Document 712gqmJ04rKjv00aLVeom5ya8

AR226-2556 June 23, 2000 Dr. Charles M. Auer, Director U, S. Environmental Protection Agency Office of Pollution Prevention and Toxics Chemical Control Division 401 .M Street NW, Room 403 Washington, D.C. 20460 Dear Dr. Auer: As you requested in your April 19, 2000 letter and during our subsequent meeting on PMearyflu1o,2ro0o0c0t,anaottaatceh(eAdPiFs Oa ,suCmAmS#ar3y8o2f5D-2u6P-1o)nta'ss U.S, uses of Ammonium a fluoropolymer reaction aid including releases from DuPont site and the fate o f APFO in fluoropolymer dispersion products, a summary of industrial hygiene data collected at our U.S. fluoropolymer manufacturing site, and a summary of the employee blood data from a site in the U.S. A summary o f the toxicology available to DuPont was sent under separate cover on May 26, 2000. It is important to emphasize the following points: y DuPont does not manufacture APFO. All APFO used in our processes as a reaction aid is purchased from an outside supplier. y Most of the APFO used is removed from the fluoropolymer products before they are sold to outside customers. A relatively small amount o f APFO p(wroodruldcwtsi.de, in the U.S.) leaves DuPont facilities in fluoropolymer dispersion > O f the APFO in the products sold, most (>97%) is destroyed during customer processing to a non-carboxylated hydrofluorocarbon. x Aff f the U.S. DuPont operations that use APFO with significant exposure potential are concentrated at one location; Washington Works in Washington, WV. Therefore, most o f the industrial hygiene data and blood serum data presented in this document are from that location. EID 156211 Dr. Charles M. Auer, Director U S, Environmental Protection Agency Page 2 > Extensive industrial hygiene data collected on workers potentially exposed to APFO show airborne exposures to be significantly below the ACGIH TLV of 0.01mg/m3 8 hr. TWA Exposure levels o f plant workers have dropped significantly since the conversion to an APFO solution from a dry powder. > As part o f the ongoing surveillance of workers potentially exposed to APFO, in March and April of this year a series of blood samples were taken from workers in the U.S., The Netherlands and Japan to be analyzed for serum APFO concentration. DuPont has not received the results from our contract ltahbeoyrbateocroymaet athviasiltaimblee.. DuPont will submit a summary of the results when The format o f the information in the attached is a modified UEIP format. If you wish to discuss the information contained in the attachment, please contact Robert F. Pinchot at (302) 999-4074 or e-mail at RobertF.Pinchot,usa.dupont.com or me at (302) 366-5259. Very truly yours, Gerald L. Kennedy Director, Applied Toxicology and Health BID56212 Voluntary UEIP, Ammonium Perfluorooctanoate VoluAnmtamryoUnisuemanPderEfxlupoorsouorcetIannfooartme a(AtiPonFOPr)ofile I. CHEMICAL IDENTIFICATION CChAeSmNicuaml Nbearm: e: 3A8m25m-o2n6-iu1m Perfluorooctanoate I t COMPANY IDENTIFICATION Company Name: E. I, du Pont de Nemours and Company Site Locations: Site where APFO is used as a reaction aid: Washington Works Route 892 Washington, WV 26181 Sites where AFFO containing products made at Washington Works are processed: Parlin Plant Cheesequake Road Parlin, NJ 08859 Spruance Plant 5401 Jefferson Davis Hwy, Richmond, VA 23234 Site which disposes o f waste containing APFO: Chambers Works Rte. 130 Deepwater, NJ 08023 Technical Contact: Robert F. Pinchot (302) 999-4074 DuPont Fluoroproducts Chestnut Run Plaza Bldg. 711/2210 Centre Boulevard Wilmington, DE 19805-0711 EID 156213 Voluntary UEIP, Ammonium Perfluorooctnnoate m . DUPONT AND CUSTOMER ACTIVITIES Narrative Description of A P F O TTse pTrhoecbeslosecskddiisacgursasmedobnetlohwe .back page titled "DuPont US APFO Balance" describes the DuPont uses APFO as a reaction aid in the production o f polytetrafluoroethylene (PTFE) and tetrafluoroethylene (TFE) co-polymers. The process utilized at DuPont's Washington Works for making PTFE and co-polymers consists of polymerizing TFE (aaidndinotthheerrceoa-cmtioonn.omers if desired) in an aqueous media with a small amount of A, PFO to Following the polymerization step, the polymer dispersion is either dried to remove water and APFO or concentrated (removing some o f the APFO), stabilized and sold as an aqueous dispersion. The dried polymer contains very little, if any, APFO. otTfofhaseiirtAeoPirnFwOaantreienrmcaiotnvteherdaetWforro,amschatiphntegutrpoeondlyWamnoderrkseissn, tretocoavneroefdfsfitoer irnedcuysctlrei,alcalapntudrfeildl,aannddd/oerstermoyitetded The stabilized polymer dispersions are sold by DuPont to industrial customers (both in the US and outside the US) for a variety o f uses, internally transferred to the DuPont Spruance Plant for the production of Teflon fibers and PTFE coated synthetic fibers, or ) internally transferred to the DuPont Parlin Plant for the production of Teflon Finishes. A small amount o f non-hazardous waste polymer, water, APFO and other additives generated at Washington Works is treated in a wastewater treatment facility at DuPont's CorhcaampbtuerresdWoonrckasr.boTnhiasnmdaltaenrdiaflililsedeiitnhearseemcuitrteedlanindtfhilel. Chambers Works water discharge The internal process at the DuPont Spurance Plant to produce Teflon fibers involves,, fdoerstmrooysetdobf ythteheprfoodlluocwt,inag"srienatcetriionng:"1step in which the APFO contained in the product is CFjiCF^eCOO-NHLf CF3(CF2)5CF2H + CO2 +NH3 This reaction goes to completion at 350C and 0.2s residence time. A small amount of product processed at DuPont's Spruance plant does not get sintered and thus contains a csmomalplraemssoournptaocfkrinesgidmuaatleAriPalFs.O. These products are used for industrial pump, valve and b1InyPte.hJri.ngKahlrtuResmeipcpo,erDtr.a.Ctu.rRe ogca,s-`Tphhaesrem,9aFl dNeMcoRm.poAsintieown AofltCer8nafltuivoeritnoattehdersmuraflagcrtaavnitms aentrdicrealnaatelydsims,aDteuriPaolsnsttudied EID1S6214 Voluntary UEIP, Ammonium Perfluorooctanoate The process for making Teflon finishes at the DuPont Parlin Plant involves a blending operation of fluoropolymer dispersions with other additives including solvents, binders, and pigments. The small amount of APFO emissions to water from this facility is due to waste generated during product changeovers. Some o f the fluoropolymer dispersion is processed at contract facilities where the material is dried at temperatures >350C thus dinecsotrrpoyoirnagtetdheinAtoPfFinOisahcecsoprdroindgucttos.the reaction above. This dried material is then The final product produced is then sold to applicators that apply the product to a substrate (such as cookware) via automated spraying or rollercoating. Emissions of APFO from these operations consist of overspray that is either captured on filters and landfilled or absorbed into water resulting in a water emission. Product that is applied to the substrate is then typically "sintered" at temperatures approaching 800F resulting in the removal of the APFO from the substrate and subsequent destruction according to the reaction above. Customers of dispersion products use the material for a variety o f applications. However, most applications involve a "sintering" step where the APFO is destroyed. There are a ' small number o f applications where the customer heats the dispersion products to temperatures that allow the APFO to sublime resulting in air emissions. There are also a small number o f applications where the customer's product is not heated resulting in the AinPdFusOtrisatlayfiilntegrwfaitbhritchse. product. These applications include industrial packings, and IV, SITE RELEASE AND TRANSFER INFORMATION FOR TRI CHEMICALS Not applicable- APFO is not listed on the TRI V, SITE RELEASE AND TRANSFER INFORMATION FOR NON-TRI CHEMICALS A. On-site Air Releases Fugitive Stack (Point Source) Estimate Washington Works Negligible 24000 Total Annual Parlin 0 0 Releases 00 ( lbs. 1999) Chambers 0 0 Works Comments Air emissions are estimated using engineering calculations and judgements and limited measurements o f specific point sources conducted in the past. IID 156215 Voluntary UEIP, Ammonium Perfluorooctanoate B. On-site Water Releases Point Source Comments Estimatec Washington Works 55000 Total Annual Paritn 3 Releases 150 fibs. 1999) Chambers W 9500 orks Water emissions are estimated using engineering calculations and judgements and limited measurements of specific sources conducted in the past. Washington Works emissions occur for approximately 350 days/yr while the other sites' emissions occur for 10-100 days/yr. Releases of APFO to the Ohio River from the DuPont Washington Works Plant were modeled using the Probabilistic Dilution Model (PDM Beta Version 4,0 Beta June 11, 1999, US EPA Office of Pollution Prevention and Toxics) and a constructed Microsoft Excel spreadsheet model. APFO release data for 1996 were used in both modeling exercises.2 The PDM indicated that APFO concentrations of 1.0 og C8/L would be exceeded about 50% o f the time during the year. APFO concentrations of in the river would exceed 0.1 pg APFO/L 90% o f the time during the year and 10 pg APFO/L about 2.2% of the time during the year. Average annual APFO concentrations in the Ohio River calculated by using a Microsoft Excel spreadsheet was 0.423 pg APFO/L. Modeled AFPO concentrations in the river ranged from a low of 0.199 pg APFO/L in March to a high of 0.965 pg APFOC-8/L in September, which correspond to high and low river flows, respectively. Average Ohio River flows and volume data calculated from the US Geological Survey was collected at the Belleville Dam and used in the spreadsheet model. The Belleville Dam is on the Ohio River 13 miles downstream of the Washington Works Plant. This river flow data is the closest location downstream from the plant where this type o f information is available. In 1999 a drinking water sample obtained from GE plastics, Washington WV, immediately downstream on the Ohio River from DuPont Washington Works' showed 0.552pg/l APFO. In addition samples obtained in January 2000 from three different wells at the Lubeck Public Service District, downstream o f Washington Works on the Ohio River, showed 0.8pg/l, 0.44pg/l and 0.313 pg/L APFO. Rz Wep.oRrt.BEeMrtiS,EM-0o5d4e-l0in0g. releases of ammonium peifluorooctanoate into the Ohio River, DuPont Internal EID 156216 Vj )> Voluntary UEIP, Ammonium Perfluorooctanoate C. On-Site Land Releases Chambers Works treats APFO containing waste in a wastewater treatment system. Engineering calculations and measurements indicate that approximately 30% of the APFO in the wastewater treated is absorbed on to a carbon media that is landfilled on site. These land releases are estimated to be 39001b in 1999. Prior operations have resulted in measurable APFO concentrations in three landfills operated by the Washington Works in West Virginia. At Letart landfill surface water measurements in 1999 and 2000ytd range from 2.23pg/l to 3240pg/l with an average of 1392ug/l. Groundwater measurements taken during the same time period at Letart landfill range from 60.3pg/l to 17400pg/l with an average o f 2537pg/l. At the "local landfill" the groundwater concentrations range from 0,046|.ig/l to 39pg/l with an average of 8.83pg/l. Surface water samples at the "local landfill" range from 0.54pg/l to 87pg/l with an average of 18.5pg/l. At Dry Run landfill there are limited measurements of groundwater and surface water with maximum concentrations in groundwater of I5pg/1 and the maximum concentration in the permitted outfall has been 33pg/l. In 1999 a RCRA Facility Investigation was completed for Washington Works and was submitted to EPA Region HI in June 19994. The report contains data on groundwater concentrations of APFO at Washington Works. .D. Transfers to Off-site Locations Washington Works: Incineration Wastewater treatment Underground Injection Hazardous Waste Landfill Other landfill Recycle or recovery Estimated Total Annual R eleases^ Transfers flb. 1929) 16000 13403 0 2600 0 IV. ON-SITE WORKPLACE EXPOSURE A. Information on the Number o f Employees Potentially Exposed 34MReapposrtowf tahsesluabnmdfiitltleldoctoatMioanrstiann.dTs.pKecoitfsicchm, Roenmitoerdiinagl PlorcoagtriaomnsManadnaregseur,ltEs ParAc RaveagiiloanblIeIIu,pPohnilraedqeulpeshti.a. 5This is the same material that was described above in paragraph 1 of section V.D. f1 IID156217 Voluntary UEIP, Ammonium Perfluorooctanoate The tables below describe the number of workers that may be exposed to APFO during tchoenitraninoirnmgaplrwoodrukctaicstpivrioticeesssfeodr.each of the three sites where APFO is used or APFO Hours/Day <0.25 0.25-1 -8 >8 <10 Washington Works Days/vr 10-100 100-250 242 >250 Routine worker activities that have potential for exposure: >>> Handling raw material APFO Handling raw dispersions containing APFO Maintenance of polymerization reaction systems > Polymer dryer operation and maintenance > Packout ofPTFE and co-polymer dispersion products > Operation and maintenance o f APFO recovery systems 1ID156218 Voluntary UEIP, Ammonium Perfluorooctanoate Hours/Day <0.25 0.25-1 1-8 >8 <10 Partin Plant Days/yr 10-100 100-250 18 >250 Routine worker activities that have potential for exposure: > Handling o f PTFE and Co-polymer dispersion products > Operation and maintenance of blending facilities > Packout of finished product Note that at no time is the material handled at the Parlin Plant at an elevated temperature where the APFO could sublime. Therefore there is little potential for exposure to airborne APFO at this facility. All exposure potential is through skin contact during hcoanntdaliinnignogf<t0h.e25p%olyAmPeFrOd.ispersion materials all of which contain <1% APFO with most Hours/Day <0,25 0.25-1 1-8 >8 <10 Spruance Plant Days/yr 10-100 100-250 <10 >250 Routine worker activities that have potential for exposure: ^ Handling of PTFE and Co-polymer dispersion products > Operation and maintenance o f fiber coating facilities > Operation and maintenance o f sintering rolls > Packaging of non-sintered product. * Note that the PTFE and co-polymer dispersion products used at the Spruance site contain <0.9% APFO with most containing approximately 0.3% APFO. B. Information on the Exposure Levels of Washington Works Employees Since most o f the processing done in the US with APFO and APFO containing intermediates and products is done at Washington Works, DuPont's airborne industrial hygiene data is concentrated at that site. The limited measurements o f airborne APFO concentrations at the other sites where APFO containing products are used have shown much lower levels (mostly non-detectable) levels of APFO. The data in the table below EID 156219 Voluntary UEIP, Ammonium Periluorooctanoate reflect monitoring done over the last 5 years at Washington Works. The sample results are a combination of chemical operator and maintenance worker personal samples. Year Sample Type 1999 Partial 1998 Shift 1997 1996 (mostly 6-8 1995 hours) # of Samples 100 83 100 73 32 Minimum Concentration (mpb6) <0.01 .001 <0.01 N/D N/D Maximum Mean Standard Concentration (mpb) Deviation (mpb) 0.58 0.061 0.151 0.78 2.4 0.103 0.145 0.146 0.378 0.29 0.055 0.069 0.16 0.067 0.063 Partial shift air samples are taken at the rate of 200 mL/min using a Tenax collection tube that has been pretreated with sodium hydroxide/ethylene glycol/methanol. The APFO is desorbed from the tubes using methanolic hydrogen chloride, which also serves as a derivatizing reagent, converting the APFO to its methyl ester. After workup, the methyl ester is quantified using a gas chromatograph equipped with an electron capture detector. The methyl ester of perfluorodecanoic acid is used as an internal standard, and at least three calibration samples are prepared to cover the concentration range of interest. Precision is estimated to be +/-10% relative. The data above show averages consistently below the AGCHITLV of Q.01mg/m3 with only a very few samples above the TLV. Where results are above or near to the TLV, the event is investigated and corrective action (additional personal protective equipment or engineering controls) to reduce the exposure levels is undertaken. Older data from the 1980's show higher levels o f exposure. In the early 1990's Washington Works switched from receiving the APFO as a powder to receiving it as an aqueous solution. This change was done to reduce the potential for exposure during handling of the dry powder. It should be noted that in the 1997 time period, the site was starting up new APFO recovery facilities. Operating and maintenance difficulties associated with the start-up o f these fdaucriilnitgietshamtayyeahra.ve contributed to the higher levels of APFO in the personal samples , Task specific monitoring data and wipe monitoring data exist. However these data are not indicative o f employee exposure and are not presented here. These samples are taken to identify areas where additional exposure controls may be necessary. Engineering controls to reduce exposure consist of the following: > Rmeoancotmionerscyosntecmenstraarteiocnlossed systems with continuous ambient monitoring for ^ Ventilation systems are installed where airborne concentrations are significant > The polymer dryers operate under negative pressure to contain APFO and other materials. > Recovery systems are in place to reduce airborne emissions. s mpb- moles per billion. 0.56mpb is equivalent to the ACGIH TLV of 0.01mg/tn3 E ID 15622Q Voluntary UEIP, Ammonium Perfluorooctanoate Personal protective equipment that workers regularly wear consist of the following: > Safety shoes and side-shield safety glasses in all areas. > Impervious gloves when handling APFO solutions or aqueous dispersion > Cprhoedmucictsa.l protective coveralls and goggles or face shields when the possibility of splashes of APFO containing solutions is present. > Airline respirators or cartridge respirators where monitoring has shown to have high exposure potential. At Washington Works, blood serum levels o f APFO have been measured since 1981. Prior measurements of blood fluoride levels have been taken prior to 1981 but are of limited value in assessing exposure to APFO. A summary of results of employees with identified APFO exposure potential the 1995, 1989-90, 1985,and 1984 volunteer sampling events is in the table below. Due to significant job assignment movement during this period of time, analysis of trends of data are difficult. The data in the table below prior to 1995 are for employees included In the 1995 sampling data so that comparisons of relative levels of APFO in blood serum can be compared. The entire data set of blood concentrations is available upon request. Year 1995 1989-90 1985 1984 #of Samples 73 23 21 19 Minimum Concentration (ppm) Maximum Concentration 0.12 0.4 (P4P.5^).____ ' 8.5 0.0678 18* ' OOT1 ~ 24" Mean Concentration (p1p.5m7)_____ 3.13 2.44 3.82 7 This individual was working in a job that has APFO exposure potential at the time of the sample. 8saTmhpisleisndwiverideutaalkecno.nsTishteisnetlmy phlaosyheaedletfhteahnigAhPeFstObleoxopdoscuornecpenotteranttiioanl aosfsAigPnFmOenstinince1A99P1F. OInsp1e9c9if5ictins employee's blood scrum level was 4.4ppm. EID 156221