Document dd208p3DyQLvebNj8xR0JzNe

CAS Number 31506-32-8 3M Company Voluntary Use and Exposure Information Pro:rile N-Methyl perfluorooctanesulfonamide 1. CBEMICAL IDENTIFICATION Chemical Name: CAS Number: N-Methyl perfluorooctanesulfonami(dMeEFOSA) 31506-32-8 11. COMPANY IDENTIFICATION Company Name: 3M Site Location: 10746 Innovation Road 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,NN 55144 111. ON-SITE ACTMTIES CAS # Mfg. (1997) 31506-32-8* < 100,000 Estimate the amount of subject chemical distributed off-site,:0 Imported 0 *Submittedin 1998 TSCA ITJR.Significanptroductionoccursthatisnon-isolateadnd non-reportabluender TSCA. CAS Number 31506-32-8 3M Company 2 Narrative Description and Process Flow Schematic: 3M Company utilizes a process known as Simons Electro-Chemical Fluorination (ECF) to synthesize organofluorinemolecules. In thisprocess,organic feedstocksaredispersedin liquid,anhydrous hydrogen fluoride,and an electricurrentispassed through the solution,causing the hydrogen atoms on the molecule to be replacedwith fluorine.The predominant components of the products created by thisprocess have the same carbon skeletalarrangement as the feedstockused, but with allof the hydrogen atoms replacedby fluorine.However, fragmentationand rearrangement of the carbon skeletoncan alsooccur and significan*tamountsof cleaved,branched and cyclicstructuresmay be formed. The degree of fluorinatioonf the organicfeedstockisalsodependent upon the specific carbon chain length of the feedstockand parameters of the ECF process such as electricaclurrentand thelengthof time the processisrun. Itispossibleto synthesizefullyfluorinatedor perfluoroorganic molecules where allof the hydrogen atoms of thehydrocarbon feedstockhave been replaced by fluorineatoms. Using these perfluoroorganicmolecules as basicbuildingblocks,unique chemistries can be createdby furtherreactionswith fimctionalizedhydrocarbon molecules. 3M has produced sulfonylbased fluorochemicalscommercially forover 40 years using the ECF process. A basicbuildingblockof such productsand thehighestproductionvolume fluorochemical 3M manufactures isperfluorooctanesulfonyflluoride(POSF). The startingfeedstockforthisreaction isI-octanesulfonylfluoride. (Reaction1) Reaction 1 C8Hl7SO2F + 17 BF 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-functionalp)erfluoroalkanesand ethers,which comprise about 20-25% of the output 4) "tars"(highmolecular weight fluorochemicalbyproducts)and otherbyproducts,includingmolecular hydrogen, which comprise about 10-15% of the output. Because of slightdifferencesin process conditions,raw materials,and equipment, themixture produced by the electrochemicalfluorinatiopnrocessvariessomewhat from lot-to-loatnd from plantto-plant.The product thatresultsfrom electrochemicalfluorinationisthus not a pure chemical but rathera mix of isomers and homologues. The commercialized POSF derivedproducts area mixture of approximately 70% linearPOSF derivativesand 30% branched POSF derivedimpurities. CAS Number 31506-32-8 3M Company 3 During production,byproductsand waste productsareformed. The volatilweaste products,such as perfluoromethaneh,ave been ventedtotheatmosphereinthepast,butplansarebeing implemented tocaptureand destroythesereleasebsy thermaloxidationoverthenextfew years.The tarshave been landfilleidna hazardouswaste landfililnthepast,butareallcurrentlbyeing incinerateadtan in-houseor externalhazardouswaste incineratorT.he byproducts,many of which areincompletely fluorinatewdithhydrogen atoms stilplresentc,an be recycledback intotheECF processor are partialldyegradedinstabilizatipornocessesand dischargedtocontrolledi,n-house,wastewater treatmentsystems.The treatmentsludgeassociatewdiththeECF processhas been eitherlandfilled orland-incorporateidnthepast,but allof thistreatmentsludgeisbeinglandfllleodff-sitseinceearly 1998. POSF isitselafcommerciallyviableproduct,butisprimarilyan importantintermediatienthe synthesisof substancesused inmany other3M fluorochemicaplroducts.The majorityisusedto produce:ftmctionaldleyrivatizefdluorochemicalasnd highmolecularweightpolymericproducts. Unique chemistriescanbe createdby derivatizinPgOSF throughthesulfonylfluoridemoiety of the moleculeusingconventionahlydrocarbonreactions.POSF isreactedwithmethyl or ethylamine to produceeitheNr-methyl orN-ethylperfluorooctanesulfonar(nMiEdFeOSA or ETFOSA). Some of the MEFOSA and ETFOSA isisolatetdobe used as intermediatetsobe reactedto form othermaterials. The majorityof theMEFOSA and ETFOSA isnot isolateadnd subsequentlyreactedwith ethylene carbonateto form eitherN-methyl or N-ethylperfluorooctasnuelfonamidoethanol.These arethe principabluildingblocksofthe3M productlines. CAS Number 31506-32-8 3M Company 4 The followingblock flow diagram describestheprocessdiscussedabove. BLOCK FLOW DIAGRAM Electro-ChemicaFlluorinatioCnells (Octanesulfonylfluoride+ BF + electricaelnergy) Perfluorooctanesulfonylfluoride (POSF) Secondary Reactors Perfluorooctanesulfonicacid (PSOF) Surfactants v ous commercialized intermediates and su -factants IF Amp ioteric surfactants (FireFighting Foams) N-ethyl(and methyl) perfluorooctanesulfonamide N-et tdmethyl) perfluorooctane- sulfonarnidoethanol 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 31506-32-8 3M Company 5 IV. SITE RELEASE AND TRANSFER INFORMATION FOR TRI CHEMICALS Not applicable. V. SITE RELEASE AND TRANSFER INFORMATION FOR NON-TRI CHEMICALS While analyticamlethodshave improvedovertime,largevariabilisttyilelxistsforcertaimnatrices and compounds, so dataavailablfeorthisreportismostlyof a qualitativneature.Although limited monitoringdataexistsm,ost emissionand wasteestimatesarebased upon processmodels and engineeringcalculationsE.ngineeringcalculationhso,wever,have limitationwsithrespectto fluorochemicalbsecause fluorochemicalosseswere notalways includedintheanalysisof each intermediatsetep. The accuracyof theemissionsdatasubmittedvariesdue to severalfactors.Batch processsystems aredifficulttomeasure due toquicklychangingprocessconditionsv,entingpressuresand difficulty inisolatinpgrocessestotakemeasurements. Additionallyt,he uniquecharacteristiocfsthese compounds causethem to behave differentlfyrom conventionalcompounds, and physicalchemical datapropertieasrenot availablfeorallintermediatreeactionstepsinthepast. A. ON-SITE AIR RELEASES ALL PLANTS - Fugitiveemissionmay occurfrom vacuum chargingfrom drums,sampling from reactorsd,rumming of product/intermediaftlea,kingmonomer, dryingoperations. Materialsmay be handledina molten or solidstatev;aporsareproduced from molten material.Industriahlygienemonitoringhas been conductedforsome compounds. Some minor amounts of thesecompounds have been detectedas fugitivemissionsduring industriahlygieneexposuretesting. DECATUR, ALABAMA ONLY: Decatur,AL Emission estimatesarebasedupon existinmgodels and engineeringcalculationfsrom the facilityF.ugitiveemissionsmay have occurredduringsome handlingstepsbuthave notbeen quantified. Wastewater fugitiveemission data was based upon wastewater testing. CAS Number 31506-32-8 Fugitive- wastewater Stack (point) 3M Company EstimatedTotal Annual Releases Obs.) Estimated% days/years Accuracy of releaseoccurs Estimate (optional) < 100 in 1997 250 < 100 in 1999 Estimated Total Annual Releases Obs.) (1997) < Estimated % Accuracy of days/years releaseoccurs Estimate(optional) CAS Number 31506-32-8 3M Company 7 Cotta2eGrove Emissionsestimatesarefrom processengineer'sestimatesand emissionmodels. Estimated Total Annual Releases Obs.) (1997) Estimated % days/years Accuracy of releaseoccurs Estimate(optional) Fugitiv(enon-point) No dataavailable. Stack(point) 0 Comments: CAS Number 31506-32-8 3M Company 8 B. WATER RELEASES FROM SITE Decatur,AL Thiscompound was not on theanalytelisdturingwastewatertesting. Water releases: No dataavailable. Cottage Grove, MN Engineering calculationsareused to estimatethe amount of materialdischargedto wastewater and/or waste. Estimated Total Annual Releases (lbs.)(1997) Estimated % Accuracy of Estimate(options[) Water releases: No dataavailable. Number of days/year releaseoccurs: Receiving Water Name: NPDES Number: Comments: CAS Number 31506-32-8 3M Company 9 C. ON-SITE LAND RELEASES Decatur,AL The landtreatmentof Decatursludgewas discontinueidn early1998. Sludge isnow transportetdo an offsitleandfilalf,terpassingthrougha thickenerand a sludgepress.An impoundment was used in 1997 as partofthewastewatertreatmentoperationbut isnow only used forback-upoperation. Estimated Total Annual Releases (lbs.)(1997) Estimated % Accuracy of Estimate (optional) Landfill Land Treatment/Land Amendment Surface Impoundments Underground Injection Other (specify): 0 No dataavailable No dataavailable/Nolongerused 0 Comments: Cottage Grove, NfN Sludge from the Cottage Grove facilityis sent to an off-siteindustriallandfill 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 31506-32-8 3M Company 10 D. OFF-SITE TRANSFERS Decatur,AL Processwastewatersaremanaged inan on-sitewastewatertreatmentfacilitaynd arenot sent tothePOTW. Dl. TransfertoPubliclyOwned TreatmentWorks (POTW) Number ofdays/yearthe releaseoccurs: Annual Transfer(lb):0 Estimated% Accuracy ofTransferEstimate(optional) POTW Name: StreetAddress: City: State: NPDES Number: Country: Zip Code: Comments: CAS Number 31506-32-8 3M Company CottageGrove, MN Processwastewatersaremanaged inan on-sitewastewatertreatmentfacilitaynd arenot sent tothePOTW. Dl. TransfertoPubliclyOwned TreatmentWorks (POTW) Number of days/yearthe releaseoccurs: Annual Transfer(lb):0 Estimated% AccuracyofTransferEstimate(optional) POTW Name: StreetAddress: City: State: NPDES Numb@r: Country: Zip Code: Comments: CAS Number 31506-32-8 3M Company 12 D2. TRANSFERS TO OTHER OFF-SITE LOCATIONS General Waste Information: There islimitedinformation by CAS number for compound specifirceportinagnd off-sitteransfecrannotbe readilyverifiedR.atherwastes areclassified by halogen contentr,egulatorywaste codes,physicalpropertieasnd non-spec' ific fluorochemicalcategoriesW.here wastesaretrackedby CAS number, theamounts have been included.Incineratioinsnow theprimarydisposalmethod forthesewastes. Decatur,AL 11,000 lbs.of MEFOSA were identifieidn the waste,but not by specificwaste disposal location.A review of plantrecordsregardingwaste disposallocationsforDecatur fluoridecontainingwastes indicatesthat70 isdisposed through incinerationatvarious off-site locationsand approximately30% islandfilleadt a hazardous waste landfill.Incinerationis now the predominant disposalmethod for thesematerials. Estimated Total Annual Releases Obs.) (1997) Estimated % Accuracy of Estimate (optional) Incineration: No specificCAS data available. Wastewater Treatment (Excluding POTW) Underground Injection Hazardous Waste (RCRA SubtitleC) landfill Other Landfill See above. 0 No specificCAS data available. No specificCAS data available. 11,000 lbs.of MEFOSA Recycle or Recovery No specificCAS data available. Unknown or Other Comments: CAS Number 31506-32-8 3M Company 13 Cottage Grove, NN Estimated Total Annual Releases Obs.) Estimated % Accuracy of Estimate (optionai) Incineration: No specificCAS number dataavailable. Wastewater Treatment 0 (ExcludingPOTW) Underground Injection 0 Hazardous Waste (RCRA 0 SubtitleC) landfill Other Landfill 0 Recycle or Recovery 0 Unknown or Other Comments: Cottage Grove facilituytilizeisncinerationforalltheirdrummed wastes. Sludge from the Cottage Grove facilitiyssentto an industriallandfill. CAS Number 31506-32-8 3M Company 14 VI. ON-SITE WORMLACE EXPOSURE 3M ComRm, Si3ecialtMyaterialsManufacturing Division,Cottage Grove, MN No informationavailablaetthistime. 3M CoMpMy, S12ecialtMyaterialsManufacturingDivision,Decatur,AL This informationwillassistEPA in characterizintghenumber of workers potentialleyxposed and the magnitude, frequency,and durationof potentialexposure. When providing monitoringdata,ensure thatdata islinkedwith worker activitiedsescribedin question2. 1. Estimate the number ofworkers potentialleyxposed routinelyto the subjectchemical for each of the exposure durationtimes.Ifa worker isinvolvedin more than one activitye,nter only his/hermost typicalactivitiyn thetable.Don't count a worker more than once. The totalnumber in the tableshould equalthe totalnumber of workers potentialleyxposed. Hours/Day <10 <0.25 0.25-1 4 1-8 >8 Days/Year 10-100 100-250 >250 4 24 24 2. Describe the routine worker activitietso which the workers in question 1 are exposed: sampling, removal offiltercake, and drumming of liquids,manufacture an article,etc. For these activitiesd,escribe the physicalstateof the subject chemical (liquid,gas, particulate, or aerosol,etc.)and, ifin a mixture, the chemical's concentration: Vacuum charging from drums, sampling from reactor,drumming of product/interinediate, maintenance(changingflange,hose,pipe,valve,filtepru,mp or sightglass);materialsmay be handledin a molten or solidstatev;aporsareproducedfrom moltenmaterialm;aterial concentratiornangesfrom <I% to80%. Wastewatertreatmentoperations:collectinagnd analyzingQC samples,operatingfilter press,monitoringprocess,and maintenanceactivitiesm;aterialtsypicallpyresentin waste stream atlessthan I%. CAS Number 31506-32-8 3M Company 15 3. Provide industrialhygienemonitoring data,ifavailablew,ith a briefdescriptionof the sampling method and exposure scenariomonitored,e.g.d,escribethe speciriwcorker activitiesperformed by the individuals monitored. For privacy considerations, please do not include any personal identifierssuch as a worker's name or social security number with any data submitted to EPA. Personal swnpling for these materials is currently (late1999 to present) done using OSHA VersatileSampler tubeswith XAD-4 resinand mixed celluloseesteror glassfiberprefilter. Sample analysisisby LC-MS. Previoussampling had employed silicagelacid mist tubes with GC-ECD analysis.See attachedtableforairsample results. There has been area/sourceairmonitoring data and/or surfacewipe sampling data collectedfor thismaterialatthe plant.Area/source sample resultsand/orsurfacewipe sample resultsare used to identifyareaswith employee exposure potentialas partof exposure assessment under 3M's industriahlygiene program and arenot measurements of actualemployee exposures. Hence, they arenot included with thissubmission. Priorto 1999, these samples were consideredto be semivalidated. Surfaces in production and administrationareas were sampled in 1998. A glassfiberfiltewretted with methyl alcoholwas wiped insidea 10 cm x 10 cm squarewith analysisby LC-MS. Results indicatedthe presence of thesematerialson floorsand equipment surfacesinproduction areas. This resultedin improvements to Hazard Communication practicesp,ersonal hygiene emphasis, personal protectiveequipment emphasis, and severalengineeringand administrativechanges. 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. CAS Number 31506-32-8 3M Company 16 Each 3M plantthatproducessulfonatedfluorochemicalhsas an industriahlygieniston staffand is supported by a corporateindustriahlygiene group. 3M's industriahlygiene program focuseson task-basedexposureassessmentand control.Exposuresareidentifieadnd assessedqualitatively and/orquantitativelQyu.alitativaessessmentsareperformedby an industriahlygienist. Quantitativeassessmentsincludetask-basedpersonalsamplingforcertains,pecific fluorochemicalsand/orsourceorareasampling.The resultosf theassessmentssupportdecisions on exposurecontrol.Engineeringcontrolsarepreferredb,utpersonalprotectivequipmentmay be used on an interimbasisor when effectivengineeringcontrolisnotfeasible. Air SamplinizData for31506-32-8 Job Sample Classification number Chemical Operator Building3 Chemical Operator Flaker Team Leader Building3 Team Leader Flaker 95-006* 95-007* 95-014* 95-040* 95-041 * 95-024* 97-091 * 98-481 * 98-098* Concentration Minimum Maximum (mgim3) (mglm3) (mglm3) Totals 4 0.005 1.3 0.009 0.005 0.007 0.42 0.043 0.011 0.03 1.3 0.14 Geometric Mean 0.041 Geometric Standard Deviation 7.1 *The valueforthissample isone of severalfluorochemicaalnalytescollectedon thesample. Samples are allpersonalbreathingzone samples taken over the durationofa specifictask. CAS Number 31506-32-8 3M Company 17 4. Briefly describe the engineering controls used to minimize exposure to this chemical: Materials are transferredusing closed piping (where possible)from reactorvessels to other containersV.acuum chargingof materialsfrom drums isa standardpractice.Localexhaust ventilatiohnoods aresituateadtsignificanptointsourcessuch as atdrum bungs when drumming. Generalroom airprovidesfordilutioonf airbornematerialsO.peratorcontrolrooms are segregatedfrom processareasand providedseparateroom airventilation. 5. Briefly fistthe personal protective equipment exposure of this chemical: your workers regularly wear to prevent Specific personal protective equipment process operators. isindicated on written operating procedures used by Respiratory protection: Tasks with significantexposure potential (charging, dnmunffig, some maintenance tasks)areperformed using positivepressure,pressuredemand fullface suppliedair respiratorsT.asks with moderate exposure potential(shortterm sampling from tapsor drums, and some maintenance tasks)areperformed using ftdlfaceair-purifyinrgespiratorwsith organic vapor cartridgesand P 100 prefilters. Hand protection: All tasksidentifiedas having potentialfor hand contact requireneoprene (Scorpio)or nitriliendustriaglloves. Body protection:Exposure significanttasksuse one or two-piecePVC suits.Aprons may be wom forsome low exposure potentialtaskssuch as sampling. Foot protection: Tasks identifiedas posing a significanftootexposure potentialrequire chemical resistanbtoots. CAS Number 31506-32-8 3M Company 18 Comments: (This sectionisavailableto clarifythe responses given. Attach additionalpages ifd desired.) Currentexposuresareexpectedtobe lessthan thosemeasured intherecentpast.Significant sourceshave been identifieadnd eliminated.In 1998 an extensiveareaairsamplingof the productionareaswas performed.Areas withhigherlevelsof airbornematerialwsere investigated furthertoidentifsyources.These sources,which includetheflakingequipment,areinthe processof being eliminatedorreducedthroughreplacementwithbetterventilateedquipment. In additiont,heventilatiosnystemintheprimaryproductionbuilding(3)isbeingupgraded. The fluorochemicahlazardcommunicationprogram was improved upon in 1998. Thishas resultedinimproved exposureavoidancebehaviorsamong productionemployees and betteruse of personal protectiveequipment requirements. Additionalhand wash facilitiheasve been installeidn primary process buildings.Food consumption and otherhand-to-mouth activitieasreprohibited.There isno smoking in process buildings.Process employees areinstructedto remove and leave theirwork boots and work coverallsat theplant.Work coverallsareprofessionallylaundered. Non-production equipment surfacessuch as floors,doorknobs and stairrailsare cleaned frequently. CAS Number 31506-32-8 3M Company 19 VU. CHENUCAL END USES A. END USE AS AN INTERMEDIATE CONSUMED TO MAKE OTHER CHEI@UCALS Al. On-Site Use as a Intermediate: Intermediate consumed in the production of a polymeric product which is used as a protective treatment fornonwovens. Product chemical class or product chemical (Include CAS number ifappropriate) 1. Fluorochemical Urethane % of total volume of subject chemical manufactured or imported 82-87% As reported in Part Ul, p.2 A2. Off-Sfte Use as an Intermediate Product chemical class or product chemical (Include CAS number ffappropriate) % of total volume of subject chemical manufactured or imported 1. Not applicable. As reported in Part III,p.2 CAS Number 31506-32-8 3M Company 20 B. END USES OTHER THAN AS A CONSUMED INTERMEDIATE Use Number I of I Descriptionof Chemical End Use: ThisCAS number isused as an intermediatteo manufacturepolymersthataresoldtoindustriaulserstobe used as a polymer meltadditiveto be used as protectiver,epellenttreatmentsfornonwoven substratesT.hese substratewsillbe made intoindustriawlorkwear ormedicalgarmentstobe usedby commercial industry.This CAS number itselwfillbe presentintheseproductsatlow levelsas a residual. Percent of totalmanufactured or imported volume goingtothisuse: 13-18 Check allphysicalforms of the chemicalduringthisuse: Ifused ina mixturecheck appropriatbeox toindicatWeeight fractionA.verage valuesareacceptable: <1% X 1-30% (<7%) 30-60% 60-90% >90% Aerosol Dry Powder Pelletsor largecrystals Water orsolvent- wet solid Gas orvapor Liquidsolution Other(Explain)