Phthalates

Entrytothemarineenvironment Effectsonthemarineenvironment

Recordedlevelsinthemarineenvironment Bioaccumulation

Fateandbehaviourinthemarine Potentialeffectsoninterestfeaturesof
environment Europeanmarinesites

Entryintothemarineenvironment

'Phthalates'isthegenericnamegiventoestersof1,2benzenedicarboxylicacid.Althoughsome27
phthalateestersaremanufactured,onlyalimitednumberareproducedinlargequantities.

AreviewbyLewisetal(1998)identifiedanumberofphthalatesofparticularinterestintermsof
theirenvironmentalfateandbehaviourorbecausetheywereontheHighProductionVolume
ChemicalsListfromtheEC:

dimethylphthalate(DMP)
diethylphthalate(DEP)
twoisomersofdibutylphthalate(DBPs)
diisobutylphthalate(DIBP)anddinbutylphthalate(DNBP)
butylbenzylphthalate(BBP)
dicyclohexylphthalate(DCHP)andthreeisomersofdioctylphthalate(DOP)
dinoctylphthalate(DNOP),diisooctylphthalate(DIOP)anddi2ethylhexylphthalate
(DEHP)

Phthalatesareestersof1,2benzoldicarbonicacid(orthophthalicacid).Thechemicalstructureof
phthalatescanbecharacterisedbyaplanararomaticringwithtwoslightlymobilesidechains.For
phthalates,ingeneral,sidechainsaremainlyalkylgroupswithasecondaryroleplayedbyallyl,
benzyl,phenyl,cycloalkylandalkoxygroups.Withalkylphthalates,afurtherdistinctioncanbe
madebetweenbranchedandunbranchedsidechains.

Intheearly1980s,annual,worldwideproductionofphthalateesterswasestimatedtobe20
milliontonnes(Schmitzeretal,1988),althoughitmaynowbecloserto5milliontonnes(Lewiset
al1998).ThetotalconsumptionofphthalateestersintheUKwasestimatedtobe122,000tonnes
in1989,ofwhich54%wasDEHPandDIOP(Brookeetal1991).

Phthalatesestersaremanufacturedworldwideonalargescale,beingmainlyproducedforuseas
plasticisersinresinsandpolymers,especiallyasasoftenerinPVC(87%ofthetotalproductionof
phthalatesisusedforthispurpose).

Phthalateestersarewidelydistributedintheenvironmentbecauseoftheirpropertiesandtheir
commonusageasplasticisers.Potentialsourcesbywhichphthalatesmayentertheaquatic
environmentarewidelythoughttobethrough:

releaseviawastewaterfromproductionandprocessingactivities,includinglossesduringphthalate
estersynthesis,resinandplasticisercompounding,fabricationofPVCintoproducts,andduring
theproductionofadhesivesandcoatings

releasefromuseanddisposalofmaterialscontainingphthalateesters,includinglossesof
plasticiserduringthelifetimeofproductsorduringincinerationorlandfillingofrefuseandother
waste.

Recordedlevelsinthemarineenvironment

Phthalatescanbeconsideredtobeubiquitousintheenvironmentandtherearemanystudieswhich
haveinvestigatedandreportedenvironmentalconcentrationsofthesesubstances.Whileafew
studieshavebeencarriedoutinthelastfewyears,themajorityofavailablestudiesarebetween10
and20yearsold.Lewisetal(1998)havecollatedanumberofthesestudieswhicharesummarised
below.
Itshouldbenotedthatcontaminationduringcollectionandanalysiscanleadtospuriousresults
andrecordedenvironmentallevelswheredueprecautionshavenotbeentakenmaywellbeinerror.

Dataontheconcentrationsofphthalateestersinenvironmentalsamplesmainlyfocusonlevelsof
DEHP,reflectingitspredominantusage.ReportedlevelsofDEHPinwatersamplesfromriversin
theUK,Sweden,USAandtheNetherlandsareallwithintherange0.31.6&microgl1(Fatoki
andVernon1990),withlevelsincoastal,marineandestuarinewatersbetween<2ngl1and
335ngl1.DOPsarethemosthydrophobicofthephthalateestersontheHPVCsListandhave
beendetectedinriverbedsedimentsatconcentrationsbetween0.11,700mgkg1,dependingon
whetherthesampleswerecollectedfromcleanorcontaminatedsites.Forexample,contaminated
sedimentcollectedfromtheMerseyEstuarycontainedupto1,700mgkg1ofDEHP(Prestonand
AlOmran1986).ItislikelythatresiduesofDOPsaccumulatinginsedimentswillpersistandthat
suchsedimentsareasignificantsinkforthoselongsidechainorhighlybranchedsidechain
phthalateesters.

Sewagesludgeisknowntocontainrelativelyhighconcentrationsofphthalateesters(12
1,250mgkg1Sheltonetal1984),thepredominantcomponentbeingDEHPwhichaccumulates
onsludgesolidsbecauseofitshydrophobicity.Thedisposalofsewagesludgetomarinewaterswas
anindirectrouteofphthalateestersenteringtheenvironment,althoughthedischargeofsewage
sludgetomarinewatersisapractisewhichhasbeenphasedoutundertheUrbanWasteWater
TreatmentDirective(December1998).Theuseofsewagesludgeasasoilconditionerin
agricultureisalsoapotentialindirectrouteofphthalateesterstotheenvironment(Rogers1987,
Crathorneetal1989,Fairbanksetal1985).

Fateandbehaviourinthemarineenvironment

Sincesomephthalateestershavelowwatersolubilityandhighoctanolpartitioncoefficient,they
canbecomeconcentratedinsuspendedmatterandsediment.

Lewisetal(1998)revieweddataonthefateandbehaviourofphthalateesters.Theauthors
concludedthat,ingeneral,thesubstanceshavelowwatersolubilitiesandthemajorityareliquidsat
ambienttemperatures,withmeltingpointsbelow0oC,althoughDMPandDCHPhavemelting
pointsof5.5and63oCrespectively.Boilingpointsare200OCandabove.

Thebehaviourofphthalateestersintheenvironmentvaries,dependingontheindividualester.In
general,thelargerthealkylsidechainordegreeofbranching,themorepersistentthecompound.

Themostimportantaquaticdegradationprocessforphthalateestersisbiodegradation.Shortside
chainphthalateesters,suchasDMP,DEPandDBPs,arealllikelytodegradequicklyinaerobic
surfacewaters.ThelongerchainPEs,suchasDOPs,arelikelytobemorepersistent,particularly
astheywillpartitionmorestronglytosedimentsandsomaybelessavailabletomicrobial
degradation.Itis,therefore,probablethatresiduesofDOPsinanaerobicsedimentswilltendto
persistforlongperiods.

Phthalateestersshowawiderangeofaffinitiesforpartitioningtoparticulatematerialsinthe
aquaticenvironment.ApartfromDMPandDEP,allotherphthalateestersconsideredbyLewiset
al(1998)showsignificantpartitioningtosuspendedsolidsandsediments.ThetransportofDOPs,
DBPs,andBBPintheaquaticenvironmentisstronglyinfluencedbytheirassociationwith
suspendedsedimentsandotherdetritus,asistheirfateduringsewageoreffluenttreatment
processes.LogKocforthephthalateestersincreaseintheorder
DMP<DEP<BBP<DNBP<DEHP<DNOPandcoverawiderangeofhydrophobicities.DMPhas
thelowestaffinityforpartitioningtoparticulatematerialsandhasthehighestwatersolubility.
Partitioningtendencyincreaseswithsidechainlength,withDNOPhavingthegreatestaffinityfor
suspended,particulatematerialinnaturalwaters.Consequently,thelongsidechainphthalateesters
thatentertheaquaticenvironmentineffluentstreamsarelikelytoshowsignificantassociation
withsuspendedparticulatematerialandsedimentsorwithparticulatesandsewagesludgeduring
treatmentprocesses.Inparticular,longerchainphthalates(e.g.DOPs)showastrongaffinityfor
sewagesludgewhichmayreducethelikelihoodofhighconcentrationsoccurringintheeffluent.

Phthalateestershavegenerallylowvolatility(vapourpressuresintherange0.021.9mPa)which
decreasewithincreasinglengthofthealcoholsidechainoftheester.Henry'sLawconstantsrange
between108and105atmm3mol1,indicatingthatphthalateesterswilltendtovolatilisefrom
water,eithernotatallorveryslowly.

DMPandDEPcanberegardedashavinglowpropensityforbioaccumulation,whilstBBPand
DBPshaveintermediatetendency.DEHP,DCHP,DNOPandDIOPallhaveahighaffinityfor
sedimentsorforpartitioningtobiota.

Effectsonthemarineenvironment

Toxicitytomarineorganisms

Anexhaustiveliteraturereviewonthetoxicityofphthalatestomarineorganismshasnotbeen
carriedoutforthepurposesofthisprofile.Theinformationprovidedinthissectionistakenfrom
existingreviewdocuments(Lewisetal1998).Themostsensitivegroupsoforganismshavebeen
identified.

Thetoxicityofphthalatestosaltwaterorganismsvaries,dependingontheesterconsidered.Esters,
ingeneral,appeartobeofmoderatetolowtoxicitytoaquaticorganisms.However,greatest
sensitivityisexhibitedwhenexposedtoshortsidechainphthalateesters,suchasDBPandBBP.

Algae

Foralgae,respectiveEC50(growth)andLC50valuesof54and125mgl1havebeenreportedfor
thediatomGymnodiniumbrevefollowing96hoursexposuretoDMP(Wilsonetal1978),while96
hourEC50sof26.1and29.8mgl1havebeenreportedforSkeletonemacostatumonthebasisof
chlorophyllaandcellnumberrespectively(SuggatandFoote1981,citedinStaples1997).For
DEP,respectiveEC50(growth)andLC50valuesof3and33mgl1havebeenreportedforthe
diatomGymnodiniumbrevefollowing96hoursexposure(Wilsonetal1978).

ForDBPs,thelimitedavailabledatasuggestthatsaltwateralgaearesensitivewith96hourEC50
(growth)andLC50valuesreportedforthediatomGymnodiniumbreverangingfrom0.00340.2
and0.0020.6mgl1respectively(Wilsonetal1978).However,asingle96hourEC50(growth
rate)of31,000mgl1DEHPhasbeenreportedforthealgaGymnodiniumbreveindicatinglow
acutetoxicity.

Invertebrates

TheavailabledatasuggestthatDMPisofmoderateacutetoxicitytocrustaceanspecies,witha96
hourLC50of68.6mgl1reportedforthemysidshrimpMysidopsisbahiafollowingexposuretoa
measuredconcentration(Adamsetal1995andSuggatandFoote1981,citedinStaples1997).This
valueissupportedbya96hourLC50of62mgl1reportedbyLindenetal(1979)forthecopepod
Nitocraspinipes.

DEPalsoappearstobeofmoderateacutetoxicitytosaltwatercrustaceans,witha96hourLC50of
10.3mgl1(measuredconcentration)reportedbyAdamsetal(1995)forthemysidshrimp
Mysidopsisbahia.OfsomewhatlowersensitivityisthebrineshrimpArtemiasalinawitha72hour
LOEC(hatching)of50mgl1reportedbySugawara(1974).Inthisstudy,acorrespondingNOEC
of20mgl1wasreported.

However,greatersensitivityisexhibitedbysaltwaterinvertebrateswhenexposedtoDNBPand
BBP.

24hourLC50sof5.6and8.9mgl1forDNBPhavebeenreportedforthebrineshrimpArtemia
salinaexposedtonominalconcentrationsintwoseparatestudies(HudsonandBagshaw1978and
Hudsonetal1981).Alower96hourLC50of0.5mgl1hasbeenreportedforthemysidshrimp
Mysidopsisbahiafollowingexposuretomeasuredconcentrations(Adamsetal1995).

ForBBP,a96hourLC50of0.9mgl1hasbeenreportedbyGledhilletal(1980)fortheshrimp
MysidopsisbahiawithacorrespondingNOECof0.4mgl1measuredinthisstudy.Afurther96
hourNOECof>0.9mgl1hasbeenreportedinasimilarstudy(Adamsetal1995).

InstudiesconductedonthecopepodNitocraspinipesandthemysidshrimpMysidopsisbahiano
effectswereobservedbelowthemaximumwatersolubilityofDEHP.L(E)C50valuesforeachof
thesespecieswerereportedtobe>0.37and>300mgl1respectivelyfollowing96hoursexposure
(Lindenetal1979andAdamsetal1995).

Fish

Forsaltwaterfish,reliable96hourLC50sof0.51,3and0.55mgl1BBPhavebeenreportedfor
shinerperchCymatogasteraggregata,sheepsheadminnowCyprinodonvariegatesandEnglish
soleParophrysvetulusrespectively(Ozretichetal1983Gledhilletal1980andRandelletal
1983).

ThelimitedavailabledataforDMPsuggestthatitisofmoderateacutetoxicitytosaltwaterfish,
with96hourLC50sof29and58mgl1reportedintwoseparatestudiesforthesheepshead
minnowCyprinodonvariegates(Adamsetal1995andHeitmulleretal1981).However,alower
96hourLC50of107mgl1(nominalconcentrationonly)hasbeenreportedforthebleakAlburnus
alburnus(Lindenetal1979),indicatingapossiblelowertoxicitytothisspecies.

ItisdifficulttoassessthetoxicityofDBPstosaltwaterfishfromthelimiteddataavailable.Ina96
hourstudy,nomortalityofsheepsheadminnowCyprinodonvariegatuswasobservedat0.6mgl1,
thehighestconcentrationtested(Adamsetal1995).Thisissupportedbytheresultsofalongterm
studyconductedontheeggsandlarvaeofacyprinidRivulusmarmoratus.Inthisstudy,24week
NOECandLOECvaluesof1and2mgl1werereportedrespectively,onthebasisofadecreasein
eggfertilityandembryoviability.

A96hourNOEC(survival)of550mgl1hasbeenreportedforDEHPbyHeitmulleretal(1981)
forsheepsheadminnowCyprinodonvariegatus.However,itisnotpossibletointerpretthisvalue
asitiswellabovethesolubilitylimitofDEHP.Similarly,nomortalitywasobservedinthesame
speciesfollowingexposuretothehighestconcentrationtested(0.17mgl1)(Adamsetal1995).

Sedimentdwellingorganisms

Someinformationonthetoxicityofphthalateesterstosedimentdwellingorganismsisavailable.
However,theseareforfreshwaterorganisms.

GiventhelowwatersolubilityofDEHPanditshighoctanolwaterpartitioncoefficient,itislikely
thatthiscompoundwillreadilyadsorbtosuspendedsolidsandsedimentsinthenatural
environment.

Streufertetal(1980)foundthatinaflowthroughstudyutilisingDEHPconcentrationsof
0.36mgl1oversandand0.24mgl1overhydrosoil,noeffectswereobservedonthelarvaeof
Chironomusplumosusovera35dayexposureperiod.Adsorptionofthedissolvedfractiontothe
sand/hydrosoilmayhavereducedbioavailabilityandhencetoxicity.Thisobservationissupported
bytheresultsofthefollowingsedimentstudies.Inastudyutilisingspikedriversediments,a
NOECof>10,000mgkg1(survival,developmentandemergence)wasmeasuredforlarvaeofthe
midgeChironomusriparius(Brownetal1996).Theauthorsfoundthatthisvaluewasseventeen
timesgreaterthanthehighestconcentrationsmeasuredincontaminatedsedimentsinthenatural
environment.TheseresultsaresupportedbythefindingsofCalletal(1997)whofoundthatspiked
sedimentconcentrationsof3,306and3,247mgkg1(dryweight)causednoadverseeffectson
survivalorgrowthofthemidgeChironomustentansorscudHyallelaaztecarespectively,overa
periodof10days.

InastudyconductedbyWennbergetal(1997),aconcentrationof600mgkg1(spikedsediments)
wasfoundtocausenoadverseeffectsonhatchingsuccessortadpolesurvivalinthemoorfrog
Ranaarvalisovera29dayperiod.

Lewisetal(1998)derivedEQSsfortheprotectionofsaltwaterlifeforarangeofphthalateesters
(seetablebelow).

ProposedEQSsfortheprotectionofsaltwaterlifeforphthalates(&microgl1)(fromLewis
etal1998)

Chemical Annualaverage Maximumallowable Notes

concentration

Dimethylphthalate(DMP) 800 4000 1

Diethylphthalate(DEP) 200 1000 1

Dibutylphthalates(DBPs) 8 40 1,2

Butylbenzylphthalate(BBP) 20 100 1

Dioctylphthalate(DOPs) 20 40 1,3

Dicyclohexylphthalate(DCHP) 4

1Tentativestandard
2TotalDBPs(DIBPDNBP)

3DOPs(DEHP,DIOP,DNOP)

4Insufficientdatatoderivestandards

Bioaccumulation

Bioaccumulationofphthalateestersdoesnotappeartobesignificant.Woffordetal(1981)exposed
theoysterCrassostreavirginica,brownshrimpPenniesaztecusandsheepsheadminnow
Cyprinodonvariegatustoconcentrationsof0.1and0.5mgl1(DEHP).Bioaccumulationdidnot
varysignificantlyamongthethreespecies,withreportedBCFsrangingfrom6.9(oyster)to16.6
(shrimp),althoughexposurewasfor1dayonly.Inlongertermstudies,BrownandThompson
(1982)recordedanaverageBCFof2,496formussels(totalsofttissues),following28days
exposuretoconcentrationsof0.004and0.042mgl1.Noapparentadverseeffectsonthemussels
wereobserved,andaccumulatedresidueswererapidlyeliminatedfollowingtransfertoclean
seawater(halflife=3.5days).Itshouldbenotedthat,sincetheBCFswerebasedon14Clevels,
thevaluesmightalsoincludemetabolitesofDEHP.

Woffordetal(1981)determinedBCFsforthebrownshrimpPenniesaztecusandsheepshead
minnowCyprinodonvariegatusforotherphthalateesters,butfoundthemtobelow(<50).

PotentialeffectsontheinterestfeaturesofEuropeanmarinesites

Potentialeffectsinclude:

toxicityofphthalatesatconcentrationsabovetherelevantEQSsinthewatercolumn
accumulationinsedimentsoflongsidechainorhighlybranchedsidechainphthalateesters
(e.g.DOPs)posingasignificanthazardtosedimentdwellingorganisms
phthalateestershavebeenidentifiedasagroupofsubstancescausingendocrinedisruption
andaprecautionaryapproachshouldbeadoptedinthecontrolofthesesubstances.

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