlutriafolPropenofosClorpirifosmetil

TebuconazolDifeconazolPirimifos metilClorpirifos

PyraclostrobinCarboxinNovaluronCialotrina

MyclobutanilMetalaxilMetxiofenocideCipermetrina

Kresoxim metilCarbendazimMetomilCartap

FlusilazolCaptanMetiocarbAlfametrina







- 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.




-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.




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DISCUSSION PAPER ON THE EVALUATION OF DISTRIBUTION OF ... · ON THE EVALUATION OF DISTRIBUTION OF PESTICIDE RESIDUES AFTER PRIMARY PROCESS IN CITRUS FRUIT, POME FRUIT, OILSEEDS AND