Document jg2934erwmLDBY5XED67KdJ0R

D u P o at H ask ell L ab o rato ry :u*bkHufcad -loarrauv w Tmeaoqi ma immm Meatiie 3 cm tart. .1 3<aJO tawwxaE '5714-181 /S S S June 13, 2000 Or. G iades M. Auer, Director U.S. Environm ental Protection Agency O ffice o f Pollution Prevention and Toxics Q tem icai Control Division 401 M Street NW , Room 403 W ashington, D.C. 20460 D ear Dr. A uer Enclosed are tw o conies of die summary on Ammonium Perfluorooctanoate. One conv is a public cony and the other copy private and madced accordingly. If you have any questions, piease call me on 202-366-5239. G L JC jhh E n c lo su re G erald L. Kennedy, JrT Director, Applied Toxicology .qid Health; 000009 EID102805 D u P o n t H a sk e ll L ab o rato ry -4xxXLisonar* *arTaaeamfir ana w u m Maaicsia 3cmteod. ? 0. 3axso Him**. Q6 :sn4-3088 June 23, 2000 Dr. C laries \ L Auer, D irector U S . Eavtronxsencai Procecaon Agency Office o f Pollution Prevention and Toxics Chexmcai Control Division 401 M Street NW, Room 403 W ashington, D.C. 20460 Dear Dr. A u er As you requested in your April 19,2000 letter and during our subsequent m eeting on May 1,2000, attached is a summary of D uP ont's U.S. uses o f Ammonium Psrfluoroocanoim (APFO, CAS# 3825-26-1) as a fluoropolym er reaction aid including releases from D uPont site and the hue o f APFO in fluoropolym er dispersion products, a summary o f industrial hygiene data collected at our U.S. fluoropolym er m anufacturing site, and a sum m ary of the employee blood data flora a site in the U S. A sum m ary of the toxicology available to DuPont was sent under separate cover on May 26,2000. It is im portant to emphasize the following points: > D uPont does not manufacture APFO. A ll APFO used in our processes as a reaction aid is purchased flora an outside supplier. > M ost o f the APFO used is rem oved from the fluoropolym er products before they are sold to outside custom ers. A relatively small am ount o f APFO - (w o rld w id e, in the U.S.) leaves DuPont facilities in fluoropolym er dispersioo > O f die APFO in the products sold, most (>97% ) is destroyed during custom er processing to a soa-caruoxylated hydrofluorocartwn. > All o f the U.S. DuPont operations chat use APFO with significant exposure potential are concentrated at one location; W ashington Worics in Wash in gton. W V. Therefore, m ost of the industrial hygiene dam and blood serum d ata presented in this document are from that location. EID102806 000010 /Ok *. .. AVM000243 Dr. G iades VL Auer, D izeaor L '.i. Environm ental Protection Agency Page 2 > E cen siv e industrial hygiene data collected on workers potentially exposed to APFO snow airborne exposures to be significantly below the ACCHH TLV o f O.Qlmgrtn1 3 hr. TW.a. Exposure levels o f pianc w odass have dropped significantly sines the conversion to an .APFO sohm ou from a dry powder. > .As part o f the ongoing surveillance of workers potentially exposed to APFO, in March and April o f this year a series of blood samples w ere taken from workers in the U.S., The N etherlands and Japan to be analyzed for serum APFO concentration. DuPont has aot received the results from our contract laboratory at this time. DuPont w ill subm it a summary o f the results when they become available. The form at o f the infonnanon in the attached is x m odified U E P form at. If you w ish to discuss the inform ation contained in the attachm ent please contact Robert F. P in c io t at (302) 999-4074 o r e-mail at R o fa y -f t o m a a o r me at (302) 366-5259. Very truly yours. Gerald L* Kennedy Director, Applied Toxicology mW H ealth AVM000244 EID102807 O O O O ll i Voluntary CEI?, Aaunomina pgflucroocaaoam Voluncary I 'se and Exposure Information Profile Ammonium Perfluorooctanoate (APFO) L CHEM ICAL IDENTIFICATION Chemical Name: CAS Number: Ammonium Periluarooctanoate 3825-26-1 IL COMPANY ID ENTIFICATION C om pany Name: E L du Pout de Nemours and Company Site Locations: Sice where AFFO is used as a reaction aid: W ashington W orts Route 392 W ashington. WV 26181 Sites where AFFO containing products made at W ashington W orks are processai: Pariin Plant Road Pariin. NJ 08859 Spruance Plant 5401 Jefferson Davis Hwy. Richmond, VA 23234 Site which disposes of waste containing APPO: Chambers W orts Rte. 130 Deepwater, NJ 08023 Technical Contac t Robert F. Pinchoc (302) 999-4074 DuPont Flnoroprodnc a Chestnut Run Plaza Bldg. 7 1 1/221Q Centre Boulevard W ilm ington. DE 1980S-QT711 000012 EID102808 AVM000245 Voiuatary CEP. Ammonium Pncdnaroocaaonm U L DUPONT AND CUSTOMER AdTVmES N arrative D tscrintfoo of A FFQ U sf The block diagram on che back page titled "D uPont US APFO Balance" describes the processes discussed below. DuPont uses APFO as a reaction aid in the production o f polytetrahieroethyieue-(FTFE) and cetrafluoroethylene (TFE) co-polymers. The process utilized at D uPont's W ashington W orks for making PTFE and co-polymers consists of polym erizing TFE (and other co-monomers if desired) in an aqueous media with a small amount o f APFO to aid in the reaction. Following the polym erization step, the polym er dispenion is either dried to rem ove 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 rem oved 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 em itted to air or w ater at che W ashington Works. The stabilized polym er dispersions are sold by DuPont to industrial custom ers (both in the US and outside the US) for a variety o f uses, internally transferred to the D uPont Spruance Plane for the production of Teflon fibers and PTFE coaled synthetic fibers, or internally transferred to the DuPont Pariin Plant for the production of Teflon Finishes. A sm all amount o f non-hazardous waste polym er, water, APFO and other additives generated at W ashington W orks is treated in a wastewater treatm ent facility at D uPont's Cham bers W onts. This material is either em itted in the Chambers W orks w ater 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 moat o f the product, a "sintering" step in which the APFO contained is the product is destroyed by the follow ing reaction:1 CFj(CFi)COO*NHr -> CF^CF^CFiH +CO* +NH* This reaction goes to com pletion at 350C and OJZs residence time. A sm all am ount of product processed at D uPont's Spruance plant does not get sintered and thus contains a sm all amount of residual APFO. These products are used for industrial pump, valve and com pressor packing 1? J. Crane. O.C Roe. "Thermal dacotnpeainoo of CS fluorinamri netiesnus m i mtamt ammriai* semia i by high tempanuue gaa-edaaa l*F XMR. A arm Aicanaave to thermal gravimetric anaiyaa. DuFooc Internal Report. EID102809 000013 V olum ar/ UEZP. Ammonium ?tiuaroocaooe<e The process for making Teflon< finishes at che DuPont Parta Plant involves a blending operation o f fiuoropoiytner dispersions with ocher additives including solvents, binders, and pigm ents. The *rn*n amount of APFO em issions to w ater from this facility is due to waste generated during product changeovers. Some of the fhioropolymer 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 produc. The final product produced is then sold to applicators that apply che product co a substrate (such as cookware) via autom ated spraying or rollercoating. Emissions 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 emission. Product chat is applied co che substrate is then typically "sintered" at temperatures approaching 300F resulting in che rem oval of the APFO from che substrate and subsequent destruction according co the reaction above. Custom ers o f dispersion products use che m aterial for a variety o f applications. However, m ost applications involve a "sintering'' step where che APFO is destroyed. There are a sm all num ber o f applications where the custom er heats the dispersion products to temperatures chat allow che APFO co sublime resulting in air emissions. There are also a sm all num ber of applications where the custom er's product is not heated resulting in che APFO sa y in g with che product. These applications include industrial packings, and industrial filter fabrics. IV . SITE RELEA SE AND TRANSFER IN FO RM A TIO N FOR T R I CHEM ICALS N ot applicable- APFO is not Usted on che TRI V. SITE RELEA SE AND TRANSFER IN FO RM A TIO N FO R NON-TRI CH EM ICA LS A. O n-site A ir Releases ; \ , Fuotive ! Stack (Point Source) Estimated Total Annual Releases ( lbs. 1999) N egligible 24000 i0 i 10 i 0 0 i ! 0 0 ! ! .Air em issions are ftim natcd using engineering calculations and judgem ents and lim ited m easurem ents o f specific point sources coadncted in the past. AVM000247 * 000014 EID102810 Voluntary L'EZP. .Xxnmomum Psruoroocsuxuua B. O n-site W ater Releases __________ Estim ated Total Annual Releases ( lbs. 1999) Point Source 55000 300 C o o in ifiiB W ater em issions ate estim ated using engineering calcuiaeons and judgem ents and lim ited measurements of specific sources conducted in the past. W ashington W orks emissions occur for approxim ately 350 days/yr while the other sites' em issions occur for 10-100 days/yr. Releases of APFO to the Ohio R iver from the DuPont W ashington W orks Plant were modeled using the Probabilistic Dilution Model (PDM Beta Version 4.0 Beta June 11,1999. US EPA Office o f Pollution Prevention and Toxics) and a constructed M icrosoft Excel spreadsheet model. APFO release data for 1996 were used in both m odeling exercises.2 The PDM indicated that APFO concentrations o f 1.0 u g CS/L would be exceeded about 50% o f cbe tim e during the year. APFO concentrations of in the river would exceed Q .liig APFO/L 90% o f the tim a during the year and 10 itg APFO/L about 1 2% o f the time during the year. Average annual APFO concentrations in the Ohio R iver calculated by using a M icrosoft Excel spreadsheet was 0.423 fig APFO/L. M odeled AFPO concentrations in the river ranged from a low o f 0.199 fig APFO/L in M arch to a high o f 0.965 fig 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 D am and used in the spreadsheet model. The B elleville Dam is on the Ohio River 13 miles dow nstream o f the W ashington W orks P la n t This river flow data is die closest location downstream from the plant where this type o f inform ation is av ailable ha 1999 a drinking w ater sample obtained from GE plastics, W ashington W V, im m ediately downstream on the Ohio River from DuPont W ashington W orks snowed CL552fig/l APFO. la addition sam ples obtained in January 2000 from three different wells at the Lubeck Public Service District* downstream of W ashington W orks on the Ohio R iver, show ed 0.3fxg/L 0.44ug/l and 0.313 figA. APFO. W.a_3ore. Modeiiag rtinaaa oc unmomum perducroocanoa imo ite Qtoo River. OuPoac buaraal Repot SMSE-OS+OO. EID102811 J 000015 Voluntary UHP. AmmnmumPsafiaorooeaeoam C On-Sice Land Releases C h im b en W aits treats APFO containing w aste in a wastewater treatm ent system. Engineering calculations and measurements indicate that approximately 30% of the APFO in the wastewater created is absorbed on to a carbon media chat is landfilled on site. These land releases are estim ated co be 39001b in 1999. Prior operations have resulted in m easurable APFO concentrations in three landfills operated by the W ashington W orks in W est Virginia. A t Letarr1 landfill surface w ater measurements in 1999 and 2000ytd range from 2-23ug/1 co 3240ugA with an average of I392ug/1. G roundw ater measurements taken during che same time period at Letart landfill range from 60J ttg fi to L7400ugrt w ith an average o f 2537jig/L At the "local landfill" che groundwater concentrations range from 0.046ugrt co 39ug/l with an average o f 8.33|igrt. Surface water sam ples at che "local landfill" range from 0.34ug/l to S7ug/1 w ith an average of 18_5fig/I. At Dry Run landfill there are lim ited m easurements o f groundw ater and surface w ater w ith maximum concentrations in groundw ater o f iiu g /l and the maximum concentration in the permitted outfall has been 33fig/l. fia !999 a RCRA Facility Investigacin was com pleted for W ashington W orks and was subm itted to EPA Region m in June 1999*. The repon contains data on groundwater concentrations of APFO at W ashington W orks. D. Transfers to O ff-site Locations W ashington W orks: i : Incineration W astew ater meatment Underground mechn H azardous W aste Landfill O ther landfill R ecvde or recovery IV. ON-SITE WORKPLACE EXPOSURE A. Ihronnation on the N um ber of Em ployees Potentially Exposed 16000 R 2600 0 . -r AVM000249 1Mapa of * landfill iocactom aad pacific a s u a n a tocados* aad m ita am avsfisbis t^ca lequot. *Report -m* uonuucd to Marea. T. &MKh. Scaadial P ropaa Maaap r . SPA Rafioa J2L Pbiladoipiaa. *This la be iaam aatsnai but -*aa Jescnbed above m p antnph 1 of cdoa VD. EID102812 6 000016 # Voluntary (HP, Aam om vm P^doareoctaaoam The tables below describe che aumber or' workers d m may be exposed to APFO during their normal work activities tor each o f the three sites where APFO is used or APFO containing product is processed. 1Hours/Day 1__________ ! <0.23 i 0-25-1 i i-8 1 >8 W ashington W orks _____________________ :______ Pays/yr_____ :________________ <10 10-100 ! 100-230 ! >230 1! 1! j 242 1" i !1 1 ! 1 Routine w orker activities d m have potential for exposure: > Handling raw m aterial APFO > Handling raw dispersions containing APFO > M aintenance o f polymerization reaction systems > Polym er dryer operation and maintenance > Packout o f PTFE and co-polym er dispersion produca > Operation and maintenance of .APFO recovery system s AVM000250 EID102813 7 000017 VoimaarrUEP.AaunommnPerfluaroocanoem ___________________________ Partin Plant______ J Hours/Day i _______________________ D ays/yr 1 <10 ( 10-100 ! 100-250 1<0.25 1 f ! 0 .2 5 -1 IS.- 1-8 1 1 ____________ i_______________ 1______________ _ Routine worker activities that have potential for exposure: 1>250 1 i i | : ! ! > Handling o f PTFE anti Co-polymer dispersion products > Operation and maintenance or*blending facilities > Packout of finished product N ote that at ao time is the m aterial handled at the Partin Plane at an elevated temperature where the APFO could sublim e. Therefore there is little potential for exposure to airborne APFO at this facility. All exposure potential is through don contact during handling o f the polym er dispersion m aterials ail of w hich contain <1% APFO w ith most containing <0.25% APFO. 1H oun/D ay i <0.25 ! 0.25-1 ! 1-8 f >8 I I <10 ! ! 1 1 Spruance Plant D ays/yr 10-100 100*250 <10 1 ! >250 1 l Routine worker activities that have potential far exposure: > Handling o f PTFE and Co-polym er dispersion products > Operation and m aintenance o f fiber coating facilities > Operation and QUUfttBEUtiQCS of sintering rolls > Packaging o f non-sintered product. N ote that the PTFE and co-polym er dispersion products used at the Spru ance site contain <0.9% APFO with most containing approximately 0J % APFO. B. M orm anon on the Exposure Levels o f W ashington W orks Em ployees Since m ost of the processing done in the US with APFO and APFO contam ini interm ediates and products is done at W ashington W orks, D uPont's airborne industrial hygiene data is concentrated at that site. The Limited m easurem ents o f airborne A PFO concentrations at the other sites where APFO containing products ate used have shown much low er levels (m ostly ooa-detecmble) levels o f APFO. The data in the table below 3 000018 EIDI02814 Voluntary112?.AmmoniumPetiuoreoeanoem reflect m onitoring done over the last 5 yean at W ashington W orks. The sample results are a com bination o f chem ical operator and maintenance w orker personal samples. j Year !* ! j 1999 1 1998 ; 1997 : 1996 i 1995 S am ple Type Partial Shift (m ostly 6-3 hours) ! 1 j ft of S am ples 100 83 100 7332 C o n cen tratio n (m ob4) <0.01 001 <0.01 N/D 1 ;V/D M aximum Mean Standard Concentration (mpb) Deviation 1 (mob)- 1i 0.58 0.061 1 0.151 f 0.78 0.103 ' 0.145 ! 2.4 0.146 0.378 l 0.29 0.055 0.069 ! 0.16 1 0.067 i 0.063 ; Partial shift air sam ples are taken at the rate o f 200 m lin u n using a Teoax collection cube that has been pretreated w ith sodium hydroxide/etbylene giycol/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 w orkup, the methyl ester is quantified using a gas chromatograph equipped with an electron capture detector. The methyl ester o f perfiuorodecanoic acid is used as an internal standard, and at least three calibration sam ples are prepared to cover the concentration range of interest Precision is estim ated to be +/- 10% relative. The data above show averages consistently below the A G CH ITLV o f O.Olmgfm3 with 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 equipm ent or engineering controls) to reduce the exposure levels is undertaken. O lder dam from the 1980's show higher levels o f exposure. In the early I9 9 0 's W ashington Works switched from receiving th e APFO as a powder to receiving it as an aqueous solution. This change was done to reduce the potential for exposure during handling o f the dry powder. It should be noted chat in the 1997 time period, the site was starting up new APFO recovery facilities. O perating and maintenance difficulties associated with the start-up o f these facilities may have contributed to the higher levels of APFO in the personal sam ples during that year. Task specific m onitoring data and wipe m onitoring dam e x ist However these data are a ct indicative o f em ployee exposure and are not presented here. These samples are taken to identify areas w h e n additional exposure controls may be necessary. Engineering co n so ls to reduce exposure-consist of the following: > R eaction system s are d o sed system s with continuous am bient m onitoring for rprinw > V entilation system s are installed where airborne concentrations are significant > The polym er dryen operate under negative pressure to contain APFO and other w --r ials. AVMOO0252 * tupos aoks per billion. OJf6opo is equivalent uj Cm ACGIHTLV of (XOlaffa1 9 EID 102815 000019 VoluntaryUEP,AmmoeuuaPtrtuarooccsneaiB > Recovery system s aze is place to reduce airborne emissions. Personal protective equipm ent chat workers regularly wear consist of che following: ` > Safety shoes and side-shield safety glasses in ail areas. > Im pervious gloves when handling APFO solutions or aqueous dispersion products. > Chem ical protective coveralls and goggles or face shields when the possibility o f splashes o f APFO containing solutions is present. > A irline respirators or cartridge respirators where monitoring has shown to have high exposure potential. A t W ashington W orks, blood serum levels o f .AFFO have bees measured since 1981. Prior measurements o f blood fluoride levels have been taken prior to 1981 but are o f value in assessing exposure to AFFO. A summary of results o f em ployees with identified APFO exposure potential the 1995,1989-90, 1985,and 1984 volunteer sam pling events is in the table below. Due to significant job assignment m ovem ent during this period o f dm e, 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 chat com parisons o f relative levels o f APFO in blood serum can be compared. The entire data set o f blood concentrations is available upon request i Year j 4 of 1 1 S am ples 1995 f 1989-90 1 1985 1984 : 73 23 21 19 1 Minimum Concentration j (ppm) 1 0.12 | 0.4 i O061* 1 M axim um Concentration _____ (P m )_____ 4.5 8J 18* 24? M ean C o n cen tratio n (com ) 1.57 3.13 2 .4 4 3.82 , 7 This tatttvidnal * w aring ia a job that bat AFFO ex p o n e pownrial as the d m of tfeesunpk. 1Thii individual caanandy ha* Had the Uffcnt blood caan an rio a of AFFO m m AFFO specific n npln wen talon. T in aptoyn left aa AFFO axpoaan pownriif m if Hiww ia I99t. Ia 1995 this amptoym's Wood a n a level was <*.4pqaL EID102816 10 000020 Vultudiiry UIIP, Ammonium DuPont U S APFO Balance S Public Cupy Captinoti and Sani lotAbda \AMor Tm alm eni| oti-dle mgi Recycled lo V _____ E ID 102817 O O c eo frSZOOOWAV External Salas lo Induxlflai Cudometa Conlalned In I Piodud/ Apptitkl | toSululnto I Cnntiad P n c a rin y Dupunl Flban } y*"IIMM TC anW iw ilnRniM i \ jiOduct (1BQU>)y