Document n939vGm9gmodB93NOap4dNQV2

' CAS Number 31506-32-8 3M Company AfLAaeJ^I Voluntary Use and Exposure Information Profile N-Methyl perfluorooctanesulfonamide I. CHEMICAL IDENTIFICATION Chemical Name: N-Methyl perfluorooctanesulfonamide (MeFOSA) CAS Number: 31506-32-8 II. COMPANY IDENTIFICATION Company Name: 3M Site Location: 10746 Innovation Road Cottage Grove, MN 55016 1400 State Docks Road Decatur, AL 35601 Technical Contact: Phone: Address: W.A. Weppner 651/733-6374 3M Center, Building 236-IB-10 St. Paul, MN 55144 III. ON-SITE ACTIVITIES CAS# Mfe. (19971 ImDorted 31506-32-8* < 100,000 0 Estimate the amount of subject chemical distributed off-site: 0 *Submitted in 1998 TSCAIUR. Significant production occurs that is non-isolated and non-reportable under TSCA. l\ 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, organic feedstocks are 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 components of die products created by this process have the same carbon skeletal arrangement as the feedstock used, but with all of the hydrogen atoms replaced by fluorine. However, fragmentation and rearrangement of the carbon skeleton can also occur and significant amounts of cleaved, branched and cyclic structures may be formed. The degree of fluorination of the organic feedstock is also dependent upon the specific carbon chain length of the feedstock and parameters of the ECF process such as electrical current and the length of time the process is run. It is possible to synthesize fully fluorinated or perfluoroorganic molecules where all of the hydrogen atoms of the hydrocarbon feedstock have been replaced by fluorine atoms.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 process. A basic building block of such products and the highest production volume fluorochemical 3M manufactures is perfluorooctanesulfonyl fluoride (POSF). The starting feedstock for this reaction is 1-octanesulfonyl fluoride. (Reaction 1) Reaction 1 C8Hi7S02F + 17 HF 1-Octanesulfonyl fluoride Energy ---------> C8Fi7S02F + 17 H2 ECF Perfluorooctanesulfonyl fluoride The electrochemical fluorination process yields about 35%-40% straight chain (normal) POSF, and a mixture of biproducts and waste of unknown and variable composition comprised of the following: 1) higher and lower straight-chain homologs, i.e., n-CnF2n+iS02F, e.g., C6Fb S 0 2F, C7FisS 0 2F, C9F i9S 0 2F which comprise about 7% of the process output 2) branched-chain, perfluoroalkylsulfonyl fluorides with various chain lengths, about 18-20% of the output 3) straight-chain, branched, and cyclic (non-functional) perfluoroalkanes and ethers, which comprise about 20-25% of the output 4) "tars" (high molecular weight fluorochemical byproducts) and other byproducts, including molecular hydrogen, which comprise about 10-15% of the output. Because of slight 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 process or are 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 all of this treatment sludge is being landfilled off-site since early 1998. POSF is itself a commercially viable product, but is primarily an important intermediate in the synthesis of substances used in many 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 moiety of the molecule using conventional hydrocarbon reactions. POSF is reacted with methyl or ethyl amine to produce either N-methyl or N-ethylperfluorooctanesulfonamide (MeFOSA or EtFOSA). Some of the MeFOSA and EtFOSA is isolated to be used as intermediates to be reacted to form other materials. The majority of the MeFOSA and EtFOSA 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 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) Perfluorooctane sulfonic acid (PSOF) Secondary Reactors l Surfactants J Various commercialized intermediates and surfactants ir Amphoteric surfactants (Fire Fighting Foams) N-ethyl (and methyl) perfluorooctanesulfonamide l N-ethyl (and methyl) perfluorooctane- sulfonamido ethanol Additional Secondary Reactors Phosphate Esters and Acrylate/polymers (Paper & Packaging) Acrylate polymers Adipate adducts Urethane polymers (Carpet and Textile Protection) Various commercialized intermediates and surfactants CAS Number 31506-32-8 3M Company IV. SITE RELEASE AND TRANSFER INFORMATION FOR TRI CHEMICALS 5 Not applicable. V. SITE RELEASE AND TRANSFER INFORMATION FOR NON-TRI CHEMICALS While analytical methods have improved over time, large variability still exists for certain matrices and compounds, so data available for this report is mostly of a qualitative nature. Although limited monitoring data exists, most emission and waste estimates are based upon process models and engineering calculations. Engineering calculations, however, have limitations with respect to fluorochemicals because fluorochemical losses were not always included in the analysis o f each 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 characteristics of these 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 ALL PLANTS - Fugitive emission may occur from vacuum charging from drums, sampling from reactors, drumming of product/intermediate, flaking monomer, drying operations. 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. ^5 CAS Number 31506-32-8 Fugitive --wastewater Stack (point) 3M Company Estimated Total Annual Releases (lbs.) Estimated % Accuracy of Estimate (optional) 6 # days/years release occurs < 100 in 1997 < 100 in 1999 250 Estimated Total Annual Releases (lbs.) (1 9 9 7 ) <1 Estimated % Accuracy of Estimate (optional) # days/years release occurs % CAS Number 31506-32-8 3M Company Cottage Grove Emissions estimates are from process engineer's estimates and emission models. Estimated Total Annual Releases (lbs.) (1 9 9 7 ) Estimated % Accuracy of Estimate (optional) # days/years release occurs Fugitive (non-point) No data available. Stack (point) 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 amount of material discharged to wastewater and/or waste. Estimated Total Annual Releases (lbs.) (1 9 9 7 ) Estimated % Accuracy of Estimate (optional) Water releases: No data available. Number of days/year release occurs: Receiving Water Name: NPDES Number: Comments: CAS Number 31506-32-8 .3,xM.* C^vo*m*^pa*n*.y, C. ON-SITE LAND RELEASES 9 Decatur. AL The land treatment of Decatur sludge was discontinued in early 1998. Sludge is now transported to an offsite landfill, after passing through a thickener and a sludge 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 (lbs.) (1 9 9 7 ) Estimated % Accuracy of Estimate (optional) 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 (lbs.) (1997) Estimated % Accuracy of Estimate (optional) Landfill Land Treatment/Land Amendment Surface Impoundments Underground Injection Other (specify): 0 0 0 0 Comments: CAS Number 31506-32-8 3M Company 10 D. OFF-SITE TRANSFERS Decatur. AL Process wastewaters are managed in an on-site wastewater treatment facility and are not sent to the POTW. D l. Transfer to Publicly Owned Treatment Works (POTW) Number of days/year the release occurs: Annual Transfer (lb): 0 Estimated % Accuracy of Transfer Estimate (optional) (%): POTW Name: Street Address: City: State: NPDES Number: Country: Zip Code: Comments: 100 CAS Number 31506-32-8 3M Company il Cottage Grove. MN Process wastewaters are managed in an on-site wastewater treatment facility and are not sent to the POTW. D l. Transfer to Publicly Owned Treatment Works (POTW) Number of days/year the release occurs: Annual Transfer (lb): 0 Estimated % Accuracy of Transfer Estimate (optional) (%): POTW Name: Street Address: City: State: NPDES Number: Country: Zip Code: Comments: I0| CAS Number 31506-32-8 3M Company D2. TRANSFERS TO OTHER OFF-SITE LOCATIONS 12 General Waste Information: There is limited information by CAS number for compound specific reporting and off-site transfer cannot be readily verified. Rather wastes are classified 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 lbs. of MeFOSA were identified in the waste, but not by specific waste disposal location. A review of plant 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 Annual Releases (lbs.) (1997) Estimated % Accuracy of Estimate (optional) 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 lbs. of MeFOSA Other Landfill No specific CAS data available. Recycle or Recovery No specific CAS data available. --^ Unknown or Other Comments: (01 CAS Number 31506-32-8 Cottage Grove. MN 3M Company Estimated Total Annual Releases (lbs.) Estimated % Accuracy of Estimate (optional) Incineration: No specific CAS number data available. Wastewater Treatment (Excluding POTW) 0 Underground Injection 0 Hazardous Waste (RCRA Subtitle C) landfill 0 Other Landfill 0 Recycle or Recovery 0 Unknown or Other Comments: Cottage Grove facility utilizes incineration for all their drummed wastes. Sludge from the Cottage Grove facility is sent to an industrial landfill. 13 103 CAS Number 31506-32-8 3M Company VI. ON-SITE WORKPLACE EXPOSURE 14 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 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 <0.25 0.25-1 1-8 >8 <10 4 Days/Year 10-100 100-250 4 24 24 >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: Vacuum charging from drums, sampling from reactor, drumming of product/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%. CAS Number 31506-32-8 3M Company 15 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. Personal sampling for these materials is currently (late 1999 to present) done using OSHA Versatile Sampler tubes with XAD-4 resin and mixed cellulose ester or glass fiber prefilter. 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. There has been area/source air monitoring data and/or surface wipe sampling data collected for this material at the plant. Area/source sample results and/or surface wipe sample results are used to identify areas with employee exposure potential as part of 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. Surfaces in production and administration areas were sampled in 1998. A glass fiber filter wetted with methyl alcohol was wiped inside a 10 cm x 10 cm square with analysis by LC-MS. Results indicated the presence of these materials on floors and equipment surfaces in production areas. This resulted in improvements to Hazard Communication practices, personal hygiene emphasis, personal protective equipment emphasis, and several engineering and administrative changes. The sample results of any air monitoring are compared to 3M's voluntary exposure guideline (EG) of 0.1 mg/m3 (milligrams of fluorochemical per cubic meter of air) for various fluorochemical compounds, including compounds covered in this submittal. The EG is an 8-hour time-weighted average (TWA) personal breathing zone exposure chosen to minimize potential for uptake. (05 CAS Number 31506-32-8 3M Company 16 Each 3M plant that produces sulfonated fluorochemicals has an industrial hygienist on staff and is supported by a corporate industrial hygiene group. 3M's industrial hygiene program focuses on task-based exposure assessment and control. Exposures are identified and assessed qualitatively and/or quantitatively. Qualitative assessments are performed by an industrial hygienist. Quantitative assessments include task-based personal sampling for certain, specific fluorochemicals and/or source or area sampling. The results of the assessments support decisions on exposure control. Engineering controls are preferred, but personal protective equipment may be used on an interim basis or when effective engineering control is not feasible. Air Sampling Data for 31506-32-8 Job Sample Classification number Chemical Operator Building 3 Chemical Operator Flaker Team Leader Building 3 Team Leader Flaker 95-006* 95-007* 95-014* 95-040* 95-041* 95-024* 97-091* 98-481* 98-098* Concentration Minimum Maximum (mg/m3) (mg/m3) (mg/m3) Totals- 0.005 0.009 1.3 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 value for this sample is one of several fluorochemical analytes collected on the sample. Samples are all personal breathing zone samples taken over the duration of a specific task. |0G CAS Number 31506-32-8 3M Company 17 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 dilution of 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. Respiratory protection: Tasks with significant exposure potential (charging, drumming, some maintenance tasks) are performed using positive pressure, pressure demand full face supplied air respirators. Tasks with moderate exposure potential (short term sampling from taps or drums, and some maintenance tasks) are performed using full face air-purifying respirators with organic vapor cartridges and P I00 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 18 Comments: (This section is available to clarify the responses given. Attach additional pages if d desired.) Current exposures are expected to be less than those measured in the recent past. Significant sources have been identified and eliminated. In 1998 an extensive area air sampling of the production areas was performed. Areas with higher levels of airborne materials were investigated further to identify sources. These sources, which include the flaking equipment, are in the process o f being eliminated or reduced through replacement with better ventilated equipment. In addition, the ventilation system in the primary production building (3) is being upgraded. The fluorochemical hazard communication program was improved upon in 1998. This has resulted in improved exposure avoidance behaviors among production employees and better use of personal protective equipment requirements. Additional hand wash facilities have been installed in primary process buildings. Food consumption and other hand-to-mouth activities are prohibited. There is no smoking in process buildings. Process employees are instructed to remove and leave their work boots and work coveralls at the plant. Work coveralls are professionally laundered. Non-production equipment surfaces such as floors, doorknobs and stair rails are cleaned frequently. CAS Number 31506-32-8 3M Company 19 VII. CHEMICAL END USES A. END USE AS AN INTERMEDIATE CONSUMED TO MAKE OTHER CHEMICALS A l. On-Site Use as a Intermediate: Intermediate consumed in the production of a polymeric product which is used as a protective treatment for nonwovens. Product chemical class or product chemical (Include CAS number if appropriate) 1. Fluorochemical Urethane % of total volume of subject chemical manufactured or imported 82-87% As reported in Part III, p.2 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. Not applicable. As reported in Part III, p.2 CAS Number 31506-32-8 3M Company B. END USES OTHER THAN AS A CONSUMED INTERMEDIATE 20 Use Number 1 of 1 Description of Chemical End Use: This CAS number is used as an intermediate to manufacture polymers that are sold to industrial users to be used as a polymer melt additive to be used as protective, repellent treatments for nonwoven substrates. These substrates will be made into industrial workwear or medical garments to be used by commercial industry. This CAS number itself will be present in these products at low levels as a residual. Percent of total manufactured or imported volume going to this use: 13-18 Check all physical forms of the chemical during this use: If used in a mixture check appropriate box to indicate Weight fraction. Average values are acceptable: ___ < 1% X 1-30% (<7%) ___ 30-60% ___ 60-90% >90% ___ Aerosol ___ Dry Powder ___ Pellets or large crystals ___ Water or solvent - wet solid ___ Gas or vapor X Liquid solution ___ Other (Explain)