Document 6BqJe4jxOgZz82B4GobwV18jE

CAS Number 2991-51-7 3M Company Voluntary Use and Exposure Information Profile Perfluorooctane sulfonamido ethyl acetate 1 I. CHEMICAL IDENTIFICATION Chemical Name: Perfluorooctane sulfonamido ethyl acetate (PFOSSA) CAS Number: 2991-51-7 II. COMPANY IDENTIFICATION Company Name: 3M Site Location: 1400 State Docks Road Decatur, AL 35601 Technical Contact: Phone: Address: W.A. Weppner 651/733-6374 3M Center, Building 236-1B-10 St. Paul, MN 55144 III. ON-SITE ACTIVITIES CAS# Mfe. (1997) ImDorted 2991-51-5* < 100,000 lbs. 0 Estimate the amount of subject chemical distributed off-site: 93.5% of manufacture/import *Submitted in 1998 TSCAIUR. If you have already provided the above information to EPA and it is still representative please reference that submission here: M3 CAS Number 2991-51-7 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 the 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fully fluorinated or perfluoroorganic molecules where all of the hydrogen atoms of the hydrocarbon feedstock have been replaced by fluorine atoms.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 C8H ,7S02F + 17 HF 1-Octanesulfonyl fluoride Energy ---------> C8F i7S02F + 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., C&Fi3S02F, C7FisS02F, C9Fi9S 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 2991-51-7 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. 45 'CASNumber 2991-51-7 3M Company The following block flow diagram describes the process discussed above. BLOCK FLOW DIAGRAM Electro-Chemical Fluorination Cells (Octanesulfonyl fluoride + HF + electrical energy) 4 Perfluorooctane sulfonyl fluoride (POSF) Secondary Reactors Perfluorooctane sulfonic acid (PFOS) l Surfactants 1 Various commercialized intermediates and surfactants Amphoteric surfactants (Fire Fighting Foams) Phosphate Esters and Acrylate/polymers (Paper & Packaging) T Acrylate polymers Adipate adducts Urethane polymers (Carpet and Textile Protection) N-ethyl (and methyl) perfluorooctanesulfonamide l N-ethyl (and methyl) perfluorooctane- sulfonamido ethanol Additional Secondary Reactors Various commercialized intermediates and surfactants % CAS Number 2991-51-7 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 emissions 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 process models and engineering calculations from the facility. Fugitive emissions may have occurred during some handling steps but have not been quantified. Estimated Total Annual Releases (lbs.) Estimated % Accuracy of Estimate (optional) # days/years release occurs Fugitive - (non-point) No data available. Stack (point) Estimated Total Annual Releases (lbs.) (1997) Estimated % Accuracy of Estimate (optional) # days/years release occurs 0 H7- CAS Number 2991-51-7 3M Company 6 B. WATER RELEASES FROM SITE Decatur. AL The data presented is part of wastewater testing conducted in 1998, since the individual compounds of interest were not analyzed in the 1997 wastewater material balance due to method availability and initial program focus. The 1998 data has not been adjusted for production levels in 1997, since most production remained at similar levels. It is not possible to distinguish the amount of chemicals generated from specific reaction steps in production of various compounds, or whether their presence may be the result of hydrolysis of more complex molecules. Estimated Total Annual Releases (lbs.) (1 9 9 7 ) Estimated % Accuracy of Estimate (optional) Water releases: 420 Number of days/year release occurs: Most compounds are manufactured on a regular basis, so releases are estimated at 250 days per year. Receiving Water Name: Baker's Creek at the junction with the Tennessee River NPDES Number: ALD004023164 Comments: CAS Number 2991-51-7 3M Company C. ON-SITE LAND RELEASES 7 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. Levels of the compound in the sludge were determined from wastewater data. Estimated Total Annual Releases (lbs.) (1997) Estimated % Accuracy of Estimate (optional) Landfill 0 Land Treatment/Land Amendment 8,100 No longerused Surface Impoundments No data available/No longer used Underground Injection 0 Other (specify): Comments: 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: 44 ` CAS Number 2991-51-7 3M Company D2. TRANSFERS TO OTHER OFF-SITE LOCATIONS 9 General Waste Information: There is limited information by CAS number for compound specific reporting and off-site transfers 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. Decatur. AL A review of plant records regarding waste disposal locations for Decatur fluoride-containing 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.) 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 No specific CAS number data available. Other Landfill No specific CAS number data available. Recycle or Recovery 0 Unknown or Other Comments: CAS Number 2991-51-7 3M Company VI. ON-SITE WORKPLACE EXPOSURE 9 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. H ours/D ay < 0 .2 5 0.25-1 1-8 >8 <10 11 16 D ays/Y ear 10-100 100-250 >250 24 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: The chemical (2991-51-7) is sampled and drained into drums in a molten state at 80-90% concentration. The material is vacuum-charged in a molten state from drums and formulated into a liquid at 42% concentration. The process mixture is sampled and the final solution is drummed at room temperature. Additional exposure may also occur during equipment maintenance. 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. There is no chemical-specific personal industrial hygiene monitoring data or area/source monitoring data for this specific material at this facility. For most areas of the facility, recent qualitative assessment of potential exposure to this material under 3M's ongoing industrial hygiene program indicates a low exposure potential to this material. CAS Number 2991-51-7 3M Company 10 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. 4. Briefly describe the engineering controls used to minimize exposure to this chemical: Local exhaust is used during drumming and charging of molten material, and during drumming of the formulated solution. 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 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. Comments: (This section is available to clarify the responses given. Attach additional pages if desired.) CAS Number 2991-51-7 VII. CHEMICAL END USES 3M Company 1 A. END USE AS AN INTERMEDIATE CONSUMED TO MAKE OTHER CHEMICALS A l. 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. Not Applicable 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. Exported 3% As reported in Part III, p.2 53 CAS Number 2991-51-7 3M Company 12 Use Number 1 of 3 Description of Chemical End Use: Chemical formulators use this chemical as a surfactant to improve the wetting of water-based products that are sold as cleaners. Percent of total manufactured or imported volume going to this use: 66 1 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: X <1% (50-100 ppm) ___ 1-30% ___ 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) Use Number 2 of 3 Description of Chemical End Use: Chemical formulators use this chemical as a surfactant to improve the wetting of water-based products that are sold as floor polishes. Percent of total manufactured or imported volume going to this use: 29 1 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: X <1% (50-100 ppm) ___ 1-30% ___ 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) CAS Number 2991-51-7 3M Company Use Number 3 of 3 Description of Chemical End Use: Formulators use this chemical as a surfactant in a personal care consumer denture cleaner. Percent of total manufactured or imported volume going to this use: 3 0.25 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: X <1% ___ 1-30% ___ 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) 55