Document 8V1b69omVnoVv52dgqd4Laogd

AR226-2733 e r e The miracles of science Study Title ADSORPTION-DESORPTION SCREENING STUDIES OF AMMONIUM PERFLUOROOCTANOATE Author William R. Berti Report Completed May 2000 Performing Laboratory E. I. du Font 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-053-00 Page 1 of 16 Company Sanitized. Does not contain TSCA CBI DuPont EMSE Report No. 053-00 GENERAL INFORMATION Material Tested: Ammonium perfluorooctanoate Synonyms/Codes: APFO, C-8, FC-143 DuPont Notebook No.: E98312 Sponsor: Robert Pinchot ------ E I du Pont de Nemours and Company BARLML CRP-711/2210-B Study Initiated / Completed: September 1999 / May 2000 Page 2 of 16 jDompany Sanitized. Does not contain TSCA CBI DuPont EMSE Report No. 053-00 ADSORPTION-DESORPTION SCREENING STUDIES OF AMMONIUM PERFLUOROOCTANOATE SUMMARY Five of nine materials appeared to adsoofrAbPa FsOig.nFifoicrafnotuar moof uthnet (fgivreeamteartethriaanls2t5o%whoifch 2 APFO APFO added) at one or more concentrations significantly adsorbed, most of the adsorbed APFO appeared not to desorb after washings at one or more concentrations of added APFO. Study Conducted by: Bamett(date) Kristi Research Technician, EMS&E Study Conducted by: Jack DeCarolis Staff Biologist, EMS&E (date) Study Conducted by: George Fisher Research Technician (date) Study Conducted by: Bogdan Szostek, Ph.D. Research Scientist, Haskell Lab (date) Report Prepared by: William R. Berti, Ph.D. Senior Research Biologist, EMS&E (date) Page 3 of 16 Company Sanitized. Does not contain TSCA CBI DuPont EMSE Report No. 053-00 INTRODUCTION AND PURPOSE APFO adsorption/desorption screening studies were performed on several test materials, including two clays, a washed sand, peat moss, and an agricultural soil from Delaware, USA. The adsorption/desorption screening studies were also performed using two surface soils and two sediments from the Ohio River collected in the vicinity of the DuPont Washington Works plant near Parkersburg, West Virginia. The adsorption/desorption procedure used in this study was adapted from a method developed by the Office of Prevention, Pesticides and Toxic Substances (OPPTS), United States Environmental Protection Agency for use in the testing of pesticides and toxic substances, and the development of test data (1). Our objectives were to develop an adsorption/desorption protocol and analytical procedure for APFO, As part of this objective, we screened a variety of test materials for their APFO adsorption/desorption characteristics. MATERIALS AND METHODS Test Materials The Kaolin (KGa-2) and Montmorillonite (SAz-1) are Clay Mineral Society "Source Clays" and were obtained from the curator of the sample collection in the Department of Geology at the University of Missouri, Columbia. Additional information on these and other Source Clays has been published (2). The Quikrete All-Purpose sand and Scotts sphagnum peat moss were purchased locally at a builders' supply store (Home Depot). The Sassafras soil is a surface (0 to 15 cm) soil collected from an agricultural field in Delaware, USA. The Garden Area soil and East Wood soil were surface soils collected from the DuPont Washington Works plant. The Upstream sediment was obtained from the bank of the Ohio River upstream of the DuPont Washington Works NPDES permitted outfall, and the Downstream sedment was from downstream of the outfall. The two soil and sediment sample from the vicinity Washington Works were collected in the fall of 1999. Physical and chemical properties of the less than 2-mm size fractions of the soils, sediments, clays, sand, and peat moss used in this study are listed m Tables 1 and 2. Except for the clays, all samples were screened through a 2-mm (10 mesh) stainless steel sieve in preparation for the absorption/desorption screening test. Furthermore, the sand was washed using DI water-through 2-ram and-50-um stainless steel sieves. Material retained on the 50 um sieve was used in the study. The sand, soils, and sediments used in the studies were air-dried prior to use in the studies. Data calculations, however, were based on oven-dry weights of the samples. Oven-dry weights were determined after drying a subsample of material in an oven at 105C for a minimum of 24 h. The pH of the sample were determined in a 1:1 test material to water. Percent organic matter was determined using the loss on ignition method. Screening Test: Adsorption Studies The adsorption test was performed in duplicate on each material. A blank containing 0.01M CaCL solution with test materials and no APFO and a single control at each APFO concentration but no material were also included. Each material was equilibrated with the aqueous phase of a solution of the test chemical at 5.0, 0.5 and 0.05 mg L'1. prepared in 0.01M CaCL, Page 4 of 16 not contain TSCA CB6 DuPont EMSE Report No. 053-00 Sterile 50 mL Coming polypropylene centrifuge tubes were used as the test vessels. One part air-dried material (4.0 g) was weighed and 5 part test solution (20 mL) was decanted into a centrifuge tube, except the control tube. The centrifuge tubes were secured on an end-over-end mixer and agitated at about 30 rpm for 24 hours- Samples were centrifuged for 20 minutes using a RT6000B Sorvall centrifuge at 4000 x g and then filtered through a 0.2 u.m nylon syringe filter into a new centrifuge tube. The volume of aqueous supernatant was measured and refrigerated at about 5C until analyzed for the parent compound using an LC-MS. The blank and the control tubes were subjected to the same steps as the test systems, including filtering. Screening Test: Desorption Studies To each solid phase (pellet) was added a fresh volume of 0.01 M CaCI:, solution without the test chemical equal to that added in the adsorption test, 20 mL. The sample was mixed, centrifuged, filtered, stored, and analyses as was done in the adsorption studies. This desorption step was repeated a second time, resulting in two washings that were analyzed separately. Calculations Data calculations included: 1. The percent of APFO adsorbed. A: A = (G - Ce x Vo)/G x 100 = x/G x 100 2. The percent of APFO which is desorbed, D; D = [(Cl + C2)V - (Vo - V)Ce]/x x 100 3. The percent of APFO which is not desorbed, R: R = [G - (Ce + Cl + C2)V]/x x 100 4. The adsorption coefficient, K': ' K'=(x/m)/Ce 5. The adsorption coefficient calculated as a function of the organic carbon content of the test material, K'oc: K'oc = K. (100/percent organic carbon) Where: 1. m = dry weight of soil employed (g) 2. Ce = concentration of APFO remaining in solution (V) in the adsorption step (u.g L"') 3. Cl = concentration of APFO in solution in the first wash (ug L'') 4. C2 = concentration of APFO in solution in the second wash (u.g L'") 5. Vo = original volume of solution employed (mL) 6. V = volume of solution obtained after the adsorption step (mL) 7; G = quantity of material recovered from the soilless control (jig) RESULTS AND DISCUSSION Of the nine materials tested, five of them (peat moss. Upstream sediment. East Wood soil. Garden Area soil, and Kaolin Clay) exhibited significant adsorption (greater than 25% of APFO added) at one or more of the added concentrations of APFO. Peat moss alone, however, adsorbed a significant amount at all three concentrations of added APFO; 50, 500, and 5,000 u.g APFO/L. Kaolin clay adsorbed a significant amount of APFO at 500 and 5,000 ug APFO/L. The Garden Area soil collected at Washington Works also adsorbed significant amounts of APFO at 500 u.g APFO/L. Upstream sediments from the Ohio River and East Wood soil adsorbed a Page 5 of 16 ISoffipanySanitized. Does not contain TSCA CBI DuPont EMSE Report No. 053-00 significant amount of APFO at 50 ug APFO/L only. Sand, Montmorillonite clay, Downstream sediment, and Sassafras soil did not adsorb a significant amount of APFO at any concentraticn ot the added APFO- Once adsorbed on peat moss, most of the APFO (>76%) did not desorb after two washings with a solution of 0.01 M CaCL. For the Kaolin clay, most the APFO adsorbed when added at 5 000 ug APFO/L desorbed with washing (>60%). At APFO added at 500 ug APFO/L, however an average of 98% did not desorb from the Kaolin clay after two washings. The East Wood soil, which adsorbed 46% of the APFO added at 50 ug APFO/L desorbed only about 2%. For the Garden Area soil 57% of the APFO desorbed when adsorbed from the 500 ug APFO/L solution. No measurable desorption of APFO from the Upstream sediment after two washings was observed when the APFO was added at 50 ug APFO/L. Page 6 of 16 eoffipany Sanitized. Does not contain TSCA CB1 DuPont EMSE Re TABLE 1. ADSORPTION-DESORPTION SCREENING STUDIES OF AMMONIUM PERFLUOROOCTAN Physical properties of test materials, Test material Moi iture coni entf 111 -" 1 - 1 o '0 Test Material Dry Wt., Sand Silt Clay m g % % % Organic Matter % Organ Carbo % Sand Peat moss Kaolin clay Montmonllonite Sassairass soil 0. 4 47 0.78 7:4 1.4 East Wood soil 14 Cjarden Area soil 9.4 Upstream sediment 13 Downstream sediment 9.0 f Based on drying at 105C for a minimum of 24 h. t Estimated from percent organic matter. ND is not determined. 4.0 100 0 0 ND 2.1 ND ND ND ND 4.0 0 0 100 ND 3.7 0 0 11)0 ND 3.9 71 19 10 1 3.5 45 40 15 1.6 3.7 37 42 21 2.9 3.5 59 30 11 1.5 3.7 69 21 10 0.6 ND ND ND ND 0.58 0.93 1.68 0.87 0.35 Page 7 of 16 TABLE 2. Chemical properties of test materials. DuPont EMSE Rep Test material pHf CECf m eq/1 UUg Exchangeable cations, meq/100g C-'a m Na K H Sand Peat moss m\ 6.6 ND ND ND ND ND 3.7 ND ND ND ND ND ND Kaolin clay 3.8 3.3 NT) ND ND ND ND MontmonHonite 7.6 120 ND ND ND ND ND Sassatrass soil 6.3 2.8 2.10 0.51 0.01 0.21 0.00 East Wood soil 5.6 Garden Area soil 4.7 Upstream sediment 7.1 Downstream 6.9 sediment 10 4,19 0.61 0.04 0.15 5.01 17.2 5.85 1.15 0.01 0.1H 10.01 7.4 6.08 0.86 0.27 0.15 0.04 5.9 4.54 1.09 0.20 0.09 0.00 f 1:1 test material to water. ^ Cation Exchange'Capacity. Exchangeable cations in milliequivalents/100 g test material determined by a modified ammonium acetate method. 1 ND is not determined. Page 8 of 16 DuPont EMSE Re TABLE 3. Absorption/desorption screening test data. Test material [sand Nominal APFO concentration Original solution volume, Vo Volume ot solution after adsorption step, V APFO in solution after adsorption step, APFO in first A Ce i wash,Cl !^gL-1 mL mL ^L-1 ^gL-1 0.00 0.05 0.5 5 20,0 -20,0 20.0 20.0 18.0 2.79E+01 ND 18.0 1.39E+02 ND 18.0 4.98B+02 NU 18.0 3.80E+03 NO Peat moss 0.00 0.05 0.5 5 20.0 20,0 20.0 20,0 18.0 18.0 18.0 18.0 4.00E+01 . 7.98E+00 6.55E+01 . 9.62E+02 . O.OOE+00 O.OOE+00 4.07E+01 5.87E+02 K-aolin clay U.OO 0.05 0.5 5 20.0 20.0 20.0 20.0 18.0 L65E+00 O.OOE+00 18.0 3.83E+01 NA 18.0 3.27E+02 : 3.31E+01 18.0 3.02E+03 : 4.52E+02 Montmorillonite 0.00 0.05 0.5 5 20.0 20.0 20.0 20.0 18.0 4.45E+01 O.OUE+00 18.0 4.68E+01 ND 18.0 3.80E+02 6.25E+01 18.0 3.69E+03 ND Page 9 of 16 w DuPont EMSE Rep TABLE 3 (cont'd) Test material Sassafrass soil Nominal APFO Original solution concentration volume, Vo Volume of solution after adsorption step, V ^gL-' mL mL u.oo U.OS 0.5 5 20.0 20.0 20.0 20.0 18,0 18.0 18.0 18.0 APFO in solution after adsorption step, Ce HgL-' O.OUE+00 4.33E+01 4.35E+02 3.63E+03 APFO in first A wash,Cl ^gL-' ND ND ND ND hast Wood soil 0.00 0.05 0.5 5 20.0 2U.O 20.0 20.0 18.0 18.0 17.8 18.0 7.50H-02 1,18E+01 3.98E+02 4.78E+03 O.OOE+00 1.63E+00 7.53K+01 7.44E+02 Garden Area soil Upstream sediment 0.00 O.U5 0.5 5 U 50 500 5000 20.0 20.0 20.0 20.0 20.0 20.0 20.0 20.0 18.0 18.0 18.5 17.0 18.0 18.0 18.5 18.0 1.15E+01 2.57E+01 2.76E+U2 3.68E+03 O.OOB+00 1.59E+01 4.12E+02 4.36H+03 6.93E+00 1.24E+01 1.19E+02 1-09E+03 O.OOE+00 8.50E-01 7.11E+01 7.71E+02 Page 10 of 16 DuPont EMSE Re TABLE 3 (cont'd) Test material Nominal APFO concentration Original solution volume, Vo Volume ot solution after adsorption step, V pgL-J mL mL Downstream sediment 0 20.0 18.5 50 20.0 18.0 500 20.0 18.0 5000 20.0 17.8 APFO in solution after adsorption step, Ce ^gL-1 O.OOb+00 1.99H+01 4.58H+02 5.54E+03 APFO in first wash,Cl UgL-1 O.OOE+00 O.OOE+00 4.63E+01 5.72E+02 Sassatrass soil 0.00 0.05 0.5 5 20.0 20.0 20.0 20.0 18.5 18.5 . 19.0 16.3 O.OOb+00 2.04E+01 4.94H+02 5.25B+03 O.OOH+00 4.50E-01 5.32E+01 8.40H+02 Page 11 of 16 DuPont EMSE R TABLE 4. Adsorption/desorption screening test calculations;. Test material Sand Vest moss. Kaolin Clay Montmonllonite yassatrass Soil APFO Adsorbed Nominal recovered from Material material Adsorbed Adsorption APFO concentration the soilless control, G Adsorbed, desorbed, material not coefficient, x x/m or Cs A D desorbed, R K' PSL-1 W /'g W'S % % % 0.00 0.05 0.5 5 0 0.896 9.99 83 -5.57E-01 -1.88E+00 3.50E-02 6.96E+UU -1.40E-01 -4.71E-01 8.77E-03 1.55+00 ... .Q...... -210 0 7 ND 1 . ..^^ . ... -- -ND 1 ......... NO ' ND NL ^ ND -5.01E-03 -2.93E-03 2.36E-05 4.U4E-W 0.00 0.05 0.5 5 . y "0.896 9.99 83 -7.99E-01 7.37E-OL 8:68E+00 6.3aE+Ol -3.77E-01 3.47E-'01" 4.09E+00 3.01E+01 LVALUE! 82 87 77 #VALUE"! -2 ,, ^ ... 23 LVALUE! 102 W 1111117711111 #VALUE! 4.36E-02 6.91E-02 3.28E-02 0.00 0.05 U.5 5. 0 0.896 ...... ..... y^....,-- y3 -3.30E-02 1.30E-01 3.45E+00 2.26E+01 -K.31E-03 3.26E-02 y.68E-01" 5.70E-IW BVALUE! 15 35 27 0 NU . ^ . 61 //VALUE! il/VALUE! 98 39 AiVALUE! 8.61E-04 2.71E-03 1.90E-03 0.00 ... .Q^.. ... .. ...^,,..... 5 u 0.896 9.99 83 -y.9UE-01 -3.90E-02 2.38JE+00 9.15E+UO -2.40E-01 -1.05E-02 6.44E-U1 "2.47E+00 LVALUE! -4 24 111111 II'11 1"11" LVALUE! WVALUE! ... ^. ....,, //VALUE! #VALUE! #VALUE! 79 #VALT)E!" #VALUE! -2.10E-04 .70G-03 6.75E-04 0.00 0.05 ...... ...y^ 5 U 0.^96 9.99 ^ O.OOE+00 O'.'CTOE+'OD #VALUE! ND 2.95E-02 7.48E-03 3 NL) 1.30E+00 3.2iiE-01 13 ND 1.04E+01 2.63E+00 12 NU - NU NU ND ND (VDIV/O! 1.76E-04 7.70E-04 7.26E^04 Page 12 of 16 TABLE 4 (cont'd) DuPont EMSE Rep Test material Bast Wood Soil APFO recovered Nominal APFO from the soilless concentration control, G X x/m or Cs Material Adsorbed, A Adsorbed material desorbed, D Adsorbed material not desorbed,R Adsorption coefncient, K' WL-1 W W ^g % . ^ % 0.00 0.05 0.5 5 ' 0 0.422 10.1 96.a -1.5011-03 l.ii6E-01 2.14ti+00 1.17E+00 -4.26E-04 6.35H-02 '/,93H-01 T12E+00 lVUlV/0! 46 iy -6 #\W/W 2 29 162 A'DIV/0! y'/ 39 -315 A'DIV/O! 5.39E-03 2.00E-03 2.34E-04 Garden Area Soil 0.00 0.05 0,5 5 0 ^ ^ ...... 10.1 %.y, -2.311i.01 -9.15E-02 4.5i{E+00 2.32E+01 -6.30E-02 -/.15E-03 173011+00 7.501i+00 #D1V/0! -18 44 iy -64 -2142 57 51 164 2726 34 9 -5.47E-03 -2.70E-04 4.72E-03 2.04E-03 Upstream iSediment 0 50 500 5000- 0 0.422 10.1 96.s O.OOE+00 1.05E-01 U6E+00 9.52E+00 O'OOH+OU 4125E-02 6;27E-01 3.23E-1-00 #VALUH! 27 Ib 3 #VALUL! -11 56 M LVALUE! 90 I'/ -82 LVALUE! O.OOE+00 O.OOE+00 7.64E-04 Uownstieam Sediment 0 50 500 5000 0 0.422 10,1 96.y O.OOE+00 2.35E-02 9.36E-01 -1.40E+01 U:OOE+00 ~2:llii-02 "4:40]:i-01 -2.29E+00 #VALUE! #VALUE! 9 -ai 71111111111 5 -23 13 LVALUE! 100 34 259 LVALUE! 1.15E-03 9.75E-04 -4.11H-04 Sassatrass Soil 0.00 0.05 0.5 5 0 0,422 10.1 96.a O.OOH+00 1.35^-02 2.1^-01 -y.2yH+oo O.OOE+00 1.46H-02 1.19E-01 T20E+00 LVALUE! 6 0 -17 #VALUli! -44 iyo -107 LVALUE! a4 -201 -2450 LVALUE! 7:35E-04 2.43E-04 2.24E-04 t ND = Not determined. Page 13 of 16 DuPont EMSE Repo FIGURE 1. Adsorption isoline ofAPFO onto Sand, Peat moss. Kaolin clay, Monlmorillonite clay, and Sassafras soil. 2000 3000 Ce, ug C-8 S-'1 Page 14 of 16 5000 ' DuPont EMSE Re FIGURE 2; Adsorption isoline ofAPFO onto East Wood soil, Garden Area soil, Upstream sediment, and downstrea 0 1000 2000 3000 4000 5000 6000 Ce, ug C-8 L'1 Page 15 of 16 DuPont EMSE Report No. 053-00 Reference: 1 US EPA. 1998. Fate, transport and transformation test guidelines: OPPTS 835.1220 sediment and soil adsorption/desorption isotherm. United State Environmental Protection Agency Office of Prevention, Pesticides, and Toxic Substances. EPA712-C-98-048. January 1998 2 Olphen, H.V., and J.J. Fripiat (eds.). 1979. Data handbook for clay materials and other non- metallic minerals Pergamon Press- New York 346 pp. tSofflpSfiy Sanitized. Does not contain TSCA CB1 Page 16 of 16