Document nMpmNwZp1GRbeZ20qNMdn881

29) OECD 104-OPPTS 830.7950, vapor pressure by spinning rotor gauge, 454C-127 c SANITIZED L DEC 09 2003 DETERMINATION OF THE VAPOR PRESSURE OF PERFLUOROBUTANESULFONATE, POTASSIUM SALT (PFBS) USING THE SPINNING ROTOR GAUGE METHOD WILDLIFE INTERNATIONAL, LTD. PROJECT NUMBER: 454C-127 3M ENVIRONMENTAL LAB PROJECT NUMBER: E00-1429 OECD Guideline for Testing of Chemicals, 104, Vapour Pressure Cuwe U.S. EPA OPPTS 830.7950 Vapor Pressure AUTHORS : Frank J. Lezotte, B.S. Raymond L. Van Hoven, Ph.D. Willard B. Nixon, Ph.D. STUDY INITIATION DATE: November 26,2001 STUDY COMPLETION DATE: April 29,2002 SUBMITTED TO: 3M Corporation Environmental Laboratory Building 2-3E-09 935 Bush Avenue St. Paul, Minnesota 55106 Wildlife Internutionul, Ltd. 8598 Commerce Drive Easton, Maryland 2 1601 USA +- 1 (410) 822-8600 _- Page 1 of 36 wildlife Internationnl, Ltd. Project Number 454C-127 -2- GOOD LABORATORY PRACTICE COMPLIANCE STATEMENT SPONSOR: 3M Corporation TITLE: Determination of the Vapor Pressure of Perfluorobutanesulfonate, Potassium Salt (PFBS) Using the Spinning Rotor Gauge Method WILDLIFE INTERNATIONAL, LTD. PROJECT NUMBER: 454C-127 3M ENVIRONMENTAL LAB PROJECT NUMBER: EOO- 1429 STUDY COMPLETION April 29,2002 The study was conducted in compliance with Good Laboratory Practice Standards as published by the U.S. Environmental Protection Agency, 40 CFR Part 792, 17 August 1989; and OECD Principles of Good Laboratory Practice (ENV/MC/CHEM (98) 17); with the following exceptions: The determination of stability of the test and reference substances under the conditions of storage at the test site, were not determined in compliance with Good Laboratory Practice Standards. STUDY DIRECTOR: Chemist SPONSOR APPROVAL: Sponsor's Representative Kent R. Lindstrom DATE wildlife International, Ltd. -3- Project Number 454C-127 QUALITY ASSURANCE STATEMENT This study was examined for compliance with Good'Laboratory Practice Standards as published by the U.S. Environmental Protection Agency, 40 CFR Part 792; and OECD Principles of Good Laboratory Practice, (ENVRLICICHEM (98)17). The dates of all inspections and audits and the dates that any findings were reported to the Study Director and Laboratory Management were as follows: ACTIVITY: DATE CONDUCTED: DATE REPORTED TO: STUDY DIRECTOR: MANAGEMENT: System Configuration December 17, 2001 December 17, 2001 January 16,2002 Test SubstancePreparation December 26,2001 December 27, 200 1 January 2,2002 Raw Data, Draft Report Final Report January 15 to 17,2002 April 29, 2002 January 17,2002 April 29, 2002 January 18, 2002 April 29, 2002 'WildEve International, Ltd. -4REPORT APPROVAL Project Number 454C-127 SPONSOR: 3M Corporation TITLE: Determination of the Vapor Pressure of Perfluorobutanesulfonate, Potassium Salt (PFBS) Using the Spinning Rotor Gauge Method WILDLIFE INTERNATIONAL, LTD. PROJECT NUMBER: 454C- 127 3M ENVIRONMENTAL LAB PROJECT NUMBER: E00-1429 STUDY DIRECTOR: Frank J. &e, Chemist B.gw-1 MANAGEMENT: Willard B. Nixon, Ph.D.' Director of Analytical Chemistry @.?h DATE WildlifeInternational, Ltd. Project Number 454C-127 -5- TABLE OF CONTENTS TitleKover Page.......................................................,............................................................................. 1 Good Laboratory Practice Compliance Statement ................................................................................... 2 Quality Assurance Statement ..................................................,............................................................... 3 Report Approval................................................................................................................. Table of Contents ................................................................................................................................... 5 Summary..................:............................................................................................................................. 7 Introduction........................................,.................................................,................................................. 8 Objective................................................................................................................................................ 8 Experimental Design ....., ............................................. .................................................................. 8 Materials and Methods ..........,...............,,..................... ........ ....... 9 Test Substance ...................................................................................................................... Reference Substances ......................... ...... ................................................................ 9 System Configuration ........................................................................................................... Test Procedures Calculations.. . . . . ...................................... . ............. .................................................................................... ....... .. .. ............. Results and Discussion ..............,................,............................ ...... .................... 12 References........................................................ ............. . ............ .. .. ....., ..... ..., .. .........., , ........ .. ................14 TABLES Table 1. Typical Operating Parameters for Pressure Measurements by Spinning Rotor Gauge .,...,,, ..... 15 *Table 2. Vapor Pressure Measurements for HexachlorobenzenerDDT and PFBS by the Spinning Rotor Gauge Method ...... ., , ..... . _... ............ _... ..,......,. ,., ,,...., .. . ... . , .. ,.. . . ..... .. . . .. ... , . ,, . . .. .16 Table 3. Out-gassing Rates for Hexachlorobenzene, DDT and PFBS by the Spinning Rotor Gauge Method . .., , ,.. ,..._,.. __ .................._ ..., _ ,.. .. . , .._ . _ . ... . , ,, , . . ,_ ., . .. _ . _ . _.. .. , _..._ . , _ . . . _..., , , , , , ,. , , _ ._ .. 1 7 wildlife International, Ltd. -6TABLE OF CONTENTS - Continued - Project Number 454C-127 FIGURES Figure 1. Diagram of high vacuum system configuration ................................................................... 18 Figure 2. Representative vapor pressure plots for hexachlorobenzene and the associated blank ..........19 Figure 3. Representative vapor pressure plots for DDT and the associated blank ............................... .20 Figure 4. Representative vapor pressure plots for PFBS and the associated blank.............................. .21 APPENDICES Appendix 1. Protocol, Protocol Amendment and Protocol Deviation ................................................. .22 Appendix 2. Certificate of Analysis for PFBS .................................................................................. ..32 Appendix 3. Personnel Involved in the Study ................................................................................... ..36 Wildlife International, Ltd. -7- SUMMARY SPONSOR: SPONSOR'S REPRESENTATIVE: LOCATION OF STUDY, RAW DATA AND A COPY OF THE FINAL REPORT: 3M Corporation Mr. Kent R. Lindstrom Wildlife International, Ltd. Easton, Maryland 21601 Project Number 454C-127 WILDLIFE INTERNATIONAL, LTD. PROJECT NUMBER: 3M ENVIRONMENTAL LAB PROJECT NUMBER: 454C-127 EOO- 1429 TEST SUBSTANCE: STUDY: TEST DATES: Perfluorobutanesulfonate, Potassium Salt (PFBS) Determination of the Vapor Pressure of Perfluorobutanesulfonate, Potassium Salt (PFBS) Using the Spinning Rotor Gauge Method Experimental Start (0ECD)- November 29,2001 Experimental Start (EPA) -December 27, 200 1 Experimental Termination - January 4, 2002 ed to be C 1.22 x Pa at 20 * 1.O"C using the spinning rotor WildliJe International, Ltd. Project Number 454C-127 -8- INTRODUCTION The vapor pressure of Perfluorobutanesulfonate, Potassium Salt (herein after referred to as PFBS) was determined using the spinning rotor gauge method. The study was conducted by Wildlife International, Ltd. for 3M Corporation at the Wildlife International, Ltd. analytical chemistry facility in Easton, Maryland. Tests were performed following procedures in the OECD Guideline for Testing of Chemicals, 104, Vupour Pressure Curve (1) and Product Properties Test Guidelines, OPPTS 830.7950, Vapor Pressure (2). Vapor pressure analyses were conducted from November 29 to January 4, 2002. Raw data generated by Wildlife International, Ltd. and a copy of the final report are filed under Project Number 454C-127 in archives located on the Wildlife International, Ltd. site. OBJECTIVE The objective of this study was to determine the vapor pressure of PFBS at 20 k 1.0 "C using the spinning rotor gauge method. EXPERIMENTAL DESIGN The vapor pressure of a substance is defined as the saturation pressure above a solid or liquid substance (2). The spinning rotor gauge (SRG) method of measuring vapor pressure is based on the measurement of the rotational frequency of a stainless steel ball, which is magnetically suspended within a vacuum chamber. In the presence of a sample in an isolated vacuum, the deceleration rate of ball rotation is proportional to the vapor pressure of the sample. Measurements were initiated with the determination of system background pressure and outgassingkak rate in the absence of sample. The background pressure and out-gassing leak rate were each determined in triplicate. The vacuum system and SRG were then exposed to the test substance, or a reference substance, maintained at 20 k l.OC, until a steady state pressure was obtained. The sample was then isolated from the vacuum pumps and the pressure increase was monitored at 30second intervals. The measurement cycle was repeated twice for a total of three vapor pressure determinations per sample. The vapor pressures of two reference materials and the test material were 4- determined from the intercept of the line fit to pressure increasi-data upon isolating the sample and SRG from the vacuum pumps. wildlife International, Ltd. Project Number 454C-127 -9- MATERIALS AND METHODS This study was conducted following procedures outlined in the protocol ``Determination of the Vapor Pressure of Perfluorobutanesulfonate, Potassium Salt (PFBS) Using the Spinning Rotor Gauge Method". The protocol was based on procedures found in OECD Guidelines for Testing of Chemicals, Method 104 (1); and U.S. EPA Product Properties Test Guidelines, OPPTS 830.7950 (2). Test Substance The test substance was received from 3M Corporation on March 27, 2000, assigned Wildlife International, Ltd. identification number 5216, and stored under ambient conditions. The test substance, a white powder, was identified as Potassium Perfluorobutane Sulfonate Lot 2), CAS Number 29420-49-3, expiration date: January 17, 2007. The test substance was further identified with the 3M environmental Laboratory test control and reference number TCR# 99131-39. The test control and reference number identified on the certificate of analysis was TCR#000 17-71. Correspondence from the sponsor inhcated that both numbers reference the same lot. The test substance purity was reported as 97.3%. Reference Substances Two reference substances were utilized in this study. The hexachlorobenzene reference substance was received from Aldrich Chemical Company on February 10, 1997, and was assigned Wildlife International, Ltd. identification number 3948 upon receipt. The reference substance, a powder, was identified as: Hexachlorobenzene; catalog no. 17105-0; Lot Number 04416KY; CAS Number 118-74-1. The reference substance had a reported purity of 99.9% and was stored under ambient conditions. The dichloro diphenyl trichloroethane reference substance (herein after referred to as DDT) was received from Sigma Chemical Company on January 20, 1999, and was assigned Wildlife International, Ltd. identification number 4749 upon receipt. The reference substance, a powder, was *. identified as: 1, I-bis (p-Chlorophenyl)-2, 2, 2-Trich1oroethane;Zot Number 77H36 14; CAS Number 50-29-3. The reference substance had a reported purity of 99.3% and was stored under refrigerated conditions. wildlije International, Ltd. Project Number 454C-127 - 10- System Configuration The high vacuum system consisted of a vacuum chamber configured with a mechanical vacuum pump (Leybold TRIVAC S 1,6 B), a turbomolecular pump (Leybold TURBOVAC 50), a spinning rotor gauge (Leybold VISCOVAC VM 2 12), all-metal isolation valves, and miscellaneous vacuum fittings required to assemble the components. The system also incorporated a pair of capacitance manometers, with an associated controller, for higher-level vapor pressure work. The capacitance manometers were not required in the present study. The valves and metal tubing of the h g h vacuum system were insulated with foam. The spinning rotor gauge controller was connected to a computer via the serial interface (RS-232 port). A diagram of the apparatus configuration is presented in Figure 1. The sample chamber consisted of a Pyrex tube (-2.5 cm O.D. X 12 cm) joined to a quick-fit type metal flange (NW-25). Empty sample chambers were used for background measurement. The temperature of the sample chamber was maintained at 20 -+_ 1.0"C during pressure measurements. Temperature control was achieved with a recirculating chiller bath system that was interfaced to the sample chamber via copper water jacket. The temperature of the sample chamber was periodically monitored using a digital thermometer. Test Procedures The entire system was initially evacuated to achieve acceptable vacuum pressure at the target operating temperature used for the study'(20 k lC). Under these conditions, the background deceleration rate (DCR) of the ball was monitored for at least thirty minutes to establish an offset value (background correction) for subsequent measurements with reference or test substance present. The parameters of the spinning rotor gauge were set to record a deceleration measurement every 30 seconds. Once obtained, the offset value (expressed as mean deceleration rate) was entered into the spinning rotor gauge controller. Typical experimental parameters for SRG measurements are summarized in Table 1. 4- For each sample type (reference and test substance), a 6ickground vapor pressure, due to a slow linear increase in pressure due to out-gassing and permeation, was deterniined a minimum of thrce times at 20 -t 1C using the appropriate molecular weight parameter (see Table 1). The sample chamber was evacuated to achievc a steady-state pressure. The mean and standard deviation of the wildlve International, Ltd. Project Number 454C-127 - 11 - steady state pressure were used as an indication of equilibration. After the system was pumped to a pressure less than 1.0 x Pa with a dnft less than 2 x Pds, the background pressure was recorded. Then the isolation valve between the vacuum pumps and the sensor head was closed and the pressure increase was monitored until a slow linear pressure increase was recorded. The cycle was then repeated twice to obtain three vapor pressure measurements per sample type. A one-gram sample of hexachlorobenzene and a one-gram sample of DDT were used as vapor pressure references to verify the accuracy of the system configuration. The vapor pressure of hexachlorobenzene measured by the SRG method was compared to published values of 2.6 x IO" Pa @ 20C by the gas saturation method and 1.1 x Pa @ 20C by the vapor pressure balance method (2). A molecular weight of 284.78 was entered into the SRG program for the vapor pressure measurement of hexachlorobenzene. The vapor pressure of DDT measured by the SRG method was compared to published values of 2.5 x Pa @ 20C (4). A molecular weight of 354.5 was entered into the SRG program for the vapor pressure measurement of DDT. A one-gram sample of the test substance, PFBS, was used for vapor pressure determination. A molecular weight of 298.9 was entered into the SRG program for the vapor pressure measurement of PFBS. The measurements were later calculated manually using 338.2 as the molecular weight. The manual calculations were required because the molecular weight entered into the SRG program did not incorporate the weight of the potassium cation. The vapor pressure of a material can be determined using the following equation (3). VP = ; BDENS x BDIAM 10 x /2 x 7 x~R x T x DCR Where: VP = Vapor pressure in Pa BDIAM = Diameter of the ball in the SRG in m BDENS = Density of the bail in the SRG in kg/m3 R = General gas constant (8.314 x 1O3 j kmoi-'K1) 6- T = Temperature in K DCR = Deceleration rate in s-' wildlife International, Ltd. Project Number 454C-127 - 12- Since the only variable to change was the molecular weight, the simplified equation below was used to determine the vapor pressure of PFBS using 338.2 as the molecular weight. V P k =JVP2x 298.9 + 338.2 Where: VPk= The vapor pressure of PFBS, potassium salt in Pa Calculations For each sample, the mean and standard deviation of the steady state pressure was calculated from pressure measurements made just prior to closing the valve to the vacuum pumps. Leastsquares-fit linear regression analysis was performed on vapor pressure measurements collected after the valves to the vacuum pump were closed to determine the outgassing/leak rate. A minimum of ten data points with a rate of change of less than 3% was used for the linear regression. In the absence of sample, the slope of the regression was equal to the outgassing/leak rate of the system, and the intercept was considered the baseline or background pressure. With sample present, the sample vapor pressure was also taken as the intercept of the corresponding outgassing regressipn line. Background subtraction of sample vapor pressure was not warranted, since background subtraction is not appropriate for the SRG method. RESULTS AND DISCUSSION The offset value was 8.99 x revolutions per second based on the average deceleration rate measured with an empty sample chamber. A sample calculation using the third measured vapor pressure for PFBS is presented below: VP = 1.86 x lo-' Pa VPI,= / (1.86 x x 298.9 + 338.2 *- = 1.75 s Pa %_ Individual and mean measured vapor pressures (intercept of linear regression functions) for the reference and test substance are presented in Table 2. The corresponding outgas rates (slope of linear regression functions) are presented in Table 3. wildlife International, Ltd. - 13 - Project Number 454C-127 The mean background vapor pressure of a blank tube using hexachlorobenzene parameters was 1.17 x Pa @ 20 f 1.0"C. The mean measured vapor pressure of hexachlorobenzene by the SRG method was 1.40 x 10" Pa @ 20 * l.OC. This vapor pressure was consistent with published values (2). The mean background vapor pressure of a blank tube using DDT parameters was 9.61 x Pa @ 20 f 1.0"C. The mean measured vapor pressure of DDT by the SRG method was 2.56 x 10" Pa @ 20 & 1.OC. ms vapor pressure was also consistent with published values (4). Representative vapor pressure plots for hexachlorobenzene, DDT and the associated blanks are presented in Figures 2 and 3, respectively. The mean background vapor pressure of a blank tube using PFBS parameters was 1.22 x 10" Pa @ 20 f 1.0"C. The mean measured vapor pressure of PFBS by the SRG method was < 1.22 x Pa @ 20 f 1.0"C. Representative vapor pressure plots for PFBS and the associated blank are presented in Figure 4. Sample Mean Background Vapor Pressure Pa Mean Vapor Pressure Pa Literature Value Pa Hexachlorobenzene 1.17 x 1O-' 1.40 10" '2.6 x 2 i . ~10" DDT 9.61 x IOe6 2.56 x io-s 2.5 PFBS 1.22 10-~ < 1.22 10`~ NA >ne using the gas saturation method (2). - 'Literature Value and Range hexachlorobenzene 'Range defined as literature value f 20 percent. using the vapor pressure balance method (2). Range Pa 1.6 x 10" - 5.7 x 10" 4.1 i o 4 - 1.5 32.0 1 0 --~ 3.0 10-~ NA - P wildlife International, Ltd. - 14- REFERENCES Project Number 454C-127 1. Organisation for Economic Cooperation and Development. 1995. Guideline for Testing of Chemicals, Method 104, "Vapour Pressure Curve". 2. U.S. Environmental Protection Agency. 1996. Product Properties Test Guidelines, OPPTS 830.7950, Vapor Pressure. Washington, D.C. 3. Leybold AG. Operating Instructions, VISCOVAC VM 212. Research Facility GmbH, Jiilich, F.R.G. 4. The Pesticide'Manual (Twelfth Edition). 2001. The British Crop Protection Council. wildlife International, Ltd. Project Number 454C-127 - 15 - Table 1 Typical Operating Parameters for Pressure Measurements by Spinning Rotor Gauge (3) PRESSURE GAUGE: Leybold VISCOVAC VM 212 Gauge Controller Leybold VISCOVAC VK20 1 Gauge Head Program parameter Description DISPLAY: DCR or PA Deceleration Rate or Pascal. MTIME: 30 Measurement time in seconds. OFFSET: TEMP: 8.99 x lo-*s-' 293 Mean DCR for empty sample tube. Temperature in K (273 + "C). MOLWT: See footnote 1 Molecular weight of measured gas, if known. VISC: See footnote 2 Viscosity of measured gas in Pa.s, if known SIGMA: 1.000 Describes properties of ball surface. BDENS: 7.72 io3 Density of stainless steel in kg/m3 BDIAM: 4.500 Ball diameter in mm. LIMITS: OFF Built-in triggering relays remain in rest position. OUTPUT OFF Analog output is passive. PFUNT: CONT Output to printer port is active. INTVL: 0 Printout interval in minutes. Zero switches this mode Off. SAMPLE: - 10 Number of values to print out in one interval of SAMP or STAT modes. Not used (CONT mode) P Effective molecular weight of air is 28.96 (3) Molecular weight of hexachlorobenzene is 284.78 Molecular weight of DDT is 354.5 Molecular weight of PFBS anion without the potassium cation is 298.9, Molecular weight of PFBS is 338.2 2 1.82 x lo-*,the viscosity of air at 2OoC,was entered. Value entered for viscosity does not significantly influence measured values < 1 Pa. A value of zero turns linearization off (3). .I+c- *-. Wildlije International, Ltd. Project Number 454C-127 - 16- Table 2 Vapor Pressure Measurements for Hexachlorobenzene, DDT and PFBS by the Spinning Rotor Gauge Method - Sample Measured Vapor Pressure Pa Mean Vapor Pressure Pa Blank 1.26 x 10`~ 1.17 (Hexachlorobenzene parameters) 1.35 x 1 0 - ~ 8.88 x lo4 Hexachlorobenzene 1.36 x 1 0 - ~ 1.40 1.33 x lo3 1.50 10" Blank (DDT parameters) 7.26 x 1.61 x 10" 5.48 x 9.61 x DDT 2.89 x 10" 2.31 10" 2.56 x lo-' 2.48 10" Blank 5.43 x 1.22 (PFBS parameters) 1.72 x 1.41 1 0 - ~ PFB S 3.19 x lov6 2.62 x < 1.22 x 1.75 10`' 'The range was defined as the mean vapor pressure f 20 percent. Range Pa' NA Standard Deviation 2.45 x 1.12 x ~ o--1~.68 10" 9.07 10" NA 5.69 x 2.05 x 10.' - 3.07 x lo-' 2.98 x NA 6.10 x NA 8.43 x P p - p I _ _ _ Wildlijk International, Ltd. Project Number 454C-127 - 17- Table 3 Out-gassing Rates for Hexachlorobenzene, DDT and PFBS by the Spinning Rotor Gauge Method Sample Measured Out-gassing Rate, Pds' Mean Out-gassing Rate, Pds Blank (Hexachlorobenzene parameters) 6.13 x lo-' 6.29 x lo-' 6.13 x 10" 6.18 x lo-' Hexachlorobenzene 1.14 10'~ 1.29 1 0 - ~ 5.82 x lo-' LOO ios7 Blank (DDT parameters) 5.49 x lo-' 5.36 x lo-' 5.84 x lo-' 5.56 x lo-' DDT Blank (PFBS parameters) 7.47 x lo-' 8.25 x lo-' 8.10 x lo-' 5.68 x lo-' 5.56 x 10" 5.75 x 7.94 x - 5.66 x lo-' PFBS 2.02 1.92 1.96 1.78 - - 'Out-gassing rate was defined as the slope of the linear regression. Standard Deviation 9.24 x lo-'' 3.73 x 2.48 4.14 ios9 - 9.61 x lo-'' 1.25 x 10.' >I wildlife International, Ltd. 1.6E-03 - 19- Project Number 454C-127 1 - OE-03 1 6.0E-04 1 2.OE-04 1 .OE-06 10:04:48 10:19:12 10:33:36 10:48:00 11:02:24 3.OE-03 7 Time 11:16:48 11:31:12 2.5E-03 1 I 2.OE-03 - (CI 0 cm n 1.5E-03 14:59:20 7 : j Rate of Change = 1.O E-03 eFigure 2. 5.OE-04 -I , , 14:38:24 % 1 1 14:52:48 15:07:12 Time -15:21:36 15:36:00 Representative vapor pressure plots for hesachlorobenzene (BOTTOM) and the associated blank (TOP). Single arrows indicate time of valve closing (vacuum isolation). Double arrows indicate data points used for liiiear regression. wildlife International, Ltd. - 20 - Project Number 454C-127 9.OE-04 8.OE-04 - 0 7.OE-04 - 6.OE-04 a 5.OE-04 1 0 v) a 4.OE-04 0,. 3.OE-04 3 2.OE-04 1 .OE-04 15:21:26 - i i Rateorchange. 2.00 % 1.OOEE--00771 , . 15:07:12 . . <, 1521 :36 1.8E-03 , i ,, 15:36:00 Time ,, j ,, 15:50:24 , , 16:04:48 1.6E-03 j1.4E-03 1.2E-03 i ! ! cn 1.OE-03 0 aa, 8OE-04 6.OE-04 4.OE-04 2 OE-04 1 OE-06 3c 07:55:12 08:09:36 08:24:00 08:38:24 '08:52:48 09:07:12 Tim e Figure 3. Representative vapor pressure plots for DDT (BOTTOM) and the associated blank (TOP) Single arrows indicate time of valve closing (vacuum isolation). Double arrows indicate data points used for liiiear regression. wildlife Intemational, Ltd. -21 - 1.4E-03 1.OE-03 4 Project Number 454C-127 4.OE-04 2.OE-04 , /+ Rate of Chance = 1.71 -1 OE-06 13:40:48 18E-03 1.6E-03 1.4E-03 1.2E-03 13:55:12 0 14:09:36 Time 14:24:00 14:38:24 08:12:19 I 5.5E-04 3.5E-04 1.5E-04 -5.OE-05 07:55:12 08:09:36 08:24:00 0&58:24 08:52:48 Time Figure 4 . Representative vapor pressure plots for PFBS (BOTTOM) and the associated blank (TOP). Single arrows indicatetiine of valve closing (vacuLim isolation). Double arrows indicate data points used for linear regression. wildlife International, Ltd. - 22 - Appendix 1 Protocol and Protocol Deviation Project Number 454C-127 e- - wildlife International, Ltd. - 23 - Project Number 454C-127 PROTOCOL DETERMINATION OF THE VAPOR PRESSURE OF PERFLUOROBUTANESULFONATE, POTASSIUM SALT (PFBS)USMG THE SPINNPIG ROTOR GAUGE METHOD 3M Environmental Lab ProjrciNo. E00-1429 Submittcd to 3M Corporation Environmental Laboratory ' Building 2-3E-09 935 Bush Avcnue St. Paul, Minnesota 5 5 106 WiIdlife Interna tiona1, L,td. 8598 Conmercc Drive Easton, Maryland 2 1601 (410) 822-8600 October 2 5 . 2001 wildlife International, Ltd. -24 - Project Number 454C-127 Wildlge International, Ltd. ............ _-. ........... -.. ............... -. ....... DETERMINATION OF THE VAPOR PRESSURE OF PERFWOROBUTANESULFONATE. POTASSIUM SALT (PFBS) USING THE SPEWING ROTOR GAUGE METHOD SPONSOR: 3M Corporation Eiwironmcntal Laboratoly Building 2-38-09 935 Bush Avenue St. Paul, Minnesota 55106 SPONSOR'S REPRESEKTATNE: TESTING FACILITY: . Wildlifc Internatioual. Ltd. 8598 Commerce Drive Easton, Maryland 21601 STUDY DIRECTOR: Frank 1.Lezotte. B.S.,Chemist Wildlife International, Ltd. LABORATORY MANAGEMENT, Willard B . Nixon. Ph.D. Managcr, Clieinistry FOR LABORATORY USE ONLY Project No.: 45'-tc' - 12..1 /y / L I Experimental Termination Date: ' '3 .al//* Inmale: .....ZL- 3 I ... PROTOCOL APPROVAL -./ / -..A.......k - 31 DATE ~ - - SPONSORS &PRESENTATIVE 4- PROTOCOL NO.: 454/1(125O 1/104/SUB454 i - 3M LAB PROJECT NO.E00-1429 wildlife International, Ltd. -25 - Project Number 454C-127 wildlife International, Ltd. -3- INTRODUCTION Wildlife International. Ltd. will dctcrmine the vapor prcssure ofPerfluorobutanesulfonate,potassium salt (hereaflcr referred to as PFBS) using thc spinning rotor gauge method. The study will be conducted at thc Wildlile International, Ltd. analytical chemistry facility in Easton, Maryland. The study will be performcd based on procedures in the OECD Guideline for Testing of Chemicals, 104, Vapor Prervure Curve (1) and Product Properties Tcst Guidelines, OPPTS 830.7950, VoporPrersure (2). Raw data for alI work perfomcd at Wildlife International. Lld. and a copy of the final report will bc filed by project number in archives located at Wildlife International, Ltd. or at an alternative location to bc specified in the final report. OBJECTIVE The objective of this study is to determine the vapor pressure of PFBS at 20 f l.OC using thc spiming rotor gauge method. EXPERIMENTAL DESIGN The spinning rotor gauge (SRG)method described in this protocol is applicable to both liquids and solids with vapor pressures in the approximate range of0.5 to IO4 Pascal (Pa). Measurement is initiatcd with a determination ofthe system background pxssurc and out-g;issing/leak rate in the absence ofsample. The background pressure and out-gassinglleak rate are determined at least thrce times. The vacuum syslem and SRG are then exposed to thc tcst substance, maintained a1a temperature of 20 f 1.O"C, until a steady st5te pressure is obtained. The sample and SRG are thcn isolated from the vacuum pumps and the pressure increase is monitored by the SRG at 30-sccond intctvals. The vapor pressure is detemined from thc intercept of the line fit to the pressure increase data upon isolating the- samp1.e and SRG from the vacuum pumps. MATERIALS AND METHODS Test Substance The test substance will be PFBS. The test substance was receivcd from 3M Environmental Technology and Safety Scrvices on March 27, 2000. assigned Wildlife International, Ltd. Identification numb& 5216, and stored under ambient conditions. The test substance, a white powdcr, was idcotified a: Potassium Perfluorobutane Sullbnatc 3 ,Lot 2). CAS# 29420-49-3, expiration date: March 2010. L-. I'ROTOCOL NO.: J54/102501/ 1 04/SUB454 3M LAB PROJECT NO, EOO-I429 'MlildliJeInternational, Ltd. -26- Project Number 454C-127 wiId1ije International, Ltd. -4- The test substancc was further identifiedwith the 3hd Environmental Laboratory test control and rcfcrcncc number TCR II 99131-39. The test substance purity was reported as 97.3%. Information on the characterizationof test, control or reference substances is required by Good Laboratory Practice Standards (GLP). The Sponsor is responsible for providingWildlife International,Ltd. written verificationthat thc test substance has been characterizedaccordingto GLPs prior to initiation ofthe study. Ifwritten verificationof GLP test substance charactcrization is not provided to Wildlife International, Ltd., it will be noted in the compliance statement of the final report. The Sponsor is responsiblc for all information related to the test substance and agrees to accept any unused test substance andor test substancecontainers remaining at the end of the study. Apparatus The high vacuum system consists ol' a vacuum chamber configured with a mechanical pump, o turbomolecular pump, a spinning rotor gauge, isolation valves, a sample chamber and miscellancous vacuum fittings. The sample chamber will be maintained at 20 f 1 . O T with a water bath conncctcd to 3 recirculating chiller. The system configuration and components may be adapted as necessary to achieve adequate vacuum, prcssure rcadings less than 1 x 10'' Pa with a drift of Less than 2 x l o 7Pa/s to conduct the study. The system configuration will be described in the raw data and summarized in thc final report. Test Praccdure Thc vacuum system will bc evacuated to achieve adequate vacuum prior to any analysis. Thc system may be heated, if necessary, to achieve adequate vacuum. An offset value (background deceleration rate) for the spinning rotor gauge will be determinedat the operating temperature used for the study. Thc sample chamber will be controlled at 20 f 1.0"C during vapor pressurc analysis. The rest ofthe apparatus may be at or above 20C. The background pressure and the rate ol' pressure increase due to out-gassing/le& rate and pcrmcation will be determined at least thrcc times The steady slate prcssure of the vacuum system in the presence of the test material will be determined at Icast three times. Background pressure and pressure - changes will each be measured for at least five minutes prior to and aftcr cycling the isolation valve to thc pump. wildlife International, Ltd. - 27 - Project Number 454C-127 WildlifeInternational, Ltd. -5- Two vapor pressure reference compounds, hexachlorobcnzenc and Dichloro diphenyl trichloroethane (DDT)or other appropriate compound(s), will beusedtoconfim the sysiem configuration and thc rneasurcment procedures. The background pressurc and the rate of prcssure increase due to out- gassingkak ratc and permeation will be determined at least three times for both compounds. Thc measured v9por pressure of the rcfcrcnce material is not used for calculating thc vapor pressure of the test substance, but will be reported and used for comparison with other measurement methods. Calculations The mean and standard deviation of the steady-state pressure will be calculated from the pressure measurerncnts made just prior to closing thc valves to thc vacuum pumps. A linear regression (least squares fit) will be performed on the vapor pressure measurementscollected aAer the valves to the vacuum pumps are closed to determine thc out-gassing/leak rate. A minimum of ten data points with a rate of change less than three percent will bc used for the linear regression. The out-gassing/leak ratc of thc systcm will be equal to the slope of the regression equation in the absence of sample. The uncorrected vapor pressure of the sample will be equal to the intercept of h e regression cquation, i.e. the vapor pressure at the moment the valves are closed. The mean vapor pressure determined for the blank sample chamber will be considered the baseline or background pressurc and will be subtracted from ench vapor pressure measurement for the test substance/reference compound if it exceeds one perccnt of the vapor pressure measurement for the test substanceheference compound. The m a n s and standard deviations of the vapor pressures and out-gassing/leak rates will bc calculated. For each reference compound, the mean vapor pressure must agree with published ranges for chat compound. If no range is available, the mean vapor pressure must not exceed 20 percent of the published vnpor pressure. Any sources used for thc published vapor pressures and/or vapor pressure ranges will be cited in the final report. For each material, individual vapor pressure measurements must not cxcced 20 percent of the mean vapor pressure for the results lo be accepted. Sample Handling nnd Safcty Important: The chemical, physical and toxicological properties of this product have not been fully investigated and its handling or use may be hazardous. Generally safe practice requirds that contact with .. the skin and eyes and breathing of vapors or fumes should be avoided. When not in use, the containcr should bc kept tightly closed. In case of eye contact tlush eyes with -plenry ofwater. Call aphysician. For PROTOCOL NO.:4j4/102501/101/SUB454 3M LAB PROJECTNO.E00-1429 wiIdI$e Intemationa1, Ltd. -28 - Project Number 454C-127 WildlifeInternational, Ltd. -6- skin contact wash with soap and water. All normal prccautions with respect to handling and storage will be taken (3). Sample and Test Substance Rctention Upon,complction oftcsting, portions of thc (est substance used as part ofthis study will be disposed of in accordance with federal, state and local regulations. The remaining portion of the test substance may be retained by Wildlifc International, Ltd., if mutually agreed upon, for future work. Otherwise, any unused portion of tbc test substance will be returned to thc Sponsor. RECORDS TO BE MAINTAINED Rccords lo be maintained for data gcnerated by Wildlife International, Ltd. will include, but not be limited to: 1. A copy of the signed protocol. 2. Identification and characterization orthe tes! substance, if providcd by the Sponsor. 3. Dates of initiation and completion of thc study. 4. Dates of expcrimental start and termination. 5. Storage conditions of the test substance. 6. Tcst substance use log. 7. Spinning rotor gauge pressure readings. 8. Statistical cnlculations. 9. Test conditions. 10. A copy of the final report. FINAL REPORT Wildlife International, Ltd will prepare a final report of the rcsults of the study. The report will include, but not be limited to the rollowing, when applicable: 1. Name and address of the facility perfoming thc study. 2. Dates upon which the study was initiated and complekd. 3. A statement of compliance signed by the Study Director addressing any exceptions lo Good Laboratory Practice Standards I'KO'I'OCOL NO.: 454/10250 1/ I 04/SUB454 --' 3M LAB PROJECT NO.E0U-1429 WildlifeInternational, Ltd. - 29 - Project Number 454C-127 WildlifeInternational, Ltd. -7- 4. Purpose and procedure, as stated in the approved protocol, including all amendmcnts and dcviations to the protocol. 5 . The test substance identification, including name,chemicalabstract number or code number, purity, composition, empirical formula. molecular formula, manufacturer's loubatch number, method of analysis. or other information provided by the Sponsor. 6 . Description ofthe test method or refercncc to the method used along with any modifications madc. lndividual and mcan valucs obtained for out-gassinglleak rates and vapor pressure. 7. Graphical representation of the data. 8. Description of any problems experienced and how they were resolved. 3. A statement prepared by the Quality Assurance Unit listing the dales that study inspections and audits were made and any findings that were recorded. CHANGING OF PROTOCOL Planned changes to the protocol will be in thc form ofwritten amendments signed by the Study Dircctor and the Sponsor. Amendments will be considered as part of the protocol and will be attachcd to the fiual protocol. Any othcr changcs will be in the form ofwritten deviations filcd with the raw data. All changcs to thc protocol will be indicated in the final report. GOOD LABOMTORY PRACTICES This study will be conducted in accordance with Good Laboratory Practice Standards for EPA (40 CFR Part 792); and OECD Principles of Good LaboratoryPractice(ENVNCICHEM (98) 17). Each study conducted by Wildlife International, Ltd. is routinelycxarnined by thc Wildlife International,Ltd. Quality Assurance Unit for compliance with Good Laboratory Practices, Standard Operating Procedures and the specified protocol. A statement of compliance with Good Laboratory Prnctices will be prepared for all portions of the study conducted by Wildlife Inlernational, Ltd. Thc Sponsor will be responsible Ibr compliance with Good Laboratory Practices for procedures performed by other laboratories. Raw data for all work performed at Wildlife International, Ltd. and a copy of the final report will be filed by project number in archives located on the Wildlife International, Ltd. site or at an alternative location to be specified in the final report PROTOCOL NO.:454/102501/104/SUB454 LC 3M LAB PROJECTNO.EOO-I429 wildlife Xnternational, Ltd. - 30 - Project Number 454C-127 - W i l d l i f eInternational, ......... Ltd. ~ Project Nuinber 454C-127 ... ........ -. ......... PagK 1 Of 1 AMENDMENT TO STUDY PROTOCOL STUDY TITLE: Dctcrmination of the Vapor Pressure of Prrfluorobutancsulfonate, Potxislum Salt (PFBS)Using the Spinning Rotor Gaugc Method PR0TOCC)L NO.: 454/IU2S01/104/SUB454 SPONSOR: 3M Corporation . SPONSOR STUDY NO.: E00-I429 AMENDMENT: Pagc 3, Test Substance Clmgc: expiration date; March 20 IO To: expiration date; January 17, 2007 AMENDMENT NO.: 1 PROJECT NUMBER: 454C-127 EFFECTIVE DATE: November 26,2001 REASON: The sponsor providrd a new cerbficatc of analysis wirh a revised expiration date LABORATORY MA~AGEMENT , SPONSOR'S REPRHENTATIVE - DATE DATE wildlife International, Ltd. -31- Project Number 454C-127 wildlife International, Ltd. IVLI Project No.:4542-127 Page 1 of 1 DEVIATION TO STUDY PROTOCOL STUDY TITLE: Determination of the Vapor Pressure of Perfliiorobutanesulfate, Potassium Salt (PFBS) Using the Spinning Rotor Gauge Method PROTOCOL NO.: 454/102501/104/SuB454 DEVIATION NO.: 1 SPONSOR: 3M Corporation PROJECT NO.:454C-127 DATE OF DEFACTO DEVIATION: January 15,2002 DEVIATION: The mean background vapor pressure for the DDT reference substancc was not subtracted from the reported vapor pressure. REASON: The subtractionof the background is inappropriate for this metJiod. IMPACT: Sincc the mean vapor pressure reported for DDT agrees with published values, then is no impact to the study. Frank TLezofte, B.S NY&//m/ LABORATORY MANAGEMENT Willard B Nixon, Ph D - ,/Y$. DATE' ` WildEveInternational, Ltd. - 32 - Appendix 2 Certificate of Analysis for PFBS Project Number 454C-127 WildlifeInternational, Ltd. - 33 - Project Number 454C-127 CEntre Anaiqtical Laboratork, Inc. 3048 Research Drive Slate College, PA 16801 www.cenlre1ab.com Fax: (814) 231-1253 or (814) 231-1580 AP~GJWICC Identification I . Calcium 2. Magnesium 3. Sodium' 4. Potassium' 5. Nickel I I I White, crystalline solid I Conforms 1. 0.003 wtJwt% 3. 0.768 wtJwt.% 4. 10.7 18 wt./wt.% 5 . <0.001 wt./wt.% 6 . 0.002 wtJwt.% 7. <0.001 wt/wt.% 1. Chloride. 2. Fluoride 3. Bromide 4. Nitrate 5 . Ninitc 6. Phosphate 7. Sulfate I Organic Acids' (IC) 1 Elemenral Analysis': I . Carbon 2. Hydrogen 3. Nitrogen I 4. Sulfur 5. Fluorinc - Theoretical Value = 14.2% Theoretical Value 0.0% Theoreiical Value = 0.0% Theoretical Vslue = 9.5% Theorctical Value = 50.6% 1. 0.016 wtJwt.% 2. <O.OOS wtJw.% 3. <0.040wifwt.% 4. 4.009wt./wt.% 5. <0.006wt/w.% G. 4.030 wtlwt.% 7. co.040 wrlwt.% 1 I . I 1.o wt./wt.% 2. 0.282wt/wt% 3. 0.465 w t J w t % 4 . 11.2 wtJwt.% 5 . 48 2 w./wt.% ~ COA023032-71 Revision 2 . d ~ Page I of) Wi1d1ife InternationaI, Ltd. - 34 - Project Number 454C-127 hone: (814) 231-8032 Fw.(814) 231-1253or(814) 231-1530 INTERIM CERTXFICATE 0F ANALYSIS Revirion 2 Centre Analytical Laboratories COA Reference #: 023-032 3 M Product: PFBS, Lot 2 Test Control Reference #: TCR-00017-71 Date of Last Analysis: 01/17/01 Expiration Date: 01/17/07 Storage Conditions: c -10 'C Re-assessment Date: 01/17/07 'Purity = 100% - (Total N h f R impurities, 2'07% +Total LCRVIS impurities. (5.56% - 4.99%*) +Total Metal impurities, 0.006% +Total inorganic anions, 0.016%) Total impurity from all tests = 2.662% Purity 100% - 2.662% = 91.3% c 3 * *1.93% of the NMR total impunty value is due to the presence of th$ JThis impurity is also observed in the LC/MS analysis at 4.99%. The impurity value is taken from the NMR analysis as it is deemed the more quantitative technique in the absence of standards (See impurity profile on page 3). 'Potassium and sodium are present as counterions and thus are excluded from the purity calculation. i ? 4Theoreticalvalue calculations based on the empirical formula, C ~ F ~ S O J X(M*W=338.2) COA07.3032-71 Revision 2.doc Page 2 of 3 *- wildlife International, Ltd. - 35 - Project Number 454C-127 w.cenlreJab.com 31-1253or (814)231-i580 INTERIM CERTIFICATE OF ANAL YSIS Revision 2 Centre Analytic& Laboratories COA Reference #: 023-032 3M Product: PFBS,Lot 2 Test Control Reference #: TCR-00017-71 L W S Purity Profile: ' Peak # I 2 3 Total Retention - Time (min) I Mass(s) J I 1 - 9.508 I 298.9 I I Identity PF-BS Area 186918 1629660 30835100 326.51678 YOImpurity ' 0.57 4.99 5.56 NMR Punty Profile: Component I CF~-CFZ-CF~-CFZ-SO,', I Linear Product Molecular Weight 298.9 Total Impurity - I Relative Weight Percent I 97.9 0.0.5 1.93 0.13 0.01 2.07 This work was conducted under EPA Good Laboratory Practicc Standards (40 CFR'IGO). Prepared By: n Scientist Centre Analytical Laboratories +L, Date 'Laboratory Manager, Centre Analytical Laboratories COA02303Z-71 Rcvision 2 . d ~ Page 3 of3 WildEveInternational, Ltd. - 36 - Appendix 3 Personnel Involved in the Study Project Number 454C-127 The following key Wildlife International, Ltd. personnel were involved in the conduct or management of this study: 1. Willard B. Nixon, Ph.D., Director of Analytical Chemistry 2. Raymond L. VanHoven, Ph.D., Scientist 3. Frank J. Lezotte, B.S., Chemist