Document mmeDmjR8rw2p7Y9p3a4djEMNJ

I. (CAS Number 31506-32-8 3M Company AR226.58] 1 Voluntary Use and Exposure Information Profile N-Methyl perfluorooctanesulfonamide L CHEMICAL IDENTIFICATION `Chemical Name: CAS Number: N-Methyl perfluorooctanesulfonamide (MeFOSA) 31506-32-8 IL COMPANY IDENTIFICATION Company Name: 3M Site Location: 10746 Innovation Road Cottage Grove, MN 55016 Technical Contact: Phone: Address: 1400 State Docks Road Decatur, AL 35601 W.A. Weppner 651/733-6374 3M Center, Building 236-1B-10 St. Paul, MN 55144 II. ON-SITE ACTIVITIES CAS# Mfg. (1997) 31506-32-8* <100,000 Estimate the amountofsubject chemical distributed off-site: 0 Imported 0 *Submitted in 1998 TSCA IUR. Significant production occurs that is non-isolated and non-reportable under 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 organofluorine molecules. In this process, organicfeedstocksare dispersed in liquid, anhydrous hydrogen fluoride, and an electric current is passed through the solution, causing the hydrogen atoms on the molecule to be replaced with fluorine. The predominant componentsofthe products created by this process have the same carbon skeletal arrangement as the feedstock used, but with allofthe `hydrogen atoms replaced by fluorine. However, fragmentation and rearrangementofthe carbon skeleton can also occur and significant amountsofcleaved, branched and cyclic structures may be formed. The degree of fluorinationofthe organic feedstock is also dependent upon the specific carbon chain lengthofthe feedstock and parameters of the ECF process such as electrical current and tmhoelelceunlgtehsofwtheirmeealtlheofprtohceehsysdirsorguenn. aItt oims spoosfstihbelehtyodsryonctahrebsoinzefefeuldlsytofclkuohrainvaetebdeeonr rpeerpfllaucoerdoboyrganic fluorine atoms. Using these perfluoroorganic molecules as basic building blocks, unique chemistries can be created by further reactions with functionalized hydrocarbon molecules. 3M has produced sulfonyl based fluorochemicals commercially for over 40 years using the ECF 3prMocemsasn.ufAacbtausriecsbiusipledrifnlgubolrooocckotafnessuuclhfopnryoldufcltusoraidned (tPheOShFi)g.hesTthpersotdaurcttiingonfeveodlsutmoeckfflourorthoicsheremaicctailon is 1-octanesulfony! fluoride. (Reaction 1) Reaction | CyHy7S0F + 17 HF 1-Octanesulfony! fluoride Energy End CsFiySOF + 17H ECFPerfluorooctanesulfonyl fluoride `The electrochemical fluorination process yields about 35%-40% straight chain (normal) POSF, and a `mixtureof biproducts and wasteof unknown and variable composition comprisedofthe following: 1) higher and lower straight-chain homologs, i.., n-CnFany SOF, e.g., CeF13SOaF, CoF1sSOoF, CsF19SO,F which comprise about 7% of the process output 2) branched-chain, perfluoroalkylsulfonyl fluorides with various chain lengths, about 18-20%ofthe output 3) astbroauitgh2t0-c-h2ai5n%, obfratnhcehoeudt,puatnd cyclic (non-functional) perfluoroalkanes and ethers, which comprise 4) "tars" (high molecular weight fluorochemical byproducts) and other byproducts, including molecular hydrogen, which comprise about 10-15%ofthe output. Becauseofslight differences in process conditions, raw materials, and equipment, the mixture produced by the electrochemical fluorination process varies somewhat from lot-to-lot and from plantto-plant. The product that results from electrochemical fluorination is thus not a pure chemical but rather a mix of isomers and homologues. The commercialized POSF derived products are a mixture of approximately 70% linear POSF derivatives and 30% branched POSF derived impurities. CAS Number 31506-32-8 3M Company 3 During production, byproducts and waste products are formed. The volatile waste products, such as perfluoromethane, have been vented to the atmosphere in the past, but plans are being implemented to capture and destroy these releases by thermal oxidation over the next few years. The tars have been landfilled in a hazardous waste landfill in the past, but are all currently being incinerated at an in-house or external hazardous waste incinerator. The byproducts, many of which are incompletely fluorinated with hydrogen atoms still present, can be recycled back into the ECF processorare partially degraded in stabilization processes and discharged to controlled, in-house, wastewater treatment systems. The treatment sludge associated with the ECF process has been either landfilled or land-incorporated in the past, but allofthis treatment sludge is being landfilled off-site since early 1998. POSF is itselaf commercially viable product, but is primarily an important intermediate in the synthesisofsubstances usedinmany other 3M fluorochemical products. The majority is used to produce functionally derivatized fluorochemicals and high molecular weight polymeric products. Unique chemistries can be created by derivatizing POSF through the sulfonyl fluoride moietyofthe molecule using conventional hydrocarbon reactions. POSF is reacted with methyl or ethyl amine to produce either N-methyl or N-ethylperfluorooctanesulfonamide (MeFOSA or EFFOSA). Someofthe MeFOSA and EXFOSA is isolated to be used as intermediates to be reacted to form other materials. `The majorityofthe MeFOSA and E{FOSA is not isolated and subsequently reacted with ethylene carbonate to form either N-methyl or N-ethylperfluorooctane sulfonamido ethanol. These are the principal building blocks of the 3M product lines. CAS Number 31506-32-8 3M Company 4 The following block flow diagram describes the process discussed above. BLOCK FLOW DIAGRAM Electro-Chemical Fluorination Cells (Octanesulfonyl fluoride + HF + electrical energy) Perfluorooctane sulfonyl fluoride | (POSF) [niRet actoe rs Perfluorooctane sulfonic acid (PSOF) Surfactants | Vari3 ous commercialized ainndtesrumrefdaictaatnetss Amphoteric surfactants (Fire Fighting Foams) N-ethyl (and methyl) perfluorooctanesulfonamide | N-ethyl (and methyl) perfluorooctane- sulfonamido ethanol Additional Secondary Reactors Phosphate Esters and Acrylate/polymers (Pape&r Packaging) Acrylate polymers Adipate adducts Urethane polymers (Carpet and 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. Vv. SITE RELEASE AND TRANSFER INFORMATION FOR NON-TRI CHEMICALS `While analytical methods have improved over time, large variability still exists for certain matrices maonndictoormipnogunddatsa,esxoisdtas,tamoavsatileambilsesfioorntahinsdrweapsotrte iessmtiomsattleysoarfae bqauasleidtautpivoennpartuorcee.ssAmlotdheolusghanldimited engineering calculations. Engineering calculations, however, have limitations with respect to fluorochemicals because fluorochemical losses were not always included in the analysisofeach intermediate step. The accuracy of the emissions data submitted varies due to several factors. Batch process systems are difficult to measure due to quickly changing process conditions, venting pressures and difficulty in isolating processes to take measurements. Additionally, the unique characteristicsofthese compounds cause them to behave differently from conventional compounds, and physical chemical data properties are not available for all intermediate reaction steps in the past. A. ON-SITE AIR RELEASES AfrLoLm rPeaLcAtoNrsT,Sdr-uFmumgiitnigvoefepmriosdsuicouninmtaeyrmoecdeiuartef,rofmlavkiancgumuomncohmaerrg,indgryfirnogmodpreurmatsi,onssa.mpling Materials may be handled in a molten or solid state; vapors are produced from molten material. Industrial hygiene monitoring has been conducted for some compounds. Some `minor amounts of these compounds have been detected as fugitive emissions during industrial hygiene exposure testing. DECATUR, ALABAMA ONLY: Decatur, AL Emission estimates are based upon existing models and engineering calculations from the facility. Fugitive emissions may have occurred during some handling steps but have not been quantified. `Wastewater fugitive emission data was based upon wastewater testing. CAS Number 31506-32-8 Fugitive - wastewater Stack (point) 3M Company Estimated Total Estimated % Annual Releases ~~ Accuracy of (bs) Estimate (pions <100in 1997 <100in 1999 6 #daysiyears release occurs 250 Estimated Total Annual Releases (bs) (1997) <1 Estimated % Accuracy of Estimate (sptiona) #dayslyears release occurs CAS Number 31506-32-8 3M Company 7 Cottage Grove Emissions estimates are from process engineer's estimates and emission models. Estimated Total `Annual Releases (bs) (1997) Estimated % Accuracy of [Estimate (optional) # dayslyears release occurs Fugitive (non-point) Stack (point) No data available. 0 Comments: + `CAS Number 31506-32-8 3M Company 8 B. `WATER RELEASES FROM SITE Decatur, AL `This compound was not on the analyte list during wastewater testing. `Water releases: No data available. Cottage Grove, MN. `Engineering calculations are used to estimate the amountofmaterial discharged to wastewater and/or waste. [Estimated Total `Annual Releases (bs) (1997) Estimated % Accuracy of `Estimate (optional) `Water releases: No data available. Number of days/year release occurs: NPDES Number: `Comments: 9% CAS Number 31506-32-8 3M Company 9 C. ON-SITE LAND RELEASES Decatur, AL `The land treatmentofDecatur sludge was discontinued in carly 1998. Sludge is now transported to an offsite landfill, after passing through a thickener aansluddge press. An impoundment was used in 1997 as part of the wastewater treatment operation but is now only used for back-up operation. Estimated Total Annual Releases (Ibs) (1997) Estimated % Accuracy of Estimate (options) Landfill Land Treatment/Land Amendment Surface Impoundments Underground Injection Other (specify): 0 No data available No data available/No longer used 0 Comments: Cottage Grove, MN Sludge from the Cottage Grove facility is sent to an off-site industrial landfill Estimated Total Annual Releases (Ibs) (1997) Estimated % Accuracy of Estimate (options) 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 Process wastewaters are managed inanon-site wastewater treatment facility and are not sent to the POTW. DI. Transfer to Publicly Owned Treatment Works (POTW) Number of dayslyear the release occurs: Annual Transfer (b): 0 Estimated % Accuracy of Transfer Estimate (optional) (%): POTW Name: Street Address: City: State: NPDES Number: Country: Zip Code: Comments: CAS Number 31506-32-8 3M Company u CottageGrove,MN Process wastewaters are managed in an on-site wastewater treatment facility and are not sent 10 the POTW. DI. Transfer to Publicly Owned Treatment Works (POTW) Number of dayslyear the release occurs: Annual Transfer (Ib): 0 Estimated % AccuracyofTransfer Estimate (optional) (%): POTW Name: Street Address: City: State: NPDES Number: Country: Zip Code: Comments: 101 CAS Number 31506-32-8 3M Company 2 D2. TRANSFERS TO OTHER OFF-SITE LOCATIONS GspeenceifriaclrWepaosrttienIgnafnodrmofaft-isoitne:trTahnesfreericsalninmoittebdeirnefaodrimlaytvieornifbiyed.CARaSthneurmwbaesrtefsorarceocmlpaossuinfdied by halogen content, regulatory waste codes, physical properties and non-specific fluorochemical categories. Where wastes are tracked by CAS number, the amounts have been included. Incineration is now the primary disposal method for these wastes. Decatur, AL 11,000 Ibs.ofMeFOSA were identified in the waste, but not by specific waste disposal location. A reviewofplant records regarding waste disposal locations for Decatur fluoridecontaining wastes indicates that 70 is disposed through incineration at various off-site locations and approximately 30% is landfilled at a hazardous waste landfill. Incineration is now the predominant disposal method for these materials. Estimated Total Estimated % Annual Releases ~~ Accuracy of (Ibs) (1997) Estimate (options) Incineration: No specific CAS data available. Wastewater Treatment (Excluding POTW) See above. Underground Injection 0 Hazardous Waste (RCRA Subtitle C) landfill No specific CAS data available. 11,000 Ibs. of MeFOSA Other Landfill No specific CAS data available. Recycle or Recovery No specific CAS data available. Unknown or Other Comments: CAS Number 31506-32-8 3M Company 5 Cottage Grove, MN AEsntniumaalteRdelTeoatsaels (bs.) AEsctciumraatceydo%f [Estimate (optional) Incineration: No specific CAS number data available. `Wastewater Treatment 0 (Excluding POTW) Underground Injection 0 Hazardous Waste (RCRA 0 Subtitle C) landfill Other Landfill 0 Recycle or Recovery 0 Unknown or Other Comments: Cottage Grove facility utilizes incineration foral thir drummed wastes. Sludge from the Cottage Grove facility is sent to an industrial landfill. 103 `CAS Number 31506-32-8 3M Company 1" VI. ON-SITE WORKPLACE EXPOSURE 3M Company, Specialty Materials Manufacturing Division, Cottage Grove, MN No information available at this time. 3M Company, Specialty Materials Manufacturing Division, Decatur, AL "This information will assist EPA in characterizing the numberof 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 eachof 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 numberof workers potentially exposed. pw Cos|TT Doma | oo| 0[ow[0] Low | T= C=1[1] 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: Vacuum charging from drums, sampling from reactor, drumming ofproduct/intermediate, `maintenance (changing flange, hose, pipe, valve, filter, pump or sight glass); materials may be handled in a molten or solid state; vapors are produced from molten material; material concentration ranges from <1% to 80%. Wastewater treatment operations: collecting and analyzing QC samples, operating filter press, monitoring process, and maintenance activities; materials typically present in waste stream at less than 1%. [oY CAS Number 31506-32-8 3M Company 1s 3. Provide industrial hygiene monitoring data, if available, with a brief description of the sampling method and exposure scenario monitored, e.g., describe the specific 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. VPeerrssaotniallesSaammppllienrgtfuobretshwesiethmaXtAerDi-al4sriessciunrarnendtlmyix(leadtece1l9l9u9lotsoepersetseernotr) gdloanses fuisbienrgpOreSfiHltAer. Sample analysis is by LC-MS. Previous sampling had employed silica gel acid mist tubes with GC-ECD analysis. See attached table for air sample results. tThhiesrmeathearsiableeatntahreeap/lsaontu.rceAraeiar/msoonuirtcoerisnagmdpaltearaensdu/ltosrasnudr/foarcesuwrifpaecesawmippleisngamdpaltea rceoslulletcsteadrefoursed to identify areas with employee exposure potential as partof exposure assessment under 3M's industrial hygiene program and are not measurements of actual employee exposures. Hence, they are not included with this submission. Prior to 1999, these samples were considered to be semivalidated. `Swuirtfhamceetshiynlparlocdouhcotliownaasnwdiapdemdiniinsstirdaetaio1n0acremasxw1e0recmsasmqpulaerde winit1h99a8n.alyAsigslabsysLfCib-eMrSf.ilteRrewseutlttesd indicated the `This resulted presenceofthese in improvements materials to Hazard on floors and equipment surfaces in Communication practices, personal production areas. hygiene emphasis, personal protective equipment emphasis, and several engineering and administrative changes. `(TEhGe)soafmple0.1 mregs/ulmt3sof(aminlyligarirammsonoiftfolruionrgocarheemciocmaplapreerdcutobi3cMm'estevroolufnatiarr)yfeoxrpvoasruiroeusguideline tfilmueo-rowcehiegmhitceadlacvoemrpaogeun(dTsW,Ai)ncpleurdsionngaclobmrpeaotuhnidnsg zcoonveereexdpoinsutrhiescshuobsmietntatlo.miTnhiemiEzGe pisotaennt8i-ahlofuorr uptake. [05 CAS Number 31506-32-8 3M Company 16 Esuapcphor3tMedpblaynatctohraptoprraotdeucinedsussturlifaolnahtyegdiefnleuogrroocuhpe.mi3cMal'sshiansduasntriinadluhstyrgiiaelnheygpireongirsatmonfsotcaufsfeasnodn is taansdk/-orbaqsueadnteixtpaotisvuerley.asQsueaslsimteanttivaenadssceonstsrmoeln.tsExarpeospuerrefsoramreedidbeyntainfiiendduasntdriaaslsheysgsieedniqsuta.litatively Qfulaunotriotcahteimviecaalssseasnsdm/eonrtssoiunrccleuodre atraesak-sbaamspeldinpge.rsoTnhael sreasmuplltsionfgtfhoer caesrsteaisns,mesnpetcsifsiucpport decisions oben uesxepdosounreancointnrtoelr.imEbnagsiisneoerrwinhgenconeftfreocltsiavreeepnrgeifneererreidn,gbcuotnpterrolsoinsanloptrfoetaescitbilev.e equipment may Air Sampling Data for 31506-32-8 ClasJsiofibcation Snaummpbleer Con(cnegntirnadt)ion Mi(nngiimmu3)m M(amxgiimmdu)m GeoMmaeatnric GSetoamnedtarridc T _-- aTotal ls > 0.005 o 3 00an 71 "CheOpmeircataolr es006 008 Building 3 95007" 0.005 9955.-004104"0 00..04027 95-041 Chemical 95-024" 00.001813 OpFearkaetror 97.091" 003 e BuidTeiamni3sgad der s13 TeaFmlaLkeerader 96-096" 01a "The value for this sample is one of several fluorochermical analytes collected on the sample. `Samples are al personal breathing zone samples taken over the duration of a specific task. CAS Number 31506-32-8 3M Company " 4. Briefly describe the engineering controls used to minimize exposure to this chemical: Materials are transferred using closed piping (where possible) from reactor vessels to other containers. Vacuum charging of materials from drums is a standard practice. Local exhaust ventilation hoods are situated at significant point sources such as at drum bungs when drumming. General room air provides for dilutionof airborne materials. Operator control rooms are segregated from process areas and provided separate room air ventilation. 5. Briefly list the personal protective equipment your workers regularly wear to prevent exposure of this chemical: Specific personal protective equipment is indicated on written operating procedures used by process operators. Rmeasipnitreantaonrcye tparsoktse)ctairoenp:erTfaosrkmsedwiutshinsgigpnoisfiitciavnet perxepsossuurre,e pporteesnstuiraeld(echmaarngidngf,ulldrfaucmemsiunpgp,liseodmaeir raensdpisraotmoers.maTianstkesnawnictehtmaoskdse)raatree peexrpfoosrumreedpoutseinntgiaflul(lshfaocret atierr-mpusraimfpyliingngrefsrpiormattoarpsswoirtdhrourmgsa,nic. vapor cartridges and P100 prefilters. Hand protection: All tasks identified as having potential for hand contact require neoprene (Scorpio) or nitrile industrial gloves. Body protection: Exposure significant tasks use one or two-piece PVC suits. Aprons may be `worn for some low exposure potential tasks such as sampling. Foot protection: Tasks identified as posing a significant foot exposure potential require chemical resistant boots. CAS Number 31506-32-8 3M Company 1s Comments: (This section is available to clarify the responses given. Attach additional pages ifd desired.) Csouurrecnets heaxvpoesbuereens iadreenetixfpieecdtaenddtoelbiemilneastsedt.hanInth1o9s9e8maenaseuxrteednsiinvethaereraecaeinrtspaamstp.linSiggonfitfhiceant Fpurrotdheurcttioonidaernetaisfywsaosurpceersf.orTmehde.se Asroeuracsews,itwhhihicghheirnclleuvdeelsthoeffaliarkbionrgneeqmuaitpermieanlts,waerreeiinntvheestigated apdrdoicteisosno,ftbheeivnegnteillaitmiionnatseydstoermreindutcheedptrhirmoaurgyhprroedpulcatcieomnenbtuiwlidtihngbe(t3t)erisvbenetiinlgatuepdgreaqdueidp.ment. In r"Tehseulftleudoirnocihmepmriocvaeldhaezxaprodsucroemamvuoniidcaantcieobnephravoigorrasmawmaosnigmpprroodvuecdtiuopnoenmipnlo1y9e98e.s aTnhdisbehatser use: of personal protective equipment requirements c`Aodndsiutimopntailohnaannddwoatshherfahcainlidt-iteso-hmaovuetbheaecntiivnistiteasllaerdeipnrporhiibmiatreyd.prTohceerses bisuinlodisnmgso.kiFnogoidn process cbuoivledrianlglss.atPtrhoeceplsasnte.mpWlooyrekescoavreerailnlsstraurcetpedrotfoesrseimoonavlelyanldaulnedearveedt.heir work boots and work Nforenq-upernotldyu.ction equipment surfaces such as floors, doorknobs and stir rails are cleaned CAS Number 31506-32-8 3M Company 1 VIL. CHEMICAL END USES A. END USE AS AN INTERMEDIATE CONSUMED TO MAKE OTHER CHEMICALS AL On-Site Use as a Intermediate: Intermediate consumed in the production ofa polymeric product which is used as a protective treatment for nonwovens. Prorodpurcotducchtemcihceamliccalalss (Include CAS number if appropriate) 1. Fluorochemical Urethane % of total chevmoilcuamlemoafnsuufbajcetctured or imported 82.87% As reported in Part III, p2 A2. Off-Site Use as an Intermediate Product chemical class or product chemical (Include CAS number if appropriate) % of total volume of subject chemical manufactured or imported 1. Notapplicable. As reported in Part III, p2 CAS Number 31506-32-8 3M Company 2 B. END USES OTHER THAN AS A CONSUMED INTERMEDIATE Use Number 1 of 1 Descriptionof Chemical End Use: This CAS number is used as an intermediate to manufacture polymersthatare sold to industrial users to be used as a polymer melt additive to bmeadueseidntaos ipnrdoutsetcrtiiavle,worerpkewleleanrt otrremaetdmiecnatls gfaorrmneonntswotvoebne suusbesdtrbatyesc.omTmheersceiaslubisntdruasttersy.wilTlhibse CAS number itself will be present in these products at low levels as a residual. Percentof total manufactured or imported volume going tothisuse: 13-18% Check all physical formsofthe chemical during this use: ItfouisnedidcianteamWiexitguhrtefrcahcteicokn.apAprvoeprraigaete box values are acceptable: an XX 130% (<7%) TT 3060% 60-90% 0% __ Aerosol "Dry Powder "Pelletsorlarge crystals Water or solvent ~ wet solid T_ Gasorvapor X_ Liquid solution Other (Explain)