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AR226-2732 The miracles c^f science" Study Title MODELING RELEASES OF AMMONIUM PERFLUOROOCTANOATE INTO THE OHIO RIVER Author William R. Berti Report Completed on May 22, 2000 Performing Laboratory E. I. du Pont de Nemours and Company Environmental and Microbiological Sciences & Engineering Corporate Center for Engineering Research Central Research & Development Glasgow, Building 300, P.O. Box 6101 Newark, DE 19714-6101 Report No. EMSE-054-00 Page 1 of 8 .Company Sanitized. Does not contai'n TSCA CBI DuPont EMSE Report No. 054-00 GENERAL INFORMATION Chemical Studied: Ammonium perfluorooctanoate Synonyms/Codes: APFO, C-8, FC-143 DuPont Notebook No.: Not Applicable Sponsor; Robert Pinchot E. I. du Pont de Nemours and Company BARLML CRP-711 /2210-B Study Initiated/Completed: September 1999 to May 2000 Page 2 of 8 Company Sanitized. Does not contain TSCA CBI DuPont EMSE Report No. 054-00 MODELING RELEASES OF AMMONIUM PERFLUOROOCTANOATE INTO THE OHIO RIVER SUMMARY PDM indicated that APFO concentrations of 1.0 |ig APFO/L would be exceeded about 50% of the time during the year. APFO concentrations of in the river would exceed 0.1 [I.B, APFO/L 90% of the time during the year and 10 [is, 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 APFO concentrations in the river ranged from a low of 0.199 p.g APFO/L in March to a high of 0.965 ^ig APFO/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 of information is available. Study Conducted and Report Prepared by: William R. Berti Senior Research Biologist (date) Page 3 of 8 Company Sanitized. Does not contain TSCA CBI DuPont EMSE Report No. 054-00 INTRODUCTION/PURPOSE APFO (ammonium perfluoroocatanoate) is a fluorinated surfactant used in the manufacturing of Teflon at Washington Works. A portion the APFO (18,416 kg in 1996) was released to the Ohio River as part of an NPDES permitted release for the facility (WV0001279). The molecular weight of APFO is 431.098 g/mole. Other properties of APFO are listed below. Made by 3M Company Health rating of 2 Exposure limits 0.01 mg/m3 skin 8 hr LDso acute oral rat = 680 mg/kg BODzo = nil Biodegradation = nil BCF=1.8 Molecular formula CF3(CF2)6COO'NFL^+ pH ~ 5 (0.5% aqueous) pKa=2.8(-COOH) Melting point = 56-58C (-COOH) COD = 700 mg/kg Koc = 25 Water solubility >1000 mgAPFO/L Vapor pressure (at 22C) =7.1*10'05 mm Hg Our objective was to calculate the concentrations of APFO that could reasonably be expected to occur in the Ohio River downstream of the NPDES permitted outfall at the DuPont Washington Works. MATERIALS/METHOD Releases of ammonium perfluorooctanoate (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. PDM inputs included the NPDES number of WV0001279. This corresponds to a reach number of 05030202039, a mean streamflow of4.75E+04 million liters per day (MLD), a low streamflow of 9980.47 MLD and an effluent How of 216.75 MLD. We assumed that APFO was released 335 days/year, the loading was 55.138 kg/day, and the wastewater treatment efficiency was 0%. We then varied the APFO concentration as the Concentration of Concern (COC) from 0.1 to 50 u,g APFO/L to determine the COC percent of year exceedence. Microsoft Excel spreadsheet used river flow data from the US Geological Survey (USGS: <http://waterdata.usgs.gov/nwis-w/WV/data.components/hist,cgi?statnum=03159530>). This is the mean daily river flow in cubic feet/sec measured at the Belleville Dam from 10/1/1974 Page 4 of 8 Company Sanitized. Does not contain TSCA CBI DuPont EMSE Report No. 054-00 to 9/30/1985. 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 of information is available. This river flow data compares well with Ohio River monthly average flows at Pittsburgh, PA, Huntington, WV, and Cincinnati, OH from the US Amy Corps of Engineers (ftp://www.lrd-wc.usace.army.mil/MonthlyJ.itm/). The average daily river flow for the month was calculated from available data between those two dates. This was then converted to the average measured flow per month. We assumed the APFO was discharged to the river at a constant rate except for the month of October when production at Washington Works is usually suspended for annual maintenance. We assumed that the total discharge of was 18,416 kg APFO (40,600 Ibs APFO) divided by 11 months. Table shows the results of this spreadsheet model. RESULTS/DISCUSSION PDM indicated that APFO concentrations of 1.0 pg APFO/L would be exceeded about , 50% of the time during the year. APFO concentrations of in the river would exceed 0.1 pg APFO/L 90% of the time during the year and 10 p.g APFO/L about 2.2% of the time during the year (Table 1). Figure 1 shows model input/output. Average annual APFO concentrations in the Ohio River calculated by constructing and using a Microsoft Excel spreadsheet mode] was 0.423 ug APFO/L (Table 2). Modeled APFO concentrations in the river ranged from a low of 0.199 pg APFO/L in March to a high of 0.965 u.g APFO/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 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 of information is available. Page 5 of 8 'Company Sanitized. Does not contain TSCA CBI DuPont EMSE Report No. 054-00 Probabilistic Dilution Model (PDM) results ot'APFO concentrations and percent of year that the concentration ofAPFO will be exceeded in the Ohio River. Concentration ofAPFO Percent of year concentration exceeded ug/L 0.1 0.5 1 3 6 10 25 50 % 90.9 71.6 51.0 17.8 6.1 2.2 0.2 0.0 Page 6 of 8 Company Sanitized. Does not contain TSCA CBI DuPont EMSE Report No. 054-00 Table 2. Month Microsoft Excel spreadsheet calculations of modeled APFO concentrations in the Ohio River. Measured flow Measured flow APFO discharge to Ohio River in 1996 Estimated APFO concentration in Ohio River January February March April May June July August September October November December Average Total ff/sec 64,001 88,909 111,236 94,017 67,107 47,379 30,989 30,502 25,339 33,030 42,330 78,986 713,824 L/mo 4.69E+12 6.74E+12 8.43E+12 6.90E+12 5.09E+12 3.48E+12 2.35E+12 . 2.31E+12 1.73E+12 2.50E+12 3.11E+12 5.99E+12 4.44E+12 5.33E+13 kg 1,674 1,674 1,674 1,674 1,674 1,674 1,674 1,674 1,674 0 1,674 1,674 18,416 f^g/L 0.357 0.248 0.199 0.243 0.329 0.482 0.713 0.724 0.965 0.000 0.539 0.280 0.423 0.345 Page 7 of 8 Company Sanitized. Does not contain TSCA CBI DuPont EMSE FIGURE 1: ADSORPTION-DESORPTION STUDIES OF AMMONIUM PERFLUOROOCTANOAT Probabilistic Dilution Mode] (RDM) Beta Version 4.0 input and output screen, Chemical ID: Scenario @: Reach. nu'm'heg Gag-incf st-ation Period ojE record 8 of obsei.-vacions Mean sI^reajnfio'KT Low st-reaMflot.T K t S 1-uen-c. flow Release days C-S 1 QS030202Q39 Facility name E.I.DU POKT DE HEHOURS & CO. ,,Paca.-.i.a-ty , loca't.xori PARKERSBURG, TiJV 6102 ^ 1 Receiving ST^reaia- name OHIO R 1996 HA 4.7e+04 [.[LD 998 0.47 HLD 21 6.75 HLD INPUT DATA 335 days/year H-P&ES ITujfl^er WVL1001279 P' Facility on r e sell? D iscliarge v.\fpe P Diract. 1Indirect Dat a source Faa.cSrch - Direct. (L isc) Ixiivo1001279 R elease a r HFG r PRO r II.ID ^J r" coini r C01.IS Loading C one ent. r at-i on of Concern <COC) Wast; ei.rac.er treacinent efficiency P,esult.s HisteoEy COC (ug/L) t YEAR COC EXCEED El; .(DAYS COC EXCEEDED E6.138 1 0 0 kg/sice/d ay Results {,(C. OC -i-ig/L Percent. Q f ye ar % Days per ye ar Exceedence) 2. 24 S. 1'^ . days/ye ar RELEASE LOADIHG. DAYS (teg/sit a/day) WASTB OTATER -i. TREATMENT 0. 1 90- 9 33.L- 6 0. S 7.1- 6 261- 5 1. S1. 186. S. 8-4 30-6 10. 2.2 8.2 33S. 33S- 33S- 335. 335- SS. 1 SS. 1 S- 1 55- 1 55.1 0. 0- ---- 0. 0. 0. ^J Sllbntit Done j Save j Pcinc Page 8 of 8 /--'"*.- Iwg^