Document znJ0kmGbDea09j6ExyDkq796

AR226-2049 Voluntary UEIP, Ammonirun Perfluorooctanoate Voluntary Uso and Exposure Information Profile Ammonium perfluorooctanoate (APFO) I. CHEMICAL IDENTIFICATION Chemical Name: CAS Number. Ammonium Perfluorooctanoate 3825-26-1 H. COMPANY IDENTIFICATION C om pany Nam e: E. I. du Pont de Nemours and Company Site Locations: S ite where APFO is used as a reaction aid: W ashington Works Route 892 W ashington, W V 26181 Sites where APFO containing products made at W ashington Works are processed: Parlin Plant Cheesequake Road Parlin, NJ 08859 Spruance Plant 5401 Jefferson D avis Hwy. Richmond, V A 23234 Site which disposes o f w aste containing APFO: Chambers Works Rte. 130 Deepwater, NJ 08023 T echnical Contact: . Robert F. Pinchot (302) 999-4074 DuPont Fluoroproducts Chestnut Run Plaza Bldg. 711/2210 Centre Boulevard W ilm ington, DE 19805-0711 AJP01742 E ID 080064 Voluntary UEIP, Ammonium Perfluorooctanoate HI. DUPONT AND CUSTOMER ACTIVITIES Narrative Description o f APFO Use The block diagram on the back page titled "DuPont U S APFO Balance" describes the processes discussed below . DuPont uses APFO as a reaction aid in the production o f polytetrafluoroethylene (PTFE) and tetrafluoroethylene (TEE) co-polym ers. The process utilized at DuPont's W ashington W orks for making PTFE and co-polym ers consists o f polym erizing TFE (and other co-m onom ers i f desired) in an aqueous media w ith a sm all amount o f APFO to aid in the reaction. Follow ing the polym erization step, the polym er dispersion is either dried to rem ove water and APFO or concentrated (rem oving som e o f the APFO), stabilized and sold as an aqueous dispersion. The dried polym er contains very little, i f any, APFO. The APFO removed from the polymer is recovered for recycle, captured and destroyed o ffsite in an incinerator, captured and sent to an offsite industrial landfill, and/or emitted to air or water at the W ashington Works. The stabilized polym er dispersions are sold by DuPont to industrial customers (both in the U S and outside the U S) for a variety o f uses, internally transferred to the DuPont Spruance Plant for the production o f T eflon fibers and PTFE coated synthetic fibers, or internally transferred to the DuPont Partin Plant for the production o f Teflon Finishes. A sm all amount o f non-hazardous w aste polym er, water, APFO and other additives generated at W ashington W orks is treated in a wastewater treatment facility at DuPont's Chambers W orks. This material is either em itted 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 m ost o f the product, a "sintering" step in which the APFO contained in the product is destroyed by the follow ing reaction:1 CF3(CF2)6COO-NH4+ CFs(CFi)5CFiH + COj +NEb This reaction g oes to com pletion at 350C and 0.2s residence tim e. A sm all amount o f product processed at DuPont's Spruance plant does not get sintered and thus contains a small amount o f residual APFO. These products are used for industrial pump, valve and com pressor packing materials. 1 P J . Kxusie, D .C . R oe, "Thermal decom position o f C 8 fluoiinated surfactants and related m aterials studied by high temperature gas-phase ,9F NM R. A new A lternative to thermal gravim etric analysis, DuPont Internal Report. E ID 080065 AJP001743 Voluntary IM P , Ammonium Perfluorooctanioale The process for making Teflon finishes at the DuPont Parlin Plant involves a blending operation o f fluoropolym er dispersions w ith other additives including solvents, binders, and pigments. The sm all amount o f APFO em issions to w ater from this facility is due to waste generated during product changeovers. Som e o f the fluoropolymer dispersion is processed at contract facilities where the material is dried at temperatures >350C thus destroying the APFO according to the reaction above. This dried material is then incorporated into finishes products. The final product produced is then sold to applicators that apply the product to a substrate (such as cookware) v ia automated spraying or rollercoating. Em issions o f APFO from these operations consist o f overspray that is either captured on filters and landfilled or absorbed into water resulting in a water em ission. Product that is applied to the substrate is then typically "sintered" at temperatures approaching SOO'T resulting in the removal o f the APFO from the substrate and subsequent destruction according to the reaction above. Customers o f dispersion products use the material for a variety o f applications. However, m ost 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 sublim e resulting in air em issions. There are also a small number o f applications where the customer's product is not heated resulting in the APFO staying w ith the product. These applications include industrial packings, and industrial filter fabrics. IV . SITE RELEASE AND TRANSFER INFORM ATION FOR TRI CHEM ICALS N ot applicable- APFO is not listed on the TRI V . SITE RELEASE AND TRANSFER INFO RM ATIO N FO R NON-TRI CHEM ICALS A. O n-site A ir R eleases F u g itiv e Stack (Point Source) . Estimatet Total Annual Releases ( lb s.1999) W ashington W orks Parlin Snmance Chambers W orks N egligible 0 0 0 24000 00 0 C om m ents Air em issions are estimated using engineering calculations and judgem ents and lim ited measurements o f specific point sources conducted in the past. ^LlO O dlV E ID 08Q 066 Voluntary UEIP, Ammonium Peffluorooetanoate B. On-site Water Releases Point Source Estimated Total Annual R eleases ( lbs. 1999) W ashington Works Parlin Snmance Chambers Works 55000 300 150 9500 Comments Water em issions are estimated using engineering calculations and judgem ents and limited measurements o f specific sources conducted in the past. W ashington W orks em issions occur for approximately 350 days/yr w hile the other sites' em issions occur for 10-100 days/yr. R eleases o f APFO to the Ohio River from the DuPont W ashington W orks Plant were modeled using the Probabilistic D ilution M odel (PDM B eta Version 4.0 Beta June 1 1 ,1999, U S EPA O ffice o f Pollution Prevention and T oxics) and a constructed M icrosoft Excel spreadsheet m odel. APFO release data for 1996 were used in both m odeling exercises.1 The PDM indicated that APFO concentrations o f l . O o g C 8/L would b e exceeded about 50% o f the tim e during the year. APFO concentrations o f in the river w ould exceed 0.1 pg APFO/L 90% o f the tim e during the year and 10 p g APFO/L about 2.2% o f the tim e during the year. Average annual APFO concentrations in the Ohio River calculated by using a M icrosoft E xcel spreadsheet was 0.423 pg APFO/L. M odeled AFPO concentrations in the river ranged from a low o f 0.199 p g APFO/L in March to a high o f 0.965 p g APFOC-8/L in September, which correspond to high and low river flow s, respectively. Average Ohio R iver flow s and volum e data calculated from the U S G eological Survey w as collected at the B elleville Dam and used in the spreadsheet model. The B elleville Dam is on the Ohio River 13 m iles downstream o f the W ashington W orks 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, W ashington W V, im m ediately downstream on the Ohio River from DuPont W ashington W orks showed 0.552pg/l APFO. In addition sam ples obtained in Januaiy 2000 from three different w ells at the Lubeck Public Service D istrict, downstream o f W ashington Works on the Ohio River, show ed 0.8pg/l, 0.44pg/l and 0.313 pg/1. APFO. z W .R.Berti, M odeling releases o f ammonium perfluorooctanoate into the Ohio R iver, DuPont Internal Report BM SE-054-00. . AJP0Q1745 E ID 080067 Voluntary TJEIP, Ammonium Perfluoiooctaaoate C. On-Site Land Releases Chambers W orks treats APFO containing w aste in a wastewater treatment system. Engineering calculations and measurements indicate that approximately 30% o f 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 file W ashington W orks in W est V irginia At Letart3 landfill surface w ater measurements in 1999 and 2000ytd range from 2.23p.g/l to ^ 3240pg/l w ith an average o f 1392ug/l. Groundwater measurements taken during the same tim e period at Letart landfill range from 60.3pg/l to I7400pg/1 w ith an average of2537(j.g/l. A t the `lo c a l landfill" the groundwater concentrations range from 0.046|Xg/l to 39pg/l w ith an average oF8.83p.g/l. Surface water samples at the "local landfill" range from 0.54pgfl to 87pg/l w ith an average o f 18.5gg/L At Dry Run landfill there are lim ited measurements o f groundwater and surface water w ith maximum concentrations in groundwater o f 15pg/l and the maximum concentration in the permitted outfall has been 33pg/l. In 1999 RCRA Facility Investigation w as com pleted for W ashington W orks and w as submitted to EPA R egion E l in June 199945. The report contains data on groundwater concentrations o f APFO at W ashington Works. D . Transfers to O ff-site Locations \I W ashington Works: Incineration W astewater treatment Underground Injection Hazardous W aste Landfill Other landfill R ecycle or recovery Estimated Total Annual R eleases or Transfers fib. 19991 16000 13400s 0 2600 0 IV . O N-SITE W ORKPLACE EXPOSURE A. Information on the Number o f Em ployees Potentially Exposed 3 M aps o f the landfill locations and sp ecific m onitoring locations and results are available upon request. AReport w as subm itted to Martin. T . K otsch, Rem edial Program M anager. EPA Region III Philadelphia. 5 This is the sam e m aterial that w as described above in paragraph 1 o f section V .D. AJP001746 E ID Q 80068 Voluntary (JEEP, Anunonivun Feifluorooctanoate The tables below describe the number o f workers that m ay be exposed to APFO during their normal work activities for each o f the three sites where APFO is used or APFO containing product is processed. H ou rs/D ay < 0 .2 5 0.25-1 1-8 >8 <10 W ashington W orks D ays/yr 10-100 100-250 242 >250 Routine worker activities that have potential for exposure: > Handling raw material APFO > Handling raw dispersions containing APFO > M aintenance o f polym erization reaction system s > Polym er dryer operation and m aintenance > Packout ofPT FE and co-polym er dispersion products > Operation and m aintenance o f APFO recovery system s AJP01747 E ID 080069 Voluntery UBIR, Ammomuin Perflporooctanoate H on rs/D ay < 0 .2 5 0.25-1 1-8 >8 <10 Parlin Plant D ays/yr 10-100 100-250 18 >250 Routine worker activities that have potential for exposure: > Handling ofPTFB and Co-polym er dispersion products > Operation and maintenance o f blending facilities > Packout o f finished product N ote that at no tim e 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. A ll exposure potential is through skin contact during handling o f the polym er dispersion materials all o f w hich contain <1% APFO with most containing <0.25% APFO. H ours/D ay < 0 .2 5 0.25-1 1-8 >8 <10 Spruance Plant D ays/yr 10-100 100-250 <10 >250 Routine worker activities that have potential for exposure: > Handling ofPT FB and Co-polym er dispersion products > Operation and maintenance o f fiber coating facilities > Operation and maintenance o f sintering rolls > Packaging o f non-sintered product. N ote that the PTFE and co-polym er dispersion products used at the Spruance site contain <0.9% APFO w ith m ost containing approximately 0.3% APFO. B . Information on th e Exposure L evels o f W ashington W orks Em ployees Since most o f the processing done in the US with APFO and APFO containing intermediates and products is done at W ashington W orks, DuPont's airborne industrial hygiene data is concentrated at that site. The lim ited measurements o f airborne APFO concentrations at the other sites where APFO containing products are used have shown much lower levels (m ostly non-detectable) levels o f APFO. The data in the table below E ID 080070 ,^ )* - 1 Voluntary UEIP, Ammonium Petfluoiooctanoate reflect monitoring done over the last 5 years at W ashington W orks, The sample results are a combination o f chem ical operator and maintenance worker personal samples. Year Sample Type 1999 1998 1997 1996 1995 Partial Shift (m ostly 6-8 hours) #of Sam ples 100 83 100 73 32 M inim um Concentration (mpb6) < 0 .0 1 .001 < 0 .0 1 N /D N /D Maximum Mean Concentration (mpb) (m pb)____ 0 .5 8 0 .7 8 2 .4 0 ,2 9 0.061 0.103 0.146 0.055 0 .16 0.067 Standard D eviation 0.151 0.145 0 .3 7 8 0 .0 6 9 0.063 Partial shift air sam ples are taken at the rate o f 200 mL/min usin g a Tenax collection tube that has been pretreated with sodium hydroxide/ethylene glycol/m ethanol. The APFO is desorbed from the tubes using methanolic hydrogen chloride, w hich also serves as a derivatizing reagent, converting the APFO to its methyl ester. A fter workup, the methyl ester is quantified using a gas chromatograph equipped w ith an electron capture detector. The methyl ester ofperfluorodecanoic acid is used as an internal standard, and at least three calibration sam ples are prepared to cover the concentration range o f interest. Precision is estim ated to be +?-10% relative. The data above show averages consistently below the AGCHITLV o f O.Olmg/m3 w ith only a very few sam ples above the TLV. W here 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 lev els is undertaken. Older data from the 1980's show higher levels o f exposure. In the early 1990ss W ashington W orks switched from receiving the APFO as a powder to receiving it as an aqueous solution. This change w as done to reduce the potential for exposure during handling o f the dry powder. It should be noted that in the 1997 tim e period, the site w as starting up new APFO recovery facilities. Operating and maintenance difficulties associated w ith the start-up o f these facilities may have contributed to the higher levels o f APFO in the personal sam ples during that year. Task specific m onitoring data and w ipe m onitoring data exist. However these data are not indicative o f em ployee exposure and are not presented here. These samples are taken to identify areas w here additional exposure controls m ay be necessary, ' Engineering controls to reduce exposure consist o f the follow ing: > R eaction system s are closed system s with continuous ambient monitoring for monomer concentrations > V entilation system s are installed where airborne concentrations are significant > The polym er dryers operate under negative pressure to contain APFO and other materials. > Recovery system s are in place to reduce airborne em issions. 6 mpb= m oles per billion . 0.56m pb is equivalent to the ACGIH TLV o f 0.01m g/m 3 AJP001749 E D 080071 I Voluntary UEIP, Ammonium Perfteorooctanoate Personal protective equipment that workers regularly wear consist o f the following; > Safety shoes and side-shield safety glasses in all areas. > Impervious gloves when handling APFO solutions or aqueous dispersion > Chemical protective coveralls and goggles or face shields w hen fee possibility o f splashes o f APFO containing solutions is present. > Airline respirators or cartridge respirators where monitoring has shown to have high exposure potential. A t W ashington W orks, blood serum levels o f APFO have been measured since 1981. Prior o f blood fluoride levels have been taken prior to 1981 but are o f limited value in assessing exposure to APFO. A summary o f results o f em ployees w ife identified APFO exposure potential fee 1995,1989-90, 1985,and 1984 volunteer sampling events is in fee table below . D ue to significant job assignm ent movement during this period o f tim e, analysis o f trends o f data are difficult. The data in fee table below prior to 1995 are for em ployees included in fee 1995 sam pling data so that comparisons o f relative levels o f APFO in Wood serum can be compared. The entire data set o f blood concentrations is available upon request. Year 1995 1989-90 1985 1984 #of Sam ples 73 23 21 19 M inimum Concentration (ppm) M axim um Concentration 0.12 0 .4 " . 006/ .. (P P fei____ 4 .5 8.5 18* -- 0.07' .....; 1 2478 M ean Concentration (ppm ) 1.57 3.13 2 .4 4 3.82 .... . fl-ciT-.y )' 7 This individual w as working in a job that has APFO exposure potential at the tim e o f the sample. 8 H us individual consistently has had the highest blood concentration o f APFO since APFO Specific cptnptp* Were taken. T his em ployee left an APFO exposure potential assignm ent in 1991. In 1995 this em ployee's blood serein level w as 4.4ppm . CD E ID 080072 I AMMONIUM PSHfLUOROOCTANOATE (C-^8) EXISTING LIMITS TLV* = 0.1 MG/M3 AEL s 0.01 MG/M3 CEG a 0.0003 MG/M3 OR 0.3 ^UG/M3 EXPOSED DAILY POSE AT UNITS - MAN TLV* = 1 MG/DAY (0.014 M6/KG) AEL = 0,1 MG/DAY (0.0014 HG/KG) CEG " 6 (0.0000? MG/KG) AJP001751 E ID 080073 ] ..J ammonium perfluoruqctanoate WATER GUIDELINE DAILY EXPOSED DOSE FOR HAN IS APPROXIMATELY 6 -UG/DAY DRINKING WATER/INHALATION EXPOSURE % s 20/80 THEORETICAL AIR a 4.8 jUG WATER * 1.2 DAILY WATER INTAKE = 2 L T.Z .AG/2 L = 0.6 <AG/L = 0.6 PPB RECOMMENDATION WATER GUIDELINE = 1 PP& ; E ID 080074 AJP001752