sources of phthalates in dairy farm equipment

SourcesofPhthalatesinDairyFarmEquipment

PreparedforEnvironmentalHealthStrategyCenter&TheCoalitionforSaferFoodProcessing&Packaging

March20,2018

pure|STRATEGIES SOLUTIONSFORASUSTAINABLEFUTURE

Tableofcontents

ExecutiveSummary..................................................................................................................1I. Introduction.................................................................................................................3II. PotentialSourcesofPhthalateinMilkfromFarmEquipment....................................5III. TestResultsforEquipment........................................................................................15IV. InformationfromDairyEquipmentSuppliers...........................................................20V. Findings......................................................................................................................23

VI. NextSteps...................................................................................................................25AppendixI:PhthalateTestResults.......................................................................................27AppendixII:CommunicationonGlitex181PVCTubing……………………………………………………..37AppendixIII:CompaniesProvidingFlexibleTubingtoFoodIndustry....................................39

ii


Executive Summary

Whiletheevidenceofadversehealtheffectsofortho-phthalateplasticizershasresultedinaprohibitionoftheuseofmostphthalatesinfoodcontactmaterialsforfattyfoods,includingdairy,intheEU,U.S.FDAhasnotimposedanysimilarrestrictions.Testingofcommercialdairyproductshasdemonstratedthepresenceofphthalates–particularlyinthoseproductswithhigherfatcontentandsubjecttogreaterprocessing.Studies,especiallyinBelgium,haveshownthatwhilelaterstepsinproductpreparationcancontributesignificantlytothelevelsofphthalatesinproducts,significantphthalatelevelsareoftenpresentalreadyintherawmilkfromdairyfarms.Thisstudyisonepartofabroaderefforttounderstandthesourcesofphthalatesatdairiesandtodevelopstrategiestoeliminatethosesources.

Thisreportfocusesontheequipmentondairyfarmsthatcancontributetothepresenceofphthalatesinrawmilk.Fortheequipmentthatislikelytohavethehighestpotentialimpactonthepresenceofphthalatesinthemilk,italsoconsiderscurrentandpotentialcontributionsofdairyequipmentsuppliersinmitigatingtheproblem.

Thefirstfocusofthestudywasontestingafewsamplesfromcommonequipmentatdairiesthatcouldpotentiallyleadtothepresenceofphthalatesintherawmilk.Sincephthalate-plasticizationofPVCandsyntheticrubberhosesandteatcuplinershasbeenwidelyavailableinthepast,theexpectationwasthatevenasmallnumberofsamplesmightprovideinformationonthepatternsofcontinueduse.Outof20samplesincluding6hoses,2teatliners,gaskets,andothermaterials,oneteatlinercontainedsignificantphthalates.

Tosupplementthetestresults,thestudygatheredadditionalinformationfromdairy-supplycompaniesandviewsofdairyexpertsontheextentofcontinueduse.Thecombinedresultoftheseeffortsdemonstratedthat,whilethereisclearlymovementamongmajorsuppliers(especiallythosewithrootsintheEU)totransitiontophthalate-freeequipment,thereissignificantcontinuinguse.Theextentofthetransitionisnotclear;viewsofdairyexpertsrangedfromseeingverylittlemovementawayfromphthalatestofeelingthattherearesomesignificantchangesintheofferingsofasignificantnumberofsuppliers.

Majorfindingsofthereportinclude:

• The combination of test results and company product reviews demonstrate thatsome suppliers continue to use phthalates to plasticize both PVC and syntheticrubberdairyequipment.

• AsubstantialrangeofalternativestoPVCorrubberequipmentplasticizedwithphthalatesiscurrentlyavailableinthemarketfordairyfarmequipment.

1


• Thereisalsoevidencethatsomesupplierseithernolongerofferproductsplasticizedwithphthalatesoratleastprovidephthalate-freealternatives.Butthereisverylittleevidencesofarabouthowgreatanimpactthisincreasedavailabilityofphthalate-freeequipmenthashadondairyfarmequipmentchoices.

• Themotivationforsupplierstodevelopreplacementsforphthalate-plasticizedmaterialshasnot,uptothispoint,comefromdairyfarmers–whoareconcernedwithequipmentfunctionalityandcost,andoftennotawareofthesignificanceofphthalates.

• Increased equipment durability is a potential competitive advantage for suppliersandanincentiveforchangeforthefarmer.Thefairlyshortlifecycleoftraditionalequipmentprovidesanopportunityforrelativelyrapidchangeiftherightbusinessincentivesareinplace.

• Understandingofcurrentequipmentuseandopportunitiesforacceleratingchangecouldbeenhancedbyastudyfocusedoncurrentofferingsofphthalateandnon-phthalateequipmentbyasignificantsegmentofthelargersuppliers.Thestudycouldalsoassesssupplierplansforphasingoutofanycurrentlyavailablephthalate-plasticizedequipment.Suppliersensitivityontheissueappearssubstantial;bothleadersandlaggardscouldberecognized.

2


I . I n t roduct ion

Evidencefromseveralstudieshasdemonstratedthatsomeproportionofthephthalates1foundinthefinaldairyproductspurchasedbyconsumersmayalreadybepresentintherawmilkfromthedairyfarms.2Thisreportispartofalargerprojecttoidentifysourcesofphthalatesindairyproducts,andtoaltertheprimarychoicesofmaterialsorprocessstepsthatarecurrentlyresultinginphthalatesindairyproducts.Thefocusofthisreportisonpotentialsourcesofphthalatesinequipmentusedatthedairyfarmthatcouldcontributetothepresenceofphthalatesinrawmilkfromdairies.Thereportincludes:

• Reviewofinformationfromavarietyofsourcestoidentifytypesofequipmentmostlikelytoleadtothepresenceofphthalatesinrawmilk.

• Testingofalimitednumberofsamplesfromcommonequipmentatthedairythatcouldcomeintocontactwiththerawmilk.

• Informationfromsomedairyequipmentmanufacturersonuseofphthalatestoprovidetheneededflexibilityforequipmentsuchasmilkhosesonthedairyfarm,aswellasindicationsofchangesbythosemanufacturerswithrespecttotheirdependenceonphthalatesasaprimarymeanstoprovidetheneededproductflexibility.

Otherstepsintheproductionofdairyproductsmaybeasourceofphthalatesinthefinalproducts–e.g.,phthalatesfromfoodcontactmaterialsinthepackagingorprocessingformilk,creamorcheesesorotherdairyproducts.3Inaddition,sincephthalatesarelipophilic,concentrationsofthephthalatesincreaseinthefattierendproducts(e.g.,

1Throughoutthisreport,theterm“phthalates”willbeusedinplaceof“ortho-phthalates.”Ortho-phthalatesisthefamilyofchemicalsthatareofconcernindairy(andotherfood)supplies,andcommonlyreferredtojustas‘phthalates.’Terephthalates,afamilyofstructurallysimilarchemicalswithafarlowerhazardprofile,aresometimesusedasreplacementsforortho-phthalatesasplasticizers,includinginequipmentsuchasmilkhosesondairyfarms.2FierensT,VanHolderbekeM,WillemsH,DeHenauwS,SioenI.PhthalatesinBelgiancow'smilkandtheroleoffeedandothercontaminationpathwaysatfarmlevel.FoodChemToxicol.2012Aug;50(8):2945-53.https://www.ncbi.nlm.nih.gov/pubmed/22659009FierensT,VanHolderbekeM,WillemsH,DeHenauwS,SioenI.Transferofeightphthalatesthroughthemilkchain--acasestudy.EnvironInt.2013Jan;51:1-7.https://www.ncbi.nlm.nih.gov/pubmed/23138015Cao,X.PhthalateEstersinFoods:Sources,Occurrence,andAnalyticalMethods.ComprehensiveReviewsinFoodScienceandFoodSafety.20109:21-43.http://onlinelibrary.wiley.com/doi/10.1111/j.1541-4337.2009.00093.x/fullCastleL,GilbertJ,EklundT.Migrationofplasticizerfrompoly(vinylchloride)milktubing.FoodAdditContam.1990Sep-Oct;7(5):591-6.https://www.ncbi.nlm.nih.gov/pubmed/2253803Fierens,Tine,IsabelleSioen,StefaanDeHenauw,etal.“PhthalateContaminationintheMilkChain.”Visie,GezondheidswinstEnToekomst :BookofAbstracts.2010.57–57.https://www.wiv-isp.be/aph/pdf/APH68_S63.pdfVanHolderbekeM,GeertsL,VanermenG,ServaesK,SioenI,DeHenauwS,FierensT.DeterminationofcontaminationpathwaysofphthalatesinfoodproductssoldontheBelgianmarket.EnvironRes.2014Oct;134:345-52.https://www.sciencedirect.com/science/article/pii/S0013935114002722?via%3Dihub3Forexample,twoenforcementcampaignsbyScandinaviangovernmentagenciesfoundviolationsofEUphthalaterestrictionsforfoodcontactmaterialsin23%and39%ofconveyorbelts,plastictubes,lidsandgloves–allduetoPVCplastics.Petersen,JensHøjslev,andLisbethKrügerJensen."PhthalatesinsoftPVCproductsusedinfoodproductionequipmentandinotherfoodcontactmaterialsontheDanishandtheNordicMarket2013-2014."InternationalJournalofFoodContamination3.1(2016):3.

(https://foodcontaminationjournal.springeropen.com/articles/10.1186/s40550-016-0026-6)3

4

pure|STRATEGIES SOLUTIONSFORASUSTAINABLEFUTUREcheesesandcream).Butwhilelaterstepsinproductionmayaddtothephthalateconcentrationsintheultimateproducts,phthalatesinrawmilkfromthedairyremainasourceofthephthalatesinthefinaldairyproducts.

Thefollowingsectionsinclude:

• Overviewofpotentialsourcesofphthalatesinrawmilk.• Testresultsforsamplesofmaterialsfromdairyfarmequipment.• Informationonphthalate-freeofferingsorinitiativesbydairyequipmentsuppliers• Summaryoffindingsandpotentialnextsteps.


II. PotentialFarmEquipmentSourcesofPhthalatesinrawmilk

Opportunitiesforreducingphthalatesinrawmilkresultingfromdairyfarmequipmentfocusonflexibleplasticorrubberequipmentthatcouldbeplasticizedwithphthalates.Themostlikelysourcesareequipmentthatcomesintodirectcontactwiththerawmilkfromthecow,suchasmilkhosesorinflations/teatcupliners.Otherpotentialsourcesinclude:

• Equipmentwithpotentialindirectcontactwiththemilk,suchassourcesofiodineorotherdisinfectants/cleaners,orplasticbrushesusedforcleaningcows’uddersinmoreautomatedsystems.

• Equipmentthatcomesintocontactwithcows’silageorotherfeed,thoughthisrequiressomeevidenceofhowphthalatefromsuchsourceswouldbemetabolizedbythecowandpassedintothemilk.

1. Equipmentwithdirectcontactwithrawmilkfromthecow

Thefollowingsectionsreviewtestsofequipment,informationfromdairyequipmentsuppliersandperspectivesofdairyexpertsoneachofthesecategoriesofequipment.Themajoremphasisisontheequipmentthatseemstohavethegreatestlikelihoodofcontributingtothepresenceofphthalatesinrawmilk.Figure1showstheequipmentintheautomatedmilkingsystemsthatmovesthemilkfromthecowtothebulktankthatstoresthemilkuntiltransferredtotransport.4

Themostimportantpartsinthediagramforpotentialmigrationofphthalatesintotherawmilkaretheliner(seeFigure2),theshortmilktubeandthelongmilktube.Duringthemilkingprocess,fourteatcupsattachtothecow’steats;theliner(orinflation)oftheteatcuppulsatestocreatetheflowofmilk.Onlytheliner(rubber,siliconeorsoftplastic)5touchesthecow’steatduringthemilkingprocess.Themilkthenpassesintotheclaw,andfromthereintothelongmilktube(ormilkhose).Thehose–rubber,siliconeorplastic(usuallyPVC)--runsfromafewfeettoasmuchasadozenfeetbeforeitconnectstostainlesssteelpipes.6Gasketsoccurthroughoutthesystem,startingwiththeclaw.Whilesomeofthejointsinthepipewillbewelded,therewillbeasubstantialnumberofgasketsando-rings.Thegasketsaregenerallymadefromrubber–oftennitrilerubber.7

4ThediagraminFigure1isfromDairyNZ,“TheMilkingPlant,”(https://www.dairynz.co.nz/milking/the-milking-plant/)5AspecificreferencetoplasticforlinersidentifiedduringthereviewwasbyDairyFlo,aNewZealandcompany,whichadvertisesthatitslinerslastthreetimeslongerthanrubberliners.Theplasticisidentifiedasathermoplasticurethaneandisplasticizerfree.ItisnotclearifDairyFloproductsarecurrentlyavailableintheUS,thoughDairyFloisapplyingforinternationalpatents.http://www.dairyflo.co.nz/faqs/6InformationfromTonyaSchoenfuss,AssociateProfessorDairyProductsTechnology&AssociateDirector,MidwestDairyFoodsResearchCenter,UniversityofMinnesota(emails11/30/17&12/10/17;phoneinterview12/1/17).7TonyaSchoenfuss,phoneinterview12/1/17;RickKersbergen,UniversityofMaineCooperativeExtension,phoneinterview11/8/17

5


Figure1:MilkingEquipment

Afterthemilkflowsintothestainlesssteelpipe,itpassesthroughbothafilterandaplatecoolerbeforeenteringthebulktank.Thefilter(whichmightbenonwovenfabricormorepermanentmeshes)8screensoutsolidssuchasdirt,hairormanure.Thefilterisplacedbeforetheplatecoolerbothtoprotectthecoolerfromthesolidsandtoallowmilkfatstopassthroughthefilterwhilethemilkisstillwarm(since,oncecooled,milkfatscouldsolidifyandbefilteredoutofthemilk).

8AccordingtoaDeLavalreportonfilters,therearetwotypesoffilters–disposablefilters,madeofnon-wovenfabrics(e.g.,polyester,cotton,cellulose,viscose)foruseinjustasinglemilkingsession,andpermanentfiltersmadeofmeshstainlesssteelorhardplasticscreens,withtheformerpredominating.“Nearlyalltherawmilkproducedonfarmsisfilteredbydisposablemilkfilters”(p.25).DeLaval,“EfficientMilkFiltration”http://www.delaval.ch/ImageVaultFiles/id_26182/cf_5/53570972BR_Filter-handbook.PDF

6


Theplatecoolerreducesthetemperatureofthemilkforstorageinthebulktank.Likethestainlesssteelpipegaskets,thegasketsintheplatesoftheplatecooleraregenerallysyntheticrubber.9

Figure2:TeatCup&Inflation/Liner10

Thebulktankisthelaststopfortherawmilkonthefarmbeforeitispumpedintoatruckfortransporttoadairyforprocessing.Onceagain,therearegasketsandsealsthataretypicallyofrubberconstruction.

Performance requirements

ThemostcommonmaterialsforlinersandhosesuntilrecentlyincludedsyntheticrubberandPVCforhoses,andsyntheticrubbersforinflations–bothofwhichcouldbeplasticizedwithphthalates.Themarketischanging,andanincreasingrangeofalternativesisavailableonthemarket,includingbothPVCandsyntheticrubberswithnon-phthalateplasticizersandalternativematerialsthatrequireverylittleornoplasticizing,suchassiliconesoradvancedsyntheticrubbers.Viewsvaryonhowextensivetheactualchangeinusehasbeen.Butthereisgeneralagreementamongthosecontactedforthisreportthatdairyfarmersbasetheirchoicesonfunctionalityandcost–thatconcernaboutphthalatesisstilllimited(orasonedairyownercapturedtheview,“probablyitisthecheapestcostforthefunctionalityyouneed”).Sowhileon-linecatalogssometimesinclude“phthalate-free”statements,dairyfarmersfocusonhowneworalternativematerialsimproveperformance.11

Boththeinflation/linerandmilkhosemustbeflexibleanddurable.Materialsmustberesistanttoheatoftherawmilk(atabout100degreesFahrenheit)andtothealkalineandacidrinsesusedforregularlycleaningthehosestoavoidmaterialormicrobialbuildupinsidethehose.Inaddition,theymustmeetFDArequirementsforfoodcontactmaterialsand3-ASanitaryStandardsformultipleuseplasticorrubbermaterials.12a

9See,forexample,https://hambydairysupply.com/stainless-steel-plate-with-nitrile-gasket-for-t4-koolway-mueller-surge-plate-cooler/10CourtesyofProfessorH.DouglasGoff,DairyScienceandTechnologyEducationSeries,UniversityofGuelph,Canada.https://www.uoguelph.ca/foodscience/book-page/automatic-milking 11InterviewswithRickKersbergen,UniversityofMaineCooperativeExtension(11/8/17);DouglasReinemann,AssociateDeanforExtensionandOutreach,CollegeofAgriculturalandLifeSciences,UniversityofWisconsin(12/1/17);TonyaSchoenfuss,AssociateProfessorDairyProductsTechnology&AssociateDirector,MidwestDairyFoodsResearchCenter,UniversityofMinnesota(emails11/30/17&12/10/17;phoneinterview12/1/17);GabeClark,FounderandDirectoratCSRConsultancy(11/16/17).12a3ASanitaryStandardsforMultiple-UsePlasticMaterials,#20-27.Availableforpurchaseathttps://www.techstreet.com/standards/3a-20-27?product_id=1800159

7


Liners(seeFigure2)needtomeetperformancegoalsthatincludefittingtightlyenoughonarangeofteatsizesandshapestobeairtight,beingcomfortableforthecow,andmeetingarangeoftechnicalneedstofacilitatefullmilkingofthecow.Aparticularchallengeforthelineristhatthematerialneedstoremainresilient,withoutpropagatingcracksthatcouldharmtheteat,whilepulsing(insidetheteatcupshell)onthecow’steatatarateintherangeof45-60pulsesperminute.12

Inadditiontobeingresistanttochemicalcleaningrinses,hosesmustremainflexiblewithinawiderangeofairtemperaturesthatcanvarysubstantiallydependingongeographyandtimeofyear.Potentialmaterialissuesformilkhosesarethattheinteriorofthehosebecomesrigidorcrackedfromthechemicalrinses,thatthehosebecomesinflexibleincoldweather,orthatthehosegenerallylosesflexibilityduetoleachingofthephthalates.(Thelastofthosechangesisananticipatedlength-of-lifefactorforthehose;thefirsttwoareperceivedasproductfailures).Inaddition,thehosesshouldberelativelyeasytohandle,sothatfactorslikeweightoreaseofcleaningcanbesignificant.13

Materials

EUprohibitionsontheuseofmostphthalatesinfoodcontactmaterialsforfattyfoods,includingdairy,haveledtothedevelopmentofawiderangeofnon-phthalatealternativesforallofthedirectcontactmaterialsinhoses,phthalatesandgaskets.14WhiletheserestrictionsarenowmandatoryintheEU,adoptionintheabsenceofregulationsintheU.S.hasbeenslow.Amongthemost-usedmaterials,bothPVCandsyntheticrubbermaterialsmayhavehighlevelsofphthalates,althoughtherearenon-phthalatealternativescommerciallyavailableforboth.

P V C

PVCplasticizedwithphthalateshasprovidedafunctional,relativelyinexpensivetypeofmilkhoseatdairyfarms.15Inadditiontolowcost,benefitsincluderelativelylightweight,durabilityandflexibilitythroughawidetemperaturerange.

12DepartmentofAnimalSciences,UniversityofIllinois,“MilkingMachine”

(http://ansci.illinois.edu/static/ansc438/Mastitis/milkmachine.html).Microscopicstudiesshowthatinflationsthatstillappearundamagedmaystillbedeterioratingfairlyquickly.(RickKersbergen,UniversityofMaineCooperativeExtension,11/8/17).13TonyaSchoenfuss,AssociateProfessorDairyProductsTechnology&AssociateDirector,MidwestDairyFoodsResearchCenter,UniversityofMinnesota(emails11/30/17&12/10/17;phoneinterview12/1/17).DouglasReinemann,AssociateDeanforExtensionandOutreach,CollegeofAgriculturalandLifeSciences,UniversityofWisconsin(12/1/17)14Forinflations,nospecificuseofPVCwasidentified,thoughtherewerecataloglistingsfor“plastic”inflations.Withoutmoreinformationit’shardtobecertainwhetherornota“plastic”isPVC,butthatseemslesslikelythanthattherubber-likepropertiesthatarevaluableforaninflationmightberealizedthroughuseofathermoplasticelastomerthathassomeplasticandrubbercomponents.Forexample,seeDairyFlo’sLeadingtheChangetoPlastic,http://www.dairyflo.co.nz/why-choose-dairyflo-products/15Expertsatdifferentgeographiclocationsstated,withequalcertainty,thatPVCmilkhosesorrubbermilkhoseswerethepreferredchoicesatdairyfarms,sotheremayberegionaldifferencesordifferencesinsizesofdairiesthataffectchoicesbetweenthetwo.Personalcommunications.

8


Withoutadditives,PVCisrigid.Toensurecontinuedflexibilityandavoidcrackingorbreakingincoldweather,PVChosesrequireincreasinglevelsofplasticizersatcoldertemperatures.ForDEHP,typicalformulationsuse30%to40%DEHPbyweight,andprovidecoldweatherflexibilitydownto-40to-50degreescentigrade.16ButthehosegraduallydegradesandbecomeslessflexiblebecausethephthalateplasticizersarenotchemicallyboundtothePVCpolymer.DEHPorotherphthalateplasticizersmigrateoutofthePVCintotherawmilkpassingthroughthehoses.Boththeheat(about100degreesF)andfatcontent(sincephthalatesarelipophilic)canacceleratethatmigration.ThehighpercentageofphthalatesinthePVCmakesthisapotentialmajorsourceforphthalatesleachingintotherawmilk.

AlternativestoPVCwithDEHPorotherphthalateplasticizersarebecomingmorewidelyavailablefordairyequipment.ThesealternativesincludebothblendsofPVCwithotherpolymers(whichmayreducerequirementsforplasticizers)anduseofnon-phthalateplasticizers.17Whiledozensofplasticizershavebeendevelopedforbothgeneralorspecializeduse,plasticizersidentifiedinmilkhosesareconstrainedbytheparticularperformancerequirementsandcostconstraintsofdairyfarms.OnecommonalternativeplasticizerisDOTP,aterephthalate.18WhileDOTP(alsocalledDEHT)sharesmanyofthesameplasticizingcharacteristicsasDEHP,itsharesfewerofDEHP’shazardousproperties(althoughdatagapsremain).19Otherplasticizers–identifiedeitherfromtestsresults(Table1below)orfrominformationprovidedbycompanies(Table6below)–includeadipates(e.g.,DEHA)andadditivesidentifiedonlyas‘bio-based.’Somebio-basedplasticizersmaybeusedassecondaryplasticizers,providingadditionalflexibilityincombinationwithprimaryplasticizers(whichmaybethecasewiththeglycerintriacetatefoundintwooftheproducts).20

Rubber

Whileafewinflationsormilkhosesmaystillbemadewithnaturalrubber,mostrubberproductsarenowmadewithsyntheticrubber.Syntheticrubbersfoundinthetestedsamples,forexample,includedEPDM,nitrilerubber,andrubbersbasedonABSandpolystyrene/polypropylene.Whilerubbermaybeplasticizedforprocessingorflexibility,plasticizingmaybeachievedwithpetroleumoilsratherthanphthalatesorotheralternatives.Butphthalatesstillareusedinsomerubbersusedindairyfarmmaterials.

16HandbookofVinylFormulating(JohnWiley&Sons,2008,2ndedition),editedbyRichardF.Grossman,pp.181182.17Specificinformationonalternativesisoftenunavailableduetoproprietaryrestrictions.18Somecompanieslabeltheirplasticizersas‘terephthalates,’withoutspecifyingthespecificchemical.19ThehazardprofilesofDEHTandDEHPcanbefoundathttps://www.pharosproject.net/material/show/2004682andhttps://www.pharosproject.net/material/show/2086424.20StudiesindicatepotentiallyproblematichazardissuesforDEHA,whileglycerintriacetatehasafavorablehazardprofile.Seehttps://www.pharosproject.net/material/show/2007649andhttps://www.pharosproject.net/material/show/2004452.Onsecondaryplasticizers,seeKirk-Othmer,ConciseEncyclopediaofChemicalTechnology(4thedition,WileyIntersciencePublication,1999),p.1578.

9


Whilenotfoundinthemilkhosesamples,phthalateswereidentifiedinoneoftherubberinflations(seeTable2below).Withoutmorecomprehensivetesting,thereisnowaytoknowwhatproportionofrubberhoses,inflationsorgasketsareplasticizedwithphthalates.Dependingonthespecificsyntheticrubber,andwhetheraphthalateplasticizerisusedonlyforprocessingorforprovidingproductflexibility,phthalateconcentrationintherubbermayrangefromaslittleas1%toasmuchas16%.21Thephthalatelevelfoundinthetestedinflationexceeded10%.Theselevels,whilelowerthaninPVC,stillprovidesignificantopportunityformigrationintothewarmrawmilk.

Butnotallsyntheticrubbersrequireplasticizers.Somecopolymercombinationsprovideinherentplasticizingwithoutadditionalplasticizingadditives.Afewareadvertisedas“plasticizerfree.”Sincetheparticularchemicalcombinationsareoftenproprietary,thereisnowayinsuchcasestoknowwhatpolymersareinvolvedexceptthroughtesting.

Silicone

Siliconeiswidelyavailableforuseinmilkhoses,inflationsandgasketsand,sinceitisinherentlyflexible,requiresnoplasticizers.22Siliconeproductshavegreaterdurabilitythanthealternatives,whichreduceslabortimerequiredforequipmentchanges.Buttheyalsoaresubjecttoabrasion,andcracksbeginningontheoutsidecanpropagatethroughthehoseorcancreateroughedgesorcracksininflationsthatcanirritateteats–bothofwhichcanreducethegeneraldurabilityadvantage.23

Siliconeproductsaresignificantlymoreexpensive,atleastintheshortterm,whichcanbeanimportantbarriertochangingtosiliconefromeitherplasticorrubber.But,atleastinsomecases,thelong-termcostsmightbesimilarorlowerduetothegreaterdurabilityofsiliconeproducts.24

21Kirk-Othmer,pp.1580-1581,1768-1769;AdditivesforPlasticsHandbookbyJohnMurphy(2ndedition,ElsevierAdvancedTechnology,2001),pp.231-233;RubberCompoundingIngredients:Need,TheoryandInnovation,PartIIbyC.Hepburn(SmithersRapraTechnology,1997).22Theword‘rubber’isusedbroadly,andmaybeappliedtosilicone,aswellastosomethermoplasticelastomersthatincludenon-rubberpolymers.Theuseinthisreportreflectsthedistinctionsgenerallymadeondairydistributorandsuppliersites,whichtreatsiliconesasaseparateclass.23InterviewwithDouglasReinemann,AssociateDeanforExtensionandOutreach,CollegeofAgriculturalandLifeSciences,UniversityofWisconsin(12/1/17).Anotherissuethatwasraisedbyonecompanyrepresentativeandappearedonsomesitesisthatmilkfatcanbothsticktothewallsofsiliconehosesandmigratethroughthesiliconetoformlumpsoffatontheoutsideofthehose.Thisapparentlydependsonthespecificformulationofthesiliconematerial;itmayalsoberesolvedbytwolayersofdifferentmaterialsinthehose.(Personalcommunication)24See“Considermaterial,value,performancewhenchoosingliners,”byNathanBrown,DeLavalSolutionManagerforlinersandtubes,ProgressiveDairyman,(12/11/2015)https://www.progressivedairy.com/topics/management/consider-material-value-performance-when-choosing-liners.Whileitappearsgenerallytobethecasethatsiliconeproductsaremoreexpensiveondistributorsites,itisdifficulttoestimatethedifference.Arepresentativeofonecompanythatsellssiliconeproductsnotedthat,consideringthegreaterdurabilityofsilicone,thedifferenceisquitesmall,

10


2. Equipmentwithnodirectcontactwithrawmilkfromthecow

Oncemilkentersthemilkingsystemthroughtheinflations,thereshouldbenocontactbetweenthemilkandequipmentonthefarmotherthanthatsummarizedabove.Still,thefactthatsomelevelsofphthalateshavebeenfoundafterhand-milkingofcows25raisesquestionsaboutotherpossiblesources.

Asnotedabove,therearesomepotentialequipmentsourcestoconsiderthatdonotinvolvedirectcontactwiththerawmilkafterthecowhasbeenmilked:

• Phthalatecontaminationfromequipmentinvolvedincleaning,includingapplicationofdisinfectantstocows’udderspriortomilking.

• Contaminationofcows’feedwithphthalatesbyequipmentusedinstoringorpreparingthefeed.

Cleaning and Disinfection

Cleaningofcows’uddersandapplicationofdisinfectantsisdonebeforemilkingtoreduceriskofbacterialcontaminationofthemilkorofmastitisforthecowsandtostimulateoxytocinreleasethatresultsinmorerapidandcompletemilkingofthecow.26Equipmentthatcouldbeconsideredaspossiblesourcesofphthalatesinclude:

• Dipcupsusedbyworkersatthedairytoapplythedisinfectantsolutiontotheteats.Theapplicatorportionofthecupisrigid,thoughinsomeabottomportionofthecontainerisflexible.

• Inpartiallyorfullyautomatedsystemstheremayalsobe:o Hosethroughwhichthedisinfectantfromthecontaineristransferredto

besprayedontheteats.o Sprayingdevice,possiblyalsocontainingarotatingbrushtoaidincleaningthe

teats.• Containers, at least if they are plastic, that contain the iodine (or other

disinfectantsolution).

Thepotentialforthisequipmenttobeasourceofphthalatesdependsonboththematerialsandpotentialphthalatecontentoftheequipmentandthelikelihoodthat,ifphthalateswerepresent,theywouldremainasresiduesontheteatsafterapplicationofwateroradisinfectantsolution.

whilearepresentativefromacompanymakingPVCproductsestimatedthedifferencetobeashighasfive-to-one.(Personalcommunications)25Fierens,Tine,etal."PhthalatesinBelgiancow’smilkandtheroleoffeedandothercontaminationpathwaysatfarmlevel."Foodandchemicaltoxicology50.8(2012):2945-2953.https://www.ncbi.nlm.nih.gov/pubmed/2265900926InterviewwithRickKersbergen,UniversityofMaineCooperativeExtension(11/8/17);interviewwithGabeClark,FounderandDirectoratCSRConsultancy(11/16/17);DepartmentofAnimalSciences,UniversityofIllinois,“MilkingProcess”(http://ansci.illinois.edu/static/ansc438/Mastitis/milkprocess.html). 11


Withrespecttotheequipment,themostlikelypotentialsourceofphthalateswouldappeartobeanyhoseconveyingthesolution,sincethehosecouldpresumablybeofanyofthematerialsusedinmilkhoses.Theplasticcontainerswiththeiodinesolutionwouldbehardplastic,solesslikelytocontainanyplasticizersthatcouldcontaminatethedisinfectantsolution.Withrespecttothedipcup,eventhosewithaflexiblebasehavelimitedtimeofcontactwiththesolution–evenassumingsomemightbePVCwithphthalates.Sprayingdevicesaremadewithhard,notflexible,plastic.Whiletherecouldbeothermaterials,bothGEAandDeLavalstatethatthebristlesintheirteatcleaningsystemsaremadeofnylon,27whichwouldnotgenerallybeexpectedtobeplasticizedwithphthalates.28

Finally,someofthoseinvolvedwithdairiesnotedthatthecleaningandpreparationformilkingrequiresdryingtheteatsaftercleaning.Thisisusuallydonewitheitherwithapowereddryingsystem,orwithsingle-usepaper.Incombination,theyviewedthisequipmentasalesslikelysourceofphthalatesthantheequipmentinvolvedinmilkingandtransferringtherawmilktothebulktank.29

Inspiteofthesecaveats,thepotentialforphthalatesfromequipmentusedforcleaninganddisinfectioncan’tbesetaside.If,forexample,phthalatesweretobepresentintheantisepticsolutionandthedryingstepwerenotadequate,residualphthalatescouldbeontheteatduringthemilkingprocess.30Todeterminethispossibilitywouldrequiretestingphthalatelevelsintheiodinesolutionappliedfromequipment(whetherhoses,applicatorsortheoriginalcontainer)madefrommaterialthattestsshowtoincludephthalates.

Phthalates from Feed

Feedforcowsconsistsoffreshforagefrompasturesandofsilage(mostlygrownandstoredon-site)andconcentrate(purchasedhighcarbohydrate,fat,proteinandvitaminmixesimportedtothefarm).31Allthreeprovidepotentialsourcesofphthalatesinthefeed–whetherfromenvironmentalsourcesaffectingthepasture,frompreparationoftheconcentratemix(predominatelyoffsite)orpreparationorstorageofthesilage.Intermsofequipment/materialsusedatthedairy,migrationofphthalatesfromequipmenttosilageistheprincipalconcern.

27https://www.gea.com/en/products/cow-brush-e-brush-and-m-brush.jsp;https://www.delaval.com/en-us/our-solutions/cow-comfort/cow-brushes/delaval-mini-swinging-brush-msb/28“Thehighdegreeofcrystallinityinnylonmeansthatplasticizationcanoccuronlyatverylowlevels.Plasticizersareusedinnylonbutareusuallysulfonamide-basedsincethesearegenerallymorecompatiblethanphthalates.Theseplasticizershelpimprovetheprocessingofthenylon.”“Plasticizers”inEncyclopediaofPolymerScienceandTechnology,V.3,p.519.29InterviewwithRickKersbergen,UniversityofMaineCooperativeExtension(11/8/17);interviewwithGabeClark,FounderandDirectoratCSRConsultancy(11/16/17)30Timepressuresduringthisstepcould,insomeinstances,beacontributingfactor.31AlbertaMilk,"Whatdodairycowseat?”https://albertamilk.com/ask-dairy-farmer/what-do-dairy-cows-eat/ 12


Previousstudiesprovideevidencethatphthalatesinacow’sfeedmaypassthroughthecowintothecow’smilk.Theextentorlimitationsofthisprocessrequireadditionalstudy,asrecommendedbyFierensetal(2012).Inthemostextensiveresearcheffortthusfar,theauthorsnotedthatsomephthalatestowhichcowswereexposedthroughfeed(DMP,DEP,DnBP,DCHP,DnOP)didnotresultinphthalatesintherawmilk,whileforothers(DiBP,DEHP)thephthalateswerefoundinthemilk.32

Theyreportedonacaseatonefarmwheresilagethecowsconsumedcontainedphthalates,inspiteoftherebeingnodetectablephthalatespresentinsoil,waterorpasture.Subsequenttestingofthecows’milkaftermanualmilkingdemonstratedthepresenceofDiBPinthemilk.Theauthorsconcluded:

...silageisalmostcertainlycontaminatedwithDiBPduetomigrationfromcontactmaterialssuchasclingfilms,sailsorsealantsusedduringproduction,mixingorduringstorageatthefarm.33

Figure3:SilageBale34 Themostlikelysourcesforphthalatesinsilageduetofarmequipmentwouldbeeitherthewrapsofbalesofsilage(Figure3)orthecoversoversilagebunkers(Figure4).Balesprovideprotectionforrelativelysmallamountssilage.Reviewofsilagewrapsavailablethroughon-linesitesindicatethatthemostcommonmaterialissomeformofpolyethylene–oftendescribedasmadefrom‘premiumgradepolyethyleneresins,’35orsimplyassuperiorto‘conventional’polyethylene.36

Figure4:SilageBunker37

For larger farmingoperations, silagemaybe stored inlargesilagebunkers suchas that inFigure4.The tireson top of the cover over the bunker are used asweightstokeepthecoversealed.Asinthecaseofthesilage wrap, a common material is polyethylene.FarmTec,forexample,describesitscoversUV-resistantknittedpolyethylenethatwilllastforyears.38

32Fierens,Tine,etal."PhthalatesinBelgiancow’smilkandtheroleoffeedandothercontaminationpathwaysatfarmlevel."Foodandchemicaltoxicology50.8(2012):2945-2953.(https://www.ncbi.nlm.nih.gov/pubmed/22659009)33Ibid.There’snowaytoknowwhatsilagewraporcoverwasusedontheBelgianfarm.34PicturefromtheUniversityofNewHampshireCooperativeExtensionhttps://extension.unh.edu/blog/utilizing-undf-dairy-cow-diets35BlueLakePlastics,http://www.bluelakeplastics.com/ag-silage-bags-and-sheeting.php;FarmPlasticSupply,https://farmplasticsupply.com/bunker-covers36BlueLakePlastics,http://www.bluelakeplastics.com/ag-silage-bags-and-sheeting.php;FarmPlasticSupply,https://farmplasticsupply.com/bunker-covers37Picture©WernerWillmann/WikimediaCommons/CC-BY-SA-3.0/GFDL38FarmTec,https://www.farmtek.com/farm/supplies/prod1;ft_hay_feed_storage;pg109200.html;FarmPlasticSupply,https://farmplasticsupply.com/bunker-covers;GlobalPlasticSheeting,https://www.globalplasticsheeting.com/ag-liners---covers


Sincepolyethyleneisinherentlyflexible,itseemsimprobablethatphthalateswouldbeusedintheformulation.39Thereare,however,numeroussitesofferingsilagewrapsorbunkercoversthatspecifyuseofplastics,butwithnoinformationonexactlywhatthematerialsare,andthelikelyuseofmultipleplasticswasconfirmedduringaninterview.39

Testingofcrumbrubberfromrecycledtiresusedonchildren’splaygroundsandrubberizedsurfacesforsportingeventshasfoundphthalatesintherubber,amonganumberofhazardouschemicals.Whilearangeofotherplasticizersareusedintires,oldertiresusedonbunkerscouldcontainphthalates.Whiletherubberinwholetireshaslessexposedsurfacethanthecrushedrubber,itisapotentialsourceofphthalatesthatshouldbetested–bothintermsofthepresenceofphthalatesinthetiresandthepotentialrateofleaching.40

Twodairyexpertsfounditmorelikelythatanyphthalatescouldcomefromwrapsthanfromthelargerbunkers.Onenotedthatthedepthofbunkerscanbeanywherefromtentothirtyormorefeet,andthatitwasunlikelythatphthalates,ifpresentinthecoverofabunker,couldpenetratethroughmorethantheverytoplayersofthesilage.Bothalsonotedthecomplexityofresolvingthesourceofaparticular,giventhemultiplepotentialsourcesoffeedorenvironmentalcontamination.41

Assessingthelinkagesofphthalatesinmilkfromthecowwitheitherparticularmaterialsinequipmentthatcontactsfeedorwithothersourcesofphthalateswasbeyondthescopeofthisstudy.Suchastudywouldneedtoconnectspecificmeasuresofphthalatecontaminationoffeedwithsourcesinthematerialsusedtostoresilage.Thatwouldprovideapositivebasisfordistinguishingbetweenequipmentandgeneralenvironmentalsourcesofphthalatecontaminationofthefeed.

39AreviewofpolyethyleneinTheHandbookofPlasticizersnotespotentialusesofphthalatesandotherplasticizersinpolyethylene.Allofthereferencesinthesectiononpolyethylene,howeverarebasedonpatentsratherthanactualapplications,soit’snotclearhowapplicableitwouldbetotheusesofpolyethylenecoversforsilage.GeorgeWypych,editor,HandbookofPlasticizers,ChemTecPublishing(2004),http://61.188.205.38:8081/hxgcx/hcjs/UploadFiles/pdf/%E6%96%87%E7%8C%AE%E5%BA%93/%E6%A8%A1%E5%9D%973%E5%90%88%E6%88%90%E6%9D%90%E6%96%99%E5%8A%A9%E5%89%82/Handbook%20of%20Plasticizers%20-%20G.%20Wypych%20(Chemtec,%202004)%20WW.pdf.GlobalPlasticSheeting,https://www.globalplasticsheeting.com/ag-liners---covers;Zuidervaart,https://www.globalplasticsheeting.com/ag-liners---covers;FarmPlasticSupply,https://farmplasticsupply.com/bunker-covers?product_id=275;interviewwithRickKersbergen,UniversityofMaineCooperativeExtension(11/8/17).40Llompart,Maria,etal."Hazardousorganicchemicalsinrubberrecycledtireplaygroundsandpavers."Chemosphere90.2(2013):423-431.https://www.ncbi.nlm.nih.gov/pubmed/22921644;MilesMoore,“Industrydefendsuseofcrumbrubberinartificialsurfaces,”RubberNews.com.http://www.rubbernews.com/article/20141027/NEWS/310209997?template=printart41InterviewwithDouglasReinemann,AssociateDeanforExtensionandOutreach,CollegeofAgriculturalandLifeSciences,UniversityofWisconsin(12/1/17);interviewwithRickKersbergen,UniversityofMaineCooperativeExtension(11/8/17). 14

pure|STRATEGIES SOLUTIONSFORASUSTAINABLEFUTUREIII. TestResultsforEquipment

Dairyfarms,andtheequipmentusedonthosefarms,arehighlydiverse.Asanyreviewofequipmentavailableaton-linesitesfordistributorsandsuppliersdemonstrates,thereisawiderangeofavailablealternativesforanydairyequipment.Forthisreport,wegatheredasmallsamplingofflexibleequipmentcomponentsandtestedthemforpresenceofphthalates.Thesampleswereidentifiedandselectedfromthoseavailablethroughon-linedistributors.

Materialsfortestingwereselectedfromthefollowing:

§ Milkhoses§ Teatcupliners/inflations§ Gaskets/o-ringsinmilkingequipmentandconnections§ Teatdipcupsandotherequipmentforcleaning/disinfectantsolutions§ Silagewrap

Thematerialswereselectedtoprovidesomeinsightsonthepresenceofphthalatesindairyequipmentandtheuseofalternativepolymersandplasticizers.Theemphasisfortestingwasonmaterialsfromequipmentthathasdirectcontactwithrawmilkfromthecow.Itisboththelikeliestmajorsourceofphthalatesinmilkduetofarmequipment,andacontributingcauseofphthalatesinmilkwherechangescouldmostreadilyandquicklybemade.Thetestsofmaterialsreviewedinthissectionincludesixteensamplesfromequipmentthatdirectlycontactstherawmilk(9fromhoses,2frominflations,4gaskets,1filter),3fromequipmentinvolvedinapplicationofdisinfectant/cleaningofthecows’teatsbeforemilking(1hose,2dipcups)andonepieceofsilagewrap.42

TestResultsforHoses

Samplesofninemilkhosesfromon-linedairysupplydistributorsweretestedforphthalates.Thegoalwastofindanyindicationsofphthalatesinthosemilkhosesthatcouldpotentiallyresultinpresenceofphthalatesintherawmilk.Thesampleincludedamixofdifferentmaterials–includingsomethatwerelabeled(accurately,thetestsdemonstrated)“phthalate-free.”Astheresultsinthefollowingtabledemonstrate,noneofthesesamplescontainedphthalates(althoughphthalateswerefoundinoneoftheinflationsamples–seebelow).

42Allthesamplesexceptthesilagewrapwerepurchasedfromdistributors.Thepieceofsilagewrapwasprovidedfromafarm.

15


Table1:TestforPhthalates:MilkHoses43

ProductNameCompanyorDistributor44

MaterialResultfromFTIRSolventExtractionFTIRresult

DairyFlowHighPerformanceMilkandDairyTransferTubing

TBL

Polystyrenecopolymer(e.g.polystyrene/ethylene-butylene)

Mineraloil

Black Rubber Milk Tubing 9/16 inI.D1ft

GEAPoly(isoprene)orEPDMrubber;kaolin

Mineraloil;Santoflex13

BlackRubberMilkTubing5/8inI.Dw/ostripe1ft

GEAPoly(isoprene)orEPDMrubber;kaolin

Mineraloil;Santoflex13

1.5inchI.D.TigerflexMilkHose/Tubing

Kuriyama PVC;DOTP DOTP

3/4IDMilkhose/tubingperfoot SaintGobain PVC;glycerintriacetateGlycerintriacetate(“triacetin”)

5/8IDSiliconeMilkHose/TubingHambyDairySupply

Polydimethylsiloxane(PDMS,asilicone) Polydimethylsiloxane

5/8IDSurgeMilkHose/Tubing GEA PVCGlycerintriacetate(“triacetin”)

Clear PVC tubing 1/2in ID x 3/4inODfoodgrade,100ft/roll

NelsonJameson PVC;DOTP DOTP

CSC200CleargardPVCclearhelix,2insuctionhose,foodgrade,100ft/roll

SaintGobain PVC;DOTP DOTP

Whilethetestsofsamplemilkhosesdidnotfindanyphthalates,theydoshedlightonsomeofthealternativestophthalate-plasticizedPVCavailableformilkhoses.

• First,thefivePVCmilkhosesareplasticizedwithtwodifferentnon-phthalateplasticizers–DOTPandglycerintriacetate.DOTP(orDEHT),aterephthalate,hasperformancepropertiesverysimilartoDEHP,butwithouttheendocrinedisruption,developmentalandotherhazardcharacteristicsofDEHP.GlycerintriacetateisapprovedbyboththeEUandFDAforfoodcontactuses.45

• Inaddition,threeotherpolymersareusedinthesehoses.Oneofthehosesissiliconeandrequiresnoadditionalplasticizer.Theothertwoaresyntheticrubber–onebased

43Alltestswerecarriedoutby,oratthedirectionof,theEcologyCenterinAnArbor,Michigan.Thecompletetestresultsforallproductstested,aswellasadescriptionofthetestingmethodology,areinAppendixI.LinkstotheequipmentatthesitesfromwhichtheproductswerepurchasedareincludedinthatAppendix.44Wherepossible,thecompaniesmanufacturingthehoses(TBL,Kuriyama,SaintGobain),orotherequipmentinsubsequenttables,areidentified.Thisincludeshosesthatarepartofmajordirectequipmentsalesandservicesfordairies(e.g.,GEA).Otherwisethedistributors(HambyDairySupply,NelsonJameson)arelisted.Basedonseparateinformationfromaninterview(seebelow),itispossiblethattheGEAhosesaremanufacturedbySaintGobain.45http://www.eastman.com/Literature_Center/T/TT141.pdf

1 6


onacrylonitrile/butadiene/styreneorpolystyrene,theotherEPDM.Allofthesyntheticrubberhosescontainmineraloil,whichmaybeaprocessingaidoraplasticizer.

Testresultsforinflations/liners

Twotypesofinflationsweretestedforphthalates.Bothweremadefromsyntheticrubberbasedonacrylonitrile/butadiene/styrene.OneincludedtheplasticizerDEHA,anadipate.Theotherusedacombinationofphthalatesexceeding10%byweightofthematerial.

Table2:TestforPhthalates:Inflations46

ProductNameCompanyorDistributor

MaterialResultfromFTIR

SolventExtractionFTIRresult

GC/MSResults

Westfaliaoriginal086,setof4 GEA

Acrylonitrile;polystyrene;polybutadiene;SiO2;carbonblack

Adipate;Santoflex13

DEHAsubstantiallypresent;DOTPtrace

NuPulseCowInflations(4)OEMparts

HambyDairySupply

Acrylonitrile;polystyrene;polybutadiene;SiO2;carbonblack

Ortho-phthalatePhthalates:DIDP9.06%,DINP1.11%;Adipates:DEHAtrace

Eventhoughthetestsonlyinvolvedtwosamples,theydemonstratedtwoimportantconcernsaboutpotentialcontaminationofmilkbyphthalatesatdairyfarms.

• Theonepieceofequipmentwithdirectcontactwiththecow’steatsduringmilkingcanbeasourceofphthalatecontamination.Itispossiblethattheactionoftheinflationduringmilkingmaypromoteleaching.

• PVCproductsarenottheonlysourceofconcernforphthalatecontamination.EventhoughthepercentbyweightofphthalatesintheNuPulseinflationislowerthanwhatwouldbeexpectedinPVC,itissubstantial.

Testresultsforfiltersandgaskets

Gasketsandinflationsareincontinuouscontactwiththerawmilkintheclaws,pipes,platecoolersandbulktanks,thoughthecontactismorelimitedthanforhosesandinflations.Whiletherawmilkishotinitially,itiscoolbythetimeitreachesthebulktank,soheatwouldplayasmallerroleinleaching.Whiletherewouldbelittleconcernforsiliconegaskets,rubbergasketsappeartobebyfarthemostcommon.Theneedforplasticizationwouldseemlikelytobelower,butphthalatescouldbepresentinrubberproducts.

46ThecompletetestresultsforallproductstestedareinAppendixI.Linkstotheequipmentatthesitesfromwhichtheproductswerepurchasedareincludedonthattable.

1 7


Table3:TestforPhthalates:Filter&Gaskets47

ProductNameCompanyorDistributor MaterialResultfromFTIR


SchwartzFilter-CleanTuffy49/16"milkfilter Tuffy

polyester+astyreneacrylicpolymer

Inconclusive;noevidenceofphthalate

1.5SurgeGasketforstainlesssteelpipeline

HambyAcrylonitrile;polybutadiene;talc

DOTP

GasketforBouMaticbarrelclaw Boumatic

Inconclusivepolymer(maybeEPDM);calciumcarbonate;silica

mineraloil;silica

WindowGasketforWestfaliaBio-Milker

GEAInconclusiveduetocarbonblackdistortionofspectrum

Inconclusive.Noevidenceofphthalates

212O-ringFDAEPDMBlack Nelson-JamesonInconclusiveduetocarbonblackdistortionofspectrum

mineraloil;othercomponents.Inconclusive.Noevidenceofphthalates

Evenwiththeuncertainpolymerreadings,ausefulresultisthatoneofthegasketsisplasticizedwithDOTP.WhileDOTPisanon-phthalate,itisacommonsubstituteforDEHP,suggestingthepotentialforphthalatesingaskets.

Thefilterisapolyester,whichisacommondescriptionofmaterialfordisposablefilters(mostcommoninmilkingsystems)availablefromdistributors.Asdiscussedabove,permanentfiltersarelikelytobestainlesssteelorhardplasticmesh.48Filtersappeartobealesslikelysourceofphthalatecontamination.

Testresultsforcleaning&disinfectionequipment

Sincethemostlikelysourcesofphthalateswouldbethehoseforautomateddisinfectantapplicationsystemsoranyflexiblecomponentforhand-heldapplicators,testswererunontwohand-heldapplicatorsandonehose.

47ThecompletetestresultsforallproductstestedareinAppendixI.Linkstotheequipmentatthesitesfromwhichtheproductswerepurchasedareincludedonthattable.48DeLaval,“EfficientMilkFiltration”http://www.delaval.ch/ImageVaultFiles/id_26182/cf_5/53570972BR_Filter-handbook.PDF

18


Table4:TestforPhthalates:Cleaning&Disinfection49



ReplacementbottleforAmbicDipCups

Ambic Polyethylene nothingextracted.

ReplacementbottleforHamby&RJBDipCups

Ambic Polyethylene nothingextracted.

CleartubingforambicteatsprayerATS410

Ambic PVC+DOTP DOTP

Theresultsconfirmthepotentialforhoseswithphthalates.Inthiscase,theplasticizerisDOTP,acommonalternative/substituteforphthalateplasticizers.Butitdoesindicatethepotentialforphthalateplasticizationofthehoseusedinautomateddisinfectantapplication.

Testresultforsilagewrap

Onepieceofusedsilagewrapwasacquiredfromadairyfarm.Nosamplesofbunkercoverswereobtainedfortesting.

Table5:TestforPhthalates:SilageWrap



SilageWrapSample Noinformationpolyethylene+poly(isobutene)

nothingextracted.

Thistestdidnotindicateanysourceofphthalates.Becauseofthecomplexityofpotentialsourcesofphthalatesinfeed,aresearchdesignfocusingfirstoninstancesofphthalatesinsamplesfromhand-milkedcows,andthentestingpotentialequipment(aswellasother)sourcesmightbemoreeffectiveinestablishinglinkages.50

49ThecompletetestresultsforallproductstestedareinAppendixI.Linkstotheequipmentatthesitesfromwhichtheproductswerepurchasedareincludedonthattable.50WhiletheBelgianstudyissuggestive,thelackofanytestingof,orinformationon,thematerialsusedmakesitdifficulttoknowwhattypeofequipmentmighthavebeenused,orhowtoapplytheresultsmorebroadly.Fierens,Tine,etal."PhthalatesinBelgiancow’smilkandtheroleoffeedandothercontaminationpathwaysatfarmlevel."Foodandchemicaltoxicology50.8(2012):2945-2953.https://www.ncbi.nlm.nih.gov/pubmed/22659009

19


IV. InformationfromDairyEquipmentSuppliers

Websitesand/orcontactedcompaniesmanufacturingand/orsellinghoseandinflationequipmentfordairiesprovidedinformationtosupplementthetests.Whilenotintendedasacomprehensivesurveyofwhattypesofmaterialareonthemarket,itdoesprovidesomeadditionalinsightintopotentialsourcesofphthalatesinequipment,andperspectivesonprevalenceofhosesandinflationsplasticizedwithphthalates.Thetablebelowprovidesasummaryofsomerelevantinformationaboutuseofphthalatesandalternatives.Allofthesecompaniesmanufactureand/orsellawidevarietyofproducts;thetablebelowincludesonlythosethat,onthebasisofwebsiteinformationorpersonalcommunications,appearedmostgermanewithrespecttouseofphthalatesasplasticizers.

Table6:CompaniesManufacturing/ProvidingMilkHoses/Inflations51

Companies MaterialinformationSaint-Gobain52 • MajorinternationalfirmwithoperationsinU.S.;businessesinclude

developingandmanufacturinghighperformancematerials. • Manufacturesmilkhosesusedbyseveraldairy

equipmentcompanies. • PrincipalmilkhoseproductsTygon-M-34-R(thermoplasticPVC

blendedwithotherpolymers,non-phthalateplasticizer)andTygonIIsiliconetubing(noplasticizer).53

• TygonM-34-Rwasreformulatedin2012toeliminatephthalates. • Patentslistalargenumberofpossibleplasticizersfor

thermoplasticelastomers,includingbio-based&terephthalates54GEA55

• InternationaltechnologyandfoodequipmentandservicescompanybasedinGermany.ComprehensiveproviderofequipmentandservicestoU.S.dairyindustry.

51Inadditiontothecompaniesincludedinthetable,twoadditionalcompanieswereidentifiedwithplanstoentertheU.S.marketwithnon-phthalatehoses:Terraflex,anIsraelifirmwithaPVChosewithDOTPplasticizer(emailfromBatshevaLerner,InternationalSalesManager,1/23/18)andUdderOne,whichalreadymanufacturesandsellsaurethane-basedinflation(http://udderone.com)52Phoneinterview(2/12/18)andemail(2/7/18),JessicaKenepp,AssociateSalesEngineer,SaintGobain;https://www.processsystems.saint-gobain.com/applications/raw-milk-collection;http://www.tygons3tubing.com/Transflow-S3-M-34-R-Tubing.pdf;https://www.processsystems.saint-gobain.com/news/silicone-vs-epdm-rubber-tubing-does-it-make-difference-milk-processing-applications.53Thereareseveraldifferentvariantsofthesetubeswithdifferentnames(e.g.,TransflowS3M-34-Rsiliconetubing)54Patent#9,416,267;“Blendcomposition,flexibletubingmaterialandmethodofmakingtheblend,”http://patft.uspto.gov/netacgi/nph-Parser?Sect1=PTO2&Sect2=HITOFF&p=1&u=%2Fnetahtml%2FPTO%2Fsearch-bool.html&r=1&f=G&l=50&co1=AND&d=PTXT&s1=9416267.PN.&OS=PN/9416267&RS=PN/941626755PhoneconversationwithChadCarlson,GEA(2/12/18);https://www.gea.com/en/productgroups/milking-systems/index.jsp;https://www.gea.com/en/productgroups/farm-equipment/index.jsp;https://www.gea.com/en/products/gea-liner-overview.jsp;

20


• Milkhosesandinflations/linersprovidedbothaspartof/replacementsforcompletedairysystemsandforseparatepurchasethroughdistributors• Bothavailableeitherinsiliconeorrubber;allphthalate-free• PrimarilypurchasetubingfromSaint-Gobainandrepackageunderownlabel

DeLaval56 • Swedish-basedinternationaldairyequipmentandservicescompanywithoperationsinUS• Alllinersandtubesphthalate-free• Initialchallenge,latersolved,whenendedalluseofphthalatesinproductsinUSmarketatendof2015:somehosesbecamehardincoldweather• Produces rubber liners and tubing in plant in US, silicone andsomeotherrubberproductsinfacilitiesinEurope

Finger-LakesExtrusion(FLE)57

• Glitex181seriesmilkhoseisPVCplasticizedwithDEHP,asignificantortho-phthalate,inrangeof30%-40%byweight• FLEcurrentlyprovideshoseswithoutphthalates,butnotthatcanwithstandtheextremecleaningconditionsfordairyhosesorremainflexibleatlowtemperaturesinwinter.• CurrentlynearendofpiloteffortatseveraldairyfarmswithPVChosewithanon-phthalateplasticizer.Expecttoputinmarketthisyear.Onceonmarket,onlyplantohaveone(non-phthalate)milkhose.

TBL58 • Manufactures one of tested hoses: DairyFlow high performancemilk and dairy transfer tubing (styrene block co-polymer withmineraloi);plasticizerfree.• Describedonwebsiteashavingsuperiortearresistanceto“traditionalsiliconeandrubbermilktubing.”

Kuriyama59 • Tigerflexoneoftestedmilkhoses(PVCwithDOTP,aterephthalate).• KuriyamaofAmericaapartofKuriyamaHoldingsCo.,aJapanesebasedcorporationmanufacturingplasticsandrubberproductsforavarietyofindustrialandconstructionapplications,includingTigerflexMILKTMSeriesLowTemperatureFoodGradePVCLiquidSuctionHose

https://www.gea.com/en/binaries/DairyFarming_Flyer_IQ_Liner_EN_tcm11-19980.pdf;https://www.gea.com/en/productgroups/milking-systems/liners-tubing/index.jsp56EmailfromSarahTolleson,DeLaval(2/7/18);https://www.delaval.com/en-us/about-us/;http://www.delavalcorporate.com/;https://www.delaval.com/en-us/our-solutions/milking/at-the-milking-point/liners-tubes/;personalcommunications57EmailsfromTedLiberatore,CustomeraccountManager(12/7/17,2/5/18);copyofgeneralletter(ToWhomItMayConcern)fromKeithEllsworth,FingerLakesExtrusionProductionManager,dated6/21/13statingthatGlitex181tubingcontainsDEHP;http://www.flextubing.com/products/dairy/glitex-181ms-milk-tubing/.SeeAppendixII58https://www.tblplastics.com/tubing/dairy-flow-milk-transfer-hose/59https://www.kuriyama.com/;https://products.kuriyama.com/keyword/kuriyama-of-america/ature-food-grade-pvc-liquid-suction-hose-1?keyword=food%20hoses&key=product&SchType=2&filter=1

21


Milkrite60 • Two-layerhose:innerlayerofthermoplasticvulcanizate(TPV)rubber;outerlayerofblackrubber• Statesthatbutterfatcan’tmigratethroughinnerliner.• Providestableofdurabilityofliners/inflations(apparentlyofsamematerial)• Theyalsohaveotherhoseswheretheydon’tspecifymaterial• Nostatementaboutwhatorifanyplasticizer.

Conewango61 • WentDEHP/phthalate-freein1999-2000forbothlinersandhoses• Providebothrubberandsiliconehoses

AceSanitary62 • FlexRiteADLdairylinetubingisDEHP-andphthalate-free• Whilenotsilicone,nodescriptionofmaterials(possiblyTPE).

LaurenAgrisystems63

• Siliconemilkhosesandliners;noplasticizers• Uses“silicone-likecompoundsusingFDAapprovedingredientsforfoodcontact”

Freelin-Wade64 • ProducesPVC80Atubingfromspecialtythermoplasticelastomercompound;nophthalates.• IdentifiedingeneralstatementfromFreelin-Wade(3/24/17)ascompliantwithREACHandProp65,andinDataDocument(September2015)asformulatedforthemedicalandfoodindustries.• Whiledescribedassuitableformilkprocessing,maynotbesuitablefordairyfarmmilkhosesincenotcompliantwith3Adairystandards.

60www.milkrite.com/US/Products/ultraclean.htm;www.milkrite.com/US/Advice/2500_milkings.htm61PhoneinterviewwithJeffreyPerkins,GeneralManager,Conewango(2/5/18);https://conewango.com62http://acesanitary.com/sites/default/files/ADL%20cut%201-13-14.pdf;63http://www.laurenagrisystems.com/milking-systems;

http://www.laurenagrisystems.com/lib/sitefiles/pdf/whitepapers/Liner-Material.pdf64Phoneconversation(2/12/18)andemail(12/7/17),LoriDurand,InsideSales,Freeing-Wade;https://www.freelin-wade.com/clear-pvc-tubing#1;PVC80ADataDocument(issuedSeptember2015);certificationstatementonPVC80AtubingbyFreelin-WadeGeneralManagerScottSchwarm(3/24/17).

2 2


V. Findings

Boththetestingofequipmentforphthalatesandthebriefreviewsofindividualcompaniesinvolvedinoneormorephasesofsupplyingtheequipmenttodairyfarmswerelimitedinscope.Buttheynonethelessprovidesomevaluableindicatorsaboutpotentialsourcesofphthalatesfromdairyfarmequipment,oftrendstowardlessrelianceonphthalates,andopportunitiestopromotegreaterreductionsinequipmentcontainingphthalates.Thissectionreviewssomeoftherelevantfindings.Thenextsectionsuggestssomepossiblenextsteps.

1.Boththetestsofmaterialsandthestatementbyacompanystillusingphthalatesinitsmilkhosedemonstratecontinueduseofphthalatesinmilkingequipment,bothinPVCandrubbermaterials.

a. BecauseofthehighpercentcontentofphthalatesusedinsomemilkingequipmentPVCandrubberproducts,andthecontinuousexposuretowarm,highfatrawmilk,suchequipmentposesthehighestriskofdairyfarmequipmentforcausingthepresenceofphthalatesintherawmilk.

b. Uncertaintiesaboutwhethercompanieshavemadeafulltransitiontophthalate-freematerialsresultfrom:

i. Questions,inthecaseofsomecompanies,aboutwhethertheyarestillsellingphthalate-plasticizedequipmentaswellasphthalate-freeequipment.

ii. Preferenceofsomecompaniestomakenostatementsaboutphthalateseventhoughtheymayhavemadethetransition.

2.AsubstantialrangeofalternativestoPVCorrubberplasticizedwithphthalatesarecurrentlyavailableinthemarketfordairyfarmequipment.

a. AlternativesincludebothPVCandsyntheticrubbermaterialswithnon-phthalateplasticizersandalternativepolymericmaterialsthatrequirenoplasticizers.

b. Alternativesarenotonly fromnichecompanies,butare readilyavailable frommajordairyfarmequipmentproviders.

3.Thereissubstantialevidencethatmanysuppliersaremovingawayfromphthalates,butlimitedinformationanddividedopinionsontheextenttowhichuseofphthalate-plasticizedequipmenthasdeclined.

a. European-basedcompanieshavemadepublicchanges–e.g.,Saint-Gobain(France)reformulatedoneofitsmainhoseproductsin2012;DeLaval(Sweden)cancelledallphthalate-basedequipmentbyendof2015;muchofGEA’s(Germany)flexiblemilking-systemequipmentissuppliedbySaint-Gobain.

b. Anincreasinglywiderangeofalternativepolymersandnon-phthalateplasticizersareavailableinthemarket,thoughspecificinformationaboutthosealternativesisoftenproprietary.

23


4. Whilemoresuppliersaremovingawayfromphthalates,dairyfarmersshowrelativelylittleinterestin(oroftenevenawarenessof)theissue.65

5. Equipmentdurabilityhasincreased,butturnoverratesformostequipmentisayearorless.

a. Oneexampleisthetransitionfromnaturalrubberliners(goodforamaximumof800-1,000milkings)tosyntheticrubberandsiliconeliners(2,500milkings)toanevenhigherclaimforanewthermoplasticurethaneliner(5,000milkings);butthelongest-lastingmaterialsarephthalate-free.

b. Becauseoftherelativelyshortlifecyclesofanyofthematerialsplasticizedwithphthalates,thereisopportunityforarelativelyrapidtransitionawayfromphthalate-plasticizedequipment.

65Onecompanythatdevelopedanon-phthalatereplacementstatedthatonlyonecustomerhadeveraskedaboutphthalatespriortonewproductdevelopment.


VI. NextSteps

BecauseofEuropeanrestrictionsontheuseofphthalatesinfoodcontactmaterials,manyofthelargeEuropean-baseddairysupplycompaniesplayingmajorrolesintheUSdairyfarmmarkethavemadeacompletetransitiontophthalate-freematerialsinmilkhoses,inflationsandotherflexibleequipment.OthercompaniesaremakingsimilarchangesinanticipationofpossibleregulationsorpressuresintheU.S.Atthesametime,thereappearstobelimitedawarenessorconcernaboutphthalatesamongdairyfarmers.

Itseemsclearthatdairysuppliersareincreasinglysensitivetotheneedtoeliminatephthalates,whiledairyfarmersarenotyetfocusedontheproblem.Thissuggestsanopportunitytofocusadditionalattentionontheequipmentsuppliers.

Whilethereareasubstantialnumberofsuppliers,alargepartofthemarketislikelycoveredbyamanageablesubsetofthosesuppliers.Developingasupplier-focusedapproachaspartoftheoverallinformation-developmentstrategywouldinvolve:

• Developinginformationaboutcurrentphthalateorphthalate-freeproductsbythesuppliersandfocusingattentionbothonthosewhohavetransitionedawayfromphthalatesandthosewhohaveyettomakethatchange.

• Gatherreadilyavailablepricepointinformation(principallythroughdistributors)forcomparableproducts(e.g.,PVCmilkhoseswithorwithoutphthalates).Totheextentinformationisreadilyavailable,thiscouldalsoincludeassessmentstocomparethecost-effectivenessofalternativematerials.Forliners,forexample,somecompaniespublishestimatesofthenumberofmilkingsafterwhichlinersshouldbereplaced.66

Todevelopinformationonmajorandmid-sizedsuppliersofrelevantequipment(e.g.,liners,milkhoses,etc.),potentialsourcescouldinclude:

o Marketstudies,totheextentavailableandrelevant.

o Dairyextensionservices.

o Dairyorganizations.

o Individualexperts.o On-linesearches.

Subsequentstepscouldinclude:

• Reviewingwebsiteinformationforthesuppliersabouttheirproducts,andwhetherornottherelevantproductsarephthalate-free.

• Contactingsuppliersbyemailand/orphonetoclarifyinformationon:

66Itwouldgenerallynotbefeasible,however,toaddressotherfunctionalissues,suchaseaseofuseorfactorsaffectingspeedorefficiencyofmilking.

2 5


o Whetherallorsomeoftherelevantproductstheysupplyarephthalate-free.

o Plansforreplacinganyproductscurrentlyusingphthalates.

Thisinformationcouldbeusedtohighlightavailabilityandprice/long-termcostcomparabilityofphthalate-plasticizedandphthalate-freeequipment.

Additionally,otherpotentialsourcesofphthalatemigrationintofoodproductsshouldbeinvestigated,including:

• Otherpotentialsourcesatthedairyfarmlevel;• Otherpotentialsourcesfurtherdownstreaminthedairyproductsupplychain,

includingprocessing,packaging,andfoodpreparation;and• Otherpotentialsourcesofphthalatemigrationintoothertypesoffoodproducts.

26

27


AppendixI

PhthalateTestResults


Ecology Center FTIR Results (Qualitative identification)

Web ID Product Type Product Name Distributor Intact material

Solvent extraction of material

25426 Tubing DairyFlow High Performance Milk and Dairy Transfer Tubing

McMaster Carr

Polystyrene copolymer (e.g. polystyrene/ethylene-propylene)

Mineral oil

25427 Tubing Black Rubber Milk Tubing 9/16 in 1.0 1 ft Leedstone

Poly(isoprene) or EPDM rubber, kaolin

Mineral oil; Santoflex 13

25428 Tubing Black Rubber Milk Tubing 5/8 in I.D w/o stripe 1 ft

Leedstone Poly(isoprene) or EPDM rubber, kaolin

Mineral oil; Santoflex 13

25431 Tubing 1.5 inch I.D. Tigerflex Milk Hose/Tubing

Hamby Dairy PVC; DOTP DOTP

25432 Bottle Replacement bottle for Ambic Dip Cups

Hamby Dairy Polyethylene

Nothing extracted.

25433 Bottle Replacement bottle for Hamby & RJB Dip Cups

Hamby Dairy Polyethylene Nothing

extracted.

25434 Inflations

Inflation (Liner) medium bore for 06 shells WESTFALIA ORIGINAL 086 set of 4

Hamby Dairy Supply

Acrylonitrile; polystyrene; polybutadiene; SiO2; carbon black

Adipate; Santoflex 13

25435 Tubing 3/4 ID Milk hose/tubing per foot

Hamby Dairy

PVC; glycerin triacetate

Glycerin triacetate

25436 Gasket/O- ring

1.5 Surge Gasket for stainless steel pipeline

Hamby Dairy

Acrylonitrile; polybutadiene; talc DOTP


Gasket for Bou-Matic barrel claw

Hamby Dairy

Supply

Inconclusive polymer (may be EPDM); calcium carbonate; silica.

Mineral oil; silica

25438 Tubing 5/8 ID Silicone Milk Hose/Tubing

Hamby Dairy Polydimethylsiloxane

Polydimethyl-siloxane

25439 Tubing 5/8 ID Surge Milk Hose/Tubing

Hamby Dairy PVC Glycerin

triacetate

25440 Gasket/O- n.ng

Window Gasket for Westfalia Bio-Milker

Hamby Dairy Supply

Inconclusive due to carbon black distortion of spectrum

Inconclusive. No evidence of phthalates

25441 Tubing Clear PVC tubing 1/2in ID x 3/4in OD food grade, 100ft/roll

Nelson Jameson PVC; DOTP DOTP

25442 Tubing CSC200 Cleargard PVC clear helix, 2in suction hose, food grade, 100ft/roll

Nelson Jameson PVC; DOTP DOTP


212 0-ring FDA EPDM Black

Nelson Jameson

Inconclusive due to carbon black distortion of spectrum

Mineral oil; other components inconclusive. No evidence of phthalate.

2 8

2 9


25444 Inflations NuPulse Cow Inflations (4) OEM Parts

Hamby Dairy Supply

Acrylonitrile; polystyrene; polybutadiene; SiO2; carbon black

Ortho-phthalate

25457 Tubing Clear tubing for ambic teat sprayer ATS410

Hamby Dairy PVC; DOTP DOTP

25458 Filter Schwartz Filter-Clean Tuffy 49/16" milk filter

Hamby Dairy Supply

Polyester, styrene acrylic polymer

Inconclusive. No evidence of phthalate.

25466 Silage Wrap Silage Wrap Sample 0

Polyethylene; poly(isobutene)

Nothing extracted.


LinksforTestedProducts

Web ID Product Type Webpage 25426 Tubing https://www.tblplastics.com/tubing/dairy-flow-milk-transfer-hose/ 25427 Tubing http://www.leedstone.com/black-rubber-milk-tubing-5.html 25428 Tubing http://www.leedstone.com/black-rubber-milk-tubing-5.html 25431 Tubing http://hambydairysupply.com/xcart/product.php?productid=1307&cat=&page=1 25432 Bottle http://hambydairysupply.com/xcart/product.php?productid=802 25433 Bottle http://hambydairysupply.com/xcart/product.php?productid=17580 25434 Inflations http://hambydairysupply.com/xcart/product.php?productid=19042 25435 Tubing http://www.hambydairysupply.com/xcart/product.php?productid=17827 25436 Gasket/O-ring http://hambydairysupply.com/xcart/product.php?productid=498 25437 Gasket/O-ring http://www.hambydairysupply.com/xcart/product.php?productid=1054 25438 Tubing http://hambydairysupply.com/xcart/product.php?productid=347&cat=325&page=1 25439 Tubing http://hambydairysupply.com/xcart/product.php?productid=356 25440 Gasket/O-ring http://hambydairysupply.com/xcart/product.php?productid=18457 25441 Tubing http://nelsonjameson.com/1-2-PVC-Tubing-Clear-p10416.html 25442 Tubing http://nelsonjameson.com/Versilon-Clear-Helix-Hose-CSC-p8597.html 25443 Gasket/O-ring http://nelsonjameson.com/O-Ring-p44994.html 25444 Inflations http://hambydairysupply.com/xcart/product.php?productid=18219&cat=309&page=

1 25457 Tubing http://hambydairysupply.com/xcart/product.php?productid=18896&cat=&page=1 25458 Filter http://hambydairysupply.com/xcart/product.php?productid=50 25466 Silage Wrap

3 0

31


Ecology Center Test Results Summary: Dairy Equipment

Feb. 28, 2018

Ecology Center’s Healthy Stuff researchers analyzed 20 samples of dairy milking equipment for the primary purpose of detecting ortho-phthalate plasticizers (abbreviated “phthalates”). The secondary purpose was to identify other plasticizers, other additives or contaminants, and the polymer matrix.

Full results for each product are displayed in the spreadsheet titled “Ecology Center Full Test Results Dairy Equipment Feb 2018”.

XRF Results Low levels of lead were measured in four black rubber items ranging from 3.1 to 21.3 ppm lead. Two of these were milk tubing and two were gaskets.

Two flexible PVC hoses contained tin at levels suggesting possible organotin compounds. Tin was measured to be 1656 and 2177 ppm.

Five of the synthetic rubber products, including tubing, gaskets, and inflations, contained sulfur between 2.2-3.4 wt% along with zinc 1.3-3.5 wt%. We did not identify the sources of the sulfur and zinc. Sulfur and zinc oxide can be used together in the vulcanization of rubber, so vulcanization compounds are a possible source.

FTIR Results

Table 1. Polymer identifications, product types and plasticizers.

Polymer matrix No. of products

Product Types Plasticizers detected

Synthetic rubber based on acrylonitrile/butadiene/styrene

3 Inflation liners; Gasket

DOTP; DEHA*; DIDP*; DINP*

Synthetic rubber based on polystyrene/polypropylene

1 Tubing/hose Mineral oil

Synthetic rubber based on polyisoprene or EPDM

2 Tubing/hose Mineral oil

PVC 6 Tubing/hose DOTP; Triacetin Polyethylene 3 Bottle; Silage wrap None Silicone rubber (PDMS) 1 Tubing/hose PDMS Polyester with styrene acrylic 1 Milk filter Inconclusive

32


Inconclusive 3 Gaskets/O-rings Mineral oil; Inconclusive

Total 20 * These specific adipate and phthalate species were identified by GC/MS.

Abbreviations: EPDM = ethylene/propylene/diene monomer PDMS = polydimethyl siloxane DOTP = dioctyl terephthalate DEHA = diethylhexyl adipate, bis(2-ethylhexyl adipate) DIDP; DINP = diisodecyl-; diisononyl phthalate Triacetin = glycerin triacetate

Table 2. Additives detected other than plasticizers.

Polymer matrix Additives Synthetic rubber based on acrylonitrile/butadiene/styrene or polystyrene

Silicon dioxide; carbon black; talc; Santoflex 13 antioxidant

Synthetic rubber based on polyisoprene or EPDM

Santoflex 13 antioxidant; kaolin

Inconclusive Calcium carbonate, carbon black

Table 3. Comparison of Ecology Center’s FTIR analysis and TUV’s GC/MS analysis.

ID# Product Name Plasticizer Identification from Solvent Extraction / FTIR

Result from GC/MS

25434 Westfalia Inflation

Adipate DEHA substantially present; trace DOTP

25444 NuPulse Cow Inflation

Phthalate DIDP 9.06%; DINP 1.11%; trace adipate

The identifications from FTIR were consistent with the measurements from GC/MS.

3 3


TEST REPORT g. TÜVRheinland

Test Report No.: Report Date:

Client:

31850466.001 Page 1 of 3 27 February 2018

Jeff Gearhart Ecology Center 339 East Lterty, Stile 300, Ann Arbor, Ml 48107 Phone: (734)369-9276 Emad: jeffgercocentrrorg

Client Number: 50008114

Order Number 156682 Date of Receipt: 22 February 2018

kem Description: Inflation Liners St of Samples Submitted: 2 Product Code: NA kern Number: NA Style Number: NA Color: Black UPC: NA PO: 1376 Country of Drein: USA Manufacturers name: NA Country of Destination: NA Retest? No Delivery condition: Apparent good Test Category: General Purpose Testing Phase: NA

Customer Test Institobons:

Test specification.

1. Selected Phthalates

Test result:

See Data For and on behalf of TUV Rhineland d of North America

...144.4

For and on behalf of TUV Rheinland of North America

Mark Smith I Laboratory Manager Phone: (479)250-0059 Emad: msmithfeus.tuv.00m

William TyeeI Chemist Phone: (479)250-1932 Emad: wtyreet2us.tuv.com

Ws lasIzapatizelales leihe aboee znaninanadlesliiam anclanuni° I sesta perbanat 'Düs losl zeparlisnalpeemalad lote aliplicaladh erkris wlhata peemission o lha les1 face. This les: 'wog does na anega any ‚dee malcon Iltis ar simiJar podace.

TuV Regere« Nue Nun. I,c 2709So4Ah Ent OZ Cal oa Diva Surn II. Soarzeena AR 72712 Phow 471,250.X66 /Fax 479254 0621 Zea> vetiYa./LCO/Tai


A TÜVRie in land

Test Reort No.: 31850466.001 Page 2 of 3 Testing Period: 26 Feb 2018 to 27 Feb 2018

Material Breakdown List - Chemical Testing

Material No. Material Color Component / Location

I Substrate Black 25434 Inflation Liner West Falia 2 Substrate Black 25444 NuPulse Inflations

RESULTS

1. PHTHALATE CONTENT IN SUBSTRATES:

Test method: The sample was analyzed by organic solvent extraction and GCMS based on CPSC-CH-C1001-09.3. Detected analytes are highlighted in red.

Test No. 1 2 Material No. 1 2

Analyte CAS Results ResultsDEP 84-66-2 <0.005% <0.005% DIBP 84-69-5 <0.005% <0.005% DBP 84-74-2 <0.005% <0.005% DPP 131-18-0 <0.005% <0.005%

DNHP 84-75-3 <0.005% <0.005% BBP 85-68-7 <0.005% <0.005%

DEHP 117-81-7 <0.005% <0.005% DCHP 84-61-7 <0.005% <0.005% DNOP 117-84-0 <0.005% <0.005%

DINP 28553-12-0 68515-48-0 <0.005% 1.11%

DIDP 26761-40-0 68515-49-1 <0.005% 9.06%

DOTP 6422-86-2 Trace ND DBA 105-99-7 ND ND

B2EHA 103-23-1 Present Trace B2PHP 53306-54-0 ND ND

Method Dezection Limit = 0.005% DIBP = Diisobutyl phthalate DNHP = Di-n-hexyl phthalate DCHP = Dizyclohexyl phthalate DIDP = Diisodecyl phthalate

DBP = Dibutyl phthalate EIBP = Benzyl butyl phthalate DNOP = Di-n-octyl phthalate DEP = Diethyl phthalate

DP P = Dipentyl phthalate DEHP = Di-(2-ethylhexyl) phthalate DINP = Diisononyl phthalate

Clualitatively Detect (Present)/ Non-Detect (ND) identified by retention time and mass spectrum

DOTP = Dioctyt terephthalate DBA = Dibutyl adipate B2EHA = Efs(2-ethylhex-yI) adipate 82PHP = Bis(2.propylheptyt) phthalate

TUV Rheinian1 of Norel America. Inc. 2703 South East Otte Caley DrNe. State 11. BentorNlie, AR 72712 Ferne: 479-250-00661 Fax 479-254-0821 Web: mem ‚Naenfuß

3 4

3 5


Methods for Ecology Center Screening of Dairy Equipment Samples Feb. 28,2018

FTIR Ecology Center's Healthy Stuff researchers analyzed 20 samples of dairy milking equipment for the primary purpose of detecting ortho-phthalate plasticizers (abbreviated "phthalates"). The secondary purpose was to identify other plasticizers, other additives, and the polymer matrix. The method is qualitative only, not quantitative. The approximate limit of detection is 1 wt% phthalate. This is a conservative LOD based on validation tests using gas chromatography/mass spectrometry carried out at third-party labs.

Before analysis, equipment samples were wiped with a Kimwipe wetted with isopropyl alcohol to remove dust and other contaminants from the surface. Pieces were cut with clean scissors or a knife to procure a sample of appropriate size.

A Thermo Scientific Nicolet iS5 Fourier Transform Infrared (FTIR) spectrometer was used in attenuated total reflection (ATR) mode with a diamond crystal. Each sample was clamped on the ATR sample stage and a spectrum was obtained from 4000-450 cm-I. To avoid cross-contamination, the ATR stage was thoroughly cleaned with isopropyl alcohol after each spectrum was obtained.

The resulting infrared spectra were analyzed visually and compared against a library of known spectra to identify the polymer types and additives such as plasticizers and antioxidants. When a likely match was identified, we visually examined the positions and intensities of the major spectral peaks to judge the closeness of the match. We reported very close matches as the results.

Some of the dairy equipment products were made of complex polymer mixtures, resulting in complex spectra that were challenging to deconstruct in some cases, additives including carbon Mack and calcium carbonate obscured spectral signals from the polymer matrix.

To separate organic additives such as plasticizers from the polymer matrix, we used a solvent extraction procedure for each sample. A solvent extraction method customized in-house was carried out for each sample. FT1R spectra collected from the solvent extractions were analyzed visually and compared against a library of known spectra to identify plasticizers and antioxidants. When a likely match was identified, we visually examined the positions and intensities of the major spectral peaks to judge the closeness of the match. We reported very close matches as the results.

We thus obtained two spectra from each equipment sample: one from the solid material and one from liquid, if any, extracted from the material. From the solid material we identified the polymer matrix and certain additives. From the extract we identified plasticizers and antioxidants.

3 6


Since the primary purpose was to identify phthalates, we checked all spectra for the unique fingerprint of phthalates. In particular we looked for characteristic peak patterns centered at 1601, 1581, 1040, and 744 cm'. These peaks, or bands, in the infrared spectrum are virtually identical for all phthalate species. Our method therefore does not distinguish between the species. This feature carries the advantage that all phthalate species are detectable.

FTIR is a well-established technique to identify polymer types and mixtures. The Healthy Stuff lab has repeatedly validated its FTIR identification of plasticizers in polymeric products by using an independent contract laboratory that uses highly sensitive gas chromatography coupled with mass spectrometry (GC/MS). These validation tests have included phthalates, adipates, dioctyl terephthalate (DOTP), acetyl tributyl citrate (ATBC), dibenzoate esters, and 1,2-cyclohexane dicarboxylic acid diisononyl esMr (DINCH).

GC/MS After FTIR screening, two products from the milking equipment sample set were sent to an independent contract lab, TUV Rheinland, to be analyzed for 12 phthalates (quantified) plus certain other plasticizers (qualitative detection) using GC/MS.

The GC/MS results corroborated the FTIR results. The Westfalia inflation liner was found to contain a substantial amount of bis(2-ethylhexyDadipate and the NuPulse inflation contained 9.06% diisodecyl phthalate and 1.11% diisononyl phthalate. The comparison is shown in Table 1.

Table 1. Comparison of Ecology Center's FTIR analysis and TUV's GC/MS analysis.

ID# Product Name Plasticizer Identification from Solvent Extraction / FTIR

Result from GC/MS

25434 Westfalia Inflation Adipate Bis(2-ethylhexyl adipate) substantially present; trace DOTP

25444 NuPulse Cow Inflation

Phthalate DIDP 9.06%; DINP 1.11%; trace adipate

XRF The 20 samples were analyzed by X-ray fluorescence for elemental composition using an XOS HD Prime benchtop analyzer. Elements heavier than magnesium are measured by this technique. The purpose was to gain insight into the composition of the products and to reveal any heavy metals or other hazardous elements that might be present Samples we placed intact under the XRF tip and analyzed in "Plastic" mode. Certified polymeric standard reference materials are used to verify accurate measurements.


Appendix II Communication on Glitex 181 PVC Tubing

37


Copy provided by email from Fingerlakes Extrusion, 12/7/2017 38


Appendix III

Companies Providing Flexible Tubing to Food Industry

39


Thefollowingspreadsheetisalistofcompaniesprovidingflexibletubingtofoodindustry,as

wellassomecompounders, representing the universe of companies we considered for examination.Forthepurposeofthecurrentstudy,wehaveconsideredsomeofthesefromthe

perspectiveofdairyequipmentsupplies.Onlyaverysmallnumberarecompanieswecontacted

directlyforthereport.Wehavealsobrieflyrevieweddataavailableonthewebsiteforsomeof

thecompaniesonthelisttodeterminetheirrelevancetothisstudy.The“Notes”column

providesthatinformation.Thosepotentiallyordefinitelyofinteresteitherfordairyorpotential

alternativematerialsarehighlightedingreen.This information has been included in the interest of transparency.

40


CompanyName Notes Web

SpectrumPlasticsGroup Focusonmedicaldevices;nomilkordairy www.spectrumplasticsgroup.com

IlpeaIndustriesInc.Appliance&construction;gasketsfor

foodservicewww.ilpeaindustries.com

Saint-GobainPerformance

PlasticsCorp.SeeTable6 www.plastics.saint-gobain.com

Tekni-PlexInc. Pharma,foodservice&packaging www.tekni-plex.com

TeelPlasticsInc. Medical www.teel.com

NewAgeIndustriesInc. Forfood&dairyproducts;nitrile www.newageindustries.com

CustomProfileInc. Medical www.custom-profile.com

PlastiflexCo.Inc.Floorcare;healthcare;industrial;sewer

&sanitationwww.plastiflex.com

PolyVinylCo.Inc. Noindicationofdairyuse www.polyvinyl.com

MarkelCorp. Automotive,coaxial,wire&cable www.markelcorporation.com

SpiratexCo. Industrial&military www.spiratex.com

FabricatedExtrusionCo.LLC Equipment;refrigeration www.fabexco.com

SunlitePlasticsInc. Medical www.sunliteplastics.com

ThermoplasticProcessesInc. Tygonequivalents;B-44-4Xfoodtubing www.excelon.com

ITWMedicalProducts Medical www.itwmedical.com

DrossbachN.A.Inc. Industrial www.drossbach.com

ReschcorInc. Household,medical,electrical www.reschcor.com

PetroPlasticsCo.Inc. Largelyindustrial www.petroplastics.com

Freelin-WadeCo. SeeTable6 www.freelin-wade.com

41


VIPRubberCo.Inc.MakesSantoprenetubingthatmeets

FDAspecs;noindicationofdairy

applications

www.viprubber.com

KellerProductsInc. Medical;anti-microbial www.kellerproducts.com

VersaprofilesProductsInc. Waterdistribution;naturalgas www.versaprofiles.com

SeaGatePlastics Possiblyfoodapplications www.seagateplastics.com

AppliedPlasticsInc.Statescanmanufactureextrusionsfor

anyapplicationswww.appliedplasticsinc.com

PlastifabIndustriesRetail,lighting,transportation,mining,oil

&gaswww.plastifab.ca

InplexLLC Multipleindustries,including‘food&candy’ www.inplexllc.com

FormtechEnterprisesInc.Listofapplicationsdoesnotinclude

food,exceptforrefrigerationwww.formtech.com

JetPlasticsAvailableproductsincatalogdon’t

includedairywww.jetplastics.com

ReevesExtrudedProducts

Inc.

www.reevesextruded.com

CertifiedThermoplasticsCo.

Inc.

www.ctplastics.com

MiddlefieldPlasticsInc. www.middlefieldplastics.com

ParkerNexgen www.nexgenhose.com

GSHIndustries www.gshindustries.com

HudsonExtrusionsInc. www.hudsonextrusions.com

CraftedPlasticsInc. www.crafted.com

FingerLakesExtrusionCorp. SeeTable6 www.flextubing.com

42


InlinePlasticsInc. www.inlineplasticsinc.com

BlackwellPlasticsLLP www.blackwellplastics.com

ExcaliburExtrusionsInc. www.excaliburextrusions.com

MeltpointPlastics

InternationalInc.

PlasticExtrusionTechnologies www.plasticextrusiontech.net

Hi-TechProfilesInc. www.hitechprofiles.com

PBSPlasticsInc. www.pbsplastics.com

PlasticsResourcesInc. www.pri-plastics.com

SeilerPlasticsCorp. www.seilerpc.com

AmericanExtrudedPlastics

Inc.Listsagriculturalapplications,butnodetail www.aeplastics.com

FramTrakIndustriesInc. www.framtrak.com

FowlerProductsInc. www.fowler-inc.com

ReissManufacturingInc.Silicone&thermoplasticsforalargerange

ofindustrialsectors;doesnotlistfoodwww.reissmfg.com

RyanDevelopmentCorp. www.ryandevcorp.com

Advanced

Extrusions/MidlandPlasticsNoindicationofmarket www.midlandplastics.com

ChristiPlasticsInc. www.christiplastics.com

AlphaPlasticsSolutionsInc. www.myapsi.com

SanDiegoCustomExtrusions www.drgassoc.com

PolyExtrusionsInc. www.polyextrusionusa.com

43


TeknorApexVarietyofnon-phthalateplasticizers;

notdairyorfoodwww.teknorapex.com

WestlakeChem/Axial

Severalphthalate-freecompounds,but

datasheetonfoodgradecompound

doesn’tspecify

www.westlake.com

PolyOne/Mexichem

Non-phthalateflexiblefoodgrade

formulations;PolyOnerecentlyacquiredby

Mexichem.Bio-derivedepoxidizedfattyacid

monoesterplasticizer

www.polyone.com

ShinTech

LargestPVCresinproducerinUS;

manufacturesfoodgradeTK1300equivalent

toOxyvinyl255F

www.shintechinc.com

44

sources of phthalates in dairy farm equipment

Documents