Document 15Kkk8zVM8qNaaYN0Ldx1ENBo

CAS Number 307-35-7 3M Company Voluntary Use and Exposure Information Profile Perfluorooctanesulfonyl fluoride (POSF) 1. CHEMICAL IDENTIFICATION Chemical Name: CAS Number: Perfluorooctanesulfofnlyulorid(ePOSF) 307-35-7 11. COMPANY IDENTIFICATION Company Name: 3M SiteLocation: 22614 Route 84 North Cordova,IL 61242 10746 IrmovationRoad CottageGrove,MN 55016 1400 StateDocks Road Decatur,AL 35601 TechnicalContact: W.A. Weppner Phone: 651/733-6374 Address: 3M Center,Building236-IB-10 St.Paul,MN 55144 111. ON-SITE ACTI"TIES CAS # MfL-.(1997) Imyorted 307-35-7'# > IMM & < 10MM lbs. 0 Estimatetheamount ofsubjectchemicaldistributeodff-site:10% Exported *Submittedin1998 TSCA IUR. CAS Number 307-35-7 3M Company 2 Narrative Description and Process Flow Schematic: 3M Company utilizeas process known as Simons Electro-CheniicalFluorination(ECF) to synthesize organofluorinmeolecules.Inthisprocess,organicfeedstocksaredispersedinliquida,nhydrous hydrogen fluoridea,nd an electriccurrentispassedthroughthesolutionc,ausingthehydrogen atoms on themoleculetobe replacedwithfluorine.The predominantcomponents of theproductscreated by thisprocesshave thesame carbonskeletaalrrangementas thefeedstockused,butwith allofthe hydrogen atoms replacedby fluorine.However, fragmentationand rearrangement of the carbon skeletoncan alsooccur and significanatmounts of cleaved,branchedand cyclicstructursemay be formed. The degreeoffluorinatioonf theorganicfeedstockisalsodependentupon thespecific carbonchainlengthof thefeedstockand parametersof theECF processsuch aselectricaclurrentand thelengthof timetheprocessisrun. Itispossibleto synthesizfeullyfluorinateodrperfluoroorganic moleculeswhere allof thehydrogen atoms of thehydrocarbonfeedstockhave been replacedby fluorineatoms. Using theseperfluoroorganimcoleculesas basicbuildingblocks,uniquechemistries can be createdby furthereactionwsithftmctionalizehdydrocarbonmolecules. 3M has produced sulfonylbased fluorochemicalcsommerciallyforover40 yearsusingtheECF process.A basicbuildingblockof such productsand thehighestproductionvolume fluorochemical 3M manufactures isperfluorooctanesulfonyflluoride(POSF). The startingfeedstockforthisreaction is I-octanesulfonylfluoride. (Reaction1) Reaction 1 C8Hl7SO2F + 17 HF I-Octanesulfonylfluoride Energy ------->-- C8Fl7SO2F + 17 H2 ECF Perfluorooctanesulfonyflluoride The electrochemicalfluorinatiopnrocessyieldsabout 35%-40% straightchain (normal) POSF, and a mixture of biproductsand waste of unknown and variablecomposition comprised of the following: 1) higherand lowerstraight-chahionmologs,i.e.n,-CnF2n+IS02Fe,.g.C,6Fl3SO2F, C7Fl5SO2F, C9Fl9SO2F which compriseabout7% oftheprocessoutput 2) branched-chain,perfluoroalkylsulfonyflluorideswith variouschain lengths,about 18-20% of the output 3) straight-chainb,ranched,and cyclic(non-functional)perfluoroalkanesand ethers,which comprise about 20-25% of the output 4) "tars"(highmolecularweight fluorochemicalbyproducts)and otherbyproducts,includingmolecular hydrogen, which comprise about 10-15% of the output. Because of slightdifferencesin processconditions,raw materials,and equipment, themixture produced by the electrochemicalfluorinatiopnrocess variessomewhat from lot-to-loatnd from plantto-plant.The product thatresultsfrom electrochemicalfluorinatioinsthus not a pure chemical but rathera mix of isomers and homologues. The commercialized POSF derivedproducts are a mixture of approximately 70% linearPOSF derivativesand 30% branched POSF derived impurities. CAS Number 307-35-7 3M Company 3 During production,byproductsand waste productsareformed. The volatilweaste products,such as perfluoromeflme,have been ventedto theatmosphereinthepast,butplansarebeing implemented to captureand destroythesereleasesby thermaloxidationoverthenextfew years.The tarshave been landfilleidna hazardouswaste landfililnthepast,butareallcurrentlbyeing incinerateadtan in-houseorexternalhazardouswaste incineratorT.he byproducts,many of which areincompletely fluorinatewdithhydrogen atoms stilplresentc,an be recycledback intotheECF processor are partialldyegradedinstabilizatipornocessesand dischargedtocontrolledi,n-house,wastewater treatmentsystems. The treatmentsludge associatedwith the ECF process has been eitherlandflued or land-incorporatedin thepast,but allof thistreatmentsludgeisbeing landfilledoff-sitseinceearly 1998. POSF isitselaf commercially viableproduct,but isprimarilyan important intermediatein the synthesisof substancesused in many other3M fluorochemicalproducts. The majority isused to produce fimctionallyderivatizedfluorochemicalsand high molecular weight polymeric products. Unique chemistriescan be createdby derivatizingPOSF through the sulfonylfluoridemoiety of the molecule using conventionalhydrocarbon reactions.POSF isreactedwith methyl or ethylamine to produce eitherN-methyl or N-ethylperfluorooctanesulfonamide(MEFOSA or ETFOSA). Some of the MEFOSA and ETFOSA isisolatedto be used as intermediatesto be reactedto form other materials. The majorityof theMEFOSA and ETFOSA isnot isolatedand subsequentlyreactedwith ethylene carbonateto form eitherN-methyl or N-ethylperfluorooctanesulfonamido ethanol. These are the principalbuildingblocks of the 3M product lines. CAS Number 307-35-7 3M Company 4 The followingblock flow diagram describesthe processdiscussedabove. BLOCK FLOW DIAGRAM Electro-ChemicaFlluorinatioCnells (Octanesulfonylfluoride+ BF + electricaelnergy) IF Perfluorooctanesulfonylfluoride (POSF) IF Secondary Re + Perfluorooctanesulfonicacid (PFOS) I v Surfactants IF Various commercialized intermediates and s factants F Amp. ioteric surfactants (FireFighting Foams) + N-ethyl(and methyl) perfluorooctane- sulfonamide N-1 Ldmethyl) perfluorooctane- sulfonamido ethanol v AdditionalSecondary Reactors Phosphate Esters and Acrylate/polymers (Paper& Packaging) Acrylatepolymers Adipate adducts Urethane polymers (Carpetand Textile Protection) Various commercialized intermediates and surfactants CAS Number 307-35-7 3M Company 5 IV. SITE RELEASE AND TRANSFER INFORMATION FOR TRI CHEMICALS Not applicable. V. SITE RELEASE AND TRANSFER INFORMATION FOR NON-TRI CHEAUCALS While analyticamlethods have improved overtime,largevariabilisttyilelxistsforcertainmatrices and compounds, so dataavailablfeorthisreportismostlyof a qualitativneature.Although limited monitoringdataexistsm,ost emissionand waste estimatesarebased upon processmodels and engineeringcalculationsE.ngineeringcalculationhso,wever,have limitationwsithrespectto fluorochemicalbsecausefluorochemicalosseswere not always includedintheanalysisof each intermediatestep. The accuracyof theemissionsdatasubmittedvariesdue to severalfactors.Batch processsystems aredifficulttomeasure due to quicklychangingprocessconditionsv,entingpressuresand difficulty in isolatinpgrocessesto takemeasurements. Additionallyt,heuniquecharacteristiocfsthese compounds cause them to behave differentlfyrom conventionalcompounds, and physicalchemical datapropertieasrenot availablfeorallintermediatreeactionstepsinthepast. A. ON-SITE AIR RELEASES ALL PLANTS - Fugitivemissionsmay occurfrom vacuum chargingfrom drums,sampling from reactorsd,rumniingof product/intermediatfel,akingmonomer, dryingoperations. Materialsmay be handledina molten or solidstatev;aporsareproduced from molten material. IndustriaHlygiene monitoringhasbeen conductedforsome compounds and isdetailedlater inthisdocument.Some minor amounts of thesecompounds have been detectedas fugitive emissionsduringIndustriahlygieneexposuret,estingb,ut do notcontributesignificanttloy overallsiteemissions. DECATUR, ALABAMA ONLY: Fugitivemissiondataisavailablfeorelectrochemical cellbuildingsw,astewaterfugitivaeiremissionsa,nd fugitiveermssionsfrom wastewater sludge.Data forthecellbuildingsisbased on engineeringcalculationussing standard emissionfactors.Wastewaterfugitivdeataisbased on testresultwshich show thepresence ofPOSF. Sludge emissiondataisbased on engineeringcalculationosftheamount of POSF inthesludge.The C8 sulfonylcompound fugitivaeiremissionshave been significantly reducedsince1997 as a resultofreductionof wastewaterdischargesofmaterialscontaining thesecompounds. Additionalreductionsareplanned. Decatur,AL EstimatedTotal Annual Releases (lbs.) Fugitiv-e (non-point) * 28,000 in 1997 * 1700 in 1999 Estimated% days/years Accuracy of releaseoccurs Estimate(optionai) 250 CAS Number 307-35-7 3M Company 6 Stack (point) Engineering calculationsand models of process vent emissions areused forestimatesof point sourceemissions. Estimated Total Annual Releases (lbs.) (1997) Estimated % Accuracy of Estimate (optional) N days/years releaseoccurs 5000 250 Cordova POSF-based productsareno longermanufacturedinCordova. Stackpointemissionestimates arebased upon existingprocessmodels and engineeringcalculationfsrom thefacility. Fugitiveemissionsmay have occurredduringsome handlingstepsbuthave not been quantified. Estimated Total Annual Releases (lbs.) (1"7) Estimated % Accuracy of Estimate (optional) days/years release occurs Fugitive (non-point) No data available. Stack (point) <1 <10 in 1997 Comments: Cottage Grove Emission estimatesare based upon existingprocess models and engineeringcalculationsfrom the facilityF.ugitiveemissions may have occurredduring some handling stepsbut have not been quantified. Estimated Total Annual Releases (lbs.) (1997) Estimated % Accuracy of days/years releaseoccurs Estimate (optional) Fugitive (non-point) <1 < 100 Stack (point) <1 < 100 Comments: CAS Number 307-35-7 3M Company 7 B. WATER RELEASES FROM SITE Decatur, AL- The datapresentedispartofwastewatertestingconductedin 1998,sincetheindividual compounds of intereswtere notanalyzedinthe1997 wastewatermaterialbalancedue to method availabiliatnyd initiaplrogram focus. The 1998 datahas notbeen adjustedfor production levelsin 1997, sincemost production remained at similarlevels.POSF was measured on an infrequentbasisbecause of analyticaldifficultiesW.hen itwas analyzed in wastewater effluent,itwas not detected. Estimated Total Annual Releases (lbs.) (1997) Estimated % Accuracy of Estimate (optional) Water releases: 0 in 1999 Number of days/year releaseoccurs: 250 Receiving Water Name: Baker's Creek atthejunctionwith the Tennessee River NPDES Number: ALD004023164 Comments: Cordova, IL Engineering calculationswere used to estimatetheamount of materialdischargedto wastewater. The amount of materialdischargedto theriverwas determined through use of existingremoval efficiencytestingresultsfrom another facility. Estimated Total Annual Releases (lbs.) (1997) Estimated % Accuracy of Estimate (optional) Water releases: <10 Number of days/year releaseoccurs: <5 times in 1997. POSF-based productsno longer produced in Cordova. Receiving Water Name: MississippiRiver NPDES Number: IL0003140 Comments: CAS Number 307-35-7 3M Company 8 CottageGrove, Engineeringcalculationwsere usedtoestimatetheamount of materialdischargedto wastewater. The amount of materialdischargedtotheriverwas determinedthroughuse of existinrgemovalefficienctyestinrgesultfsrom anotherfacility. Estimated Total Annual Releases (lbs.) (1997) Estimated % Accuracy of Estimate (optional) Water releases: 0 Number of days/year release occurs: Receiving Water Name: NPDES Number: Comments: C. ON-SITE LAND RELEASES Decatur, AL The land treatmentof Decatur sludgewas discontinuedin early1998. Sludge isnow transportedto an offsitelandfilla,fterpassing through a thickenerand a sludge press. An impoundment was used in 1997 as partof the wastewater treatmentoperationbut isnow only used for back-up operation. Levels of POSF in thesludge were estimatedfrom engineeringcalculations. Estimated Total Annual Releases (lbs.) (1997) Estimated % Accuracy of Estimate (optional) Landfill Land Treatment/Land Amendment Surface Impoundments Underground Injection Other (specify): 0 26,000 - No longerused No data available/Nolonger used 0 Comments: CAS Number 307-35-7 3M Company 9 Cordova,IL Lessdm 10 pounds totalof allcompounds per yeararereleasedto wastewatertreatment(see wastewatersectionf)rom process.The amount of materialdischargedtolandtreatmentwas determinedthroughtheuse oftestingresultfsrom anotherfacility. The sludgeformed intheprimaryclarifiiesrmost likelyto containtheinsolublesulfonated materials.Thissludgeisremoved and incineratedT.he sludgeimpoundments arelined. The use of POSF containingmaterialshas been discontinuedatCordova so thesereleases have alsobeen discontinued. Estimated Total Annual Releases (lbs.) (1997) Estimated % Accuracy of Estimate (optional) Landfdl 0 Land Treatment/Land Amendment <10 Surface Impoundments 0 Underground Injection 0 Other (specify): 0 Comments: Cottage Grove, MN Sludge from the Cottage Grove facilitiyssentto an off-sitiendustrialandfill Estimated Total Annual Releases (lbs.) (1997) Estimated % Accuracy of Estimate (optional) Landfill 0 Land Treatment/Land Amendment 0 Surface Impoundments 0 Underground Injection 0 Other (specify): Comments: CAS Number 307-35-7 3M Company 10 D. OFF-SITE TRANSFERS Decatur, AL Processwastewatersaremanaged inan on-sitewastewatertreatmentfacilitaynd arenotsent tothePOTW. Dl. TransfertoPubliclOywned TreatmentWorks (POTW) Number ofdays/yeatrhereleasoeccurs: Annual Transfer(lb):0 Estimated% AccuracyofTransferEstimate(optiona(l%)): POTW Name: StreeAtddress: City: State: NPDES Number: Country: Zip Code: Comments: Cordova,IL Processwastewatersaremanaged inan on-sitewastewatertreatmentfacilitaynd arenotsent to thePOTW. Dl. TransfertoPubliclOywned TreatmentWorks (POTW) Number ofdays/yeatrhereleasoeccurs: AnnualTransfer(lb):0 Estimated% AccuracyofTransferEstimate(optional) POTW Name: StreeAtddress: City: State: NPDES Number: Country: Zip Code: CAS Number 307-35-7 3M Company CottageGrove, Processwastewatersaremanaged inan on-sitewastewatertreatmentfacilitaynd arenotsent tothePOTW. Dl. TransfertoPubliclyOwned Treatment Works (POTW) Number ofdays/yearthereleaseoccurs: Annual Transfer(lb):0 Estimated% Accuracy ofTransferEstimate(optional) POTW Name: StreetAddress: City: State: NPDES Number: Country: Zip Code: Comments: CAS Number 307-35-7 3M Company 12 D2. TRANSFERS TO OTHER OFF-SITE LOCATIONS General Waste Information: There islimitedinformation by CAS number for compound specifirceportingand off-sitteransfercsannotbe readilyverifiedR.ather,wastesare classifiebdy halogencontentr,egulatorywaste codes,physicalpropertieasnd non-specific fluorochemicalcategoriesW.here wastesaretrackedby CAS number, theamounts have been included. Decatur,AL A reviewofplantrecordsregardingwastedisposalocationfsorDecaturfluoride-containing (notCAS number specificw)astesindicatetshat70% isdisposedthroughincineratioant variousoff-sitleocationasnd approximately30% islandfilleadta hazardouswastelandfill. Incineratioinsnow theprimarydisposalmethod forthesematerials. Estimated Total Annual Releases (lbs.) Estimated % Accuracy of Estimate (optional) Incineration: No specificCAS niunber data available. Wastewater Treatment 0 (Excluding POTW) Underground Injection 0 Hazardous Waste (RCRA Subtitle C) landfill No specificCAS number data available. Other Landfill No specificCAS number data available.. Recycle or Recovery 0 Unknown or Other 0 Comments: CAS Number 307-35-7 3M Company 13 Cordova,IL Cordova wastesthatcontainedPOSF were allincineratedW.astes includedsome off-spec product,empty bags and empty drums and containedthecompounds isresidualamounts. These productsareno longermade atCordova. EstimatedTotal Annual Releases Obs.) Estimated% Accuracy of Estimate (optional) Incineration: No specificCAS number data available.. Wastewater Treatment 0 (ExcludingPOTW) Underground Injection 0 Hazardous Waste (RCRA 0 SubtitleC) landfill Other Landfdl 0 Recycle or Recovery 0 Unknown or Other 0 Comments: CAS Number 307-35-7 3M Company 14 CottageGrove, MN CottageGrove facilituytilizeisncineratiofnoralltheirdrummed wastes. Sludgefrom theCottageGrove facilitiyssenttoan industriallandfill. Incineration: Wastewater Treatment (ExcludingPOTW) Underground Injection Hazardous Waste (RCRA SubtitlCe) landfill Other Land:rdl Recycle or Recovery Unknown or Other Comments: EstimatedTotal Annual Releases (lbs.) 6490 0 Estimated% Accuracy of Estimat(eoptional) 0 0 0 0 CAS Number 307-35-7 3M Company 15 VI. ON-SITE WOREPLACE EXPOSURE 3M CompM. SpecialtyMaterialsManufacturiniDzivision,Cordova,IL This informationwillassisEtPA in characterizingthe number ofworkers potentialleyxposed and the magnitude, frequency, and duration of potential exposure. When providing monitoring data, ensure that data is linked with worker activitiesdescribed in question 2. 1. Estimate the number of workers potentially exposed routinely to the subject chemical for each of the exposure duration times. If a worker is involved in more than one activity,enter only his/her most typical activity in the table. Don't count a worker more than once. The total number in the table should equal the total number of workers potentially exposed. Hours/Day <10 <.25 .25-1 1 1-8 5 >8 Days/Year 10-100 100-250 >250 2. Describe the routine worker activitiesto which the workers in question I are exposed: sampling, removal of filtercake, and drumming of liquids, manufacture an article, etc. For these activities,describe the physical state of the subject chemical (liquid, gas, particulate, or aerosol, etc.)and, if in a mixture, the chemical's concentration: The chemical (307-51-7) isproduced as a by-product in the electrochemical fluorination process for307-51-7. Employees take qualitysamples during the fluorinatiopnrocess. The liquid product containing3% 307-35-7 ispiped to a processvesselwhere itiswashed and then drained intodrums. The washed, drummed materialisshipped to 3M Cottage Grove. Employees also perform turnaround maintenance on fluorinationequipment. CAS Number 307-35-7 3M Company 16 3. Provide industrialhygiene monitoring data, ifavailable,with 2 brief description of the sampling method and exposure scenario monitored, e.g.,describe the specwic worker activitiesperformed by the individuals monitored. For privacy considerations, please do not include any personal identifierssuch as a worker's name or socialsecurity number with any data submitted to EPA. There isno chemical-specificpersonal industrialhygiene monitoring data or area/source monitoringdataforthisspecifimcaterialatthisfacilityF.or most areasof thefacilitrye,cent qualitativaessessmentofpotentiaelxposuretothismaterialunder 3M's ongoing industrial hygieneprogram indicateaslow exposurepotentiatlothismaterial. Each 3M plantthatproduces sulfonatedfluorochemicalshas an industriahlygieniston staffand is supportedby a corporateindustriahlygiene group. 3M's industriahlygiene program focuses on task-based exposure assessment and control.Exposures are identifiedand assessed qualitatively and/or quantitativelyQ.ualitativeassessments areperformed by an industriahlygienist. Quantitativeassessments includetask-basedpersonal sampling forcertain,specific fluorochemicalsand/or source or area sampling. The resultsof the assessments support decisions on exposure control.Engineering controlsarepreferred,but personal protectiveequipment 4. Briefly describe the engineering controls used to minimize exposure to thischemical: Local exhaust ventilationisused atthe drum tops duringdrainingand sampling. Both room dilutionventilationand localexhaust ventilationisscrubbed. Production and work-up rooms are negativelypressuredwith respectto otherpartsof the building. 5. Briefly listthe personal protectiveequipment your workers regularlywear to prevent exposure of thischemical: During sampling, fluofimtionequipment turnaround,and drumming tasks,employees wear supplied air-fedfullyencapsulatingsuitswith attachedbutylgloves and rubber boots. Comments: desired.) (This sectionisavailableto clarifytheresponsesgiven. Attach additionalpages if CAS Number 307-35-7 3M Company 17 3M CoMpMy, Socialty MaterialsManufacturingDivision,Cottage Grove, MN This information willassistEPA in characterizingthe number ofworkers potentiallyexposed and the magnitude, frequency, and duration of potentialexposure. When providing monitoring data, ensure thatdata islinkedwith worker activitiedsescribed in question2. 1. Estimate the number ofworkers potentiallyexposed routinelyto the subjectchemical for each of the exposure duration times. Ifa worker isinvolved in more than one activitye,nter only his/hermost typicalactivityinthe table.Don't count a worker more than once. The totalnumber in the tableshould equal the totalnumber of workers potentiallyexposed. Hours/Day <10 <.25 14 .25-1 14 1-8 20 >8 1 Days/Year 10-100 100-250 16 16 8 1 1 >250 2. Describe the routine worker activities to which the workers in question 1 are exposed: sampling, removal of filter cake, and drumming of liquids, manufacture an article, etc. For these activities, describe the physical state of the subject chemical Oiquid, gas, particulate, or aerosol, etc.) and, if in a mixture, the chemical's concentration: The chemical (307-35-7) is a clear liquid. The chemical is handled as a raw ingredient in its pure form (95-100%), and as a component in other raw materials at concentrations typically < 5%. After initial processing of raw materials containing 307-35-7, the chemical may be carried over as a tracematerial(typicall<y I%) intoa varietyof othermaterialsduring subsequent manufacturing steps.Workers may be exposed to 307-35-7 during collectionof qualitysamples from drums, vacuum chargingthematerialfrom drums intoreactors,or during drainingof materialsfrom reactorsintodrums or other containers. CAS Number 307-35-7 3M Company 18 3. Provide industrial hygiene monitoring data, if available, with a brief description of the sampling method and exposure scenario monitored, e.g.,describe the speciric worker activities performed by the individuals monitored. For privacy considerations, please do not include any personal identifiers such as a worker's name or social security number with any data submitted to EPA. There is no chemical-specific personal industrial hygiene monitoring data or area/source monitoringdataforthisspecificmaterialatthisfacilityF.or most areasofthefacilityr,ecent qualitativaessessmentofpotentialexposuretothismaterialunder 3M's ongoing industrial hygiene program indicatesa low exposurepotentiatlo thismaterial. Each 3M plantthatproduces sulfonatedfluorochemicalshas an industriahlygieniston staffand is supportedby a corporateindustriahlygienegroup. 3M's industriahlygieneprogram isbased on the concept oftask-basedexposure assessmentand control.Exposures are identifieadnd assessed qualitativelaynd/orquantitativelyQ.ualitativaessessmentsareperformed by an industrial hygienist.Quantitativeassessmentsincludetask-basedpersonalsampling forcertain,specific fluorochemicalsand/orsourceor areasampling. The resultsof the assessmentssupportdecisions on exposure control.Engineeringcontrolsarepreferredb,ut personalprotectiveequipment may be used on an interimbasisorwhen effectivengineeringcontrolisnot feasible. 4. Brieflydescribethe engineeringcontrolsused to minimize exposure to thischemical: Local exhaust ventilatioinsused atdrum top and reactoropenings during sampling,charging,and drainingactivitieVsa.cuum chargingof materialsfrom drums isa standardpractice.General room airprovidesfordilutionof airbornematerials. 5. Brieflylistthe personal protectiveequipment your workers regularlywear to prevent exposure of thischemical: During sampling and chargingof pure (95%) 307-35-7,workers use fullfacepieceair-purifying respiratorwsith organicvapor/acidgas cartridgesr,ubber gloves(butylorneoprene),and a twopieceor one-piecefullbody acidsuitsThe type ofpersonalprotectivequipment used may vary (may be downgraded) formaterialscontaining307-35-7 as a traceingrediente;xactPPE used depends on thehazard posed by the main ingredientand specificationosf theprocessoperating standard. Comments: (This sectionisavailableto clarifythe responses given. Attach additionalpages if desired.) CAS Number 307-35-7 3M Company 19 3M Coml)M, St)ecially Materials Manufacturing Division, Decatur, AL This information will assist EPA in characterizing the number of workers potentially exposed and the magnitude, frequency, and duration of potential exposure. When providing monitoring data, ensure that data is linked with worker activities described in question 2. 1. Estimate the number of workers potentially exposed routinely to the subject chemical for each of the exposure duration times. If a worker is involved in more than one activity, enter only his/her most typical activity in the table. Don't count a worker more than once. The total number in the table should equal the total number of workers potentially exposed. Hours/Day <10 <0.25 0.25-1 12 1-8 21 >8 4 Days/Year 10-100 100-250 24 32 12 8 >250 2. Describe the routine worker activities to which the workers in question 1 are exposed: sampling, removal of filter cake, and drumming of liquids, manufacture an article, etc. For these activities, describe the physical state of the subject chemical (liquid, gas, particulate, or aerosol, etc.) and, if in a mixture, the chemical's concentration-. Operating fluorination cell system (closed), sampling, drumming, charging, and equipment maintenance activitie(schange pipe,flange,valve,filterp,ump or sightglass); perfluorooctanesulfonyflluorideishandled as a liquid;exposure isby inhalationor directskin contact;materialconcentrationranges up to 80%. Wastewater treatmentoperations:collectingand analyzingQC samples, operatingfilter press,monitoring process,and maintenance activitiesp;erfluorooctanesulfonyflluorideexposure istypicallyto vapors; concentrationin waste streamtypicallylessthan 2%. CAS Number 307-35-7 3M Company 20 3. Provide industrialhygiene monitoring data,ifavailablew,ith a briefdescriptionof the sampling method and exposure scenariomonitored, e.g.,describethe specificworker activities performed by the individuals monitored. For privacy considerations, please do not include any personal identifiers such as a worker's name or social security number with any data submitted to EPA. Personal sampling for perfluorooctanesulfonyl fluoride vapor is currently (late 1999 to present) done with evacuated canisterswith analysisby GC-MS. Previous sampling had employed silica gel acidmist tubesand XAD4 tubeswith GC-ECD analysis.Perfluorooctanesulfonyflluoride was found to hydrolyze on sorptiontubes resultingin an underestimateof exposure. See attached tableforairsample results. There has been area/sourceairmonitoring dataand/or surfacewipe sampling data collectedfor thismaterialatthe plant.Area/source sample resultsand/orsurfacewipe sample resultsareused to identifyareaswith employee exposure potentialas partof exposure assessment under 3M's industriahlygiene program and arenot measurements of actualemployee exposures. Hence, they arenot includedwith thissubmission. Priorto 1999, these samples were consideredto be semivalidated. The sample resultsof any airmonitoring arecompared to 3M's voluntaryexposure guideline (EG) of 0.1 mg/m3 (milligramsof fluorochemicalper cubicmeter of air)forvarious fluorochemicalcompounds, includingcompounds covered in thissubmittal.The EG isan 8-hour time-weighted average (TWA) personalbreathingzone exposure chosen to minimize potentialfor uptake. Each 3M plantthatproduces sulfonatedfluorochemicalshas an industriahlygieniston staffand is supportedby a corporateindustriahlygiene group. 3M's industriahlygiene program focuses on task-based exposure assessment and control.Exposures are identifiedand assessed qualitatively and/or quantitatively.Qualitativeassessments areperformed by an industriahlygienist. Quantitativeassessments includetask-basedpersonal sampling for certain,specific fluorochemicalsand/or source or area sampling. The resultsof the assessments support decisions on exposure control.Engineering controlsarepreferred,but personalprotectiveequipment may be used on an interimbasisor when effectiveengineeringcontrolisnot feasible. CAS Number 307-35-7 3M Company 21 Air Sampling Data for 307-35-7 Job Sample Concentration Classification number (mg/m3) Minimum (mgim3) Chemical Operator Building3 Team Leader Building3 95-042* 96-028* 96-053* 96-067* 96-071 * 97-124 98-098* 98-481 Totals 4 0.24 <0.07 0.43 0.07 0.1 1.12 0.12 0.18 34.436 Maximum (mg/m3) 34.4 Geometric Mean 0.4 Geometric Standard Deviation 7.5 The value forthissample isone of severalfluorochemicalanalytescollectedon the sample. Samples are allpersonal breathingzone samples taken over the durationof a specifictask. 4. Briefly describe the engineering controls used to minimize exposure to this chemical: Area surveys using FTIR are performed to identifysources such as system leaks. Perfluorooctanesulfonyflluorideistransferredusing closedpiping (where possible)from reactor vesselsto othercontainers.Vacuum chargingof perfluorooctanesulfonyflluorideor perfluorooctanesulfonyflluoride-containinmgaterialsfrom drums isa standardpractice.Local exhaust ventilationhoods are situatedat significantpointsources such as atdrum bungs when drumming. Some drumming operationsaredone in an enclosed ventilationchamber. General room airprovidesfordilutionof airborneperfluorooctanesulfonyflluoride.Operator control rooms are segregated from process areasand provided separateroom airventilation. CAS Number 307-35-7 3M Company 22 5. Brieflylistthe personal protectiveequipment your workers regularlywear to prevent exposure of thischemical: Specificpersonalprotectivequipment isindicatedon writtenoperatingproceduresused by processoperators. Respiratory protection:Tasks with significanetxposurepotential(charging,dnmuning, some maintenancetasks)areperformedusingpositivperessurep,ressuredemand fullfacesuppliedair respiratorsT.asks withmoderateexposurepotentia(lshorterm samplingfrom tapsor drums, and some maintenancetasks)areperformedusingfullfaceair-pufifyirnegspiratorwsithorganic vapor cartridgeasnd P 100 prefilters. Hand protection:Alltasksidentifieadshavingpotentiaflorhand contactrequireneoprene (Scorpio)ornitriliendustriagloves. Body protection:Neoprene suits(primarilfyorhydrogenfluoridexposurepotentiala)reusedin fiuorochemicalcellareasfortasksidentifieads havingexposurepotentialE.xposure significant tasksinotherareasuse one or two-piecePVC suits. Foot protection:Tasks identifieadsposinga significanftootexposurepotentiarlequire chemicalresistanbtoots. Comments: (Thissectionisavailablteoclariftyheresponsesgiven.Attachadditionaplages if desired.) Currentexposuresarelessthanthosemeasured intherecentpast.Significanstourceshave b een identifieadnd eliminated.In 1998 an extensiveareaairsamplingof theproductionareaswas' performed.Areas withhigherlevelsofperfluorooctanesulfonfylluoridewere investigatefdtirther usingFTIR toidentifysourcesofperfluorooctanesulfonfylluoride.Eliminatedsourcesincludea leakingpipeflangeina processareaand vaporsfrom an open chemicalsewer. In additiont,he ventilationsystem in theprimary production building(3)isin theprocess of being upgraded. The fluorochemicalhazard connnunication program was improved upon in 1998. This has resultedin improved exposure avoidance behaviorsamong production employees and better use of protectiveequipment requirements. I CAS Number 307-35-7 3M Company 23 VIII. CHEMICAL END USES A. END USE AS AN INTERMEDIATE CONSUMED TO MAKE OTHER CHEMICALS Al. On-Site Use as a Intermediate: Product chemical class or product chemical (Include CAS number if appropriate) % of total volume of subject chemical manufactured or imported 1. Perfluorooctanesulfonyl fluorides (POSF) 2% are used as an intermediateto make consumer and commercial upholsteryand carpet protectorsand cleaners. 2. Perfluorooctanesulfonylarnidoethylacetate CAS #2991-51-7 POSF isused as an intermediateto make a household cleaner. < 0.5% 3. N-methylperfluorooctylsulfonamide CAS #31506-32-8 POSF isused as an intermediateto make polymers in protectivetreatmentsfor nonwoven materials. < 1.0% 4. N-methylperfluorooctylsulfonamidoethanol 36% CAS #24448-09-7 POSF isused as an intermediateto make polymers in protectivetreatmentsfor Carpet,upholstery and leathermaterials. 5. N-methylperfluorooctanesulfonamidoethylacrylate CAS #25268-77-3 POSF isused as an intermediateto make Consumer carpetprotectors. < 1.0% 6. N-ethylperfluorooctylsulfonamideothanol 48% CAS #1691-99-2 POSF isused as an intermediateto make polymers in protectivetreatmentsfor carpet,upholstery,appareland leather products. Itisalsoconsumed in products manufactured forsurfactantsand coating additives. CAS Number 307-35-7 3M Company 7. N-ethylperfluorooctylsulfonamide CAS #4151-50-2 POSF isan intermediatceonsumed inthe Productionof surfactantpso,wder additives, Foarn tapeand insecticide. 8. Fluorinateadlkylamine oxide CAS #178094-69-4 POSF intermediatceonsumed inthe productionof foamerforuse infire fightingfoams. 9. FluoroalkylQuaternaryAmmonium CAS #38006-74-5 POSF intermediatceonsumed inthe productionof surfactantfsorthemining and oilwellindustries. A2. Off-Site Use as an Intermediate Product chemical class or product chemical (Include CAS number ffappropriate) 1. Exported. 24 < 1.0% < 1.0% < 1.0% As reported in Part HI, p.2 % of total volume of subject chemical manufactured or imported < 10% As reported in Part III,p.2 CAS Number 307-35-7 3M Company 25 B. END USES OTHER THAN AS A CONSUMED INTERMEDIATE Use Number I of 1 DescriptionofChemical End Use: Used asa reactivientermediatienthesynthesiosfa foamer foruse infirefightingfoams. These productsaredesignedforprimaryuse by fire fightingprofessionalsC.AS 307-35-7would be presentinthefmal productas a low level residual. Percentoftotalmanufacturedor imported volume goingtothisuse: <1 =L Check allphysicalforms of the chemicalduringthisuse: Ifused ina mixturecheck appropriatbeox to indicatweeightfractionA.verage valuesareacceptable: X <1% 600 - 1200ppm) 1-30% 30-60% 60-90% >90% Aerosol Dry Powder Pelletosr largecrystals Water orsolvent- wet solid Gas or vapor X Liquidsolution Other(Explain)