Document 9Jg071dyJwz9GgjQJJ3B5ZMbe

RX&-O05I - yf c . AIR/WATER PARTITION COEFFICIENT TEST SUBSTANCE Identity: Perfluorooctanesulfonate; may also be referred to as PFOS or FC-95. (1-Octanesulfonic acid, 1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,8heptadecafluoro-, potassium salt, CAS # 2795-39-3) Remarks: The test substance is a white powder. No information was recorded on the purity. METHOD Method: There is no standardized methodology used to determine this value for regulatory purposes. The experiment was designed by Dr. Richard Purdy of 3M's Environmental Laboratory and Don Mackay of D. Mackay Environmental Research Limited. GLP (Y/N): No Year completed: 1999 Remarks: The following method was devised and used: 1. Weigh approximately 0.01 gram of the test substance directly into a tared 250-mL Pyrex beaker. Record weight. 2 . Transfer 200 mL of NANOpure water into the beaker using a Class A glass volumetric pipet. 3. Prepare solvent blank sample. Using a gas-tight syringe, transfer a 250 pL aliquot of NANOpure water into a 25-mL Class A glass volumetric flask partially filled with 50% methanol / 50% ammonium acetate buffer reagent. Bring to volume with 50% methanol / 50% ammonium acetate buffer reagent. Ampulate in an amber glass autosampler vial. 4. Mix and sonicate the test substance in water sample (50 pg test substance/mL target nominal concentration) for approximately 10 minutes to ensure dissolution of the test material. 5. Prepare the control sample. Transfer a 250 pL aliquot of the test substance in water sample into a 25-mL Class A glass volumetric flask partially filled with 50% methanol / 50% ammonium acetate buffer reagent. Bring to volume with 50% methanol / 50% ammonium acetate buffer reagent. Ampulate in an amber glass autosampler vial. 000095 6. Place the test substance in water sample beaker on a hotplate and bring solution to a boil. After approximately 10 ml_s (5%) of water has evaporated, remove beaker from hotplate and cool to room temperature in an ice-water bath. Transfer contents of sample into a graduated cylinder and record actual volume. 7. Process a 250 pL aliquot of sample as described above for solvent blank and control samples. 8. Return sample to original beaker and bring sample to boil. 9. Repeat steps 6-8 until sample has evaporated to 100 mLs. Submit all ampulated samples for LCMS analysis. RESULTS Kaw: 0* Temperature C: Not recorded. Remarks: *Don Mackay provided the following interpretation of the analytical results: "As I interpret the lab results they established an initial concentration of 50 mg/L in 200 mL water then distilled off 10 mL aliquots and analyzed the residue. They then calculated the percentage of the original test substance present which remained in the beaker unevaporated. These `percentage recoveries'; ranged from 136 to 105 with no real trend. I conclude that the test substance did not evaporate to any measurable extent. This is a very sensitive method of measuring low air-water partition coefficients. It can be shown that if water and the solute evaporate equally (e.g., the contents do not change in composition as would occur with an azeotrope) then Kawor H is identical for water and the solute. For water, H is approximately 2400 Pa (approximately 20C) divided by 55000 mol/m3or 0.044 Pa m3/mol or a Kawof about 2 x 10-5. The test substance must thus have a Kaw considerably less than this, i.e. less than 2 x 10'6. It is thus essentially non-volatile from aqueous solution. This is probably because of its ionic nature. The simple expedient is to assign it a Kawof zero, i.e. is a type 2 involatile chemical in our nomenclature." DATA QUALITY Reliability: Klimisch ranking 2. Data has limited reliability. Sample purity was not noted. Study temperature was not recorded. 000096 CONCLUSIONS Testing indicates this substance is essentially non-volatile from aqueous solution. Submitter: 3M Company, Environmental Laboratory, P.O. Box 33331, St. Paul, Minnesota, 55133 REFERENCES Study conducted at the request of 3M Company by Wildlife International, Ltd. of Easton, Maryland. Study review by Don Mackay of D. Mackay Environmental Research Limited, OTHER Last changed: 5/1/00 000097 INTERNAL CO RRESPONDENCES TO: Dale Bacon - Env Lab 2-3E-09 Craig Burton - FC Tech. Center 236-3C-89 Mike Nash- OGC 220-12E-02 Bill W e p p n e r-C h e m EHS&R 236-1B-10 CC: Rich Purdy - Env Lab 2-3E-09 Joseph Fiksel - Battelle Columbus Denise Appleton - Env. Lab 2-3E-09 Janine Seiffert - Env. Lab 2-3E-09 FROM: SUSAN A. BEACH SUBJECT: Testing Results: Air-Water Partition Coefficient (KAW) for PFOS DATE: March 19,1999 Wildlife International conducted a study to estimate the air-water partition coefficient (KAW) for PFOS. There is no standardized methodology used to determine this value for regulatory purposes; thus it was conducted as a nonGLP study. The experiment was designed by Rich Purdy and Don Mackay. Wildlife International provided Rich and Don with analytical results; Don provided the interpretation below: "As I interpret the lab results they established an initial concentration of 50 mg/L in 200 mL water then distilled off 10 mL aliquots and analyzed the residue. They then calculated the percentage of the original PFOS present which remained in the beaker unevaporated. These "percent recoveries" ranged from 136 to 105 with no real trend. I conclude that the PFOS did not evaporate to any measurable extent. This is a very sensitive method of measuring low air-water partition coefficients. It can be shown that if water and the solute evaporate equally (i.e. the contents do not change in composition as would occur with an azeotrope) then KAWor H is identical for water and the solute. For water, H is approximately 2400 Pa (approximately 20C) divided by 55000 mol/m3 or 0.044 Pa m3/mol or a KAWof about 2 x 10 _s. PFOS must thus have a KAWconsiderably less than this, i.e. less than 2 x 10'6. It is thus essentially non-volatile from aqueous solution. This is probably because of its ionic nature. The simple expedient is to assign it a KAWof zero, i.e. it is a type 2 involatile chemical in our nomenclature". Please see the attached analytical results for more information. Questions should be directed to Rich Purdy. Regards, Attachment (1) 000098 \1 W ilrlllfe IntJer1LnAAtadVtA.iAoAAnt al 8598PChoonme:m(41e0r)c8e22D-8r6iv0e0 FEAaXst:o(n4,1M0)ar8y2l2an-0d63221601 FAX TRANSMISSION I f this transmission is not received correctly or ifpages are missing, please call Wildlife International Ltd. at (410) 822-8600 From: NOTES: Fax Number: (651) 778-6176 3 page(s) follow this cover sheet. Rich Purdy 33MMECnovriproonramtieonntal Technology and Safety Services Raymond L. Van Hoven Scientist Rich: Etdhanetcafliosnusdemidnmgysoa,ruyow,rmtiollepfthirnoodvdiaodcueotalminnype,laeadtndedidtiidonanstatarluesmxupmeenmrtiamalrecynottnahdleidtPeioFtanOilssSu. maIimrl-owaorakyt.eforPrpwleaaartrsidetitdooonsncpooeetafhkfeiicnsigietanwtteietthxopyceooruinmitnaecntthtmeinenceltuoarddifniusgtcuutrhsees. 000099 WILDUTE INTERNATIONAL, LTD. PFOS Air-Water Partition Coefficient Sequence LD.: 12JAN99 Project No.: 454C-101 Date of Analysts .01/12/99 Sample Name 4466775SAA--000011AA34 4675A-001A2 4675A-001A1 4675A-001A4 4675-001A2 33773366--O00011AA34 3736-001A2 3736-001A1 AWP1.XLS Vial (ng/mL) 1 250 2 500 3 4 750 1000 9 250 13 750 18 250 19 500 20 750 21 1000 Peak Ana 4155837 7388823 10491144 13024361 4246855 11036778 4308786 8493724 10834410 13561071 12195.2 1437081.661 537.33 355408.849 0.985 473031.497 515.1 8.000 1.1526E+14 #N/A 1790070380970 #N/A Fit 222.9372 488.0412 742.4307 950.1538 230.4007 787.1725 235.4790 577780..65472884 994.1639 Y -intercept SLRO2PE Sample Identification 4S4C-101-REB-1 454C-101-AWP-1 454C-101-AWP-2 445S44CC--110011--AAWWPP--34 454C-101-AWP-5 4S4C-101-AWP-6 4S4C-101-AWP-7 4S4C-101-AWP-8 454C-101-AWP-9 4S4C-101-stabOity N om inal Concentration (ug/mL) 0.0 50.00 5527..6134 60.61 64.94 69.44 75.63 80.65 8570..7020 Vial No. 5 6 7 8 10 11 12 14 15 16 22 Peak Area 178690 9753678 8606177 8811737 9642044 10220321 11137255 11133423 11851738 13073257 7869398 Initial Volume (mL) 0.250 0.250 0.250 0.250 0.250 0.250 0.250 0.250 0.250 0.250 0.250 Y-evaluate (ng/mL) - ((Peak area-y-intercept)/slope) Analytical result (ng/ntL) - (Y-evaluate * dilution factor) Dilution factor -( Final volume/initial volume) Percent recovery - [analytical result (ng/mL)/nommal concentration (ng/mL)] X 100 All spreadsheet calculations performed using EXCEL 5.0 V in the hill precision mode. Final Volume (mL) 25.0 25.0 25.0 25.0 25.0 25.0 25.0 25.0 25.0 25.0 25.0 114231790582 0.9847 '$ H 3 - W Dilution Factor 100.000 100.000 100.000 100.000 100.000 100.000 100.000 410000..000000 100.000 100.000 Y-Evaluate Analytical Result (ng/mL) (ug/mL) 68<12.955087 587.8639 604.7197 672.8047 720.2233 795.4116 <25.0 68.1959 58.7864 60.4720 67.2805 72.0223 79.5412 795.0974 79.5097 853.9990 85.3999 954.1632 95.4163 527.4482 52.7448 Percent Recovery (V .) NA 136.4 111.7 105.8 111.0 110.9 114.5 105.1 105.9 108.8 105.5 CERTIFIED COPY OF THE ORIGINAL i-n M l -- INITIATE DATE OliJihJl L u i / oJ OOOIOO Wildlife International Ltd. METHOD OUTLINE FOR THE DETERMINATION OF PFOS AIR-WATER PARTITION COEFFICIENT Project Num.ber.454C-101 1. Weigh appproximately 0.01 gram of PFOS (WIL# 4675A) directly into a tared 250-mL Pyrex beaker. Record weight. 2. Transfer 200 mL of Nanopure water into the beaker using a Class A glass volumetric pipet. 3. PAiancrmteeoptpaaautre2leab5tseu-omfilfnvLeeranCnrtelbaaamglsasenbnAekt.rgsgaBllamarssipsnslvgeao.utlotuUovmssoaienlmtugrmipcaleefgrlwaavssiitk-ahtlip.g5ah0rt%tisaylmlryientfghielal,entdoralw/n5is0tfh%er50aam%25mm0oenptiLhuamanloiaqlc/u5eot0at%toefabNmuafmfneoorpnruieuraemgenwt.ater 4. Mix and sonicate the PFOS in water sample (50pg PFOS/mL target nominal concentration) for approximately 10 minutes to ensure dissolution of the test material. 5. rPCerlaeagpsesanrAte. tghBlearsicnsogvnottorlouvlmosleautmrmipcelefwl.aistTkhrap5na0sr%tfiearmllayet2fh5ial0lneodplL/w50iatl%hiq5ua0om%tmomof tnehituehmaPnFaoOcl/eS5t0ait%newbaumaftefmerrosnraeimuagmpelenatci.nettAoatmea pb2uu5lf-afmeterLin an amber glass autosampler vial. 6. Pi1cl0ea-cmweLatsthee(r5Pb%FatO)ho.SfTiwnraawtneasrtfeehrrasscaoemnvtpaeplneotsbraeotaefkdse,arrmeompnloeavihenotbotpealaakgteerraadfnruodamtberdhinocgtyplslloainltuedteaironnadntcdooroaelbctooorildr.oaoAcmtfuteaterlmvaopplpeurrmoatxeui.rmeaitnelayn 7. Process a 250 pLaliquot of sample as described above for solvent blank and control samples. 8. Return sample to original beaker and bring sample to boil. 9. Raneaplyeasitss.teps 6-8 until sample has evaporated to 100 mLs. Submit all ampulated samples for LCMS O O O lO l W il d l if e In t e r n a t io n a l ltd . LC/MS Operational Parameters for the Determination of PFOS Air-Water Partition Coefficient MASS SPECTROMETER: ION SOURCE: ION POLARITY: ION SOURCE VOLTAGE: ION SOURCE TEMPERATURE: ION MONITORED: LIQUID CHROMATOGRAPH: ANALYTICAL COLUMN: MOBILE PHASE: FLOWRATE: INJECTION VOLUME: R U N TIM E: Perkin-Elmer Sciex API 100 LC Mass Spectrometer Perkin-Elmer Turbo Ionspray Negative 5200 V 450 C 49S.6 amu Hewlett-Packard 1090 Series II Keystone Betacil C-18 (2 mm ID, 100 mm, 3 pm particle size) 65% methanol/35% ammonium acetate buffered water 240pL/min 10 pL 8 minutes 000102 DMER D. Mackay Environmental Research Limited 1664 Champlain Drive Peterborough, Ontario Canada K9L1N6 Tel (705) 740-P91 I GST Reg. # R -101420263 P 02 3M991 To: Dr. Rich Purdy, 3M Dr. Joyce SmiTffCooper, Bundle Dear Rich and Joyce I received the "Fluorochemical Fugacity Modeling Requirements" statement. Tt is generally in agreement with our expectations and we will do our best to satisfy your needs. The principal problem will, Lsuspect, be gathering the input data. We cam keep in close contact with you regarding the model development. Wc obtained from you the PFOS air-water partitioning data. As I interpret the lab results they established an initial concentration o f 50 mg/L in 200 mL water then distilled off 10 mL aliquots and analysed the residue. They then calculated the percentage o f the original PFOS present which remained in the beaker unevaporated. These "percent recoveries" ranged from 136 to 105 with no real trend. J conclude that the PFOS did not evaporate to any measurable extent. This is a very sensitive method o f measuring low air-water partition coefficients. It can be shown that if water and the solute evaporate equally (Le. the contents do not change in composition as would occur with an azeotrope) then KAWor H is identical for water and the solute. For water H is approximately 2400 Pa (approximately 20"C) divided by 55000 mol/m3or 0.044 Pa mJ/mol or a Kaw o f about 2 x 10'5. PFOS must thus have a KAWconsiderably less than this, i.e. less than 2 x 1O'4. It is thus essentially non-volatile from aqueous solution. This is probably because o f its ciohneimc incaatluirne.ouTrhneomsimenpclleateuxrpee.dient is to assign it a KaWo f zero, i.e. it is a type 2 involatile Wc did sample EQC model runs using a KAWo f zero, and partition coefficients L/kg for soil-water o f 2.4, sediment-water o f 4.8 and fish-water (dimensionless) o f 1000. The dimensionless partition coefficients are higher by a factor corresponding to the density. The degradation half lives were all set at 10 years. I attach the Level 1,11 and III results. 1whitehT2^0%veli1nrseosiul.lts show that PFOS has a strong tendency to remain in water, i.e. typically 80% The Level II results show an identical distribution. The major loss is by advcction in water with 000103 P 03 only very slow degradation. The overall persistence in a region is controlled by the water residence lime. The Level 111 results show that:If discharged to air it will rapidly deposit to soil (90%) and water (10%). If discharged to soil it tends to remain there with the major loss being run-off to water because o f its low suiption tendency. If discharged to water it tends to remain in solution and is subject to removal by advective flow (90%). There is little sorption to sediments. ** In summary, it behaves much as one would expect o f strongly ionic compound. I believe it is important to measure real partition coefficients for inclusion in the model and perhaps refine the halflives. In the present regulatory climate a substance which is so persistent is gwoeiankgnteosscoinmtoe tuhnedmerovleecruylec?lose scrutiny. I wonder if it is possible to build a degradation In conclusion, wc are ready and willing to do modeling at your request. Please regard this as just a small first step. Yours truly Don Mackay DM/nm 000104