Current legislative framework for nanomaterials ......•A revised definition is being discussed. •Largely the same but with some important changes. •Clarification that it does

NanoMONITOR is partly funded by the European Commission Life+ withgrant agreement LIFE14 ENV/ES/000662

Currentlegislativeframeworkfornanomaterials:supporting

REACHregulationNanoMONITOR 1st Stakeholder’sDay

DrNeilHunt


• LegislativeframeworkaroundchemicalsintheEU• NanomaterialsandREACH

• Definitionofnanomaterialsandnanoforms• CharacterisationandrecentBoA decision• HazardassessmentofnanomaterialsunderREACH• ExposureassessmentofnanomaterialsunderREACH• RiskassessmentandriskcommunicationofnanomaterialsunderREACH

• NanomaterialsandotherEUregulations• NationalReportingSchemes• Conclusion

Contents


REACH

Biocides

PlantProtectionProducts

Cosmetics

Foodcontact

Medicinalandveterinaryproducts

• Regulationsareusebased.• REACHcoversallusesnotcoveredbyotherregulations.

• Nonano-specificregulation.• Eachregulationmayrequirenanomaterialstobeassesseddifferentlytobulkforms

RegulatoryframeworkforchemicalsintheEU


• Nanomaterial(draft):• Anatural,incidentalormanufacturedmaterialcontainingparticles,inanunboundstateorasanaggregateorasanagglomerateandwhere,for50%ormoreoftheparticlesinthenumbersizedistribution,oneormoreexternaldimensionsisinthesizerange1nm- 100nm.

• Nanoform(ECHA,RIVM,JRC(2016))• Theterm…….todistinguishformsofasubstancethatfulfiltheECRecommendationonthedefinitionoftheterm‘nanomaterial’butdifferwithregardtosizedistributions,shapeand/orsurfacechemistry.”

Usefuldefinitions


• Areviseddefinitionisbeingdiscussed.• Largelythesamebutwithsomeimportantchanges.

• Clarificationthatitdoesnotcoverindividualmolecules(macromolecules,dendrimers).• Notclearwhetherparticleswithadimensionof<1nmwillremainnanomaterialsornot.• SpecificSurfaceAreaof<5m2/cm3maybeusedtodefinesubstancethatarenotnanomaterials.

• The50%bynumbersizedistributionmayberegardedasindicativeandothervaluesmightbemorerelevantincertainsituations.

• Lotsofdebateanddiscussion,sothesemightchange!• HopefullywillbeinplacebeforeanyrevisionofAnnexXIVtoavoidreplicationofworkforregistrants.

Reviseddefinitionofnanomaterial


Primaryparticlesinunboundstate

Primaryparticlesasanagglomerate

Primaryparticlesasanaggregate

• “particles,inanunboundstateorasanaggregateorasanagglomerate”.

• Definitionbasedondimensionsofprimaryparticles

• Agglomeratecanberelativelyeasilybroken,butaggregatesarenoteasytobreakintotheirconstituentprimaryparticleswithoutdamagingparticles.

• Isprimaryparticleoragglomerate/aggregatesizekeyforriskassessment?

Definitionofnanomaterial– Keypoints


• 50%ormoreoftheparticlesinthenumbersizedistribution

• Modalaverageofnumberdistribution

• Cananalyticalmethodsmeasurenumberdistribution?

• Numberdistributionwilllookdifferenttovolumeorresponsedistributions.

• Arealotofpowdersgoingtofallunderthedefinitionunexpectedly?



• Oneormoreexternaldimensionsisinthesizerange1nm- 100nm.• Particles,rods,needlesandplatescanallbenanomaterials.• Shortestdimensionisthekeyparameter.• Doanalyticalmethodsmeasurethisdimension?• Nanoscaleporesandspacesdonotdefineananomaterial.



Nanoforms– Interconvertibility

Agglomerate

Original primary particles

Smaller primary particles

Coated (deliberate or environmental) particles


• Organicliquidsubstance• Onlychangeofstateisbetweensolid,liquidandgas.• Hazardsareintrinsictothesubstance.• Changesinstatemainlyaffectexposure.

• Nanomaterialpowder• Differentnanoformsofthesamesubstancemay displaydifferenttoxicologicalprofiles.

• Differentnanoformsofthesamesubstancemay displaydifferentexposurebehaviours.

• Whichformexistsateachpointinthelifecycle?• Isthehazard,exposureandriskassessmentappropriateforthenanoform?

Nanoforms– DifficultiesinLifecycleAssessment


Thehazardsandrisksarisingfromasubstanceshouldbeknown,andtheappropriateriskmanagementmeasurescommunicated,forsubstancesmanufacturedinorimportedtotheEU.

Toxicological/Ecotoxicological/PhysicalChemicalHazardsidentifiedbyoneentity(LeadRegistrant)

Otherregistrantsshouldreceivepermissiontousethisdataintheirregistrationdossierandensurethatitisrelevanttothesubstancethattheyplaceonthemarket

NanomaterialsandREACH

KeyaspectsofREACH



• AspectsofREACHapplytonanomaterialsastootherformsofasubstance.• Thesameinclusionandexclusioncriteria(polymers,mixtures,exemptions).• Timetableisthesame.• Samebasicinformationrequirementsbasedonproductionvolumesoftheregistrants.

• Informationintheregistrationdossiershouldapplytothesubstanceplacedonthemarket.

• Testingshouldbeadaptedtothepropertiesofthesubstance.




• Allsubstancesshouldbeidentifiedbytheirchemicalcomposition.• Requireidentificationandquantificationofconstituents

• Somesubstancesmaybefurtheridentifiedbyotherparameters(Guidanceforidentificationandnamingofsubstances,Section4.2.3)

• Particlesizementionedasapossibleparameter.• Whetherornotasubstanceisananomaterialisapossibleparameter.

• Substanceidentificationshouldbesufficienttoassesswhetherthedataintheregistrationdossierisapplicable.

Substanceidentification– GeneralpointsinREACH



ECHAdecision

• Registrantsoftitaniumdioxideshouldincludedetailsofallnanoformsaspartofsubstancecharacterisation.

Industry(Registrants)Appeal

• Thiswouldmeannanoformsofasubstancehadadditionalrequirementstobulkforms.ThisisnotinlinewithAnnexVIofREACH.

BoardofAppeal(BoA)Decision

• BoA foundinfavourofregistrantsBUTitwashighlightedthatitshouldbeshownthatdatainthedossierisapplicabletothesubstanceplacedonthemarket.

ImpactofrecentBoardofAppealdecision


• AnnexXVIstatesthecharacterisationrequirementsforREACH.• Currentlyparticlecharacterisationisanoptionnotanobligation.KeyissueinrecentBoA decision.

• Absenceofparticlecharacterisationmakesdossierandsubstanceevaluationdifficult.

• REACHrevisionscurrentlyestimatedtobeofficiallyinplacein2020.• ItiscurrentlyexpectedthatparticlecharacterisationtoidentifynanomaterialsandnanoformswillbemoreprominentinAnnexXVI.

• Thiswillapplytoallpowdersnotonlydeliberatelymanufacturednanomaterials.

RevisionofAnnexVIofREACH


Particlecharacterisationtoidentifynanomaterials


• UsesfluctuationsinscatteredlightcausedbyaparticletodeterminehowfasttheparticlemovesinasuspensionthroughBrownianMotion.

• Advantages:• Relativelycheapandeasytouse• Measuresastatisticallysignificantdistributionof

particlesizerelativelyrapidly• Disadvantages

• DistributionmeasuredbysignalintensityorvolumeNOTnumber

• Doesnotdistinguishagglomerate/aggregatesfromprimaryparticles

• Measureshydrodynamicradius• Conclusion

• Goodscreeningtool.• IfDLSindicatesasampleisananomaterial,italmost

certainlyis!• Shouldnotbeusedinisolation

DynamicLightScattering


• Useelectronbeamstovisualiseparticlesatmagnificationsthatcannotbeachievedusingopticalmicroscopy.

• Advantages• Primaryparticlescanbedistinguishedfrom

agglomerates/aggregates• Particlesizeandshapecanbemeasured• Shortestdimensioncanbemeasured

• Disadvantages• Multipleimagesneededtogiveastatisticallysignificant

samplesize• Probablyrequiresoperatorinputandjudgementtoidentify

primaryparticles• Givesa2-Dimageof3-Dobject

• Conclusion• Essentialtoolforparticlecharacterisation• Canbeusedtocheckwhetherresultsfromothermethods

canbeusedtomeasureprimaryparticlesizedistribution.

ParticleCharacterisationofNanomaterials

ElectronMicroscopy(ScanningorTransmission)


• Tracksscatteredlightpatternscausedbyindividualparticles.Usesvelocitythroughamediumtocalculateparticlesize.

• Advantages• Measuresnumberdistribution• Relativelylowcost• Canbeusedwithlowconcentrationsamples

• Disadvantages• Measureshydrodynamicradius• Cannotdistinguishprimaryparticlesfromagglomerates/aggregates

• Conclusion• Usefultooltodirectlymeasurenumberdistributionofparticles

• Needsmicroscopytoconfirmexactlywhatisbeingmeasured.

ParticleTrackingAnalysis


• CalculatesSSAbymeasuringamountofagasthatcanbeadsorbedontothesurfaceofthesample.

• SSA>60m2/cm3 regardedasindicatingananomaterial.

• SSA<5m2/cm3may beacutoffornot beingananomaterial(newdefinitionofnanomaterial).

• Advantages• Wellknownmethodwithmanyproviders.Standard

methodsavailable.

• Disadvantages• Notameasurementofprimaryparticlesizedistribution.• Internalstructures(pores,tubeinteriors)canbiastowards

highervalues.• Knowledgeofdensityisrequired.

• Conclusion• Cannotbeusedinisolationbutisveryusefultosupport

conclusions.

SpecificSurfaceArea(SSA)byBrunauer EmmettTeller(BET)analysis


• Samplepreparationkeytomeasuringwhatyouthinkyouaremeasuring.• Howareagglomeratesbroken?• Areadditivesrequiredtokeepprimaryparticlesunbound?• Isthesubstancesoluble/stableinthetechniquemedium?• Ensureprimaryparticlesarenotdamagedduringtreatment.

SamplePreparation


• Inmanysituations,nosinglemethodcanbeusedtoproveasubstanceasubstanceisananomaterialaccordingtothecurrentdefinition.

• Techniquesshouldbeappropriatetothesubstance.• Differenttechniquesmightbeappropriateforriskassessment(measuringparticlesizeasitexists).

• Mustbeawareofexactlywhatisbeingmeasured.

ParticleCharacterisation


• TestingrequirementsbasedonthetonnageperannumofthesubstancemanufacturedinorimportedintotheEU.

• ClearlydefinedinAnnexesVIItoXofREACH.• Waiversforsomestudiesavailable.• Read-across,QSARandgroupingareallpermittedbutmustbescientificallyjustified.

REACHandHazardAssessment


• Sameendpointsrequiredasforothersubstances.• Endpointmethodologymightneedtobealteredtoaccountforcharacteristicsofnanomaterials.

• Somewaiversmightnotbeappropriatetouse.• ComprehensiveguidancegivenbyECHAinAnnexestoguidancedocuments

REACHHazardAssessmentofNanomaterials


EndpointTestingofNanomaterials

REACHendpointmodifications


EndpointTestingofNanomaterials

• Invitro,insilico,QSARandread-acrosswillbevitaltoavoidlargescaleanimaltesting.

• Researchongoing• EUfundedprojects(MARINA,NanoReg,SUNetc.)

• Riskassessmentshouldaccountforchangestonanoformthroughthelifecycle.

• Propercharacterisationbothbeforeandduringstudiesessential

Intelligenttestingstrategiesfornanomaterials– REACHandbeyond


• AllREACHregistrationsrequirecommunicationoftheusesofasubstance.

• Ifthesubstanceishazardousandisregisteredatover10t/a,exposurescenariosmustbeincludedinaChemicalSafetyReport.

• Exposureisoftenestimatedusingestablishedoccupationalandenvironmentalfatemodellingtools.

• Theregistrantmustchoosetheappropriatetool.

REACHandExposureAssessment


• Choosethecorrectnanoformforthelifecyclestage.• Canstandardtoolsbeappliedtonanomaterials?

• Possiblyforworkerexposureifread-acrosstobulkformscanbeproved.• Unlikelyforenvironmentalexposureasmosttoolsusepartitionco-efficientasakeyparameter.

• Somenano-specifictoolsavailable• NanomoduleofStoffenmanger• SimpleBox4nano

• EUfundedprojectsshouldimprovethechoiceandqualityofmodels.• Themodelswillneedtobevalidatedagainstmeasureddata.

• NanoMONITOR

ExposureAssessmentandNanomaterials


• Riskismeasuredbyensuringexposureviaagivenrouteislowerthanacalculated“safe”value.

• Ifriskisnotacceptable,appropriateriskmanagementmeasuresshouldbeimplemented.

• ThemeasuresrequiredtoensureacceptableriskfromasubstancemustbecommunicatedinexposurescenariosfoundintheannexofanExtendedSafetyDataSheet(eSDS).

• AnyrecipientofaneSDS mustimplementthemeasuresstatedorprovethatalternativemethodsareequivalentorsuperior.

• Measurementcanalsobeusedtoprovecompliance.• NanoMONITOR

REACH,RiskAssessmentandCommunication


• RiskAssessmentofbulksubstance. • Interconversionanddifferent(eco)-toxicologicalprofilesofnanoformsmakeriskassessmentmorecomplex.

RiskAssessmentandNanomaterials


• Hazardofananomaterialisnotintrinsicduetodifferentnanoforms.• HazardcanbereducedbySafeDesignofthenanomaterial.

• SeeSUNproject.• Riskmanagementmeasuresshouldbeappropriatetonanomaterial.

• Facemasksshoulduseappropriatefinefilters.• Settlingtankswithhumates mightbeusefulforon-siteremediationofwastewaters.

• Exposurescenariosfornanomaterialsuncommon.• SeeMARINAproject(oraskme!).

RiskAssessmentandNanomaterials


• BiocidalProductsRegulation• Anactivesubstanceinananoformmustbeauthorisedseparatelytothesamesubstanceinthebulkform.

• CosmeticsRegulation• Nanomaterialsascosmeticingredientsmustbeassessedseparatelytobulkformsofthesamesubstanceiftheyperformcertainrolesinthecosmetic.

• Theingredientslistmustshowthatasubstanceexistsasananomaterial.• FoodContactMaterials

• AnanoformofasubstancecannotberegardedasbeingontheUnionListofauthorisedsubstancesevenifthebulkformisonthelist.

• Assessmentandauthorisationismadeonacasebycasebasis.

NanomaterialsandotherEUregulations


• Medicaldevices• Degreeofriskassessmentrequireddependsonlikelihoodofreleaseofnanomaterialsfromthedevice.

• US• OneoffreportingschemetoEPA.

• Australia• NICNASrevised,mayintroducenewhazardsymbolfor“nanohazard”.• Mayrequirenewnanospecific hazardstatements.

Nanomaterialsandotherregulations


• ThereisnoEU-widenotificationscheme.

• Somecountrieshaveimplementedreportingschemesfornanomaterialsusedorplacedonthemarketinthatcountry.

• Eachschemehasdifferenttargetsandrequirements.

NationalRegistriesandVoluntaryNotificationSchemes


BelgianScheme

• Mandatoryreportingscheme• Notificationofanynanomaterialmanufacturedonover100gifitisplacedonthemarketforprofessionaluse.

• Decreetonotifyarticlesandcomplexobjectscontainingananomaterialwhosereleasecannotbeexcludedandispresentat>0.1mass%hasbeenpostponed.

• Proposedinclusionofmixturesinschemehasbeenpostponed.


FrenchScheme

• Mandatoryreportingscheme• Manufacturednanomaterialsproduced,importedordistributedinFrancetoprofessionalusersinover100g,wherethenanomaterialisasubstance,partofamixtureorinanarticlewherereleasewouldbeforeseeableundernormalconditions.


DanishScheme

• Mandatoryreportingscheme• Notificationofmixturesandarticlesthatcontainnanomaterialsintendedforsaletothegeneralpublic.

• EitherwherethenanomaterialisreleasedundernormaluseORwherethenanomaterialisnotreleasedbutitisaCMRorenvironmentallyhazardous.

• Nomassthreshold.• Manyexemptions.


• Mandatoryreportingscheme• Fallswithinthecurrentregisterofallchemicalproducts(substancesandmixtures)thatareclassifiedashazardouswithrespecttohealth,environmentorfire/explosivity,ifmorethan100kgaremanufacturedorimported.

• Nanomaterialsarenowreporteddistinctlytobulkforms.

NorwegianScheme


• SimilarschemetoFrench.• Duetobeactivein2019.

SwedishScheme


• TobesetupbyECHAbutwillbeseparatetoECHAwebsite.• Intendedtoimprovetransparencyaroundnanomaterials.• WillusenationstateregistriesandothersourcestotrackuseofnanomaterialsinEU.

• Notintendedtobeobligatoryreportingscheme.

ObservatoryforNanomaterials


• Therearenonano-specificregulationsintheEU.• Currentchemicalregulationscanbeappliedtonanomaterials.• Somemodificationofindividualstudiesmightberequiredwithinaregulation.

• ParticlecharacterisationisnotanobligationunderAnnexVIofREACH,butaregistrantshouldbeabletoprovedatainthedossierisapplicabletotheirproductthroughoutitslifecycle.

• Individualcountriesmayhavereportingprocedures.

Summary

Documents

Current legislative framework for nanomaterials ......•A revised definition is being discussed. •Largely the same but with some important changes. •Clarification that it does