Phthalate contamination in olive oil production chain

PhthalatePhthalate contaminationcontamination in olive oil in olive oil production production chainchain

M. M. MaregaMarega aa, K. , K. GrobGrob bb, S. , S. MoretMoret aa, G. , G. PurcaroPurcaro aa,c,c, , L.S.L.S. ConteConte aa

aa DepartmentDepartment of Food Scienceof Food Science -- University of Udine, ItalyUniversity of Udine, Italyb b KantonalesKantonales LaborLabor ZZüürichrich , Switzerland, Switzerland

c c DepartmentDepartment Farmaco Chimico Farmaco Chimico -- University of Messina, ItalyUniversity of Messina, Italy

WORKSHOP WORKSHOP

CONTAMINANTS OF EDIBLE FATS AND OILS: ANALYTICAL, CONTAMINANTS OF EDIBLE FATS AND OILS: ANALYTICAL, NORMATIVE ISSUES AND PREVENTIONNORMATIVE ISSUES AND PREVENTION

Udine, 12Udine, 12 --1313thth NovemberNovember 20092009

What are phthalates?What are phthalates?

Family of chemical compounds mainly used asFamily of chemical compounds mainly used as

Dimethyl phthalate (DMP) Diethyl phthalate (DEP) Dibutyl phthalate (DBP)Diisobutyl phthalate (DIBP)

Butyl benzyl phthalate (BBP) Di(2-ethylhexyl) phthalate (DEHP) Diisononyl phthalate (DINP)

�� PlasticizersPlasticizers in the polymer industry in the polymer industry →→ mainly mainly high molecular high molecular weight phthalates: DEHP, DINP, weight phthalates: DEHP, DINP, DnOPDnOP (but also DBP)(but also DBP)

�� CarriersCarriers →→low molecular weight phthalates: DIBP, DBP, DEP, BBPlow molecular weight phthalates: DIBP, DBP, DEP, BBP

Where can they be found?Where can they be found?

Many commercial products contain these chemicalsMany commercial products contain these chemicals

��building materialsbuilding materials��clothing clothing ��cosmeticscosmetics��medical devicesmedical devices��pharmaceuticalspharmaceuticals��flooring and wallflooring and wall--coveringcovering��food packagingfood packaging��printing inksprinting inks��glues glues

Due Due toto theirtheir widespreadwidespread useuse phthalatesphthalates are are ubiquitousubiquitousenvironmentalenvironmental contaminantscontaminants

HealthHealth problemsproblems

NO HUMAN STUDIESNO HUMAN STUDIES

No No reliablereliable evidenceevidence of of healthhealth effectseffects in in humanshumans

Great public Great public attentionattention becausebecause of the of the suspicionsuspicion of of theirtheir estrogenicestrogenic(endocrine (endocrine disruptorsdisruptors ) ) andand carcinogeniccarcinogenic propertiesproperties

ItIt ’’s s notnot possiblepossible toto excludeexclude healthhealth problemsproblems

��IARC: IARC: groupgroup 3, 3, notnot carcinogeniccarcinogenic forfor humanshumans

BUTBUT

��problemsproblems of the of the reproductivereproductive systemsystem

��asthmaasthma and and respiratoryrespiratory infectionsinfections in in childrenchildren

Phthalate exposurePhthalate exposure

consumer products and different indoor sources dominate the consumer products and different indoor sources dominate the exposure to DMP, DEP, BBP, DINP and DIDPexposure to DMP, DEP, BBP, DINP and DIDP

while while food has a major influence on the exposure to DIBP, food has a major influence on the exposure to DIBP,

DBP and DEHPDBP and DEHP

Major sources of human exposureMajor sources of human exposure

��Food and food containersFood and food containers

��Outdoor and indoor airOutdoor and indoor air

��Cosmetics and personal care productsCosmetics and personal care products

Food contaminationFood contamination

Foods represent an important source of phthalate exposure Foods represent an important source of phthalate exposure for humans, especially for humans, especially oily and fatty foodstuffsoily and fatty foodstuffs , due to the , due to the lipophiliclipophilic characteristics of phthalatescharacteristics of phthalates

�� during the production processduring the production process

�� during the food preparation steps during the food preparation steps

�� due to the migration from packaging materials and due to the migration from packaging materials and printing inksprinting inks

Food can Food can bebe contaminatedcontaminated

EU EU legislationlegislation

�� REGULATION (EC) 1907/2006REGULATION (EC) 1907/2006 ((REACHREACH) () (lastlast AmendmentAmendment →→→→→→→→ RegulationRegulation(EC) 552/2009)(EC) 552/2009)

�� REGULATION (EC) 790/2009REGULATION (EC) 790/2009 →→→→→→→→ ClassificationClassification , , labellinglabelling and packaging of and packaging of substancessubstances and and mixturesmixtures

�� DIRECTIVE 2005/84/ECDIRECTIVE 2005/84/EC →→→→→→→→ ToysToys and and childcarechildcare productsproducts

�� DIRECTIVE 2004/93/ECDIRECTIVE 2004/93/EC →→→→→→→→ CosmeticCosmetic productsproducts

�� DIRECTIVE 2007/47/ECDIRECTIVE 2007/47/EC →→→→→→→→ MedicalMedical devicesdevices

NO FOODNO FOOD

�� DIRECTIVE 2007/19/ECDIRECTIVE 2007/19/EC (last (last RegulationRegulation (EC) 975/2009) (EC) 975/2009) →→→→→→→→ PlasticsPlasticsin contact in contact withwith foodfood

�� REGULATION (EC) 1935/2004 REGULATION (EC) 1935/2004 →→→→→→→→ Food contact Food contact materialsmaterials

�� REGULATION (EC) 597/2008REGULATION (EC) 597/2008 →→→→→→→→ PlasticisersPlasticisers in in gasketsgaskets in in lidslids

FOODFOOD

EU EU legislationlegislation

DIRECTIVE 2007/19/ECDIRECTIVE 2007/19/EC →→→→→→→→ PlasticsPlastics in contact in contact withwith foodfood

SMLSML ((SpecificSpecific MigrationMigration LimitLimit ) ) →→→→→→→→ calculatedcalculated fromfromTDI TDI specifiedspecified byby EFSA EFSA ((EFSAEFSA Opinion, 2005)Opinion, 2005)

DBP DBP →→→→→→→→ 0,3 mg/kg0,3 mg/kg

DEHP DEHP →→→→→→→→ 1,5 mg/kg1,5 mg/kg

DIBP DIBP →→→→→→→→ ??

�� UsedUsed asas substitutesubstitute forfor DBPDBP

�� LimitLimit →→→→→→→→3 mg/kg3 mg/kg ((SynopticSynoptic DocumentDocument , , versionversion 2005)2005)

�� New limits New limits proposedproposed byby the the BfRBfR : 1mg/kg of food : 1mg/kg of food and 0.5mg/kg and 0.5mg/kg forfor baby baby foodsfoods

DIBPDIBP

Problems in phthalate analysis

ToTo reduce reduce blankblank levelslevels //problemsproblems

�� UseUse asas lessless solventsolvent and and glasswareglassware asas possiblepossible

��AppliedApplied fast and short fast and short proceduresprocedures

MainMain ProblemProblem →→→→→→→→ SecondarySecondary contaminationcontamination

Phthalates are ubiquitous contaminants Phthalates are ubiquitous contaminants →→→→→→→→ they are they are not covalently bound to the polymeric material not covalently bound to the polymeric material

⇒⇒⇒⇒⇒⇒⇒⇒ they can be easily released in the environment they can be easily released in the environment

��present in laboratory air, solvents, glassware present in laboratory air, solvents, glassware

Phthalate analysis in oil

LiquidLiquid --liquidliquid extractionextraction + + severalseveral purificationpurification stepssteps ((Mariani Mariani

etet al., 2006al., 2006))

HSHS--SPME SPME methodmethod ((HoladovHoladov àà etet al., 2007al., 2007))

Direct Direct injectioninjection of a of a diluteddiluted oil oil solutionsolution in a PTV in a PTV injectorinjector((FankhauserFankhauser --NotiNoti and and GrobGrob , 2006, 2006))

Mariani C., Mariani C., etet al., al., RivRiv . . ItalItal . Sostanze Grasse, 2006, 83, 251. Sostanze Grasse, 2006, 83, 251 --256256

HolodovHolodov áá K., et al., Anal. K., et al., Anal. ChimChim . . ActaActa , 2007, 582, 24, 2007, 582, 24--3333

FankhauserFankhauser --NotiNoti A. and A. and GrobGrob , K., J. , K., J. SepSep. Sci., 2006, 29, 2365. Sci., 2006, 29, 2365 --23742374

TraditionalTraditional methodsmethods

Innovative Innovative methodsmethods

AimAim of the of the ResearchResearch

MonitoringMonitoring of of fieldfield contaminationcontamination levelslevels of of olivesolives

MonitoringMonitoring of the of the contaminationcontamination in the olive oil production in the olive oil production chainchain

�� quantificationquantification of the basic of the basic phthalatephthalate levelslevels in in olivesolives in the in the fieldfield

�� identificationidentification of the of the factorsfactors and and mechanismmechanism thatthat can can affectaffectthisthis kindkind of of contaminationcontamination

�� quantificationquantification of the of the phthalatephthalate levelslevels of the of the olivesolives , olive paste , olive paste and oiland oil

�� identificationidentification of the of the criticalcritical pointspoints of the of the contaminationcontamination in the in the oil oil extractionextraction processprocess

ANALYTICAL PROCEDUREANALYTICAL PROCEDURE

GC GC –– MS ANALYSIS (SIM mode: m/z 149) MS ANALYSIS (SIM mode: m/z 149) withwith programmedprogrammedtemperature vaporizing temperature vaporizing ((PTV)PTV) injectioninjection equippedequipped withwith a a

backflushbackflush systemsystem

OIL SAMPLESOIL SAMPLES OLIVES AND OLIVE PASTEOLIVES AND OLIVE PASTE

EXTRACTION STEP NEEDEDEXTRACTION STEP NEEDED

No other extraction and purification procedures of the No other extraction and purification procedures of the sample are requiredsample are required

Reduced sample contamination and blank problemsReduced sample contamination and blank problems

CharacteristicsCharacteristics requiredrequired forfor the procedurethe procedure

SET UP OF THE EXTRACTION PROCEDURESET UP OF THE EXTRACTION PROCEDURE

��quantitative quantitative extractionextraction of of phthalatesphthalates

��low low levelslevels of sample of sample contaminationcontamination

Low Low phthalatephthalate levelslevels in the olive in the olive samplessamples

TestedTested differentdifferent solutionssolutions and and conditionsconditions

STRATEGY FOR THE EXTRACTION PROCESS

EXTRACTION OF AN OIL FREE PHTHALATE SOLUTION

EXTRACTION OF THE OIL

LOW EXTRACTION YIELD MECHANICAL EXTRACTION SOLVENT EXTRACTION

PROBLEM: PRESENCE OF WATER

MIX WITH DESSICANT AGENT (Na 2SO4)

DRY BY HEAT

DIRECT EXTRACTION WITH HEXANE

LOW EXTRACTION YIELD

PRELIMINARY MIXING WITH A SOLUTION 10% WATER IN ETHANOL

EXTRACTION WITH HEXANE

MIX WITH POLYTRON MIX IN ULTRASONIC BATH

LOW EXTRACTION YIELD

HIGH EXTRACTION YIELDS BUT HIGH BLANK LEVELS HIGH YIELDS HIGH YIELDS ANDAND LOW BLANK LEVELSLOW BLANK LEVELS

SET UP OF THE EXTRACTION PROCEDURESET UP OF THE EXTRACTION PROCEDURE

Oil Oil solutionsolutionin in hexanehexane

Grind olives with the Grind olives with the PolytronPolytron ; the procedure must be as fast as possible to redu ce ; the procedure must be as fast as possible to redu ce sample exposure to airsample exposure to air

Weigh 2.5 g of paste and add 100 Weigh 2.5 g of paste and add 100 µµgg/kg paste of a 5 mg/Kg solution of DHP (1/kg paste of a 5 mg/Kg solution of DHP (1 stst

internal standard)internal standard)Oven dry the sample at 120Oven dry the sample at 120 °°C for 2 hoursC for 2 hours

Put the dry paste in a centrifuge tubePut the dry paste in a centrifuge tubeAdd 0.5mL of a solution 10% water in Add 0.5mL of a solution 10% water in EtOHEtOH

Put the tube to soak in water at 60Put the tube to soak in water at 60 °°C for 30 minutesC for 30 minutes

Add to the paste 6mL of hexane and 100 Add to the paste 6mL of hexane and 100 µµgg/kg paste of a 5 mg/Kg of /kg paste of a 5 mg/Kg of DHePDHeP (2(2ndnd

internal standard)internal standard)Mix the sample in ultrasonic bath for 10 minutesMix the sample in ultrasonic bath for 10 minutesCentrifuge at 3000 rotations/min for 2 minutesCentrifuge at 3000 rotations/min for 2 minutes

Add 2 Add 2 mLmL of a solution 5% Kof a solution 5% K 22COCO33 in waterin waterMix the sample in ultrasonic bath for 2 minutesMix the sample in ultrasonic bath for 2 minutesCentrifuge at 3000 rotations/min for 10 minutesCentrifuge at 3000 rotations/min for 10 minutes

Transfer the solution in a 1.5 Transfer the solution in a 1.5 mLmL autoauto --sampler vialsampler vialGC GC –– MS analysis with PTV injectionMS analysis with PTV injection

Scheme of the final procedureScheme of the final procedure

Sample Sample preparationpreparation

ExtractionExtractionprocedureprocedure

InstrumentalInstrumentalanalysisanalysis

RESULTS

�� olives directly collected from different olive orch ardsolives directly collected from different olive orch ards

�� olives, olive paste and oil collected in several mi llsolives, olive paste and oil collected in several mi lls

SAMPLESSAMPLES

�� monitoring and quantification of the field contamin ationmonitoring and quantification of the field contamin ation

�� attempt to identify the origin and the mechanism of the attempt to identify the origin and the mechanism of the contaminationcontamination

�� monitoring and quantification of the contamination of olives monitoring and quantification of the contamination of olives in the millin the mill

�� monitoring the contamination at each step of the pr oduction monitoring the contamination at each step of the pr oduction chainchain

DIBPDIBP [1,5[1,5--14,6 14,6 µµµµµµµµg/kgg/kg ]]

MedianMedian valuevalue 6,1 6,1 µµµµµµµµg/kgg/kg

DBPDBP [0,3[0,3--4,0 4,0 µµµµµµµµg/kgg/kg ]]


DEHPDEHP [4,1 [4,1 –– 109,7 109,7 µµµµµµµµg/kgg/kg ]]


Basic Basic contaminationcontamination

levelslevels

ValuesValues regardingregarding olivesolives collectedcollected fromfrom sevenseven olive olive orchardsorchards (A(A--G) in G) in severalseveralpositionspositions and at and at differentdifferent timestimes duringduring ripeningripening

FIELD CONTAMINATION OF OLIVESFIELD CONTAMINATION OF OLIVES

BASIC PHTHALATE LEVELS OF OLIVES in the FIELD BASIC PHTHALATE LEVELS OF OLIVES in the FIELD

a)a) CLOSENESS TO OR DISTANCE OF THE ORCHARD FROM CLOSENESS TO OR DISTANCE OF THE ORCHARD FROM CONTAMINATION SOURCESCONTAMINATION SOURCES

b) DIFFERENT POSITIONS OF THE OLIVE TREES IN THE b) DIFFERENT POSITIONS OF THE OLIVE TREES IN THE ORCHARD ORCHARD

c) DIFFERENT POSITIONS OF THE OLIVES ON THE OLIVE c) DIFFERENT POSITIONS OF THE OLIVES ON THE OLIVE TREETREE


2) EFFECT OF THE TIME OF EXPOSURE2) EFFECT OF THE TIME OF EXPOSURE

IDENTIFICATION OF ORIGIN AND MECHANISM OF IDENTIFICATION OF ORIGIN AND MECHANISM OF FIELD CONTAMINATIONFIELD CONTAMINATION

1) EFFECT OF THE POSITION1) EFFECT OF THE POSITION

a) a) CLOSENESS TO OR DISTANCE FROM CONTAMINATION SOURCESCLOSENESS TO OR DISTANCE FROM CONTAMINATION SOURCES

0,0

5,0

10,0

15,0

20,0

25,0

30,0

amou

nt o

f pht

hala

tes

(µµ µµ

g/kg

)

A C D B E F

DEHP

DBP

DIBP

distant from polluted areasclose to polluted areas

ResultsResults

�� No No differencesdifferences regardingregardingtotal total concentrationconcentration of of phthalatesphthalates

�� SignificantSignificant differencesdifferences(p<0,05) in the (p<0,05) in the distributiondistributionof of individualindividual phthalatesphthalates ((forforDIBP and DBP)DIBP and DBP)



0,0

10,0

20,0

30,0

40,0

50,0

60,0

70,0

80,0

90,0

amou

nt o

f pht

hala

tes

(µµ µµ

g/kg

)

north west east

DEHP

DBP

DIBP

0,0

10,0

20,0

30,0

40,0

50,0

60,0

70,0

80,0

90,0

amou

nt o

f pht

hala

tes

(µµ µµ

g/kg

)

north w est east

DEHP

DBP

DIBP

0,0

10,0

20,0

30,0

40,0

50,0

60,0

70,0

80,0

90,0

amou

nt o

f pht

hala

tes

(µµ µµg/

kg)

north west east

DEHP

DBP

DIBP

b) b) DIFFERENT POSITIONS OF THE OLIVE TREES IN THE ORCHARDDIFFERENT POSITIONS OF THE OLIVE TREES IN THE ORCHARD

Olive orchard (D) Olive orchard (E)

Olive orchard (F)

ResultsResults

�� No No clearclear and precise and precise behaviourbehaviour in the in the variationvariation of the total of the total concentrationconcentration and and distributiondistribution of of individualindividual phthalatesphthalates in in relation relation toto a a specificspecific position/position/ exposureexposurein the olive in the olive orchardorchard



0,0

5,0

10,0

15,0

20,0

25,0

30,0

amou

nt o

f pht

hala

tes

(µµ µµ

g/kg

)

internal part of thetree

upper outside part ofthe tree

lower outside part ofthe tree

DEHP

DBP

DIBP

c) c) DIFFERENT POSITIONS OF THE OLIVES ON THE OLIVE TREEDIFFERENT POSITIONS OF THE OLIVES ON THE OLIVE TREE

ResultsResults

��SignificantSignificant differencesdifferences (p<0,05) in (p<0,05) in bothboth qualitative and quantitative qualitative and quantitative distributionsdistributions of of phthalatesphthalates betweenbetweeninternalinternal and and externalexternal part of the part of the treetree

��No No significantsignificant differencesdifferences in the in the amountamount and and distributiondistribution betweenbetween the the upper and the upper and the lowerlower outsideoutside part of part of the the treetree

PossiblePossible mechanismmechanism forforolivesolives contaminationcontamination : : depositiondeposition fromfrom the airthe air



0,0

10,0

20,0

30,0

40,0

50,0

60,0

amou

nt o

f pht

hala

tes

(µµ µµg

/kg)

Ai Af Bi Bf Ci Cf Di Df Gi Gf

DEHP

DBP

DIBP

ResultsResults

��No No clearclear and precise and precise behaviourbehaviour in the in the variationvariation of of the the concentrationconcentration and the and the distributiondistribution of of phthalatesphthalates in in timetime

AA BB CC DD GG

PhthalatePhthalatedegradationdegradation in the in the

outdoor outdoor environmentenvironment((photodegradationphotodegradation , , biodegradationbiodegradation and and

anaerobicanaerobicdegradationdegradation ))

2) EFFECT OF THE TIME OF EXPOSURE2) EFFECT OF THE TIME OF EXPOSURE


�� olives directly collected from different olive orch ardsolives directly collected from different olive orch ards

�� olives, olive paste and oil collected in several mi llsolives, olive paste and oil collected in several mi lls

SAMPLESSAMPLES

�� monitor and quantify the field contaminationmonitor and quantify the field contamination

�� attempt to identify the origin and the mechanism of the attempt to identify the origin and the mechanism of the contaminationcontamination

�� monitor and quantify the contamination of olives in the millmonitor and quantify the contamination of olives in the mill

�� monitor the contamination at each step of the produ ction monitor the contamination at each step of the produ ction chainchain

CONTAMINATION IN OLIVE OIL PRODUCTION CHAINCONTAMINATION IN OLIVE OIL PRODUCTION CHAIN

SamplesSamples collectedcollected in in fivefive olive olive millsmills (PG1(PG1--PG5) in PG5) in differentdifferent stepssteps ((possiblepossible criticalcriticalpointspoints ) of the oil ) of the oil extractionextraction processprocess

PHTHALATE LEVELS OF OLIVES in the OLIVE MILL PHTHALATE LEVELS OF OLIVES in the OLIVE MILL

DIBPDIBP [6,0 [6,0 -- 15,6 15,6 µµµµµµµµg/kgg/kg ]]


DBPDBP [2,3 [2,3 –– 23,8 23,8 µµµµµµµµg/kgg/kg ]]


DEHPDEHP [13,4 [13,4 -- 7077 7077 µµµµµµµµg/kgg/kg ]]


InitialInitial contaminationcontaminationlevelslevels of of olivesolives in the in the

millmill

ValuesValues regardingregarding olivesolives collectedcollected in in fivefive olive olive millsmills (PG1(PG1--PG5) in PG5) in differentdifferent stepssteps


MedianMedian valuesvalues forforolivesolives in in fieldfield

DIBPDIBP 6,1 6,1 µµµµµµµµg/kgg/kgDBPDBP 0,8 0,8 µµµµµµµµg/kgg/kgDEHPDEHP 16,0 16,0 µµµµµµµµg/kgg/kg

0,0

50,0

100,0

150,0

200,0

250,0

300,0

350,0

400,0

450,0

1 2 3 4

amou

nt o

f pht

hala

tes

(µµ µµ

g/kg

)

DIBP

DBP

DEHP

0,0

10,0

20,0

30,0

40,0

50,0

60,0

70,0

80,0

90,0

100,0

1 2 3 4

amou

nt o

f pht

hala

tes

(µµ µµg/

kg)

DIBP

DBP

DEHP

0,0

10,020,0

30,0

40,0

50,060,070,0

80,0

90,0100,0

110,0

120,0

1 2 3 4 5 6

amou

nt o

f pht

hala

tes

(µµ µµ

g/kg

)

DIBP

DBP

DEHP

Monitoring of the contamination during the extracti on process Monitoring of the contamination during the extracti on process –– OLIVES and OLIVE PASTEOLIVES and OLIVE PASTE

PG5 ResultsResults

��No No significantsignificant differencesdifferences in the in the olivesolives

��VeryVery high high increaseincrease in the in the concentrationconcentrationof DEHP and DBP after of DEHP and DBP after crushingcrushing

olives olives

olives

Olive paste

Olive paste

Olive paste

PG3 PG4

EffectEffect of of solubilisationsolubilisation of the oil of the oil on the on the phthalatesphthalates presentpresent in the in the

tubestubes


0,0

5,0

10,0

15,0

20,0

25,0

30,0

35,0

40,0

45,0

1 2 3 4

amou

nt o

f pht

hala

tes

(µµ µµ

g/kg

)

DIBP

DBP

DEHP

olives Olive paste

0,0

1000,0

2000,0

3000,0

4000,0

5000,0

6000,0

7000,0

8000,0

1 2 3 4 5

amou

nt o

f pht

hala

tes

(µµ µµ

g/kg

)

DIBP

DBP

DEHP

olives Olive paste

ResultsResults

��No No increaseincrease in the in the concentrationconcentrationof DEHP after of DEHP after crushingcrushing →→→→→→→→ ““ oldold ””tubestubes withwith lowerlower phthalatephthalate contentcontent

ResultsResults

��VeryVery low low amountsamounts of of phthalatesphthalates in in the paste the paste withwith respectrespect toto thosethosefoundfound in the in the olivesolives →→→→→→→→ problemsproblemsduringduring the the samplingsampling

PG1 PG2


Monitoring of the contamination during the extracti on process Monitoring of the contamination during the extracti on process –– OLIVES and OLIVE PASTEOLIVES and OLIVE PASTE


Monitoring of the contamination during the extracti on process Monitoring of the contamination during the extracti on process –– OILOIL

0,0

50,0

100,0

150,0

200,0

250,0

DIBP DBP DEHP

amou

nt o

f pht

hala

tes

(µµ µµ

g/kg

)

PASTE OIL CENTRIFUGE

0,0

50,0

100,0

150,0

200,0

250,0

DIBP DBP DEHPam

oun

t of p

hth

alat

es (

µµ µµg/

kg)

PASTE OIL DECANTER OIL CENTRIFUGE

0,0

50,0

100,0

150,0

200,0

250,0

300,0

350,0

400,0

450,0

DIBP DBP DEHP

amo

unt

of p

hth

alat

es (

µµ µµg

/kg)


0,0

50,0

100,0

150,0

200,0

250,0

300,0

350,0

400,0

450,0

DIBP DBP DEHP

amo

unt o

f pht

hala

tes

(µµ µµ

g/kg

)


0,0

500,0

1000,0

1500,0

2000,0

2500,0

3000,0

3500,0

4000,0

4500,0

5000,0

DIBP DBP DEHP

amou

nt o

f ph

thal

ates

(µµ µµ

g/kg

)


ResultsResults

FromFrom paste paste toto oil:oil:

��DecreaseDecrease in the in the concentrationconcentration of DIBP of DIBP

�� SlightSlight variationsvariations forfor DBP DBP and DEHPand DEHP

PG1PG1 PG3PG3PG2PG2

PG4PG4 PG5PG5

CONCLUSIONSCONCLUSIONS

ConclusionConclusion 1 1 -- EXTRACTION PROCEDURE EXTRACTION PROCEDURE

�� Fast and suitable for every day laboratory useFast and suitable for every day laboratory use

�� Low blank levels because less solvents and materials are Low blank levels because less solvents and materials are usedused

��High extraction yields of phthalates (85High extraction yields of phthalates (85 --95%)95%)

��Repeatability: RDS% 15Repeatability: RDS% 15 --20%20%

ConclusionConclusion 22 –– FIELD CONTAMINATIONFIELD CONTAMINATION

�� VeryVery low low levelslevels forfor fieldfield contaminationcontamination

�� Origin of the contaminationOrigin of the contamination →→→→→→→→ no correlation between no correlation between contamination levels of olives and the two considere d contamination levels of olives and the two considere d factors (time and position)factors (time and position)

different types of degradationdifferent types of degradation

�� Mechanism of contaminationMechanism of contamination →→→→→→→→ deposition by the airdeposition by the air

ConclusionConclusion 33 –– CONTAMINATION IN OLIVE OIL CONTAMINATION IN OLIVE OIL PRODUCTION CHAINPRODUCTION CHAIN

Different types of contamination sourcesDifferent types of contamination sources

�� during the harvesting and the transportduring the harvesting and the transport of the olives (DBP of the olives (DBP and DEHP)and DEHP)

�� during the extraction chainduring the extraction chain (DBP and DEHP)(DBP and DEHP)

CRITICAL POINTS CRITICAL POINTS olive paste and oilolive paste and oil

Thank you

for your

kind attention

Documents

Phthalate contamination in olive oil production chain