Document ExoZX7mRjqEY221j2ejQG0v3L

AR226-2049 Voluntary "UEIP, Ammonium Perflaorooctanoate Voluntary Use and Exposure Information Profile Ammonium Perfluorooctanoate (APFO) X. CHEMICAL IDENTIFICATION Chemical Name: CAS Number. Ammonium Perfluorooctanoate 3825-26-1 n. COMPANY IDENTIFICATION Company Name: E. I. du Font de Nemours and Company Site Locations; Site where APPO is used as a reaction aid: Washington Works Route 892 Washington, WV 26181 Sites where APFO containing products made at Washington Works are processed; Parlin Plant Cheesequake Road Parlin, NJ 08859 Spruance Plant 5401 Jefferson DavisHwy- Kichmond,VA 23234 Site which disposesofwaste containing APPO: Chambers Works Rte. 130 Deepwater,NJ 08023 Technical Contact: Robert P. Pinchot (302) 999-4074 DuPont Fluoroproducts Chestnut Run Plaza Bidg. 711/2210 Centre Boulevard Wumington,DE 19805-0711 EID080064 Voluntary UEIP, Ammonium Perftnoiooctaaoate 1) nL DUPONT AND CUSTOMER ACTIVITIES Narrative Description ofAPFO Use The block diagram on the back page titled "DuPont US APPO Balance" describes the processes discussed below. DuPont uses APFO as a reaction aid in the production ofpolytetrafluoroethylene (PTFE) and tetrafluoroethylene (TFE) co-polymers. The process utilized at DuPont's Washington Works for making PTFE and co-polymers consists of polymerizing TFE (and other co-monomers if desired) in an aqueous media with a small amount ofAPFO to aid in the reaction. Following the polymerization step, the polymer dispersionis either dried to remove water and APFO or concentrated (removing some of the APFO), stabilized and sold as an aqueous dispersion. The dried polymer contains very little, if any, APFO. The APFO removed from the polymer is recovered for recycle, captured and destroyed off site in an incinerator, captured and sent to an offsite industrial landfill, and/or emitted to air or water at the Washington Works. The stabilized polymer dispersionsare sold by DuPont to industrial customers (both in the US and outside the US) for a variety of 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 ofnon-hazardous waste polymer, water, APFO and other additives generated at Washington Works is treated in a wastewater treatment facility at DuPont's Chambers Works- This material is either emitted in the Chambers Works water discharge or captured on carbon and landfilled in a secure landfill. The internal process at the DuPont Spurance Plant to produce Teflon fibers involves, for most of the product, a "sintering" step in which the APPO contained in the product is destroyed by the following reaction:1 CF3(CF2)6COO-NH4+"> CF3(CF2)5CPzH + COi +NHa 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 small amount ofresidual APFO. These products are used for industrial pump, valve and compressor packing materials. ' PJ. Krusic, D.C. Roe, "Thennal decomposition of C8 fhionnated StU-factants and related materials studied > by high temperature gas-phase TNMR- A new Alternative to thermal gravimetric analysis, DuPont Internal Report, o ^ L> EID080065 Vohwaaiy VESP, Amuanmm Perflnarooctanoale The process for making Teflon finishes at the DuPont Parim Plant involves a blending -wa^* operation offluoropolymer dispersionswith other additives including solvents, binders, and pigments. The small amount ofAPPO emissions to water from this facility is due to waste generated during product changeovers. Some of the fluoropolymer dispersionis processed at contract facilities where the material is dried at temperatures >350C thus destroyingthe APFO according to the reaction above. This dried material is then incorporated into finishes products. The final product produced is them sold to applicatorsthat apply the productto a substrate (such as cookware) via automated spraying or rollercoating. Emissions ofAPPO from these operations consist ofoverspray that is either captured on filters and landfilled or absorbed into water resulting in a water emission. Product that is appliedto the substrate is then typically"sintered" at temperatures approachingSOOT resulting in the removal of the APFO from the substrate and subsequentdestruction according to the reaction above. Customers of dispersionproductsuse the material for a variety of applications. However, most applicationsinvolve a "sintering" step where the APFO is destroyed. There are a smaH number of applicationswhere the customer heats the dispersionproducts to temperatures that allow the APFO to sublime resulting in air emissions. There are also a small number of applications where the customer's product is not heated resulting in the APFO staying with the product. These applications include industrial packings, and industrial filter fabrics. 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) Estimated Total Annual Releases (lbs.1999) Washington Works Negligible Parim 0 Spruance 0 Chambers Works 0 24000 0 0 0 Comments Air emissions are estimated using engineering calculations and judgements and limited measurements of specific point sources conducted in the past. EID080066 Voluntary UEIP, Ammoaiian Perfluorooctanoate B. On-site Water Releases Point Source Estimated Total Annual Releases (Ibs. 1999) Washington Works Parlin Spruance Chambers Works 55000 300 150 9500 Comments Water emissions are estimated using engineering calculations and judgements and limited measurements of specific sources conducted in the past. Washington Works emissions occur for approximately350 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 (RDM 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 i>g C- 8/L would be exceeded about 50% ofthe time during the year. APFO concentrations of in the river would exceed 0.1 ug APFO/L 90% ofthe time during the year and 10 ug 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 ug APFO/L. Modeled AFPO concentrations in the river ranged from a low of0.199 ug APPO/L in March to a high of 0.965 ng 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 Pla-nt. This river flow data is the closest location downstream from the plant where this type of 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 0,552ug/l APFO. In addition samples obtained in January 2000 from three different wells at the Lubeck Public Service District, downstream of Washington Works on the Ohio River, showed 0.8pg/l, 0.44ug/l and 0.313 ug/1. APFO. 2 W.R.Berti, Modeling releases of ammonium perfluorooctaimte into the Ohio River, DuPont Internal Report BMSE-054-00. . EID080067 Voluntary UEIP, Ammonnnn Petfluoiooctaaoate C. On-Site Land Releases Chambers Works treats APFO containing waste in a wastewater treatment system. Engineering calculations and measurements indicate that approximately30% 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 Letart3 landfill surface water measurements in 1999 and 2000ytd range from 2.23ug/l to 3240ug/l with an average of 1392i.)g/l. Ground-water measurements taken during the same time period at Letart landfill range from 60.3u.g/l to I7400ug/l with an average of2537u.g/l. At the 'local landfill" the groundwater concentrations range from 0.046ng/l to 39ug/l with an average of8.83u.g/l. Surface water samples at the "local landfill" range from 0.54ug/l to 87ug/l with an average of 18.5ugA. At Dry Ran landfill there are limited measurements of groundwater and surface water with maximum concentrations in groundwater of 15ug/l and the maximum concentration in the permitted outfall has been 33ug/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 ofAPPO 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 Releases or Transfers (Ib. 1999) 16000 13400s 0 2600 0 IV. ON-SITE WORKPLACE EXPOSURE A- Information on the Number of Employees Potentially Exposed 3 Maps of the landfill locations and specific monitoring locations and results are available vpoa request. 4 Report was submitted to Martin. T. Kotsch, Remedial PirogramManager, EPA Region ni, Philadelphia. 5 Tilis Is the same material that was described above in paragraph 1 of section V.D. EID080068 Voluntary "UEIP, Ammonium Peifluorooctanoate The tables below describe the number of workers that may be exposed to APFO during their normal work activities for each of the three sites where APFO is used or APFO containing product is processed. _ _ _ HoursflDay <0.25 0.25-1 1.8 >8 _ _ _ _ W a s h i n g t o n _ Works Days/yr _ _ _ _ _ _ _ _ _ _ _ _ _ <10 10-100 100-250 >250 242 Routine worker activities that have potential for exposure: > Handling raw material APFO > Handling raw dispersionscontaining APFO > Maintenance of polymerization reaction systems > Polymer dryer operation and maintenance > Packout ofPTEE aad co-polymer dispersion products > Operation and maintenance of APFO recovery systems EID080069 VoluntaiyUBIP, AnunoimuttPerfloorooctanoate Hours/Day <10 <0.25 0.25-1 1-8 >8 Parlin Plant Days/yr 10-100 100-250 18 >250 Routine worker activities that have potential for exposure: > Handling ofPTFB 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 handling ofthe polymer dispersion materials all of which contain <1% APFO with most containing <0.25% APFO. Hours/Day <10 <0.25 0.25-1 1-8 >8 Spruance Plant Days/yr 10-100 100-250 <10 >250 Routine worker activities that have potential for exposure: > Handling ofPTFB and Co-polymer dispersion products . > Operation and maintenance of fiber coating facilities > Operation and maintenance of sintering rolls > Packaging ofnon-sintered product Note that the PTFB and co-polymer dispersionproducts 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 of 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 of 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 EID080070 Vohmtaiy UEIP, AnttBOluuni Peifluorooctanoate reflect iBonitoring done over the last 5 years at Washington Works. The sampleresults are a combination of chemical operator and maintenance worker personalsamples. Year Sample Type 1999 1998 1997 1996 1995 Partial Shift (mostly 6<8 hours) #of Samples 100 83 100 73 32 Minimum Concentration (mpb6) <0.01 .001 <0.01 N/D N/D Maximum Concentration (mpb) 0.58 0.78 2.4 0.29 0.16 Mean Standard (mpb) Deviation 0.061 0.103 0.146 0.055 0.067 0.151 0.145 0.378 0.069 0.063 Partial shift air samples are taken at the rate of 200 mL/mm using a Tenax collection tube that has been pretreated with sodium hydroxide/ethylene glycol/methanol. The APPO is desorbed from the tubes using methanolic hydrogen chloride, which also .serves as a derivatizmg reagent, converting the APFO to its methyl ester. After worfcup,the methyl ester is quantified using a gas chromatograph equippedwith an electron capture detector. The methyl ester ofperfluorodecanoic 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 AOCHI TLV ofO.Olmg/m1with 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 ofexposure. 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 ofthese facilities may have contributed to the higher levels of APFO in the personal samples during that year. Task specific monitoring data and wipe monitoring data exist. However these data are not indicative of 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: > Reaction systems are closed systems with continuous ambient monitoring for monomer concentrations > 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. <smpb= mote perbiBion. 0.56mpb is equivalent to the ACGIH TLV ofO.Olmg/Bi3 EID080071 Voluntary UEIP, Annnonium Perfteorooctanoate 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 APPO solutions or aqueous dispersion products. > Chemical protective coveralls and goggles or face shields when the possibility of splashesofAPFO containing solutions is present. > Airline respirators or cartridgerespirators where monitoring has shown to have high exposure potential. At Washington Worlsa, blood senun levels ofAPFO have been measured since 1981. Prior measurements ofblood 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 potentialthe 1995,1989-90,1985,and 1984 volunteer samplingevents is in the table below. Due to significantjob 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 comparisonsof relative levels ofAPFO in blood serum can be compared. The entire data set ofblood concentrations is available upon request. Year 1995 1989-90 1985 1984 #of Samples 73 23 21 19 Minimum Concentration (ppm) 0.12 0.4 0.067 0.077 Maximum Concentration (Ppm) 4.5 8.5 1^ ^ Mean Concentration (Ppn) 1.57 , 3.13 2.44 3.82 7 This individual was woridng in a job that has APFO exposure potential at the time of the sample. 8 This individual consistently has had the highestblood concentorftatt ofAPFO since APPO Specific sampleswere lateen. This employee left an APFO exposure potential assignment in 1991. In 1995 ihis employee's blood senna level was 4.4ppm. EIDOS0072 AMMONIUM PERFLUOROOCTANQATE (C-8) EXISTING LIMITS TLV = 0.1 MG/M3 AEL s 0.01 MG/M3 CEG s 0.0003 MG/M5 OR I?.? ^UG/M3 EXPOSED DAILY POSE AT LIMITS - MAN TLV = 1 MG/OAY (O.Q-IA MS/KG) AEL = 0.1 MG/DAY (0.&OT4 M6/KG) CEG = 6 ^6 (0.00009 MG/KB) EID080073 ;Mfi;; -1-; ' > .iay-': AHMONI UN ^E RFt. UOROOC rANgA rE MATER GUIDELINE DAILY EXPOSED DOSE FOR MAN IS APPROXIMATELY 6 -UG/DAY DRINKING WATER/INHALAriO.N. EXPOSURE S s 20/80 THEORETICAL AIR s 4.8 JU>C WATER s 1.2 ^.G DAILY WATER INTAKE =21. T.Z.AG/2 L = 0.6/<*G/L = 0.6 PPB RECOMMENDATION WATER GUIDELINE s 1 PPB EID080074