Document RK37Ook6BjD623MgyKYrV6Ln

BACK TO MAIN 3M EnvironmentalLaboratory Report No.E00-2192 Study Tit/e Screening Studies on the Aqueous Photolytic Degradationof PerfluorooctanoicAcid (PFOA) Data Requirement Consistent With: OPPTS: 835.5270 "Indirect Photolysis Screening Test" -and- OECD Draft Document "Phototransformation of Chemicals in Water - Direct and Indirect Photolysis", August 2000 Author Thomas L. Hatfield, Ph.D. Study Completion Date April 20th,2001 Performing Laboratory 3M Environmental Laboratory Building 2-3E-09, 935 Bush Avenue St. Paul, MN 55106 Project Identification a 3M Laboratory Report No: E00-2192 Total Number of Pages 148 Page 1 of 148 BACK TO MAIN 3M EnvironmentalLaboratory Report No. E00-2192 This page has been reserved for specific country requirements. Page 2 of 148 BACK TO MAIN 3M Environmental Laboratory Report No. E00-2192 Non - Compliance Statement Study Title: Screening Studies on the Aqueous Photolytic Degradation of Perfluorooctonic Acid (PFOA) Study Identification Number: E00-2192 By design, this study does not comply with the requirements of the US EPA Good Laboratory Practices Standards at 40 CFR Part 792 (TSCA). However, the 3M Environmental Laboratory Quality Assurance Unit has performed audits of all data, related documentation and final report. Test and reference substance receipt and use, dosing and incubation of the test system, and analyses were conducted and documented according to procedures developed by 3M, based on References 1 and 2. Sponsor Representative Date Page 3 of 148 BACK TO MAIN 3M Environmental Laboratory Report No.E00-2192 Quality Assurance Statement Study Title: Screening Studies on the Aqueous Photolytic Degradation of Perfluorooctanoic Acid (PFOA) Study Identification Number: E00-2192 This study has been inspected by the 3M Laboratory Quality Assurance Unit as indicated in the following table Inspection Dates 03/30/01-03/3I/O1 04/18/01-04/19/01 Phase Data Draft Report Date Reported to Management I Study Director 03/31/O1 03/31/O1 0411 910 1 04/19/01 Quality Assurance Unit Date Page 4 of 148 BACK TO MAIN 3M Environmental Laboratory Report No. E00-2192 Table of Contents Non.Compliance Statement.......................................................... ....................................... 3 Quality Assurance Statement ................................................................................................ 4 Table of Contents................................................................................................................... 5 Study Personneland Contributors......................................................................................... 7 Summary................................................................................................................................ 8 Introduction.............................................................................................................................. 9 Materials and Methods ........................................................................................................... 11 Chemical Characterization................................................................................................ 11 Method Summaries ........................................................................................................... 11 Deviations.......................................................................................................................... 13 Results and Discussion......................................................................................................... 14 Data Quality Objectives..................................................................................................... 14 Analytical Results .............................................................................................................. 14 Data Summary and Discussion........................................................................................ 15 Conclusions ........................................................................................................................... 18 References............................................................................................................................. 19 Signatures .............................................................................................................................. 20 Appendix A: Analytical Methods.............................................................................................. 21 Appendix B: Chemical Characterization................................................................................ 105 Appendix C: Kinetics Model and Kinetics Calculations.......................................................... 109 Appendix D: Representative Chromatograms....................................................................... 119 Appendix E: Soil Types and Characterizations...................................................................... 138 Appendix F: Light Intensity Measurements at 45" South Latitude (Miami FL) ....................... 140 Appendix G: Characteristics of the Spectral Output of the Suntest Instruments..................142 Page 5 of 148 BACK TO MAIN 3M Environmental Laboratory Report No. E00-2192 List of Tables Table 1. Typical Sample PreparationScheme Used in the Present Investigation...............12 Table 2. Observed Productsand Mass Balance Determinationsfor pH 7 Buffer. Synthetic Humic Water and Iron Oxide Containing Water ................................................................. 16 List of Figures Figure 1. Structures of the CompoundsTargeted by LC/MS Analysis................................. 9 Figure 2. Pooled concentration data from the iron oxide rich matrix.................................... 17 Page 6 of 148 BACK TO MAIN 3M Environmental Laboratory Report No. E00-2192 Study Personnel and Contributors Study Director Thomas L. Hatfield, Ph.D. 3M Environmental Laboratory Building 2-3E-09 935 Bush Avenue St. Paul, MN 55106 (651) 778-7863 Sponsor 3M Corporation 3M Environmental Laboratory Contributing Personnel Kent Lindstrom Anh Dao Vo 3M Environmental Laboratory Professional ServicesContributing Personnel Anthony (Tony) Scales Debra Wright Jan Schutz Rufat Mischiev (Pace Analytical Services, Inc., 1700 Elm St., Minneapolis, MN 55144) Kristin Terrell Jill Maloney Karen Johnson (Braun lntertec Corporation, 6875 Washington Ave. South, Minneapolis, MN 55439) Location of Archives Digital copies of original data, and all original paper data have been archived and will be retained in the 3M EnvironmentalLaboratory archives for at least I O years Page 7 of 148 BACK TO MAIN 3M Environmental Laboratory Report No. E00-2192 Summary We report here the results of studies performed to determine the aqueous photolytic behavior of perfluorooctanoic acid (PFOA) and to identify its primary degradation products. Our techniques are based on both EPA and OECD guidance documents.lS2 In this study, both direct photolysis (the interaction of light with the target molecule leading to a chemical change) and indirect photolysis (the interaction of light with the sample matrix to produce radical species that subsequently react with the target material) were studied using a synthetic light source. Neither direct nor indirect photolytic decomposition of PFOA were observed based on loss of starting material, nor were any of the predicted degradation products detected above their limits of quantitation. The rates of photolytic degradation are highly dependent on the experimental conditions. However, using an iron oxide (FenOs) photoinitiator matrix model, we estimate the PFOA half-life to be greater than 349 days. Page 8 of 148 BACK TO MAIN 3M EnvironmentalLaboratory Report No. E00-2192 Introduction Photolysis reactions, hydrolysis reactions and biodegradation are the primary routes of degradation of chemical compounds in the environment. Studies of photo-induced reactions yield information on the persistence of the parent material as well as information on the identity and stability of products formed. Photolytic reactions occur by two types of mechanisms. The first mechanism, direct photolysis, can be defined as the direct absorption of a photon by the target species that leads to a chemical change. The second mechanism, indirect photolysis, can be defined as a chemical or electronic excitation transfer from a light absorbing species to the test substance, which then undergoes some type of chemical change. In the present investigation, an artificial light source was used to study both the direct and indirect photolysis reactions of PFOA. The test material, PFOA, was dissolved in pH 7 buffered water and then exposed to simulated sunlight to test for direct phot~lysis?T'~o test for indirect photolysis, PFOA was dissolved into three separate matrices and exposed to simulated sunlight for periods of time from 69.5 to 164 hours. These exposures tested how each particular matrix would effect the photolytic decomposition of PFOA. The first test matrix was a pH 7 buffered aqueous solution to which H 2 0 2 was added as a well characterized source of .OH radicals?*6 This was used to test for the propensity of PFOA to undergo indirect photolytic decomposition. The second matrix contained Fez03 in water, as this matrix has been shown to generate hydroxyl radicals via a Fenton-type reaction in the presence of both natural and artificial sunlight.7g8The third matrix contained a standard humic material, diluted to levels that have been shown to approximate an environmental environment."' To effectively determine photolytic decomposition, the concentration of parent material must be monitored over time. Further, it is also important to understand what the degradation - products are and how much of each are formed. The present investigation quantified the parent material and two predicted degradation products (PFHpA perfluoroheptanoicacid and PFPA perfluoropentanoicacid) and monitoredfor any change in concentrationof PFHxA - perfluoro- hexanoic acid by LC/MS. Structures of the pertinent compounds are illustrated in Figure 1. Figure I.Structures of the Compounds Targeted by LClMS Analysis PFOA FFFFF F PFHxA PFHpA PFPA Page 9 of 148 BACK TO MAIN 3M Environmental Laboratory Report No. E00-2192 Because it was possible that volatile degradation products could be produced, we decided to monitor for selected C2 through c8 2-or 3- substituted pemuoronatedolefins (e.g. c8F16) and 1or 2-substituted hydrides (e.g. C8F17H) in both the iron-rich matrix and the pH 7 buffer matrix by dynamic purge and trap gas chromatography/mass spectrometry. The selected target compounds are representative of the types of volatile compounds that could be generated in the photolysis of PFOA. Determinationof a maximum kinetic rate constant (kp)- was based on the data from the iron rich matrix (as the experimental error was lowest in this matrix) using the following first order kinetics equation. (See Appendix C for a complete kinetic derivation and the exact mathematical solution. This equation is valid for essentially constant parent concentrations with a mean value p, and a standard deviation of q,.) Page 10 of 148 BACK TO MAIN 3M Environmental Laboratory Report No. E00-2192 Materials and Methods Chemical Characterization Information on the chemical characterization of both reference substances and control substances is presented in Appendix B. Method Summaries Copies of all analytical methods used in this investigation are attached in Appendix A. Equipment settings, conditions and complete quality control parameters are listed in the pertinent methods. UVNisible analysis were performedfollowing 3M EnvironmentalLaboratory Method ETS-946.0 "Operation and Maintenance of the Hewlett Packard 8453 UV-Visible Spectrophotometer" An aqueous saturated solution of PFOA was prepared and an initial UVNlS spectrum recorded. No absorbance above baseline over the range 190-1I 0 0 nm was detected. Sample preparationfor this analysisfollowed 3M EnvironmentalLaboratory Method ETS-8177.0 "Indirect Photolysis Screening Test in Synthetic Humic Water" or ETS-8476.0 "Preparation of Samples for Photolytic Exposure Studies in Aqueous Matrices". A typical sample preparation table for an indirect photolysis screening test is shown in Table 1 on the following page- The general method of sample preparation is as follows. For each time point under each condition shown in Table 1, ten 40-mL sample screw cap VOA vials were prepared: sample, duplicate, triplicate, sample spike, matrix blank, matrix blank spike (assured no accidental contamination of matrix by target compounds), direct photolysis sample, direct photolysis sample spike (assured that degradation observed was due to indirect photolysis and not another process), control blank and control blank spike (assured no accidental contamination of the blank had occurred). All vials contained 5 mL of appropriate matrix: pH 7 buffer, Fe+3at a 24X molar excess in water, or HZOZat 1:l molar equivalent, added every 24 hours. Aliquots of PFOA were added to the vials as indicated in Table 1. The initial time point vials (labeled as "Time Zero" on the sample preparationsheets in Appendix B) were then refrigerated at 4S"C. These samples served as controls with which to determine what change, if any, occurred during the time the remaining vials were in the photo-reactor. Exposed samples were placed upside down in a custom built holder in the photo-reactor. Unexposed samples were wrapped in aluminum foil, sealed in a plastic bag and placed under the sample rack inside the photo-reactorto assure that any degradation or difference in degradation was due to photolysis and not some other process. During the course of the exposure, a water bath held the temperature of the water surrounding the bottom of the vials (which contained the aqueous samples) at 25 f 3C. The temperature of the chamber itself was allowed to drift to 70 t-I0C. After exposure, the samples were removed for analysis. Selected portions of the sample setup were modified to accommodate additional samples and controls, to improve the quality control of the analysis or out of experimental necessity. Details of these modifications are shown on the individual sample data sheets shown in Appendix D. For example, the portion of the study employing iron oxide as a radical generating species was set up with both triplicate samples and duplicate sample spikes. Page 11 of 148 BACK TO MAIN 3M Environmental Laboratory Report No. E00-2192 The artificial light chamber used in this analysis was either a Suntest CPS+ or Suntest XLS+, the operation of which followed 3M EnvironmentalLaboratory Method ETS-9-44.0 "Operation and Maintenance of the Sunlight Exposure System, Immersion Unit, and Recirculating Water Chiller System". The output intensity was held at the desired level (680 w/m2)by a continuous feed back loop between an internal radiometerand the variable light source. Table 1. Typical Sample Preparation Scheme Used in the Present Investigation Description Ind. Photo. Sample Rep 1 Ind. Photo. Sample Rep 2 Ind. Photo. Sample Rep 3 Ind. Photo. Sample Spike Matrix Blank Matrix Blank Spike Direct Photo. Sample Direct Photo. Spike Control Blank Control Blank Spike Test Matrix (e.g. Fe203 in water) I I + + + + + + 0 0 0 0 Control Matrix (e.g. water) 0 0 0 0 0 0 + + + + Test Substance (PFOA) I + + + + 0 0 + + 0 0 Post Photolysis Target Analyte spike 0 0 0 + 0 + 0 + 0 + Sample Type (Conditions) Initial Initial Initial Initial . Initial Initial Initial Initial Initial Initial LC/MS* With W/out Y 4 YO2 X X X X X X X X X X X X X X X X X X X X GC/MS* With W/out Y4 w 2 X X X X X X X X X X X X X X X X X X X X Ind. Photo. Sample Rep 1 + 0 + 0 Ind. Photo. Sample Rep 2 + 0 + 0 Ind. Photo. Sample Rep 3 + 0 + 0 Ind. Photo. Sample Spike + 0 + + Mabix Blank + 0 0 0 Matrix Blank Spike + 0 0 + Direct Photo. Sample 0 + + 0 Direct Photo. Spike 0 + + + Control Blank 0 + 0 0 Control Blank Spike 0 + 0 + Light X X X X Light. X X X X Light X X X X Light X X X X Light X X X X Light X X X X Light X X X X Light X X X X Light X X X X Light X X X X Ind. Photo. Sample Rep 1 + Ind. Photo. Sample Rep 2 + Ind. Photo. Sample Rep 3 + Ind. Photo. Sample Spike + Matrix Blank + Matrix Blank Spike + Direct Photo. Sample 0 Direct Photo. Spike 0 Control Blank 0 Control Blank Spike 0 0 + 0 + 0 + 0 + 0 0 0 0 + + + + + 0 + 0 0 NoLight 11 X X X X 0 No Light X X X X 0 No Light X X X X + No Light X X X X 0 No Light X X X X + No Light X X X X 0 No Light X X X X + No Light X X X X 0 No Light X X X X + No Light X X X X + = added to test vial; 0 = NOT added totest vial; *Duplicate sets, one with H202,one wit1 u t (excludes e Humic material test where H202was not added) GC/MS analysisfollowed 3M Environmental Laboratory Method ETS-8-182.0 "Analysis of Fluorochemicals by Archon Purge and Trap Autosampler, Tekmar Purge and Trap Concentrator and Agilent Gas Chromatograph/Mass Spectrometer". Equipment settings, separation conditions and ions monitored are presented in this method. Equipment procedures for the GC/MS system followed 3M EnvironmentalLaboratory SOP ETS-9-49.0 "Routine Maintenance Page 12 of 148 BACK TO MAIN 3M Environmental Laboratory Report No. E00-2192 of Archon Purge and Trap Autosampler, Tekmar Purge and Trap Concentrator and Agilent Gas Chromatograph/Mass Spectrometer". The HPLC/MS analysis followed 3M Environmental Laboratory Method ETS-8-181.0 "Analysis of Photolysis Samples for Fluorochemicals by High Performance Liquid Chromatography With Mass Spectrometry Detection". Equipment settings, separation conditions and ions monitored are presented in this method. Deviations Calibration points were deleted at both ends of the PFHpA and PFPA curves. The lowest point on the curve was deleted due to poor integration and the two highest points were deleted to improve quantitation. The resulting effective concentration ranges were 5.5-219 ppb for PFPA and 5.2-206 ppb for PFHpA. While setting up additional studies on the photochemical behavior of other compounds in synthetic humic material, it was determined that the commercial humic material (Aldrich) did not contain the appropriate amount of dissolved organic carbon when the solution is prepared as recommend in reference I.The study director believes that this may have inhibited any possible photodegradation of PFOA and that these data should therefore be considered of screening quality only. Further, the samples from this matrix showed high levels of background ions with the same charge to mass ratio as that of the targeted materials and the manual intergration of some peaks was therefore required. PFHxA was identified as a possible degradation product. However, no suitable standard of this material could be obtained for the LC/MS portion of this study. Area of the chromatographic peak corresponding to the PFHxA anion (m/z = 313) were monitored. No changes greater than 10% relative were observed above the small amounts of PFHxA initially present in the PFOA standard. The PFOA samples numbered 0515-PFOAfe-07, and 30 (LC/MS) failed to meet spike recovery criteria in the iron oxide portion of this investigationand 0515PFOAfe-30and 90 failed control sample recovery. LC/MS method blanks 0515-PFOAfe-21,3Il45,55 showed low recovery. The GC/MS CCV R0602046 failed to pass criteria. The samples numbered 0515PFOAshw-04, 14 and 28 failed to meet spike recovery criteria and control sample 0515shw-28 showed low recovery in the synthetic humic portion of this investigation. Samples numbered 0515-PFOA-08, 50, 14 and 48 failed to meet spike recovery criteria in the pH 7 buffer portion of this investigation. Control sample 0515-PFOA-48 showed low PFOA recoverywhile four sample triplicate sets for PFPA analysis had high RSD. The GC/MS samples numbered 051500PFOAfe-067,077 and 090 failed to meet spike recovery criteria in the iron oxide portion of the investigation. Two samples, 051500-PFOAshw-12and 051500-PFOAshw-17 leaked. These failures represent only 2% of all samples and QC data and therefore have no significant impact on the results. During the exposure time of the pH 7 buffered matrix, the lamp went out and the temperature drifted. However, this represents less than 3% of the total time the samples were exposed. The conclusions are not effected and the kinetic determinations didn't rely on this data. Page 13 of 148 BACK TO MAIN 3M Environmental Laboratory Report No. E00-2192 ~~ Results and Discussion Data Quality Objectives The following data quality objectives are summaries of those found in the methods from Appendix A. Calibration curves. An acceptable coefficient of determination (R2)for linear curves is 0.990 or greater. Curve linearity, intercept, and quantitation accuracy should be verified, particularlyat upper and lower calibration limits. Residuals generated in curve-fitting must be within k 25% of the known standard value. Alternative methods of curve-fitting (e.g., quadratic) require a correlation coefficient (r) of 0.990 or greater. Reasons for the use of quadratic curve-fitting must be documented in the raw data. Solvent blanks, Matrix blanks, Control blanks. Blanks should show no more than 5% of the level of a high standard or CCV and should show less than 25% of the lowest point of the calibration curve. If solvent blanks show more than a 5% carryover, it may be necessary to rule out instrument contamination using duplicate solvent blank injections. If, after duplicate solvent blanks, there is still more than 5% carry-over, or the LOQ is adversely affected, the run should be stopped. This indicates that the instrument is contaminated and should be thoroughly cleaned. Sample spikes, Matrix spikes, Control spikes. Acceptable spike recoveries must be between 75 and 125% for both LC/MS and GC/MS analysis. Values outside these ranges must be documented and evaluated by the Team Leader or designated supervisor. Sample triplicates. All samples are prepared in triplicate (unless otherwise noted). Acceptable RSD precisionvalues are lessthan or equal to 25%. Values above 25% must be documented and evaluated by the Team Leader or designated supervisor. Continuing calibration verification (CCV). The analyte concentrations must not vary by more than Q5% of their expected values, relative to the initial calibration curve. Accept only those samples analyzed before the most recently accepted calibration verification. Reanalyze remaining samples with a new calibration curve. Limit of Quantitation. The limit of quantitation (LOQ) is equal to the concentration of lowest standard in the calibration curve that has an area greater than or equal to four times the solvent blanks and possessing a residual less than 25% of the actual value. Control Samples. Control samples must be within =5% of the nominal concentration. Analytical Results Data quality objectives for this study, outlined in the 3M laboratory method for this study (see Appendix A), were met, with the exceptions noted in the Deviations section. Calibration curves. Calibration curves were prepared according to the particular target at the required levels. For example, calibration curves for PFOA ranged from 25 to 2000 ppb. Calibration curves for degradation products for analysis by LC/MS typically ranged from 2200 ppb. Calibration curves for GC/MS analysis ranged from 1 ppb to 15 ppb. Using these standards, calibration curves were run before and after every analytical sequence. A correlation coefficient (r) of 0.990 or greater was achieved for all curves. Page 14 of 148 BACK TO MAIN 3M Environmental Laboratory Report No. E00-2192 Solvent blanks. All solvent blanks (MeOH) were less than 25% of the method LOQ. In certain cases, as noted in the Deviationssection, the LOQ was raised so that the solvent blanks met this criteria. Sample spikes. All spike recoveriesfor the LC/MS portion of the investigationwere between 75 and 125%, except where noted in the Deviations section. All spike recoveries were between 75 and 125% for the GUMS portionof the investigation, except were noted in the Deviations section. Sample triplicates. All sample RSD values were 25% or less. Continuing calibrationverification. All CCV sampleswere within 25% of the expected value. Limit of Quantitation. The LOQ varied dependant upon target. In some cases, the LOQ was defined as the lowest standard that was greater than 4X the solvent blank level, see deviations section for additional information. Method Blanks. All method blanks were below 25% of the LOQ. Control Samples. All control samples were within 25%. Data Summary and Discussion Direct and indirect photolytic decomposition of PFOA was tested in three separate matrices: a pH 7 buffered water, a synthetic humic water and an iron rich water. The samples were exposed to 680 w/m2 over the wavelength range of 290-800 nm and for time periods of 69.5-164 hours. Results from the quantitation of the parent material and the potential degradation products over time, as well as mass balance determinations, are shown in Table 2. As observed in Table 2a, direct photolytic decompositionof PFOA could not be detected within experimental error. Indirect photolysis was not observed in any of the three matrices - (the H202 rich pH 7 buffer - Table 2a, the Fe+3containing matrix Table 2b and the humic - containing matrix Table 2c). There was a slight increase (4 ppb) in the PFHpA concentration in the Fe+3and H202 containing matrix. However, because of the small size of the increase, it is unclear whether this increase was due to indirect photolysis of PFOA, to photodegradation of an unknown impurity in the PFOA standard, or to experimental error. Page 15 of 148 BACK TO MAIN 3M Environmental Laboratory Report No. E00-2192 Table 2. Observed Products and Mass Balance Determinationsfor pH 7 Buffer, Synthetic Humic Water and Iron Oxide Containing Water 2a. Sample Conditions Matrix: pH 7 Buffer, With and Without H202 I PFPA I PFHxA 164 hour Exposure nanomoles nanomols Ind. Photo. Sample' Initial Time Point Dir. Photo. Sample' Initial Time Point Ind. Photo. Sample' Exp. to Light 1 Dir. Photo. Sample` Ind. Photo. SamDle' ~ Dir. Photo. Sample' Exp. to Light Not Exuosed Not Exposed I Detection Limits I ND Nc ND Nc ND Nc ND Nc M ) I ND 0.292 Nc Nc I r4 0.178 0.394 0.385 0.404 55.1 0.385 56.8 0.356 56.4 I 0.356 55.7 I 0.2019 4.06 1 ND I 0.0095* I 99.3% 97.9% 95.8% 98.8% 97.9% 96.8% Vials initially contained 57.9 nMoles PFOA. 1. Indirect Photloysis Sample: These samples had H202added as a radical source, results are from triplicate samples. 2. Direct Photolysis Sample: These samples did not have H 2 4 added, results are from triplicate samples. *Sum total of all volatiles. ND = non detect. NC = No Change- Detection limit represents the change in the initial concentration that could be relaiably determined, see deviations section for discussion. 2b. Matrix: Fe203in Water, With and Without H202 Sample Conditions PFPA PFHxA PFHpA PFOA Volatiles BMalaansces 69.5 hour exposure Fe203W/yO; Fez03 WO/@O,` Initial Time Point Initial Time Point F e z 0 3 W/yO: Fez03WO/yO,' Exp. to Light Exp. to Light F e z 0 3 w/yO: Not Exposed Fe203WO/yO,' Not Exposed Detection Limits nanomoles nanomoles nanomoles ND ' Nc 0.846 ND Nc 0.808 ND NC 1.27 ND Nc 0.808 ND Nc 0.769 ND NC 0.789 0.729 f 0.348 0.500 nanomoles nanomoles 122 ND 121 ND 105 ND 116 ND 121 ND 118 . ND 2.03 0.0095` (percent) 106% 105% 91.8% 101% 105% 102% Vials initially contained 116 nMoles PFOA. 1. Samples had H202and Fe2O3 added as a radical generating species, results are from triplicate samples. 2. Samples contained just Fe203as a radical generating species, results are from triplicate samples. *Sum total of all volatiles. ND = non detect. NC = No Change- Detection limit represents the change in the initial concentration that could be relaiably determined, see deviations section for discussion. Sample Humic Water` Water* Humic Water` water' Humic Water` WaterZ Conditions 164 hour exposure Initial Time Point Initial Time Point Exp. to Light Exp. to Light Not Exposed NotExposed PFPA nanomoles ND ND ND NA I ND ND PFHxA PFHpA nanomoles nanomoles Nc 0.433 Nc 0.469 Nc 0.404 NA N4 Nc Nc I 0.394 0.391 I PFOA nanomoles 55.7 60.2 52.0 NA 59.3 55.0 Mass Balance (percent) ~ 96.8% 105% 90.5% NA I 103% 95.6% Vials initially contained 57.9 nMoles PFOA. 1. Samples contained Humic Materials, samples are from triplicate analysis. 2. Samples were plain water, results are from a single replicate. 3. Vial leaked, all data listed as NA or not applicable. ND = non detect. NC = No Change- Detection limit represents the change in the initial concentration that could be relaiably determined, see deviations section for discussion. Page 16 of 148 BACK TO MAIN 3M Environmental Laboratory Report No. E00-2192 The Fez03 data were used as an environmental model to generate a half-life estimate for the degradation of PFOA. Because no degradation was observed, data from Table 2b, Fe203with and without H202, was pooled to determine the experimental error of the analysis. This data, shown graphically in Figure 2, yielded an estimated environmental half-life of 2 349 days. The exact mathematical solution is shown in Appendix C. Figure 2. Pooled concentration data from the iron oxide rich matrix. 0 0 I 0 Dashed linesindicatethe l a limits. 0 Solid line indicates the maximum slope. Page 17 of 148 BACK TO MAIN 3M Environmental Laboratory Report No. E00-2192 Conclusions A quantitative preliminary investigationwas undertakento determine the photolytic stability of perfluorooctonic acid (PFOA) and to identify the primary degradation products. The investigation included experimental conditions that addressed both direct and indirect photolysis. To test for direct photolysis, samples of PFOA in pH 7 buffer were exposed to a synthetic light source for selected periods of time. Direct photolytic decomposition of PFOA was not observed based on loss of starting material, nor were any of the predicted degradation products detected above their limit of quantitation. To test for indirect photolysis, a synthetic light source was used to initiate radical formation in three separate matrices: a synthetic humic matrix, a hydrogen peroxide rich matrix, and an iron containing matrix (as Fe203). Degradationof PFOA was not observed in any matrix outside of the experimental precision of the analytical methodology. Mass balance for the degradation study was 100 k 10% under all experimental conditions. A minimum half-lifefor PFOA based upon these preliminary studies was calculated to be 2 349 days. Page 18 of 148 BACK TO MAIN 3M Environmental Laboratory Report No.E00-2192 References 1. Fafe, Transporf and Transformation Test Guidelines, OPPTS 835.5270 lndirecf Phofolysis Screening Test; EPA712-C-98-099; United States Environmental Protection Agency, U.S. Government Printing Office: Washington, DC, 1998, pp. 1-22. 2. OfCD Guideline for Tesfing of Chemicals, Phofofransformationof Chemicals in Wafer-Direct and lndirecf Phofoysis, (Draft Document); OECD, 2000, pp. 1-59. 3. Scrano, L.; Bufo, S. A.; Perucci, P.; Meallier, P.; Mansour, M. Photolysis and Hydrolysis of Rimsulfuron. fesfic. Sci. 1999, Vol. 55, pp. 955-961. 4. Nubbe, M. E.; Adams, V. D.; Moore, W. M. The Direct and Sensitized Photeoxidation of Hexachlorocyclopentadiene.Waf. Res. 1995, Vol. 29, No. 5,pp. 1287-1293. 5. Ogata, Y.; Tomizawa, K.; Furuta, K. Chemistry of Peroxides, in S. Patai (ed.). The Chemistry of Peroxides 1983, p. 720. 6. Lunak, S.; Sedlak, P. PhotoinitiatedReactions of Hydrogen Peroxide in the Liquid Phase. J. Phofochem. Photobiol. A.: Chem. 1992, Vol. 68, pp. 1-33. 7. Kachanova, Z. P.; Kozlov, J. N.Zh. Fiz. Khim. 1973, Vol. 47, p. 2107. , 8. Behar, B.; Stein, G. Science 1966, Vol. 154, p. 1012. 9. Takahashi, N.;Ito, M.; Mikami, N.; Matsuda, T.; Miyamoto, J. Identificationof Reactive Oxygen Species Generatedby Irradiationof Aqueous Humic Acid Solution. J. Pesticide Sci. 1988, Vol. 13, pp. 429-435. Page 19 of 148 BACK TO MAIN 3M Environmental Laboratory Report No. E00-2192 Signatures The final draft of this report is a true representationof the data developed in this study. It has been issued by: Management 09/2A/ Date Page 20 of 148 BACK TO MAIN 3M Environmental Laboratory Report No. E00-2192 Appendix A: Analytical Methods This appendix presents the analytical methods and Standard Operating Procedures used in the present study. ETS-9-46.0 Operation and Maintenanceof the Hewlett Packard 8453 UV-Visible Spectrophotometer ETS-9-44.0 Operation and Maintenance of the Sunlight Exposure System, Immersion Unit, and Recirculating Water Chiller System ETS-9-49.O Routine Maintenance of Archon Purge and Trap Autosampler, Tekmar Purge and Trap Concentrator and Agilent Gas Chromatograph/Mass Spectrometer ETS-8-182.0 Analysis of Fluorochemicals by Archon Purge and Trap Autosampler, Tekmar Purge and Trap Concentrator and Agilent Gas Chromatograph/Mass Spectrometer ETS-8-177.0 Indirect Photolysis ScreeningTests in Synthetic Humic Water ETS-8-176.0 Preparationof Samples for Photolytic Exposure Studies in Aqueous Matrices ETS-8-181.O Analysis of Photolysis Samples for Fluorochemicals by High Performance Liquid Chromatography With Mass Spectrometry Detection Page 21 of 148 BACK TO MAIN 3M Environmental Laboratory Report No. E00-2192 3M ENVIRONMENTLAALBORATORY METEOD ANAlLYSIS OF PHOTOLYSIS SAMPLESFOR FLUOROCHEMICALS BY HIGH PERFORMANCELIQUIDCHROMATOGRAPHY WITH MASSSPECTROMETRY DETECTION Method Number:ETS-8-181.0 Approved by: -&/& Laboratory Management Adoption Date: jd/L 4 1 Effective Revision Date: uc/-aJ ~ t ) Date Page 22 of 148 BACK TO MAIN 3M Environmental Laboratory Report No. E00-2192 Comuound Acronvm Perfluorooctanoic acid PFOA Pefluorooctanesulfonate PFOS Perfluorooctanesulfonamide FOSA N-methylpefluorooctanesulfonamide N-MeFOSA N-ethylperfluorooctan~~ulfonamide N-EtFOSA 2-(NmefhylperfluoIooctanesulfonamido) N-MeFOSE-OH ethyl alcohol ~-(N-e~yl~~uo~terfluorooctanesulfonamidoN) -EtFOSE-OH ethyl alcohol COfnOOUIId Pduorobutanoic acid Perfluorobutanesutfonate Pdluorabucanesu!fanamide N-methylperfluorobutanesulfonamide N-eth ylperfluorobutanesul fonamide 2-(N-methylperfluorobutanesulfonamido) ethyl alcohol 2-(N-ethylperfluorobutanesulfonamido) ethyl alcohol Acronvm PFBA PFBS FBSA N-MeFBSA N-EtFBSA N-MeFBSE-OH N-EtFBSE-OH I I 1.3 Compatible matrices for analysis. Aqueous (Millipore ASTM Type I water), buffered water, lake water, sea water and metal slurries (TiO2, Fez03, etc.) that have been diluted with an appropriateanalytical solvent such as acetone or methanol. 2.0 SUMMARY OF METHOD 2.1 This method describes the analysis of fluorochemicalsin a specifiedmatrix, using HPLC electrospraymass spectrometry for chemical separation and detectiodquantification. The analysis is performed by separatingtarget analytes on an HPLC analyticalcolumn such as a Dionex NGl (35x 4.6mm, lOpmpar!kle), Betasil C18 column (50x2mm, 5 pm particle) or equivalent using an ammoniumacetateh4eOH solvent gradient. Detection by electrosprayionizationmass spectrometeryin either the positive or negative mode is utilized to quantifydata. The MSD may be runin SelectedIon Monitoring(SIM)mode, looking for specific, pre-selectedand set analyte ions (ie. m/z 499 for PFOS (deprotonated)), or SCAN mode which collects and stores data for all ions in a specified massrange. Data quantificationis then performedusing either HP ChemStationor Target S o h a r e . ETS-8- 18 1.O AnaIysis ofPhotolysis Samplesfor Fluorochemicals by HpLC/MS Page 2 of 15 Page 23 of 14% BACK TO MAIN 3M Environmental Laboratory Report No. E00-2192 - 3.0 DEFINITIONS 3.1 Calibration Standard. A dilution of various amounts of a stock, intermediate or purchased standardto achievestandard solutionsin a concentrationrange of interest. 3.2 CaIibration Curve. The graphical relationship between known values, such as concentration of a series of calibration standardsand their instrumentalresponse. 3.3 Internal Standard Quantification. Process of establishinga relationship betw;eenthe ratio of the target analyte(s)response to internal standard or surrogateresponse and a known concentrationof the target analyte(s). The ratio of analyteto internal standard response is used to generate the calibration curve and determineunknown concentrations. 3.4 External StandardQuantification. Process of establishingthe concentrationofa target mdyte by plotting the theoretical amount (in units of ppb or ppm, etc.) versus the response of the target andyte(s) on column. The resultant curve(s) shall be used to determineunknown concentrationsby comparing the area response of target analyte(s) to the area response and correspondinganalyte amount on the appropriateanalyte's calibrationcurve. Differencesin samplemasdvolume analyzed, if noted, must be compensated for by a factor applied to the value. 3.5 CorrelationCoefficient(r). A measure of the degree of correlationbetween two variables. This term is generally used to evaluate the linearity of a Least Squares Linear regression. An r value of 0.98 is at the lowerbounds of what is consideredlinear. Values of r may range .from-1 to +l. A value of +1 denotesperfect direct functionalrelationship between two variables. A value of -1 also denotes a perfect inverse relationship. When r = 0, there is no effect of one variable upon the other variable. 3.6 Coefficient of Determination(r2). The square of the correlationcoefficient. It is the proportion of the variationin the dependent variable that is accountedfor by the independent variable. 3.7 Internal standard. A h o r n amount of a compoundor element similar in analytical behavior to the compound(s) or element@)of interest, added to all samples and standards, and carried throughthe entire measurementprocess (post-photolysis,after solvent dilution). It provides a reference for evaluatingand controllingthe precision and bias of the applied analytical method. Samples are to be quantified using the internal standard. 3.8 Surrogate. An organic compound similar to the target analyte(s) in chemical composition and behavior in the analyticalprocess but is not normally found in the sample@). A surrogatemay be added to samples alongwith the test analyte&re and/or post photolysis) to monitor the sample integrity (leaks or matrix effects). The surrogate may be added to the calibrationstandardsto serve as a qualitativereference for the samples. ,3.9 ContinuingCalibrationVerification (CCV). Standards analyzed during an analytical runto verify the continued accuracyof the calibration curve. Thissolutionmay or may not be prepared from a different source or lot number than the calibration curve standards. ETS-8-18 1.0 Analysis ofPhotolysis Samples forFluorochemicalsby HPLClMS Page 3 of 15 Page 24 of 148 BACK TO MAIN 3M Environmental Laboratory Report No. E00-2192 3.10 Solvent Blank. A sampleof analyte-fieemedium (for example, methanol, 1:7 diluted buffer:methanol) that is not taken through the sample preparation process. This blank is used to evaluate instrument contamination. 3.1 1 Blank. For photolysis studies, there are multiple blanks to adequatelyrepresent the variables of the study exposed, Unexposed and Day 0 samplesWitWwithout peroxide addition). These blanks are carried throughthe samplepreparation, photolytic and analyticalproceduresto monitor for contaminationduring any step. It is also used to establisha chromatographicbaselinebackgroundand monitor for analyticalinterference or suppressionof target analyte(s) from the matrix. 3.11.1 Matrix Blank: An analyte-freematrix (buffered water, lake water, etc.) to which all reagents are added in the same volumes or proportions as used in sample processing. It is used to documentthe test systemwithout test analyte present. 3.11.2.ControlBlank An analyte-freematrix (ASTMType IIwater) to which all reagents are added in the same volumes or proportions as used in sample processing. It serves as a control for the test matrix to monitor background levels, interferencesor suppressionof target analyte(s) from the test matrix. 3.12 Limit of Quantitation(LOQ). The lowest concentrationthat can be reliablymeasured within specified limits of accuracy during routine laboratory operating conditions. The LOQ is generally5 to 10timesthe minimum concentrationwith a 99% confidence limit that the concentration is greater than zero. However, it may be nominally chosen within these guidelinesto simpliedata reporting. For many analytes, the LOQ is selectedas the lowest non-zero standard in the calibrationcurve that is greater than 4 times the level of the matrix blank. Sample LOQ are highly matrix-dependent. 3.13 Sample Triplicates. Three samples taken from and representative of the same sampIe s o m e and separatelycarriedthrough aI1steps of the extraction, photolysis and analytical procedures in an identical manner. There are multiple sets of triplicate samples to adequatelyrepresent the photolyticvariablesof the study (Exposed, Unexposed and Day 0 WiWwithout peroxide addition). Triplicate samples are used to assess variance of the photolytic method, including sample preparation, photolysis, and analysis. 3.14 Control Sample. A known matrix (ASTM Type IIwater) containingthe test analyte(s) carried throughoutthe entire samplepreparation, photolytic and analyticalprocedure. There are multiple sets oftriplicate samplesto adequatelyrepresent the photolytic variables of the study (Exposed, Unexposed and Day 0 witWwithoutperoxide addition). This is used to document method performance and matrix effectsby comparing recoveries from the different matrices and sample types. 3.15 Relative Standard Deviation (RSD). A measure of precision defined as the standard deviation of three or more values divided by the average of the values and multiplied by 100. (Also reported as Coefficient of Variation (CV)). 3.16 Analytical Spike (AS). Prepared by adding a known mass of target analyte(s) to a specified amount of a sample or control matrix prior to analysis. This assumes that an independentestimate of target analyte concentrationis available. Analytical spikes are used to determinethe effect of the matrix on recovery efficiency. There are multiple ETS-8-18 1.O Analysis of PhotolysisSamplesfor Fluorochemicalsby HpLClMS Page 4 of 15 Page 25 of 148 BACK TO MAIN 3M Environmental Laboratory Report No. E00-2192 types of spiked samples to adequatelyrepresent the photolytic variables of the study Gxposed, Unexposed and Day 0 ;withlwithout peroxide addition.) 3.16.1 3.16.2 Matrix Spike. The test matrix (bufferedwater, lake water) sample containingthe test analyte or blank to which a known mass of target analyte(s) is added prior to analysis. Control Spike.The control matrix (ASTMType IIwater) sample containingthe test analyteor blank to which a known mass of target analyte(s) is added prior to analysis. 3.17 Accuracy. The closenessof agreement between an experimentallydeterminedvalue and an accepted reference value. When applied to a set of observed values, accuracyis a combination of a random (precision) and a common systematic (bias) component. For purposes of the study, the acceptance criterion is 75% to 125% of the nominal value. 3.18 Dilution. A step in the sample preparation procedure in which a solvent (Le. methanol, acetone) is added to the test analyte/samplematrix (i.e. water, buffer, etc.) to prepare it for instrumental analysis. 3.19 Atmospheric PressureIonization (MI):The Agilent TechnologiesHPLC 1100MSD system allows for ionizationof incomingliquid samplefrom the analyticalcolumn to the mass spectrometerinterfaceby utilizinga source, probe, hot gas, and specific voltages. 3.20 ElectrosprayIonization @S, ESI): A method of ionizationperformed at atmospheric pressure, whereby ions in solution are transferred to the gas phase via tiny charge droplets. These charged droplets are produced by the applicationof a strong electrical field. 3.21 Mass Spectrometry,Mass Spectrometer(MS), Mass SpectrometerDetector (MSD): The API HP1100 MSD system equipped with a quadrupole mass selective detector, Ions are selectivelydiscriminatedby mass to charge ratio ( d z )and subsequentlydetected, 3.22 Geometric Mean of the calibration curve: The squareroot of the product of the high standard concentrationand the low calibrationcurve standard. When preparing calibrationcurve standards, the number of calibration standardsbelow the geometric mean shall equal the number ofcalibrationstandardsabovethe geometricmean. Having equal distribution of calibration standards above and below the geometric mean when analyzingand reprocessing data, effectivelyweights the curve such that both the high and low ends of the curve are given equivalent significance. 4.0. WARNINGS AND CAUTIONS 4.1 Health and safety warnings 4.1.1 Wear the proper lab attire for all parts of this procedure. Wear gloves and proper eyewear when performing sample preparation in the laboratory at all times. Wear proper eyewearwhen working at the instrument in the laboratory. ETS-8-181 .O Analysis of Photolysis Samplesfor Fluorochemicals by HPLC/MS Page 5 of 15 Page 26 of 148 BACK TO MAIN 3M Environmental Laboratory Report No. E00-2192 4.1.2 Handle all solvents in a hood for all parts of the described sample preparation procedure. Wheneverpossible andpractical, dilute sampleswith solvent in a hood. 4.1.3 For potential hazards of each chemical used, refer to material safety data sheets, packing materials, and the 3M Environmental Laboratory Chemical Hazard Review. 4.2 Cautions 4.2.1 All glassware in which standards are prepared should be rinsed with acetone and methanol to reduce the possibility of contamination. 4.2.2 Ensure that the HPLC mobile phases are prepared prior to beginning a run sequence,and that there is sufficient quantityto completethe run.Do not allow the pump to rundry. 4.2.3 Ensure that before starting the run sequence there is ample hard disk space on the computer to save all rundata. 4.2.4 Ensure that there is enough nitrogen in the supply tank to complete sequence runs. 5.0 INTERFERENCE 5.1 Contaminantsin solvents,reagents, glassware, and other sampleprocessing or analysis hardware may cause interference. Use the routine analysis of laboratorymethod blanks to demonstrate that there is no such interference. 5.2 Contaminationfiom columns, HPLC tubing, and detector componentsmay cause interference at low detection levels. The routine analysis of solvent blanks must be used to demonstrate that there is no such interference. 6.0 EQUIPMENT 6.1 Analytical balance sensitive to 0.1 mg. 6.2 Hewlett-Packard(HP) 1100HPLC System,or equivalent. 6.2.1 Pump, binary, Model G1312; Quaternary,Model G1311A, or equivalent. 6.2.2 Solvent degasser, Model G1322A or equivalent. 6.2.3 Autosampler, A L S Model G1313A, variable injection volume or equivalent. 6.2.4 Column heater, Model G1316A, or equivalent. 6.3 Betad* C18,50 x 2 mrn; Dionex IonPac@NG1 Guard column, 4 x 35 mm; or equivalent. 6.4 Mass spectrometer. Hewlett-Packard MSD Model G1946A, or equivalent. 6.5 Refrigerator capable of maintaining 4 5 3 "C. 6.6 Data system. A personal computer capableof controllingthe HPLC system as well as recording and processing signals from the detector. ETS-8-181 .O Analysis ofPhotolysis Samples for Fluorochemicalsby HPLCMS Page 6 of 15 Page 27 of 148 BACK TO MAIN 3M Environmental Laboratory Report No. E00-2192 6.7 System control/dataanalysis software: Hewlett Packard ChemStationQ Version A.6.03 or later. 6.8 Data reprocessing software: Thru-Put Systems Target NT, Revision 4.03, Build 157 or later. Hewlett Packard ChemStation@,Version A.6.03 or later. 7.0 SUPPLIESAND MATERIALS 7.1 Vials, 40 mL, VOA (I-Chem or equivalent) 7.2 Crimp cap autovials, 1.8 mL 7.3 Labels 7.4 Graduatedpipets, glass, disposable, 1mLto IO mL 7.5 Pasteur pipets, gIass, disposable 7.6 Hamilton Gastight@syringes(precisionf 1%of total volume), 10pL-1000 pL 7.7 Volumetric flasks,various sizes 7.8 Beakers, glass, various sizes 7.9 Automatic pipettor, capable of dispensing 10-5000 pL 8.0 REAGENTASND STANDARDS 8.1 Methanol (MeOH). HPLC/SPEC/GC grade from EM Science, or equivalent 8.2 Acetone. HPLC/SPEC/GCgrade from EM Science,or equivalent 8.3 ASTM Type I1 Water. Water with lower resistance must not be used. 8.4 Ammonium acetate, 2 mM in water. This solutionis chromatographicsolvent A (see Section 12.2.1). (Example: An acceptable eluent solution is made by adding 0.15 g ammonium acetate crystalsto a l-L volumetric flask containingabout 500 mL water, adding 10mL of methanol, diluting to the mark with 18.0MQ water and mixing.) 8.5 Stock, internal standard, surrogate, post-photolysis spike and calibration solutions All weights should be recorded to the nearest 0.0001 g in a standardspreparation log: 85.1 Fluorochemicalor target malyte prepared in acetonitrile(or suitable analytical solvent). (Example: A stock solutionis prepared at a concentrationof approximately30,000 p g / d by weighing 0.3 g of target analyte in a 10-mL volumetricflaskandbringingto the mark with suitable analyticalsolvent. This solution is diluted in solvent to make additional, appropriate standards. Follow specified guidelinesfor documentingremoval of test analyte and target analyte(s), use of balance, preparation of diluted solutionsand calibrationstandards in the appropriatelog books. Maintainphotocopies of the preparationpages and worksheets in a raw data file, ETS-8-1 81.0 Analysis of Photolysis Samplesfor Fluorochemicalsby HPLCMS Page 7 of 15 Page 28 of 148 BACK TO MAIN 3M Environmental Laboratory Report No. E00-2192 9.0 SAMPLEHANDLING 9.1 Standards and diluted samples are stored in capped autovials or capped 40 mL VOA vials until analysis. 9.2 If analysiswill be delayed, standardsand sample extracts may be stored at 4OC f3 "C or room temperature, until analysis can be performed. Document storage conditions on sample prep worksheet with date and initials. 10.0 QUALXTYCONTROL 10.1 CalibrationStandards. Calibration standards (Section 11)used to .generatea calibration curve should be prepared in the same type of solvent or matrix as in the study samples. The number of calibrationstandards and the concentration levels should be sufficientto encompass the expected concentrations of the study samples. In general, a minimum of five calibration standards is required for fit of linear regression. Broad calibration ranges (greater thanthree orders of magnitude between low and high standards),may require use of a quadratic fit of the data and requires more points to adequatelyrepresent the calibration range. 10.2 ContinuingCalibrationVerification (CCV). Analyze a mid-range calibration standard after a maximum of every fifteen samples. 10.3 Solvent blank. Solventblanks are runbefore and after every calibrationcurve, CCV, matrix and control blank (if contaminationis noted), and after batches of no more than 30 injections. Acceptable values for the blanks are values below 25% of the limit of quantitation (LOQ)of the instrument. If analyte carryoveris a problem, use back-to-back solvent blanks. 10.4 Sample Triplicates. Analyze all sets of triplicate samplesto provide a measure of the precision of analysis. Study samples will be analyzed in batches of no more than 30 samples. Multiple batches in an analytical sequence will be bracketed by calibration standards at the beginning and end of each study sample batch. AX1 samples (matrix and control samples, blanks and spikes) from a specified exposure type or time may be analyzed within the same analyticalbatch. 10.5 Analytical spikes. Prepare analytical spike sample for each sample type as applicable to determine the matrix effect on the recovery efficiency. Concentrations of the spike should be approximately equal to a mid-range calibration standard. The matrix spike sample should be analyzed periodically to measure the precision associated with the analysis. The analyst shall acceptpercent spike recoveries of 100k 25%. Spike recoveries outside of this range should be noted and used with other criteria to evaluate the condition of the analyticalrunor necessity for repeat analysis. Consult with the Team Leader or designeefor direction and fmal acceptanceor rejection of the analyticalrun. Samplesmay be spiked at two differentconcentrationsto ensurethat the resulting levels of target analyte(s) are within the viable range of the calibration curve. ETS-8-181.O Analysis ofPhotolysis Samplesfor Fluorochemicalsby HPLCMS Page 8 of 15 Page 29 of 148 BACK TO MAIN 3M Environmental Laboratory Report No. E00-2192 11.0 CALIBRATION AND STANDARDIZATION 11.1 Analyze standardsprior to and following each set of samples. The linearregression will be calculated from the plot of all individual calibration points, including but not forced through zero, using HP ChemStationor Target NT Software. A minimum offive calibration standardsis required to generate linear regression for target analyte(s). If the calibration curve residuals are greater than 25% deviation fiom the theoretical value, quadratic curve fitting and/or droppinglowhigh curve points may be required if data review shows this to be a consistent and more accuraterepresentation of the instrument response. Document in the raw data the technicaljustificationfor any deviation and consult with the team leader or designee for direction and for final acceptanceor rejection of the data. 11.1.1 Use the followingdocumentatiodfootnotesmaybe used tojustify dropping highflow curve points. 1) "Higb/low calibrationpoints (list points) were excludedto provide a better fit over the linear range appropriate to the measured data." 2) "Low level calibrationpoint(s) were not 4x higher than the extractionblank; these points were excluded &om the curve to disqualify a data range that may have been significantlyaffectedby backgroundlevels of the analyte." 3) " H i w o w calibrationpoint(s) (list points) were excluded as they were not within the 4 2 5 % accuracyrequirementsof the method when the curves were evaluated over a linear range appropriate to the data.' 11.2 If the curve does not meet requirementsperform routine maintenance or prepare a new standard curve (if necessary) and reanalyze. 12.0 PROCEDURES 12.1 Instrument set up. Within "Method and Run Control"in the HP ChemStation SootWare window, turnthe system "on" to: turnonthe drying gas flow; initiate solvent flow through the column and nebulizing needle; equilibratethe column compartment;and equilibrate the MSD spray chamber temperatures and conditions. The system module displays should turn a green color to indicate the instrument is "ready" for analysis. A yellow color indicatesthat the system is not ready, but is working to "get ready." A red colored module icon indicates a type of systematic failure and should be corrected prior to proceeding. Check the runlog for error messages and error codes if the problem is not apparent. 12.2 MSD set-up. Turn the MSD "on" in the software to equilibrate the system. 12.2.1 Check the level of nitrogen in the tank and ensure there is enough to complete the impending run. 12.2.2 Clean the MSD accordingto the Equipment Procedure ETS-9-34.0Operation and Maintenance ofHP LCMS System. ETS-8-181.0 Analysis of Photolysis SamplesforFluorochemicalsby HPLCMS Page 9 of 15 Page 30 of 148 BACK TO MAIN 3M Environmental Laboratory Report No. E00-2192 12.2.3 Perform a Check Tune or Autotune to ensure system operational qualification and performanceverification of the MSD.Log the Tune results and keep a copy with the analyticalraw data 12.2.4 Load the method file and ensure that the followingparameters are appropriately set for the target analyte(s): Example mass spectrometer set up': I MSD: 1 Ionization mode I API-ES lor API-APCI) ~~ Polarity NegaUve (or Positive) Acquisition mode SIM (or SCAN) Gain 1.O (up to 7.0) Fragmentor 70 (may be set to one voltage, or ramped for each ion) Dwell time 183 msec (time is a function of the amount of ions). Carillaw voltaae 3500. or eauivalent Drying gas Nitrogen, or equivalent Nebulizer pressure Drying gas flow 30 pig, or equivalent 8 Umin, or equivalent ~ ~.~ Drying gas temp 300' C, or equivalent 12.3 LCCheck 12.3.1 Check that the appropriateHPLC column is in the instrument for analysis. 12.3.2 Check that the correct eluent solutions are in bottles to be used and that enough is available to complete the sequence run. Adjust the solvent bottle level electronicallywithin the method and run control window. 12.3.3 Ensure that the method file has the appropriate LC pump parameters for solvent flow/gradientprogram ,column LDjtemperature,injection volume and stop time. Solvent A: Ammonium Acetate 2mM in water (with 1% MeOH) (or equivalent). Solvent B: Methanol (or equivalent). Example Solvent Gradient: TIME(MIN) 0.0 1 .o 4.0 11.0 *%A %0 FLOWRATE 60 40 0.3 mUmin 60 40 0.3 mUmin 5 95 0.3 mumin 5 95 0.3 mUmin Page 31 of 148 BACK TO MAIN 3M Environmental Laboratory Report No. E00-2192 increasesto a higher organic content over time to separatethe analytes, and elute them off the column in a timely fashion. After all analytes have eluted, the solvent ratio is then switched back to "initial conditions" and held until the column pressure has stabilized ( indicating re-equilibration to initial conditions) prior to the next injection. 12.3.4 Auto-sampler setup: I I I AUTO-SAMPLER: ~ ALS Model GI313A - AUTO-SAMPLER PROORAM: None INJECTION VOLUME: 5.0 vL, or equivalent I 12.3.5 Place the samples in the autosampler tray and construct a sequence table with appropriatecalibrationstandards,calibration check standards and solvent blanks. 12.3.5.1 Verifythat all samples and standardsare positioned correctly. 123.5.2 Enter the identificationcode for each standard and samples. For solvent blanks, identiethe solvent and the traceability number. 12.3.5.3 Use one injectionper sample. 12.3.5.4 Ensure the method file is correctly entered for all samples. 12.4 Sequence and electronic storage of data files. 12.4.1 12.4.2 12.4.3 12.4.4 12.4.5 Within the sequenceparameters, enter sequence information (brief sample population description and instrument name). Set post-sequence command macro to shut down system after the run is completed (Example: "STANDBY" on HP1100iMSD systems). Save all data to a subdirectorylabeled with instrumentand analysisdate (e.g. H100200 for analysis on "Hillary,)`on 2 October, 2000). Name datawithin the subdirectorywith instrument ID and injectiodrun number (e.g. for samples acquired on "Hillary7',data files shall be "HILLOOOl".... "`~LLOO##"')D. O NOT exceed five identification characters for analysis of more than 99 samples since eight characters total are available for sample ID, and the last three digits are for sample numbering purposes (leaving the first five characters for data file identification). Save sequence as analysis date and instrument letter (e.g. For analysis on instrument"Hillary"on October 2,2000 save sequencetable as H100200.s). 12.5 Sample analysis 12.5.1 Enter the standard,sample, blank identification into the sequencetable. Analyze calibration standards first, then up to 30 injections, followed by the calibration standardsre-injected. Multiple sets of samplescan be set up in the sequencetable with each set bracketed by calibrationstandards. Analyze a single continuing calibrationstandard (CCV)after a maximum of 15 injections. Solvent blanks shall be analyzedbefore and after the CCV and before method and control blanks, if ETS-8-18 1.O Analysisof Photolysis Samples for FIuorochemicalsby HPLCNS Page 11 of 15 Page 32 of 148 BACK TO MAIN 3M Environmental Laboratory Report No. E00-2192 12.5.2 12.5.3 necessary. Two solvent blanks shall be analyzed at the end of the calibration standards to ensure that there is no cany over from the highest standard concentration. Solvent blanks may also be used to separate groups of samples and evaluate for carry over problems fiom actual samples. Ensure standards, blanks, samples, and matrix spikes in the auto-sampler tray vials are in same order as listed in the sequence. Print a copyof the tune results,method and sequenceto be stored with raw data. Start the sequence. 12.6 Post Analysis. Prepare a folderidentifiedspecificallyto the project and save data, method and sequence files. This will be considered the raw electronic data to be archived. 13.0 DATAANALYSIS AND CALCULATIONS 13.1 Peak Evaluation. Peaks must be symmetric in shape and identified by extracting compound-specificions. Peaks consideredfor quantificationmust have peak heights greater than 4 times any baseline level for that region of the chromatogram. Peak area integration is from baselineto baseline using automaticor manual integration. Manual integration is not acceptable for calibration standards and should only be used in extreme cases as designatedby the Team Leader. Samples and standardsthat may need to be manually integrated must be documented in the raw data as to why the peak was manually integrated. 13.2 Integration Codes. The followingintegrationcodes may be utilized to documentwhat type of manual integrationwasperformed. A Adjust Left Anchor B: Adjust Right Anchor C: Delete Integration D: Add Integration Additionally, QAU encourages the data reviewer to write comments directly on the chromatogramif there is anythingunusual. Date and initial all documentation. 13.3 Matrix spikes. Calculatethe percent recovery for each of the matrix spikes. Calculate the matrix spike percent recoveries using the following equation: % Recovery=(observed stiked samtde result -observed samule result) x 100 Nominal amount spiked Using the observedmatrix spike recoveries, calculatethe average spike recovery. ' 13.4 Accuracy, Calculate the accuracy of each calculated calibration standard and CCV samples using the following equation. Accuracy = (Measured Conc.) x 100 Nominal Conc. ETS-8-18 1.O Analysis ofPhotoIysisSamplesfor Fluorochemicalsby HPLCMS Page 12 of 15 Page 33 of 148 BACK TO MAIN 3M Environmental Laboratory Report No. E00-2192 . 13.5 Sample Triplicates. Calculatethe relative standarddeviation(%RSD) for the triplicate samples: RSD = StandardDeviation of Samde Set x 100 Average of Sample Set . 14.0 METHODPERFORMANCE 14.1 Coefficientof Determination (9).The coefficientof determination(r') for the calibration curves should be 0.990 or greater. The curves should be examined closely for linearityand intercept,particularlyfor accuracyof quantitationat the low and hi& ends of the curve. The accuracy of all standards used for calibrationmust be within 75-125%. It may be necessaryto use quadraticfits of the data, usually when broad range curves (greater than 3 orders of magnitude between the low and high concentrationstandards) are used. Document in the raw data the technicaljustification for using quadratic equations. Consult with the Team Leader or designee for direction and for final acceptance or rejection for the data. 14.2 Calibration Standards. The acceptancecriterionfor the calibration standards is that the accuracy of each standardis 75% to 125%(k25 % difference) of the nominal value. Calibration standards outsidethisrange are to be noted. Document in the raw data the technicaljustificationfor deviations. Consult with the Team Leader or designee for direction and for final acceptance or rejection for the data. 14.3 Internal Standard (IS) and Surrogate. Review of the internal standard and surrogate performance is performed by averaging the area response throughout the analytical run and calculating%RSD. Inconsistenciesin the internal standard peak area may indicate instrumentalchangesover time. Inconsistenciesin the surrogatepeak area may indicate instrumental changes, injection error, or changes in the test-system. Consult with the Team Leader or designee for direction and final acceptance or rejection of the analytical run. 14.4 Continuing CalibrationVerification. If the accuracyfor the amount ofmeasured analyte is greater than 25% from the nominal value relative to the initial standard curve, the Team Leader should be consulted. Only those samples analyzed before the last acceptablecalibrationcheck standardmay be used. Consult with the Team Leader or designee for direction and for final acceptance or rejection for the data. 14.5 Solvent Blanks. Solvent blanks should show no more than a 5% canyover from a high standard or calibration check standard. If so, two solvent blanks may be necessary to rule out instrumentalContamination. If peaks greater than 25% of the peak area of the designatedLOQ value are observed in sequentialsolvent blanks, this is indicativeof instrument contamination. The instrumentshall be servicedby thoroughly cleaningthe electrospraysource, and replacingkleaningc o l m s , tubing, etc. (asdesignated in the Equipment Procedure, ETS-9-34.0) and the analysis restarted. Consult with the Team Leader or designee for direction and final acceptance or rejection of the analytical run. 14.6 Matrix Blanks. Matrix blanks are the basis for determining the LOQ and are monitored at various times in the analyticalrun. Samples with greater than 25% of the peak area of the designatedLOQ value observedin matrix blanks are indicativeof matrix effect, ETS-8-181.O Analysis of Photolysis Samples for Fluomchemicalsby IPLCIMS Page 13 of 15 Page 34 of 148 BACK TO MAIN 3M Environmental Laboratory Report No. E00-2192 . sample contamination or instrument contamination. Evaluation of the solvent and control bIanks may be necessary to determine these effects. Use of solvent blanks prior to the matrix blank may be necessary to rule out instrumental or sample contamination. 14.7 Control Blanks. Control blanks are the basis for determiningmatrix effect(interference or suppression) and also to monitor for instrumental or sample contamination. Use of solvent blanks prior to the matrix blank may be necessary to rule out instrumental or sample contamination. 14.8 Limit of Quantitation (LOQ).The LOQ is equal to the lowest acceptable standard (i.e. % accuracyis S 25 % nominal value) in the calibration curvethat is greater than 4 times the level of the matrix blanks. 14.9 Sample Triplicates. The analyst shall accept %RSDvalues < 25%. %RSD values =- 25% should be noted. Data used in the finalreport that is deemed out of control will be required to have technicaljustification for why the data is used, documented in the final report and raw data. Consultwith the Te,mLeader or designee for direction, and for find acceptanceor rejection of the data. 14.10 Control Samples. The acceptance criterion for the control samples is that the accuracy is 75% to 125% of the nominal value. These will be used as a reference for matrix effect and overall method performance. Control samples outside this range are to be noted. Consult with the Team Leader or designee for directionand for final acceptanceor rejection for the data. Data used in final report that is deemed out of control will be required to have a technical justification for why the data are being used, documented in the final report and raw data. 14.11 ' Analytical Spikes. The analyst shall acceptpercent spike recovery values of 100rt 25%. Spike recoveries outside of this range should be noted. Consult with the Team Leader or designee for direction, and for final acceptance or rejection of the data. Data used in final report that is deemed out of control will be required to have a technicaljustification for why the data are being used, documentedin the final report and raw data. 14.12 System SuitabWty. Without performing a method validation, system suitability can be demonstratedby acceptableinstnunental checks (e.g. abbreviated&z check-tune, or full auto-tune routines. Consult the appropriate instrumental manuals (Reference 18.2). Furthermore, overlaying calibration curves and implementing check standards(CCV),the method shall be self-validatingif all data quality objectives are satisfied. 15.0 POLLUTION PREVENTION AND WASTE MANAGEMENT 15.1 Disposeof samplewasteby placing in high or low BTU containersas appropriate. Use broken glass containers to dispose ofglasspipettes. 15.2 Collect HPLC solventwaste in the satelliteaccumulationcan. Empty into the flammable storagedrum in the hazardous waste collection area on the 2nd floor. 15.3 Use smaller bore columnswhen possible to minimize waste generation. ETS-8-181.O Analysis ofPhotolysis Samples for Fluorochemicalsby HPLCMS Page 14 of 15 Page 35 of 148 BACK TO MAIN 3M Environmental Laboratory Report No. E00-2192 16.0 RECORDS 16.1 Print hard copies of all graphics and data analysis summaries for archiving. 16.2 Sign and date all graphics and label with instnunent ID. 16.3 Fill out appropriatepreparation worksheets completely,making sure to include all initids and dates, along with the study number and sample identification. 16.4 Print out the sampleacquisition sequencetable, reduce the size with photocopyingand tape the photocopy into the instrument log. Keep the original copy for the raw data files. 16.5 Print chromatograms, reprocessing sequence and batch reports for all analyses. 16.6 Print calibrationtables and curve informationand store in the raw data file. 16.7 Enter all standardpreparationinfomation in the standardspreparation logbook. Make a photocopyof the logbookpage and include the copy in the raw data file. 16.8 Archive electronic data to appropriate media when necessary. 17.0 ATTACHMENTS 17.1 None. 18.0 REFF,RENCES 18.1 ETS-9-34.0,Hewlett Packard 11OOiMSD Equipment Procedure. 18.2 Hewlett Packard 1100/MSDinstruction CD/ROM. 19.0 AFFECTEDDOCUMENTS 19.1 None. 20.0 REVISIONS Revision number Reason for revision Date of Revision ETS-8-18 1.0 Analysis of Photolysis Samplesfor Fluorochemicalsby HPLClMS Page 15 of 15 Page 36 of 148 BACK TO MAIN 3M Environmental Laboratory Report No. E00-2192 3M ENVIRONMENTLAALBORATORY Method Preparation of Samples for Photolytic Exposure Studies in Aqueous Matrices Method Number: ETS-8-176.0 Adoption Date: Approved By: Laboratory Manager fl Date ETS-8-176.OPreparation of Samplesfor Photolysis Studies in Aqueous Matrices Method Page 1 of 18 Page 37 of 148 BACK TO MAIN 3M Environmental Laboratory Report No. E00-2192 1.0 SCOPE AND APPLICATION 1.1 Purpose. Chemicals dissolved in aqueous solutions are subject to two types of photoreaction. The first type (direct photolysis) occurs when the chemical of interest absorbs sunlightdirectly and is transformedto products when unstable, excited states of the molecule lead to decomposition. The second type is indirect photolysis, where degradationof the dissolved chemicalis the result of chemical or electronic excitation transfer fkom light-absorbing species in the water. The simplest reaction involves the absorption of W energy by hydrogen peroxide (H202) to produce 2 hydroxl radicals. These may react with any species in the water, including solvent, b a e r , dissolved organicmaterial and target material. Use of water and H202is very controlled and predictable. Other sources in other matrices are not as controlled or predicable, but are more environmentallyrelevant, Natural waters such as lake and sea water can be used for the photolytic reaction matrix because it may ,containdissolved organicmaterial thatabsorbs sunlight and produces reactive intermediatesthat include singlet oxygen ( ' 0 2 ) which may promote indirect photolysis of the test substance. Anothertransient speciesphotochemically produced by the reaction of W light and dissolved organic materials (humic) is hydrogenperoxide (H202)which may react further to formthe hydroxyl radical. The addition of HzO2 to test solutions may be utilized as a free radical source to initiate indirect photolyticreactions in controlledtest solutionssuch as MilliQ water or buffers. Further studies involving the use of either naturally occurring metal complexes such as Fe(II1) which undergo photoreductionto Fe(I1) and free radicals or addition of Ti02 as a catalytic surface for indirect photolysis may also be evaluated within this method. 1.2 CompatibIe analytes. Test substance and degradation products for photolytic exposure include but are not limited to: 1 Comaound I Acronym I Compound I Acronym I Perfiuomoctanoic acid PFOA Peffluorobutanoicacid PFBA Perfluorooctanesulfonate PFOS Perfluorobutanesulfonate PFBS PcrfYuorooctanesulfonamide N-methylperfluorooctanesulfonamide N-ethvluemuomoctanesulfonamide Z-(N-methylperfluoro octanesulfonamido)ethyl alcohol Z-(N-ethylperfluorooctanesuIfonamido) ethyl alcohol 1 -oeduorooctene 1 FOSA N-MeFOSA I N-EtFOSA N-MeFOSE-OH N-EtFOSE-OH - Perfluorobutanesulfonamide N-methylperfluorobutanesulfonamide I N-ethvl~erfiuombutanesulfonamide Z-(N-methylperfluorobutancsulfonamidoe) thyl alcohol 2-(N-ethy$e~uorobutanesuIfonamido)ethyl alcohol 1-ueffluombutene I FBSA N-MeFBSA ~~ 1 N-EtFBSA N-MeFBSEOH I 4 N-EtFBSE-OH r . . , -~ and other C.,thru Cl a h o m o l o g u e s . and ~~ o o l y m e r i c materials based on the aforementioned c o m K u n d s . I ETS-8- 176.OPreparation ofSamplesfor PhotolysisStudies in Aqueous Matrices Method Page 2 of 18 Page 38 of 148 BACK TO MAIN 3M Environmental Laboratory Report No. E00-2192 Other possible degradation products include, but are not limited to: C2 lMpcrfluomthanc(lH-pE2) IH-perfluoroethane (IH-pfCz) C, 1H-perfluompropane (IH-pE3) LH-perfluobpmpane (ZH-plC3) pcffluom-1-propene (pE3-lenc) C, perfluom-l-buttoe(pR;Q-lene) Pcrtluom-2-butenc(pE4-2ene) 2H-pcfflwmbutane(2H-prOr) C, 2H-perfluororpcnmeOH-PES) perfluom-1-pen~e@fCS-lcne) pcrfluorPZ-pentcac@CS-Zenc) Cs perUuom-2lmene (pfC6-2cnc) 2H-pcrfluorohexene (2H-pE6) C, 2H-pcrfluorohcptane(2H-pE5) lfi-perfluorohcxaoe (1H-pE6) perfluom-1-hcxene(pE6-lenc) Perfluom-l-hcptene(ptC7-lene) IH-ptrfluoroheptane(IH-ptC'?) Ce perfluom-lsctene (pfC8-lene) 2H-perfluomoctane(2H-pE8) Perfluor0-2-octene (pfC8-2ene) 1 1H-perfluombutane (1H-pE4) IH-perfluomhcxme(IHpE6) IH-perfluomme (IH-pE8) 1.3 Acceptablematrices. Aqueous solutionof test substance includingbut not limited to the followingmatrices: pH 7 phosphateb a e r , 18.2MR resistivitywater, seawater and metal solutions. 2.0 SUMMARY OF METHOD 2.1 The objective of the photolyticexposure study is to determine whetherthe test substance undergoes degradationby either direct or indirect photolysis, and to identify and quanti@ degradationproducts formed in the test matrix under these conditions. Study samples (5 mL aqueous matrix) are prepared in 40 mL glass VOA vials equipped with screw-top caps with septa. Study sets are prepared in duplicatefor separate analysis by LCMS and dynamicpurge and trap GC/MS. When required, the addition of 30% H20z solutionto initiate radical formation is performed prior to the photolyticexposure and at specified intervals throughoutthe exposurestudy. Vials are placed in the photo-reactor and immersed in a water bath controlled at 23-26 OC. Samples are exposed to approximately 261 W/m2of 3 10-800nm photo-irradiancefor a specified number of %hour periods. An %hour period of irradiance is defined as one day's worth of sunlight. Other parameters are acceptable,with the time and settingsnoted for each study. The number of days to expose samples is determined by the Team Leader. The amount of irradiation received by the samples may be monitored in one of the following three ways: 1) calculating the total wattageper length of exposure2) use of a radiometerto measure irradiance output, a d o r 3) use of a quininemonohydrochloridedihydrate (QMD) actinometersolution exposed along with the samplesand monitored for change UV absorptionover time. The use of the radiometer provides an accurate measurement at specified time-points; whereas calculatingthe total wattage per exposure length and use of the QMD actinometerprovide time-averagedtotal integrated energies. Suntest instruments contain an internal radiometer for maintenance of constant irradiance. A second radiometer may be used as a check for consistency. At the end of the exposure time, samples are removed from the photoreactor and either subsequently analyzed or stored at 1-5 "C. Study samples to be analyzedby LCMS are prepared for analysis by diluting the 5 mL sample volume with 30 mL of suitable analytical solvent (e.g. methanol) containing internal standard. The GCMS study samples are stored invertedprior to purge and trap GCMS anaIysis. ETS-8-176,OPreparationofSamplesfor PhotolysisStudies inAqueous Matrices Method Page 3 of I8 Page 39 of 148 BACK TO MAIN 3M Environmental Laboratory Report No. E00-2192 2.2 An example of samplesto be prepared for each study is shownin the table below. Exact lists may vary, dependent upon the test specificsfor each study and will be noted in individual study reports. Typically, there are extra control samples for certain matrices such as Fe203. LCMS GCMS 7?%=mEz 77E-YEz WA Hi01 HzOr H20, Sample Rep 2 + 0 + + SampleRep 3 0 + + Sample Spike 0 + MatrixBlank + 0 0 MatrixBlankSpike + 0 0 + Control Sample Contml Spike 0 0 + f + + ControlBlank 0 0 Control Blank Spike 0 + 0 kc+p.,. - x X X X X 0 Time 0 X X X X 0 + Time 0 X X X X Time 0 X X X X 0 Time 0 X X X X + Time 0 X X X X._ 0 + Time 0 X X X Time 0 X X.. X X 0 Time 0 X X X X + Time 0 X X X X 7 Sample Rep 2 + 0 0 + + Sample Rep 3 Sample Spike + 0 + 0 + + Matrix Blank + 0 0 Matrix Blank Spike + 0 Cantml Sample 0 + + 0 Conhol Spike 0 + + Control Blank 0 Control Blank Spike 0 + + 0 0 0 0 + 0 0 + 0 + + 0 _I___ Exposed Exposed fipo=d Exposed Exposed Expo=d Exposed Exposed Exposed Exposed 7 Ssmp e Rep 1 + 0 UmXpiZ Sample Rep 2 Unexposed Sample Rep 3 Unexposed Sample Spike Unexposed I Matrix Blank Matrix Blank Spike Unexposed Unexposed Control Sample Unexposed Unexposed , CMltrol Blank Unexwsed w/H24,One set w/o H202 3.0 QUALITCYONTROL-DEFINITION/FREQUENCY/PCERRITFEORRIAMANCE 3.1 Blanks 3.1.1 Definition: Matrix Blank An analyte-freematrixto which all reagents are added in the same volumes or proportions as usedin the sample processing. For photolysis studies, there are multiple matrix blanks to adequately represent the variables withinthe study in reference to the matrix (e.g. Exposed, Unexposed, Time 0; with peroxide, without peroxide). The matrix blanks are carried through the complete sample preparation, experimental treatment and analytical procedure. The matrix blank is used to documentcontaminationresulting from the experimentaltreatment and analytical process. Refer to the table below for an example of matrix blank types. The matrix blank is used to document the actual test systemwithout the test substance. The controlblank is used to control the test matrix and trace any background levels of target'analytethat may be matrixspecific. The table below shows an example of a control blank ETS-8-176.OPreparationof Samplesfor Photolysis Studies in Aqueous Matrices Method Page 4 of 18 Page 40 of 148 BACK TO MAIN 3M Environmental Laboratory Report No. E00-2192 Matrix ID Matrix descrintian Freauency Performance Criteria Matrix Blank Conbpi Blank Example: 0.0 1 M Phosphate Buffer, pH 7 Example: ASTM Type I1 Water 1 Replicate per light and dark exposure, for each h e point and for each analytical methodology. backWJmd level of target analfie shall be less than 25% the area Counts Of *e LOQ. I I I I J 3.2 Limit of Quantitation (LOQ) 3.2.1 Definition: The lowest concentration that can be reliably measured within specified limits of accuracy during routine laboratory operating conditions. Sample LOQs are highly matrix-dependent. 3.2.2 Qual@ Controland Performance Criteria: The LOQ is generally 5 to 10times the minimumconcentrationwith a 99% confidence limit that the concentrationis greater thanzero. However, it may be nominally chosen within these guidelines to simplifydata reporting. For many analytes, the LOQ is selected as the lowest non-zero standard in the calibration curve that is greater than 4 times the level of the solventblaaks and indicatesgood accuracy (225%) of the nominal calibration standard concentration. 3.3 Sample Triplicate 3.3.1 Definition: Three aliquotsprepared as representatives of the same sample source (i.e. test substance) and carried through all steps of the photolytic study process and analyticalproceduresin an identical manner. The results fiom triplicate analyses are used to evaluate variability of the total method, including sample preparation, photolytic process and analysis. 3.3.2 PetformcmceCriteria:The samples in the test matrix will be prepared in triplicate. Each replicate wilI be prepared for each treatment type: light and dark exposures, with and without hydrogen peroxide, for EACH time-point, and for each analyticalmethodology (e.g. LC/MS andor GCMS). See the following table: Matrix Descridion Frequencv of Use PerformanceCriteria Test Matrix containing test analyte(s) 3.4 Control Sample 3.4.1 Definition: A known matrix containing the test analyte(s)carried throughout the entire analytical procedure. This is used to document laboratory performance (Le. precision of sample preparation by comparing spike recoveries from the different matrices and sample types). A control sample consists of a control matrix spiked with test analyte(s). A control sample should be analyzed with each batch of samples processed to verify that the precision and bias of the analytical process ETS-8-176.0Preparation of Samplesfor PhotolysisStudies in Aqueous Matrices Method Page 5 of 18 Page 41 of 148 BACK TO MAIN 3M Environmental Laboratory Report No. E00-2192 are within control limits. The results of control sample analyses are compared to control limits established for both precision and bias to determineusability of the data. 3.4.2 Performance Criteria. One control samplewill be prepared per matrix, per treatment type. See the following table: Il)latrixDescription Freauencv of Use I PerformanceCriteria 1 Control matrix with test anal@(@added 3.5 Analytical Spike (AS) 3.5.1 Deftition: Prepared by adding a known mass of target analyte(s) to a specified amountof a dilutedandor aliquoted sample. This assumesthat an independent estimate of target analyte concentration is available. Analytical spikes are used to evaluate the recovery efficiency of the analyte and the effect of the matrix on the measurements. 3.5.2 Quality Control and Performance Criteria: One sample spike will be prepared in the actual test matrix sample, and one control spike in the control matrix will be prepared. Each replicate will be prepared per treatment type: for light and dark exposures, with and without hydrogen peroxide, for each time-point, and for each analyticalmethodology (i.e. LCMS andor GCMS). In addition, one matrix blank spike and one control blank spike will be prepared. See the following table: I I Matrix Descriotion I E s t Ma& andtest substance,spiked with target analyte(s) just prior to Freauency of Use 1 Replicate per treatment type. analysis II 1I PerformanceCriteria The analyst shall accept Control Matrix rmdtest substancespiked with target analyte(s)just prior to analysis Test Matrix without test substance, spiked with target analyte(s)just prior to anaiysis Control Matrix without test substance, spiked with target analyte(s) just prior to analysis 1 Replicate per treatment type. 1 Replicate per treatment type. ~ 1 Replicate per treatment type. of 1002 25%. Ifspike recoveries are greater than 125%or less than 7% document that the spike sample is out of the specifications and justie, if possible, the reason, ETS-8-176.OPreparafion of Samplesfor Photolysis Studies in Aqueous Matrices Method Page 6 of 18 Page 42 of 148 BACK TO MAIN 3M Environmental LaboratoryReport No. E00-2192 to be quantifiedusing the internal standardprovidingthat the response of the internal standardis consistent (k 5% relative). Use of external calibration methodology requires written justification by the Team Leader. 3.6.2 Surrogaie DeJinition (appliesio L W S and GWSsampies): A known amount of a compound similar in analyticalbehavior to the target analyt~(s)of interest may be added to all samples and standards(pre- or post-irradiation,at the discretionofthe Team Leader) and carried through the nzmaining sample preparationand analyticalprocess. If added before exposure, it monitors the presence of vial leaks duringphotolysis, as well asthe performanceof the purge and trap auto-sampler and concentrator. Surrogate analysis is used to evaluate and control the precision and bias of the analytical method. Surrogates are not used for quantitation. Note: Internal standardr are used in all experiments. The use of surrogate standards may or may not be used. Matrix Description Sample diluted with 30 mL of internal standard compound dissolved in a suitable analytical solvent with surrogate compound spiked into it. Freauencv of Use Every LclMS sample analyzed Every sample analyzed Performance Criteria The Coefficient of Variation, or %RSD shall be calculatedfor the arearesponse ofall appropriatesamplesper analyticalbatch. The - analyst shall accept %RSD values of 4 5 % . The recovery and precision ofthe surroEates shouldbe 100 %?S% and 4 5 % , respectively. Unacceptable values shall be documented and justified, if poss,.le. 3.7 Other Definitions. 3.7.1 Test AnalyteISubstance: Any substance (mixture or controlled compound) added or administered to the test system for the purpose of chemical analysis. 3.7.2 Degradation Product(@:Secondaryd y t e s of interestproduced as a result of chemical reactions during the photolysis and monitored (qualitatively or quantitatively)duringthe sample analysis procedure. 3.7.3 Target Analyte(s): The analyte(s) singled out in the analyticalphase of the study is the target analyte. The target analytemay be identicalto the test substanceused in the experimental phase of the study, a by-product or degradation product that is monitored (qualitatively or quantitatively)during the sample analysis procedure. 3.7.4 Test Matrix: The physical matrix in which the study will be conducted. Also referred to as the test system. 3.7.5 Control Matrix: A known physical matrix to be included with the study for comparison with the test matrix. 3.7.6 Relative Standard Deviation (RSD): A measure of relative precision for three or more sample replicates; defined as the sample standard deviation divided by the sample average and multiplied by 100. This is expressed as percent (%RSD). 3.7.7 Accuracy: The closeness of agreementbetween an experimentallydetermined value and an accepted reference value; defined as the measured value divided by the nominal value and multiplied by 100. ETS-8-176.OPreparation of Samplesfor PhotolysisStudies inAqueous Matrices Method Page 7 of 18 Page 43 of 148 BACK TO MAIN 3M Environmental Laboratory Report No. E00-2192 4.0 HEALTHAND SAFETY WARNINGS 4.1 Safety 4.1.1 Wear the proper lab attire, gloves and eye protection for all parts of these procedures. 4.1.2 Handle all solvents in a hood for all parts of the described sample preparation procedure. 4.1.3 For potential hazards of each chemical used,refer to material safety data sheets, packing materials, and 3M Environmental Laboratory's Chemical Hazard Review. 4.1.4 No mouth pipetting is allowed. 4.2 Cautions 4.2.1 Glassware in which standards are prepared shouldbe rinsed with solventto reduce the possibility of accidental contamination. 4.2.2 The photoreactorsare equipped with a continuous flow of cooling water, which poses a threat of electrocution during the handling of the photoreactor during irradiation sequences. To avoid possible injury, inspect the units frequently for water leakage and electrical outlets and wiring for wear and'tear. Replace any worn parts immediately. 4.2.3 Wear dark protective eyewear when operating the reactor. Do not look directly at the activated lamp. Use caution when handling samples in the reactor; the interior walls of the reactor and exposed glass vials become extremely hot. 5.0 Interference 5.1 Solvents, water and matrixcomponents could interferewith detectionthereby decreasing sensitivity in the sample analysis. Care must be taken to prevent a11possible contaminantsby using fresh reagents, analyticalgrade solventsand clean glassware during the sample preparation processes. 6.0 EQUIPMENT 6.1 Analytical balance sensitiveto 0.1 m g 6.2 Photoreactor: Suntest CPS+, =Si-, or equivalent, equipped with a xenon arc-lamp and capable of producing integrated inadiance values from 100-680 W/m2 over the wavelengthrange of 290-800 nm. Lamp output must be filteredto allow only 290-800 nm wavelengths. A flowing water bath with circulatingpump is required. Consult the appropriate 3M SOP for instructions. 6.3 Water recirculatingcooler capable of maintaining temperature at 25 O C f 5 OC, from Poly Science,Model 1177-Por equivalent. 6.4 Agilent Technologies W-visible Spectrophotometer,equippedwith tungsten and deuterium lamps, Model 8453, or equivalent. Consult the appropriate3M SOP for instructions. 6.4.1 Autosampler equipped with eight sample cell holders: Agilent Technologies Model GI 1ZOA, ThermostattedCell Holder: Model 08451-60104, or equivalent. 6.4.1.1 1.0-cm path length quartz spectrophotometercell fiom Hewlett Packard, or equivalent. 6.4.2 Long Path-Length Cell Holder, Hewlett Packard (# 89076C) or equivalent. ETS-8- 176.OPreparation of Samplesfor PhotolysisStudies in Aqueous Matrices Method Page 8 of 18 Page 44 of 148 BACK TO MAIN 3M Environmental Laboratory Report No. E00-2192 6.4.2.1 10-cm path length quartz cell equipped with stopcocks, Hewlett Packard Part # 5061-3392,or equivalent. 6.4.3 Data acquisition and analysis software, HP ChemStationfor W-Visible Spectroscopy, GI 116AA,Rev. B.01.02,or later. 6.4.4 PC Computer capable of d n g appropriate analysis software to acquireand report data. 6.5 Centrifige capable of maintaining >2000 rpm for 10minutes at ambient temperature. 6.6 Radiometer (optionaI) capable of monitoring the energy from a xenon source from 290 to 480 ntn over time. Model PMA2100,Version 1.16,SolarLight Company, Inc., or equivalent. Consult the appropriate 3M SOP for instructions. - 7.0 SUPPLIESAND MATERIALS 7.1 40 mL amber and clear glass VOA vials with screw caps with septa. 7.2 Crimp cap autovials-1.5 mL, caps, crimper, and decapper. 7.3 Adhesive-backed labels (return address size) for labeling quartz vials and autovials. 7.4 Disposable glass graduated pipettes, 1mL to 10mL. 7.5 Disposable glass Pasteur pipettes and rubber bulbs. 7.6 Glass beakers, various sizes. 7.7 Volumetric flasks,from 10mL to 1000mL. 7.8 Hamilton Gastight@syringes (precisionf1%of the total volume), 5 pL to 1000pL. 7.9 10mL Bottle-top dispenser, Calibrex, Model # 511, or equivalent. 7.10 Adjustable repeater pipette, Wheaton Step-pette 411, or equivalent, equipped withthe appropriatevolumetric range pipette tips. 7.11 Ziploc@plastic bags, or equivalent. 8.0 REAGENTSAND STANDARDS 8.1 Methanol (MeOB). HPLC/SPEC/GC andor purge and trap grade (EM Science, or equivalent. 8.2 Acetonitrile (ACN). HPLC/SPEC/GC and/or purge and trap grad fiom EM Science, or equivalent. 8.3 Aqueous Matrix, includes but is not i i t e d to the followingmatrixtypes: 8.3.1 ASTM Type I water. Milli-Q@or equivalent, witha measured resistivity> I 8.0 MR-cm. 8.3.2 0.01M pH 7.0 PhosphateBuffer. Example: Weigh 1.36g m z P 0 4 into a 2L volumetric flask and dissolve into 1 L of Type I water. Add 600 mL of 0.1% NaOH. Adjust to pH 7.0 k 0.1% with 0.1% NaOH or dilute Hzs04 and diluteto the mark with Type I water for a fmal conc. of 10 mM. 8.3.3 Lake Surfacewater. Collected from a known source, with known specifications for Dissolved Organic Carbon (DOC) and Total Organic Carbon (TOC). 8.3.4 Sea water. Collected froma known source, with known DOC and TOC specifications. 8.3.5 Aqueous metal solutions and slurries (e.g. TiOz, Fe203). Example: Dilute 0.015 g of Ti02 (Aldrich Chemical or equivalent) to 500 mL with Milli-Q@water. 8.3.6 Aqueous solutions containing soil. Example: Prepare samples containing 0.7g of characterized soil or sediment in 5 mL of MilIi-Q@water. ETS-8-176.OPrepurationofSumplesfor Photolysis Studies in Aqueous Matrices MethodPage9 of 18 Page 45 of 148 BACK TO MAIN 3M EnvironmentalLaboratory Report No. E00-2192 8.4 Hydrogen Peroxide (Hz02). 30% aqueous solutionfiom EM Science, or equivalent. 8.5 Potassium phosphate. Reagent grade fiom JT Baker or equivalent. 8.6 Stock Solutions 8.6.1 Stock solutions for the test analyte, target analytes, internal standard are prepared in an organic solvent (e.g. methanol, acetonitrile) at concentrationsof approximately 10,000pg/d by weighting approximately 0.Ig of the appropriate substanceinto a lO.-mL volumetricflask and dilutingto the mark withsolvent. This solutionis then dilutedto make appropriateworking solutions. 8.7 Test Analyte Solution: 8.7.1 Example for water soluble analvtefs): Example: A 1 pg/mL. test substance solution in the test matrix (Section 8.3) is prepared by diluting 0.050 mL of stock solution (Section 8.6.1) to 500 mL with test matrix. Aliquots (5 mL) of this solution will transferred to VOA vials for subsequent photolysis. 8.7.2 Example for poor water soluble analvtefs) or those with adsorption difficulties: Prepare a solution of the test substance in acetonitrile (Example: A 500 pg/mL test analyte solution is prepared by diluting 500 pl of stock solution (Section 8.6.1) into a 10 mL volumetric flask and diluting to mark with acetonitrile). Calculatethe test analyte concentrationsuch that the organic content in the test vial is no more than1% of the total sample matrix volume. Example: A 1 pg/mL test analyte in the test matrix (Section 8.3) is prepared by injecting 10 pL of a 500 pg/mL test substance stock (Section 8.6.1) into a VOA vial containing 5 mL of the test matrix. *Acetonitrileis currently thepreferred solvent to use when introducingthe test substance to the test matrix because it does not interfere. Methanol is a radical scavenger, which canphotooxidizeduring the exposure and decrease the indirect photolysis of the intended test substance. Evidence of thisphenomenon (approximately10% decrease in the concentrations of thefinalproducts) has been observedin a study here at 3M (EtFOSE-OHphotolysisinpH 7buffer, with and withoutpresence of Meow). 8.8 Target Analyte(s) Spiking solution: Example: A spike solutionof test analyte and target analyte(s) (e.g. projected degradationproducts) in methanol or acetonitrile is prepared by diluting 500 pL of test analyte stock solutionand 100pL of target analyte(s) stock solution (Section 8.6.1) into 10mL with MeOH. The final concentrationis approximately 500 p g / d test substance/ 100pg/mL target analytes. Addition of 10 pL of this target analyte spiking solutioninto the 35-mL diluted samplevolume will result in approximately140ng/ml and 30 ndnd concentrationsfor the test analyte and targ6t analyte(s), respectively. We-estimation of the degradationpotential of the test analyte and subsequent degradationproducts is not alwayspossible. Ifpossible, an analyticalprescreening of representative samples should beperformedfor accurate spiking. Generalrule of thumb has been that the test analjte spike amount be ETS-8-176.QPreporationof Samplesfor Photolysis Studies in Aqueous Matrices Method Page 10 of 18 Page 46 of 148 BACK TO MAIN 3M Environmental Laboratory Report No. E00-2192 approximately 25%- 50% of the initial concentratioR The target analyte(s) spike amount has been 10-I 00ng/ml, depending on expected levels under specifc conditions, More than one spike solution may be utilizedto adequatelyrepresent the levels in the samples. &ample: A test analyte that undergoessignificantdegradation duringphotolysis will require a lower spike concentrationin the Exposed sample set due to less test analyte remaining. TheDay 0and Unexposedsample sets, which have not degraded, may require higher test amlyte spike concentrations. 8.9 Dilution Solution containing Internal Standard: The diluting solution shall contain internal standard at an area response level equivalentto approximatelyhalf the are response of the test analyte's high standard in the calibrationcurve. Enough dilution solution shall be prepared for use in all the study samplesand in preparation of the calibrationcurve samples. Example: Internal standard solution is prepared by diluting 100 pL of stock solution (Section 8.6.1) to 4.0 L with MeOH to a concentration of 250 ng/mL. 8.10 Quininemonohydrochloridedihydrate(QMD). 90%from Aldrich Chemical. 8.11 QMD solution: A 2%(wh) solutionof quininemonohydrochloridedihydrate solution is prepared by weighing approximately2.0 g into a weigh boat, transferringto a 100mL . flask and diluting to volume with Milli-Q" water. - 9.0 9.1 9.2 9.3 9.4 SAMPLE HANDLING Record times of initial preparation, reference numbers of reagents used and the amounts, appropriatedates, times and initials on the photolysis sample preparationworksheet.. Record photolysis reactor used, radiometer ( if applicable), computer for data collection, photolysis start and end on the samplepreparation sheet and in the photolysis reactor log books. Record times, dates and initials of sample treatment post-photolysis, reference numbers of reagents used, and storage conditions. Upon addition of the test substance solution, invert the 40 mL. VOA sample vials (capside down) to prevent loss of any potential volatile target analytes during the rest of the procedure. This is particularly important for the G C M S samples. GCMS samples may only be turned upright immediatelybefore being loaded onto the purge and trap autosampler. The LCMS samplesmay be turned upright after the photolysis process has been completed. The exception to this being the need to briefly turn the samples upright for H202 injectionthrough the septa of the appropriate VOAsample vials at specified time intervals (See Section 12.6 and Section 12.I l ,7). The completed photolysis samplesremain inverted and refrigeratedat 1-5'C prior to analysis by LC/MS or sample purge and trap GCMS. Samplepreparationprior to LCMS analysisrequiresthe additionof 30 mL of diluting solvent containing internal standard to the 5-mL photolysis samples. This is to ensure complete recovery of the target analytes fkom the glass VOA vial surface and to dilute the samples into a working analytical range. Day 0 study samples stored at 1-5 OC during the time of photolytic exposure. are removed and prepared for analysis at the same time as the exposed and unexposed samples. ETS-8-176.OP~eparatjoonf Samplesfor Photolysis Studies inAqueous MatricesMethod Page 11 of 18 Page 47 of 148 BACK TO MAIN 3M Environmental Laboratory Report No. E00-2192 10.0 QUALITYCONTROL 10.1 Refer to the definitionssection for the quality control specifiedfor each respective sample type. 11.0 CALIBRATION AND STANDARDIZATION 11.1 The compounds of interestmust be characterizedaccordingto laboratory specifications. 11.2 All equipment used, such as the analytical balance, radiometer, etc. should be calibrated prior to use (daily, weekly, etc.) as specifiedin the standard operatingprocedure(s). 11.3 All samples analyzed will be run against a standard curve containing varying amounts of target andytes, and a fixed amount of internal standard or surrogate compound. Refer to the appropriateLC/MS and GCIMS methodologiesfor further analyticalinformation. 12.0 PXOCEDURE 12.1 Obtain the absorbance spectraof the test compoundin aqueous solutionusing a W- Visible Spectrophotometer(ETS-9-46.0). 12.1.1 Using a 10-cmquartz spectrophotometercell, obtain a blank water absorbance reading over the range 290-800 nm to determine a background or baseline reading. 12.1.2 Aliquot a solutionof water containingtest substance, at a concentrationless than half the solubility limit, into a 10 cm quartz spectrophotometer cell and obtain an absorbance reading over the range 290-800 nm. A positive absorbance may indicate the potential of the analyte to undergo direct photolysis. Non-absorbing d y t e s would be more likely to undergo indirectphotolysisas the potential degradation pathway. 12.2 Obtain the appropriate number ofclear and amber 40-mL glass vials with caps and cardboard boxes. Label the vial caps using a black permanent pen to distinctly identify samples. Paper labels will be applied post-hydrolysis as they don't stick in water. 12.3 Prepare appropriatesamplepreparation worksheets and create labelsfor each sample to affix to the 40 mL VOA vials and the autovialsfor analysis after photolysis. The labels should include the study number, sample number, test compound, matrix, exposure type (exposed unexposed Day 0), date and initials of the analyst. 12.4 Aliquot 5 mL of the following solutions into clear (for EXPOSED samples) and amber (for UNEXPOSED and DAY 0 samples)40 mL glass VOA vials: 12.4.1 Matrix with test substance (sample reps 1,2,3, and sample spike). 12.4.2 Matrix without test substance(matrix blank and matrix blank spike). 12.4.3 Control matrix with test substance (control sample and control spike). 12.4.4 Control matrix without test substance (control blank and control blank spike). (When appropriate, festsubstance may be added after 5mL aliquots of matrix have been added to the vials. See Section 8.7) 12.5 All exposed, unexposed, and day 0 samples will contain sample sets with and without peroxide and prepared for LCMS and GCMS analyses accordingto the following table: ETS-8-176.OPreparation of Sumpiesfor Photolysis Studies in Aqueous Matrices Method Page 12 of 18 Page 48 of 148 BACK TO MAIN 3M Environmental Laboratory Report No.E00-2192 Sample Treatmenmype Matrix with test substance Matrix without test substance Control matrix with test substance Control matrix without test substance EXPOSED,UNEXPOSED,& DAY 0 # of Samples 6 +HZ02(3LC/MS,3GC/MS) 6 -HzOz(3LCMS ,3GC/MS) 2 i&O2 (1LCIMS,lGCIMS) 2 -HZ02 (1 ILCIMS,IGCMS) 2 +HzO2 (lLC/MS,IGCiMS) 2 -HzOz (IlLCIMS,lGC/MS) 2 +HzOz(lLC/MS,lGC/MS) 2 -HzOz (I lLCIMS,IGCIMS) 24x 3perexptypes72 # of Spikes 2 +HzO2 (lLcIMS,lGCIMS) 2 -HzOz(lLC/MS,lGC/MS) 2 +HZ02 (lLCIMS,lGCIMS) 2 -H24(lLC/MS, 1GCIMS) 2 +HZ02 (lLC/MS,lGC/MS) 2-H24 (1 lLC/MS,lGC/MS) 2 +HzOz(ILC/MS,lGCIMS) 2-Hz02 (1 lLC/MS,lGCMS) 16x3=48 12.6 Separatethe vials into three boxes labeled "Day 0,""Exposed," and "Unexposed." Initial - addition of peroxide (Section 8.4) is done at this time by removingthe cap and injecting the appropriateamount (e.g. 10 50 pL) into the vial. (Subsequent additionsof peroxide shall be injected through the septa of the VOA vials.) 12.7 For use of quinine actinometer (Optional): Prepare a batch of quinine irradiation control samples by aliquoting 5 mL of the 2% aqueous solution (Section 8.8) into the appropriatenumber of clear and amber 40 mL I-CHEM vials. Prepare one clear and one amber vial per reactor, per day ofexposure. Store the vials at 1-5 OC and protected from light prior to use. Place one clear vial in the reactor per day, while removing exposed quinine controls. Exposed quinine controlsneed to be wrapped in foil upon removal to protect from furtherexposure. Store at 1-5 "Cprior to measuring the absorbance via W-Vis Spectrophotometer. The absorbancemeasurement should be performed as soon as possible, as the absorbance increase rate after light source removal may be 20% of the rate of when light is present. (Reference 18.5). 12.8 Place all the "Day 0" samples immediately in a cooler at 1-5 OC or freeze at a continuos temperatureof less than 0 "C,inverted and protected from light. 12.9 Place "Unexposed" samplevials (amber) into Ziploc@bags separated and labeled as "with peroxide" and " without peroxide", respectively. Place the bags in the bottom of the water bath, under the photoreactor tray that holds the exposed samples. The "unexposed" sampleswill remain immersed in the 23-26 "Cwater bath under the exposed samplesfor the duration of the exposure. Includeone quininecontrol sample in an amber vial with the unexposed sample set. 13.01 PHOTOREACTORSET UP ETS-8-176.0Preparation ofSamp/esfor Photolysis Studies in Aqueous Matrices Method Page 13 of 18 Page 49 of 148 BACK TO MAIN 3M Environmental Laboratory Report No. E00-2192 13.1 Set the irradiationintensity at the desired output. For most experimentalconditions, an intensity of 261 W/m2is chosen because it yields the equivalent average optimum natural daylight d i t i o n for 300-400 nm at known latitude. (see the table below): Irradiance Source Average Optimum Natural Daylight' Atlas Photoreactorwith intepted irradiance output of 261 W/m 300-800 nm using the IR Reflecting and 290 cuton filters Approximate Inteerated and Individual Irradiances in W/mz 250-300 nm 300-400nm 400-800 nm 340nm 420 nm 0.0 27.8 259.0 0.30 0.67 -~ 0.08 27.8 234.36 0.24 0.71 Parameter Flowing Water CIFW") Irradiation intensity Duration of exposure Setting ON Example: 261 watts/rn* Example: Bhours ETS-8-176.OPrepurrationofSamplesfor Photolysis Studies in Aqueous Matrices Method Page 14 of 18 Page 50 of 148 BACK TO MAIN 3M Environmental Laboratory Report No. E00-2192 13.9 13.10 13.11 13.12 for the unexposed samples, reactor tray holder for the exposed samples, or the cooler for the Day 0 samples). Note: Don't forget to addperoxide to appropriateDay 0 samples! Remove the exposed quininecontrol sample from the reactor tray and visually c o n f m a color change as an indicator of photoreactor performance. The solution should be a grayhrown color after irradiation. Record the total time exposure of the sample, wrap the sample in foil to protect from light and analyze the quinine sample. Place a new quinine solution vial into the photoreactor tray with the exposed samples. Note: Quininesamples do NOT receiveperoxide. Record the chambertemperaturedaily on the sample prep sheets. Upon completion of the photolytic exposure, samples are removed, labeled with adhesive-backed labels and the study sets (Exposed,Unexposed and Day 0) organized for LC/MS or GCMS analysis. If subsequentanalysis can not be performed immediately, store samples in a cooler at 1-5 OC. Pertinent information regarding start and stop times of photoreactor exposure study, water bath and chamber temperatures, addition of peroxide, and an explanation of unexpected occurrencesshall be documentedon the sample preparationworksheets, with appropriatedates, timesand initials, 14.0 SAMPLEPREPARATIONFOR ANALYSIS. 14.1 LC/MS sample extraction and prep. 14.1.1 Dilute all 5 mL samples by a factor of 1:7 v/v by adding 30 mL of an appropriate analytical solvent containing internal standard (Section 8.6.2) to all vials. 14.1.2 Add spike solution (Section 8.6) containing the target analytes to the appropriate samples. 14.1.3 Ensure the sample vials are inverted several times to ensure adequate mixing. 14.1.4 If samples appear cloudy, and/or the sample matrix appears unclear, it may be necessaryto centrifige the samples, at an appropriate speed and duration (e.g. 2000 rpm for 10minutes), until no noticeableparticulate matter is suspended in the sample. 14.1.5 Aliquot approximately 1mL into autovials and tightly cap. 14.2 G C M S sample preparation. 14.2.1 Set up autosamplerand concentratormethods. If samples'havebeen kept in cold storage, bring samplesto room temperature (approximately23-26"C). 14.23 Spike vials through the septa and place in the autosampler. 15.0 DATAANALYSISAND CALCULATIONS 15.1 The amount of target analytes in the sample will be quantified against a standard curve regression. 15.2 Means will be calculatedby addingthe individualentities and dividingthe resultant sum by the number of individualentities. 15.3 Standard deviationswill be calcdated using either Microsoft Excel@or Microsoft Access@to calculate standarddeviation. The built in function contains the following equation which is based on the individual entities (n) being less than 30: JnCx2 -(Cn)2 n(n-1) ETS-8-176.0PrepurutionofSamplesfor Photolysis Studies in Aqueous Mairices Method Page 15 of 18 Page 51 of 148 BACK TO MAIN 3M Environmental Laboratory Report No. E00-2192 15.4 Sample precision will be reported as % relative standard deviation (% RSD). Sample % RSD will be calculated using the following equation: where: A B X 100=Sample % RSD A= standard deviation of averaged samples B= average of samples 16.0 METHOPDERFORMANCE 16.1 Refer to the definitions section for the method performance specificationshiteria for each respective sample type. 17.0 POLLUTION PREVENTION AND WASTE MANAGEMENT 17.1 Dispose of samplewaste by placing in high or low BTU containersas appropriate. Use broken glass containersto dispose of glass pipettes. -18.0 RECORDS 18.1 Fill out the photolysissample preparationworksheet documents completely,makiig sure to include all initials and dates. Store photolysis sample preparationworksheets in the raw data file. 18.2 Enter all standard, stock, solutions,etc. preparation information in the proper preparation logbook(s). Make a photocopy of the logbook pages used, and include the copy in the raw data file. Photocopied logbook pages will be included in the final data packet. 18.3 Archive electronic data to compact disc media. ~ 19.0 ATTACHMENTS -~ 19.1 Attachment A: Example Photolysis Prep sheet. 20.0 REFERENCES 20.1 Crosby,Helz, and Zepp. Aauatic SurfacePhotochemistrv.p 480 20.2 Interpersonalconversationwith Carrie O'Connor, Optical Systems Engineer, Atlas Electric Devices. 20.3 "Suntest CPS/CPS+ Spectral Irradiance Distribution," table distributed by Atlas Electric Devices Company, sent via fax by Richard Sherwin, SalesRepresentative,26 July,2000. 20.4 "Atlas Xenon Filter Combination and Sunlight Measurements," information generated by Atlas Electric Devices Company sent via fax by Richard Sherwin, Sales Representative, 26 July, 2000. ETS-8-176.OPreparationof Samplesfor Photolysis Studies in Aqueous Matrices Method Page 16 of 18 Page 52 of 148 BACK TO MAIN 3M Environmental Laboratory Report No. E00-2192 20.5 Bergstrom, David H., Thomas C. Kester, and Shangdong Zhan."Quinine Chemical Actinometry StudiesUnder TwoLight Sources Specifiedby the ICHGuidelineon Photostability Testing." 21.0 AFFECTEDDOCUMENTS 21.1 None 22.0 REVISIONS Revision Number. - - Reason For Revision ___ ~ ~ Revision - Date ETS-8-176.OPreparationofSamplesfor Photolysis Studies in AqueousMutrices Method Page 17 of 18 Page 53 of 148 BACK TO MAIN 3M Environmental Laboratory Report No. E00-2192 Attachment A - Photolysis Sample Prep Sheet Tu1Andyte P r o j a t h h Requat Number ExpamreType: Nomind Eipor Annlylir: Control Matrix: FluorocbemicalDegradation(Photolysis)AnalysisSamplePrep Sheet *FoNowlnglnltld sampleptvp all sumplea 1~11b1aplaced caprl&Lwn mrdverrlcd. Fd/owit@oto/pk Lky 0smnplrc wfllkpulled mrdeXUUWd withE r p a r r d d Wnuparedsumplcs I I I I I ETS-8-176.OPreparation of Samplesfor PhotolysisStudies in Aqueous Mowices Method Page 18 of 18 Page 54 of 148 BACK TO MAIN 3M Environ-mentalLaboratory Report No. E00-2192 3M ENVIRONMENTALLABORATORY EQUIPMENPTROCEDURE OPERATIONAND MAINTENANCE OF THE SUNLIGHT EXPOSURE SYSTEM, IMMERSION U",AND RECIRCULATINGWATER CHILLER SYSTEM Procedure Number: ETS-9-44.0 Exact Copy of Original @? ,3-zy-4J Initial Date Approved by: Revision Effective Date: ETS-944.0 Equipment Procedurefor the Atlm S W E S T Sunlight ExposureSystem Page 1of8 Page 55 of 148 BACK TO MAIN 3M Environmental Laboratory Report No. E00-2192 1.0 SCOPE AND APPLICATION 1.1 This equipmentprocedure describesthe regular operation and maintenanceof the Atlas SUNTEST"SunlightExposure System equippedwith an immersion unit and recirculating water chiller. 2.0 DEFINITIONS 2.1 Photon energy: U =hv =hc/h where h is Planck's constant, c is the speed oflight, and v and h are the frequencyand wavelengthof light. Therefore, the energy ofa photon, U, is inverselyproportionateto the wavelength. 2.2 Irradiance: The energy output ('TJ" in the above equation for energy of a photon) in Wattsfm2specific to a wavelengthor wavelengthrange. The irradianceoutput specificto the types of Atlas wavelength filters available(Reference 14.9) shouldbe used as a guide to calculating the global irradiance (in units of W/(m2nm)needed to give a specific energy over a desiredwavelength range. 3.0 DESCRIPTION 3.1 The Atlas SUNTEST"SunlihtExposureSystem CPS+ or XLS+) produces visible and ultraviolet light (250-765 W/lm2).Light proiuced is filtered with afilter or combination of filters to aIIow specificwavelengthranges. Samples are exposed to the light in a reflecting chamber. An immersion unit with water recirculation through a chiller provides a cooled, constant sample temperature. 4.0 IDENTIFICATION 4.1 Atlas SUNTEST@XLS+, equippedwith a xenon arclamp, lamp filter(s) available from Atlas to allow specific irradianceranges, and immersion unit. 4.2 Atlas SUNTEST@a s + , equippedwith a xenon arclamp, lamp filter(@available from Atlas to allow specific irradiance ranges, and immersion unit. 4.3 Neslab CFT-33Refrigerated recirculator or equivalent 5.0 WARNINGS AND CAUTIONS 5.1 Health and Safety Warnings: 5.1.1 Wear appropriate laboratory safety personal protective equipment. 5.1.2 The xenon lamp emits ultraviolet light which can cause burns to the skin and permanent damage to the eyes. Never attempt to operate the unit with the test chamber door open. 5.1.3 When filling the sample immersion unit with water, always shut off all power to the SUNTEST@device and the immersionunit to prevent electrical shock. 5.2 Cautions: 5.2.1 Handle optical parts carefully; fingerprints on the lamp, filter or quartz dish can result in altered spectral output or early lamp failure. 53.2 The reflective coating of the test chamber walls is sensitive to scratches. Do not use any abrasives or harsh cleaning agents that may cause scratches and nonuniform illumination of the test chamber. ETS-9-44.0 Equipment Procedurefor the Atlus SUNTEST Sunlight Exposure System Page 2 of 8 Page 56 of 148 BACK TO MAIN 3M Environmental Laboratory Report No. E00-2192 5.2.3 Keep SLJNTES'Punit clear of obstructionsthat would block vents; overheating may cause blown fuses, shortened lamp life or other damage. 5.2.4 After beginning the experiment, always make sure that the sample vials are sufficientlysubmerged. Excessive heat may affect the results of the experiment. 5.2.5 Manually drain the immersion tank on the XLS+ models after stopping the run; otherwise, the water will overflow. 6.0 SPECIAL INSTRUCTIONS 6.1 None. 7.0 RESPONSIBILITY 7.1 The analyticalgroup of personnel who routinelyoperates the equipment is collectively responsible for the instrumentoperation as described in this document. The person responsible for maintenance and calibration (and an alternate)will be identified in the h n t of the equipment logbook. 8.0 SUPPLIESAND MATERIALS 8.1 Xenon lamp for XLS+, Atlas PN 56077798 8.2 Xenon lami for CPS+,Atlas PN 56001794 8.3 Hand-tools as required 8.4 --WipesTM 8.5 Optionalradiation filter(s) for lamp available h m Atlas: Filter1 Atlas Part Number Quartz Dish w/ IR reflective coating, PN 56052388 Quartz Dish, PN 56052373 W Special SupraxQFilter,PN 56052371 Window Glass Filter, PN 56052372 Window Glass Solar ID 65 Filter, PN 56077769 Solar StandardFilter, PN 56077759 i ProDerties IEt reflective coating (supplied standard with unit) Uncoated (to allow higher black standard temperatures) Cut-on at 290 nm,simulatesoutdoor solar 1 radiation. I Cut-on at 310nm, simulates exposurebehind 3 mm (0.118in.) window glass. Cut-on at 320 nm, simulates exposure behind 6 mm (0.236in.)window glass. (Must be used with Window Glass Filter above.) Cut-on at 290 nm,simulates outdoor solar radiation at optimal U V intensity. ETS-9-44.0 Equipment Procedurefor the Atlas SUNTESTSunlight ExposureSystein Page 3 of 8 Page 57 of 148 BACK TO MAIN 3M Environmental Laboratory Report No. E00-2192 9.0 CLEANINPGROCEDURES All routine and non-routine cleaningprocedures will be performed by person(s) designated in the front of the instrument logbook;see Section 12). 9.1 Routine cleaning 9.1.1 Clean the inlet air filters at the back of the SUNTEST@unit every 6 months with a mild soap solution. Rinse in clean water. When more severe contamination is present, vacuum the filters or replace them. 9.1.2 Clean the reflector in the test chamberwhen it is dirty,using a soft cloth and mild soap solution. DO NOT use any abrasive,cleaningmaterials or the reflector may be permanentlydamaged and irradianceuniformitywill be altered. 9.1.3 Clean and/or flush the water tank and water lines on the immersion unit monthly to prevent build up of residuein the circulatingwater system. 10.0 MAINTENANCPREOCEDURES 10.1 Routine maintenance will be performed by the person(s) designated in the front of the equipment log (see Section 12): 10.1.1 Replace the xenon lamp after 1500hours or when the required irradiance level cannot be achieved (e.g. error message reads "E MAX Power reached; CHANGEXENON L W " ) Refer to the SUNTESP instructionmanual for details on how to replace the lamp. 10.1.2 If the temperaturenear the lampbecomes too high, the h e blows to interrupt power and save the lamp (indicated by the error message "DOOR OPEN or TEMPERATUREFUSE"). Refer to the SUNTEST" instructionmanual for details on how to replace the fuse. 10.1.3 Record routine maintenance in the equipment log (see Section 12). 10.2 Non-routinemaintenancewill be performed by the person@)designatedin the ftont of the equipment log (see Section 12): 10.2.1 If the equipment fails to operate, refer to the equipment manual for further instructions, if necessary. Contact the Team Leader for instructions if the equipment cannot be made operational. 10.2.2 If an abnormal operating situation occurs or if calibration verification fails, contact the responsibleindividual identified in the equipment log. Label the equipment as "out of service" if it cannot be immediately repaired. 10.2.3 Record non-routine maintenance in the equipment log (see Section 12). 11.0 INSTRUMENT CALIBRATION 11.1 The photoreactor is set to maintain a specified integrated energy output. The amount of energy output fkom the lamp may be monitored with the use of a radiometer. The radiometer system will provide and record instantaneous energy output. Refer to ETS-950.0 Operation and Maintenance of Radiometer and Detector. 11.2 Calibration of SUNTEST" systems will be performed two times each year by Atlas Electric Devices Company. ETS-9-44.0 Equipment Procedurefor the Atlas SUNTESTSunlight EXpOSltre System Page 4 of 8 Page 58 of 148 BACK TO MAIN 3M Environmental Laboratory Report No. E00-2192 12.0 OPERATINPGROCEDURES 12.1 For more detailed operating instructionsrefer to the equipmentoperatingmanuals. 12.2 Immersion Unit 12.2.1 To begin operation, fill the tank with water until the level indicator is up to the full mark. 12.2.2 T u the power on. 12.3 Chiller 12.3.1 Turn the power on. Set water temperatureknob to desired set point. Allow temperatureto equilibratebefore igniting the SUNTEST" lamps. 12.4 SUNTEST" XLW or SUNTEST@CPS+ unit set-up 12.4.1 Select the desired wavelength filter b m the parts listed under Section 8.4 to achieve the proper irradiation specified in the program, and program the photoreactor with the filtertype information: With the photoreactor menu in the ''Program" mode, select the appropriate filter combination type: ODtical filter System Designations A: Coated quartz glass only B: Coated quartz glass with W special glass C: Coated quartz glass with window glass D: Uncoated quartz glass only E: Uncoated quartz glass with W special glass F: Uncoated quartz glass with window glass I I 12.4.2 Selectioddetemination of energy output (W/m') 12.4.2.1 Irradiancecontrol and display is between 250-765 W/m2(nominally300800nm). The irradianceis determined by the settingsof the test program [includingtype of filter@)used]. The selectablerange is from 250 W/m2 to 765 W/m2 (page 12, XLS-t Instruction manual). T h e total (integrated) energy output (300-800 nm) is directly dependent on the type of lamp filter@) used. E.g. if the filter has a narrow range such as a cut-on at 400 nm, all irradiance energy coming from wavelengths c400 nm will not reach the samples, and the total integrated irradiancewill be less than if the filter's cut-on was at, for example, 290 nm. 12.4.2.2 Oncethe proper filter(s) idare designated,the photoreactor will base the energy output on what type of wavelengths are being allowed to pass through the filter system to reach the samples. To calculate the energy output to program into the system, refer to References 14.7, 14.8 and 14.9 as guides to calculate the desired spectral irradiance. Reference 14.7 may be used to calculate the programmed global irradiance necessary to achieve desired irradiances at specific wavelengths or wavelength ranges. Reference 14.8 may be used to reference sunlight measurements and to correlate natural sunlight to the Atlas Suntestmphotoreactors. Reference 14.9 is a useful reference for determiningirradiancesat a specific ETS-9-44.0 Equipment Procedurefor the Atlas SUNTESTStmlight Exposure System Page 5 of 8 Page 59 of 148 BACK TO MAIN 3M Environmental Laboratory Report No. E00-2192 wavelength or a wavelengthrange using specific filter combinationsat specified global irradiances of 250,500, and 765 W/(m2nm). 12.5 Photoreactor M y s i s set up 12.5.1 Place VOA (volatile organic analysis) vials containing samples (see the appropriateanalyticalmethod) into the test chamber. Sample vials to be exposed must be cap side down to allow light to enter the vial. Tighten caps securely to prevent leakage. Secure the vials in the chamber to prevent floating once the water begins to circulate. 12.5.2 Close the chamber door and turn the power on. 12.5.3 From the initial LCD display, use the arrow keys to select Program. Press "Enter". 12.5.4 If programming a new method is necessary, use the arrow key to select Programming. Press "Enter". 12.5.5 Input program number, number of phases, desired irradiance, immersion hction, phase time and switch offcriteria. Each entry is followedby the "Enter" key. 12.5.6 To start the program, select "Program Start" and press the "Enter" key. 12.5.7 Press "Escape" for the next screens if the filter has not been changedand no printout is desired. Input program number and press "Start" 12.5.8 Program will begin with lamp ignition. Note: Due to the modified sample chamberin the SUNTEST@XLS+ models, the water initiallypresent in the immersiontankis not sufficientto fill the samplechamber once a program has started. Refill the immersion Unit as the water level drops below the fill line. Once a program has finished,drain the immersiontank so that it does not overflow when water from the sample chamber drains back down into the immekion unit. Failure to do so may result in remote flooding. 12.59 To interruptoperation(e.g. to add peroxide reagent)Press"Stop". If it is necessaryto turn the power off (to exchange the lamp, for example)wait until the fanturnsoff in 1-3 minutes before turning power switch to "Off' and unplugging the power cod. When ready to continue operation, turn power "On". 12.5.10 To resume operation, press "Start". The program will continue at the point of interruption. 12.5.11 To read parameters during the program run, scroll through the parameters of the running program by using the arrow keys. This is helpful to see how many more hours are remaining in the running program. 12.5.12 The SUNTEST@will shut off automaticallywhen the switch-off criteria are reached. To display the total time and irradiance, press "Enter". Record exposuretime in instrument run log. Then turn power "Off'. 12.5.13 To manually stop the program, press "Stop". Wait until lamp is cooled, then press "Escape". Power can then be turned "Off'. ETS-944.0 Equipment Procedurefor the A t I a SUNTESTStinlight ExposureSystem Page 6 of 8 Page 60 of 148 BACK TO MAIN 3M Environmental LaboratoryReport No. E00-2192 13.0 RECORDS 13.1 Instrument logbooks 13.1.1 Equipment Log: The person(s) designated at the front of the equipment log will record all cleaning and maintenance activities in the appropriate log for each SUNTEST@system. Records for routine maintenance of equipmentmust include the dates of the operation, whether the operations followedthe SOP,and the initials of the person performing the operation. Records for non-routine repairs performed as a result of instrument failure or malfunction must include the nature of the defect, how and when the defect was discovered, any remedial action taken in response to the defect, and the date and initials of the person performingthe maintenance. Maintenanceby outsidecontractors should include their name and company affiliation. 13.1.2 Run Log: Record each experiment in the appropriate instrument logbook. Enter the operatorsinitials, time and date of exposure, lamp intensity and water temperature as the samples are placed in the chamber. When samples are finished, record the time and date when samples came out, the ending chamber temperature and the actual hours of exposure. All entries made in the run log should be initialed and dated. 13.1.3 SUNTEST"Data Output Log: XENOVIEW@2.2Storage S o h a r e will receive and record the measurement data transferred from the SUNTEST@ system to a computer or printer, while a program is in progress. The measurement data recorded includes: number of phases, phase time, chamber temperature, radiant exposure, irradiance, running time, date and time data is recorded. Refer to XENOVDEW" software instructionmanual for details on how to operate software. Any printoutsof program or other data should be initialed and dated prior to adding to the study file. 13.2 1dentification.recordsfor each system include equipment ID, manufacturer, model number, and serial number of each individualcomponent. In addition,if components are removed or added,the above informationmust be writtenin the logbookincludingthe date the change was made and initials of the analyst completing the change. 14.0 REFERENCES 14.1 SUNTEST@XLS/XLS+ Instruction Manual, Doc. No. 20-8036-00Rev. 0 12/98Atlas Electric Devices Company. 14.2 SUNTEST@CPS/CPS+ OperatingManual, 6/97 Atlas Company. 14.3 SUNTEST@X L S + ImmersionDevice OperatingManual, 2/99Atlas Company. 14.4 SUNTEST@CPS+/XLS+ Software Documentation 1.4 Atlas Company. 14.5 XENOVmV 2.2 Storage Softwareoperating Instructions. 14.6 ETS-9-50.0,Operation and Maintenanceof Radiometerand Detector. 14.7 *`SUNTEST%adiance in W/m2*nm". Tables finished by Atlas Company, 14.8 "Atlas Xenon Filter Combination". Table furnished by Atlas Company. 14.9 "SUNEST" CPS/CPS+Spectral IrradianceDistribution". Table furnished by Atlas Company. ETS-94.0 EquipmentProcedurefor the Atlas SUNTEST SunlightExposure Systein Page 7 of 8 Page 61 of 148 BACK TO MAIN 3M Environmental Laboratory Report No. E00-2192 15.0 AFFECTEDDOCUMENTS 15.1 None. 16.0 REVISIONS Revision Number. Reason For Revision Re- Dvaistieon ETS-944.0 Equipment Procedurefor the Atlas SUNTEST Sunlight Exposure System Page 8 of8 Page 62 of 148 BACK TO MAIN 3M Environmental Laboratory Report No. E00-2192 3M ENVIRONMENTLAALBORATORY ANALYSIS OF FLUOROCHEMICBAYLASRCHOPNURGEAND TRAPAUTOSAMPLER, TEKMARPURGEAND TRAP CONCENTRATORAND AGILENTGAS, CHROMATOGRAPHBSVP~EACSTSROMETER Procedure Number: ETS-3-1820 Exact Copy of Original "r sizz+ Initial Date Approved by: T Laboratoj Manager Adoption Date: 112a 00 Revision Date: ,h/&/Ud Date ETS-8-182.0 Analysis of FCs by Purge & TrapAutosampler/Concentrator/GC/MS Page 63 of 148 BACK TO MAIN 3M Environmental Laboratory Report No. E00-2192 1.0 SCOPEAND APPLICATION 1.1 Scope. This method is used for the analysis of selected hydrolysis and photolysis samples for the presence of degradationproducts such as olefins and hydrides using gas chromatographylmassspectrometryina fullscan mode. An Archon autosampler and Tekmar Purge and Trap concentrator (or an equivalent system) is coupled to a GC for purging analytes from the liquid matrix and concentrating them on the trap column before injecting on to the GC. 1.2 Applicable compounds. Compoundsthat may be analyzed by this method are listed below. Other fluorochemicalsmay be detected by monitoring mass spectra and running library comparison. Compoundsthat are detectedbut do not have appropriatestandards, will be quantifiedrelative to structurallysimilarstandard compounds listed below. 1.2.1 lH-perfluoroethane (1H-pfC2) 1.2.2 Perfluro-2-butene(pfC4-2ene) 1.2.3 1H-perfluropropane(1H-pfC3) 1.2.4 IH-perfluorobutane(lH-pC4) 1.2.5 Perfluoro-2-heptene (pfC7-2ene) 1.2.6 Perfluoro-l-heptene (pfC7-lene) 1.2.7 1H-perfluorohexane(1H-pE6) 1.2.8 Perfluoro-2-octene (pfC8-2ene) 1.2.9 1H-perfluoroheptane(1H-pfC7) 1.2.10 2H-perfluorooctane (ZH-pfC8) 1.2.11 1H-perfluorooctane(1H-pfC8) 1.3 Instrument Surrogate compounds.Added at the time of analysis and used to monitor performance of purge and trap autosampler and concentrator. 1.3.1 Dibromofluoromethane 1.3.2 Toluene-d8 1.3.3 4-Bromofluorobenzene 1.3.4 Pentafluorobenzene 1.3.5 1,4-Difluorobenzene 1.3.6 Chlorobenzene-d5 13.7 1,4-Dichlorobenzene-d4 1.4 Sample Surrogate compounds. May be added at the time of sample preparation. 1A.1 Perfluorocyclohexane 2.0 SUMMARY OF METHOD 2.1 A dynamic purge and trap system (autosampler and concentrator) is coupled to a temperatureprogrammed GC for analyte separation and subsequent mass spectrometer detection and quanitation. The liquid sample is purged for 20 min. in the sample vial, and the volatile components are swept onto a chemical trap in the concentrator. In the subsequent desorption mode, gas flowsin opposite direction and temperatureof the chemical trap increases to 250 "C. The trapped analytes are transferred onto the GC column for GCMS separation, detection, and quanitation. Through this process, a high volume of sample is injected and most of the non-volatile matrix components stay in the samplevial, allowinglow level detection of fluorochemicals. ETS-8-182.0 Analysis of FCs by Purge & TrapAutosampler/Concentrator/GC/MS Page 2 of 12 Page 64 of 148 BACK TO MAIN 3M Environmental Laboratory Report No. E00-2192 3.0 DEFINITIONS 3.1 Calibration Standard. A dilution of various amounts of a stock, intermediateor purchased standard to achieve standard soIutions in a concentration range of interest, 3.2 Calibration Curve. The graphical relationship between known values, such as concentrationof a seriesof calibration standardsand their instrumentalresponse. 3.3 External Standard Quantification. Process of establishingthe concentrationof a target analyte by plotting the theoretical amount (in units of ng/mL or pg/mL, etc.) versus the response of the target analyte(s) on column. The resultant curve(s) shall be used to determine unknownconcentrationsby comparingthe area response of target analyte(s) to the area response and correspondinganalyteamount on the appropriateanalyte's calibration curve. 3.4 Coefficient of Determination (r"). The square of the correlation coefficient, It is the proportion of the variation in the dependent variable that is accounted for by the independent variable. 3.5 Instrument Surrogate. An organic compound similar to the target analyte(s) in behavior in the analyticalprocess, but is not normally found in the sample(s). A surrogate may be added to sample vial during instrument analysis. 3.6 Sample Surrogate. An organic compound similar to the target analyte(s) in chemical compositionand behavior in the analyticalprocess, but is not normally found in the sample(s). A surrogatemay be added to sampletriplicates and matrix spike samples along with the test analyte (pre-photolysis). 3.7 Continuing Calibration Verification (CCV). Standards analyzed during an analytical nm to verify the continued accuracyof the calibration curve. This solutionmay or may not be prepared from a different source or lot number than the calibration curve standards. 3.8 Solvent Blank. A sampleof analyte-freemedium that is not taken through the sample preparation process. This blank is used to evaluate instrument contamination. 3.9 Blank, For photolysis studies,there are multipleblanks to adequately represent the variables of the study (Exposed,Unexposed and Day 0 sampleswitldwithoutperoxide addition). The blank is canied through the sample preparation, photolytic and analytical procedures to monitor for contamination during any step. It is also used to establish a chromatographicbaselinehackground and monitor for analyticalinterferenceor suppression of target andyte(s) from the matrix. 3.9.1 Matrix Blank A sample of analyte-fkee matrix (buffered water, lake water, etc.) to which all reagents are added in the same volumes or proportions as used in sampleprocessing. It is used to documentthe test system without test analyte. 3.9.2 Control Blank: A sample of analyte-fleematrix (Milli-Q water) to which all reagents are added in the same volumes or proportions as used in sample processing. It is used to control the test matrix and monitor matrix specific ETS-8- 182.0 Analysk of F a by Purge & TrapAutosampIer/Concentrator/GC/MS Page 3 of 12 Page 65 of 148 BACK TO MAIN 3M Environmental Laboratory Report No. E00-2192 background levels, interferencesor suppressionof target analytgs) from the matrix. 3.10 Limit of Quantitation (LOQ). The lowest concentrationthat can be reliably measured within specified limits of accuracy during routine laboratory operating conditions. The LOQ is generally 5 to 10 times the minimum concentration with a 99% confidence limit that the concentration is greater than zero. However, it may be nominally chosen within these guidelines to simplifydata reporting. For many analytes, the LOQ is selected as the lowest non-;BO standardin the calibrationcurve that is greater than 4 times the level of the matrix blank. 3.11 Sample Triplicates. Three samples taken from and representativeof the same sample source. These are prepared separately and canied through all steps of the exposure, extraction and analyticalproceduresin an identicalmanner. There are multiple sets of triplicate samplesto adequatelyrepresent the photolyticvariables of the study (Exposed, Unexposed and Day 0 WiWwithout peroxide addition). Triplicate samples are used to assess variance of the photolytic method, including sample preparation, photolysis exposure, and analysis. 3.12 Relative Standard Deviation (RSD). A measure of precision defined as the standard deviation of three or more values divided by the average of the values and multiplied by 100.(Also reported as Coefficientof Variation (CV)). 3.13 Analytical Spike. Prepared by adding a known mass of target anaIyte(s) to a specified mount of a sampleor controlmatrixprior to analysis. This assumesthat an independent estimate of target analyte concentration is available. Matrix spikes are used to determine the effect of the matrix on method recovery efficiency. 3.14 Accuracy. The closeness of agreement between an experimentallydetermined value and an accepted reference value. When applied to a set of observed values, accuracy is a combination of a random (precision) and a common systematic (bias) component. For purposes of the study, the acceptancecriterion is 75% to 125%of the nominal value, 3.15 Geometric Mean of the calibration curve: The square root of the product of the high standard concentration and the low calibration curve standard. When preparing calibration curve standards,the number of calibrationstandardsbelow the geometric mean shall equalthe number of calibrationstandardsabovethe geometricmean. Having equal distribution of calibrationstandardsabove and below the geometricmean when analyzing and reprocessingdata,effectivelyweights the curve such that both the high and low ends of the curve are given equivalent significance. 4.0 WARNINGS AND CAUTIONS 4.1 Health and Safety Warnings: 4.1.1 The operatormust be familiarwith the purge and trap autosampler/concentrator/GC/MSsystem and associatedhazards, such as high temperature, effluent venting, solvent use, and low-pressure vacuum system. See instrument manuals ETS-8-182.0 Analysis of FCs by Purge & TrapAutosampler/Concen#rator/GU~S Page 4 of 12 Page 66 of 148 BACK TO MAIN 3M Environmental Laboratory Report No. E00-2192 4.1.2 All exhaust vents, including the GC oven vent, Tekmar concentrator purge vent, split vent and mass spectrometerpump exhaust must be connected to the laboratory vent system to keep potentially hazardous effluent from mixing with laboratory air. 4.2 Cautions: 4.2.1 It is recommended that a grounded antistatic Wrist strap be worn while disconnectingal1wires, contacts, or cableswhich are connected to printed circuit boards within the Archon autosampler, Tekmar concentrator or MS analyzer. 4.2.2 To prevent the breakage of the Standard Vial on the Archon autosampler, do not use my tool and do not overtightenthe thumbnut. 5.0 INTERFERENCE 5.1 Methanol, water and other co-extracted matrix components could interfere with detection decreasing sensitivity. 6.0 EQUIPMENT 6.1 System: "Rufus",or equivalent: 6.1.1 Autosampler: Varian, Archon 6.1.2 Concentrator: LSC2000, Tekmar 6.1.3 GC:6890, Agilent 6.1.4 MS: 5973N,AgiIent 6.1.5 Column, GS-GASPRO 60m x 0.23mm, J&W 7.0 SUPPLKESAND MATERIALS 7.1 Helium, ultra-high-purity 7.2 401111 VOA vials, e.g. I-Chem, S236-0040 8.0 REAGENTS AND STANDARD 8.1 Methanol, Purge and Trap grade or equivalent 8.2 Standards. Typically a minimurnof five calibration standards, ranging fiom 1ng/ml to 20 ng/ml are prepared. This concentrationrange shouldbracket the concentrationof samples and matrix spikes; if the analyte concentrationexceeds thisrange, then the calibration range should be increased, 8.3 Instrument Surrogates. Used only to monitor performance ofpurge and trap autosampler and concentrator and not for quantitation. 8.4 Sample Surrogates.May be used to monitor sample preparation, photolytic exposure and analytical perfonnance. 9.0 SAMPLEHANDLING 9.1 Store standardsand samples in the refrigerator at 4 'C 5 3 C until analysistime. ETS-8-182.0 Analysis of FCS by Purge & TrapAutosampler/Concenhator/GC/MS Page 5 of 12 Page 67 of 148 BACK TO MAIN 3M Environmental Laboratory Report No. E00-2192 9.2 For the analysis, pull samples and standards out of the freezer and bring them to room temperature. 10.0 QUALITCYONTROL 10.1 Calibration Standards. Calibration standards (Section 11) used to generate a calibration curve. The number of calibration standards and the concentration levels should be sufficientto encompass the expected concentrationsof the study samples. In general, a minimum of live calibration standards is required for fit of linear regression. 10.2 Continuing CalibrationVerification ( 0 . Analyze a mid-range calibration standard after a maximum of every fifteen samples. 10.3 Solvent blank. Solvent blanks are run before and after every calibration curve, CCV, matrix and control bIank (see 3.9.2), and after batches of no more than 30 injections. Acceptablevalues for the bIanks are values below 25% of the limit of quantitation 0;OQ of the instrument. If analyte carryover is a problem, use back-to-back solvent blanks. 10.4 Sample Triplicates. hepare and analyze all samples in triplicateto provide a measure ofthe precision of analysis. 10.5 Analytical Spikes. Prepare a matrix spike sample for each sample type as applicable to determine the matrix effect on the recovery efficiency. Concentrations of the spike should be approximately equal to a mid-range calibration standard. The matrix spike sample shouldbe analyzedperiodicallyto measurethe precision associatedwiththe analysis. The analyst shall accept percent spike recoveries of 100 f 25%. Spike recoveriesoutside of this range shouldbe noted and used with other criteria to evaluate the condition of the analyticalrun. Consultwith the Team Leader or designee for direction and final acceptance or rejection of the anaIytica1run. 11.0 CALIBRATIONAND STANDARDIZATION 113.1 Analyze standardsprior to each set of samples. The linear regression will be calculated from the plot of all individualcalibration points, without includingor not forcingthrough zero, using Target NT Software. A minimum of five calibration standards is required to generate. linear regressionfor target analyte(s). If the calibrationcurve residuals are greater than 25% deviationfrom the theoreticalvalue, quadratic curve fitting andor dropping lowhigh curve points may be required if data review shows this to be a consistent and more accuraterepresentation of the instrument response. Document in the raw data the technicaljustification for any deviation and consultwith the team leader or designee for directionand for final acceptanceor rejection of the data. 11.2 If the curve does not meet requirementsperform routine maintenance or prepare a new standard curve (if necessary) and reanalyze ETS-8-182.0 Analysis of FCs by Purge & TrapAutosampler/Concentrator/GUMS Page 6 of 12 Page 68 of 148 BACK TO MAIN 3M Environmental Laboratory Report No. E00-2192 12.0 PROCEDURES 12.1 Set Archon autosampler 12.1.1 Archon System Settings US Probe Temp 180 Xfer line Temp 180 US Valve Temp 105 Gripper Open 750 Gripper Closed 999 Standby Pol CLOSED DesDrn Pol CLOSED STOP Pol. CLOSED Equilb. Count 0 Equilb. Time 0 12.1.2 Archon System Options Barcode Scanner NO Needle Sparge? YES Ign. Vial Type? YES Ignore No Vial? NO HotWater Rinse? NO Vial Checks? YES Beep on Error? YES 12.1.3 Archon Method Sample Type Soil First Vial 1 Last Vial up to 51 Sample VoIume 10 Standard1 ( l a ) YES Standard 2 NO S.PreHeat Stir NO Stir NO Syring Flushes 0 PreHeat YES PreHeat Temp 35 PreHeat Time 1 .o Purge Time 20.0 Desorb Time(m) 0.5 Oper. Mode Remote Cycle Timer 0.0 Am. Timer 0.0 Link to Method 0.0 Soil Purge Flow 40mVmin Soil Purge Pressure 2Opsi ETS-8- 182.0 Analysis of FCS by Purge & TrapAutosumpler/Concentrarator/GU!S Page 7 of 12 Page 69 of 148 BACK TO MAIN 3M Environmental Laboratory Report No. E00-2192 12.2 Set Tekmar options Standby 40C (30C by purge) Purge 20.0omin Dry Purge 2.0Omin Desorb Preheat 245C Desorb 0.5Omin at 250C Bake 1O.OOrnin at 26OOC BGB OFF BGB Delay Osec Auto Drain ON VaIve 180C Line 180C Mount 100C Runs per Sample 1 Purge Flow Purge Pressure Trap 4OmLlmin 2Opsi VOCARB 3000 Containing: Carbopack B Carboxen 1000 Carboxen 1001 12.3 Set GC conditions 12.3.1 Oven: Initial temp: 40 C Initial time: 4.00min Ramp at 15.00 C/min to 28OoC Final time: 1O.Oomin 12.3.2 Front Inlet: Mode: Split Initial temp: 180OC Pressure:8.5Opsi (on) Split ratio: 10.7 : 1 Split flow:16.1mYmh Total flow:20.6 mumin 12.4 Set MS conditions 12.4.1 Adjust conditions as needed to optimize system performance and document operating conditions in the instrumentrunlog. Acquisition mode: Scan (&om 10 m/z to 650 m/z) MS source temp: 230 C MS quadruple temp: 150 C Interface temp: 260 C MultipIier voltage: adjust to give required low standard sensitivity ETS-B- 182.0 Analysis of FCs by Purge & TrapAutosampler/Concentrator/GCLMS Page 8 of 12 Page 70 of 148 BACK TO MAIN 3M Environmental Laboratory Report No. E00-2192 12.5 Set up the instrumentacquisition method. Name the sequence. T h e sequence includes a samplelist documentingthe method used and datafiles created. The sequence should be documented n the run files. 12.6 Sample analysis. 12.6.1 Set up autosampler and concentratormethods. Bring samplesto room temperature (-22 C), spike them and place them on autosampler. Generate a mass spectrometertune report and review. Operatingconditionsprovided above are recommended and may be adjusted to optimize system performance. Analyze all standard, samples, and spiked samples using the same analytical conditions. Document the conditions in the m Iog. ' 12.6.2 When data acquisition is complete, data files shouId be transferred to Target version 4.0 for processing. 13.0 DATA ANALYSIS AND CALCULATION 13.1 Each batch of data should be processed using Target Genie integrator. Integration parameters should be set to minimize the number of manual integratidns required yet still result in uniform integrationof peaks at all concentration levels. If manual integrations are required, a review code should be assigned to indicate the reason. Review dodes are listed below. Reviewcode M- 1- _ M2 M3 M4 M5 -Explanation Peak was not automatically integrated by Target, therefore, integrated _m_an__ u~ a.ll_ v __ Peakwas automaticallyintegrated; was reintegrated manually to improve sample-to-sampleintegrationconsistency. Incorrect quantificationion peak was integrated;manual integration was done to select the correct peak. Incorrect monitor ion peak was integrated; manual integration was done to select the correct peak. Others (sDecifvl 13.2 When data processing is complete, summarizethe data using an appropriateform. Formula is provided below for some of the calculations that may be required. 13.2.1 Calculate matrix spike percent recoveries using the following equation: %Recovery= (observedconcentration-background concentration)'x100 expected concentration 14.0 METHODPERFORMANCE 14.1 Coeficient of Determination (9).The coefficient of determination (?) for the initial calibration curves should be 0.990 or greater. The curves should be examined closely for ETS-8-182.0 Analysis of FCs by Purge & Trap AutosmpIerlConcentraior/CC/MS Page 9 of 12 Page 71 of 148 BACK TO MAIN 3M Environmental Laboratory Report No. E00-2192 linearity and intercept,particularly for accuracy of quantitation at the low and high ends of the curve. Consultwith the Team Leader or designee for direction and for final acceptance or rejection for the data. 14.2 Calibration Standards. The acceptancecriterion for the calibration standardsis that the accuracy of each standard is 75% to 125% (A 25 % difference) of the nominal value. Calibrationstandardsoutsidethis range are to be noted. Documentin the raw data the technicaljustification for deviations. Consult with the Team Leader or designee for direction and for final acceptanceor rejection for the data. 14.3 Instrument Surrogate. Review of the instrument surrogateperformanceis performed by monitoringinstrumentsurrogaterecoveriesthroughout the run. Inconsistenciesin the recoveries may be the result of instrumental changes, or injection error. Consult with the Team Leader or designee for direction and final acceptance or rejection of the analytical run. 14.4 Sample Surrogate. Samplesurrogateperformanceis evaluatedby averagingthe area response throughout the analytical runand calculating %RSD. Inconsistenciesin the surrogatepeak area may indicateinstrumentalchanges, injection error, or changes in the test-system. Consult with the Team Leader or designee for direction and final acceptance or rejection ofthe analyticalrun. 14.5 Continuing Calibration Verification. If the accuracy for the amount of quantified analyte is greater than 25% from the nominal value relative to the initial standard curve, the Team Leader shouldbe consulted. Only those samples analyzed before the last acceptablecalibration check standardwill be used. Consult with the Team Leader or designee for direction and for final acceptance or rejection for the data. 14.6 Solvent Blanks. Solvent blanks should show no more than a 5% carryover from a high standard or calibrationcheck standard. If so, two sequential solventblanks may be necessary to rule out instrumental contamination 14.7 Matrix Blanks. Matrixblanks are the basis for determiningthe LOQ.and aremonitored at various times in the analyticalrun. Peakswith greater than 25% of the peak area ofthe designated LOQ value observed in matrix blanks are indicative of either matrix effect, sample contamination or instrument contamination. Use of solvent blanks prior to the matrix blank may be necessary to rule out instrumental contamination or sample contamination. 14.8 Control Blanks. Control blanks are the basis for determining matrix effect (interference or suppression). Peaks with greater than 25% of the peak area of the designated LOQ value observed in control blanks are indicative of either matrix effect, sample contamination or instrument contamination. 14.9 Limit of Quantitation (LOQ). The LOQ is equal to the lowest acceptablestandard (i.e. % accuracy is f; 25 % nominal value) in the calibration curve that is greater than 4times the level of the matrix blanks. 14.10 Sample Triplicates. The analyst shall accept %RSD values < 25%. %RSD values > 25% should be noted. Data used in the finalreport that is deemed out of controlwill be ETS-8-182.0 Anahsir of FCs by Purge & Trap Autosampler/Concentrator/GCYMS Page 10 of 12 Page 72 of 148 BACK TO MAIN 3M Environmental Laboratory Report No. E00-2192 required to have technicaljustification for why the data is used, documented in the final report and raw data. Consult with the Team Leader or designee for direction, and for final acceptanceor rejection of the data. 14.11 Analytical Spikes. The analyst shall accept percent spike recovery values of 100f25%. Spikerecoveriesoutside of this range shouldbe noted. Consult with the Team Leader or designee for direction, and for finalacceptanceor rejection of the data. Data that are used in final report that is deemed out of controlwill be required to have a technical justification for why the data are being used, documentedin the final report and raw data. 14.12 System Suitability. 14.12.1 Tuning: A mass spectrometertune report shall be generated before starting each analyticalsequence. If the tune parametersdo not meet the criteria suggestedby the mass spectrometer manual, then the mass spectrometer should be re-tuned. If mass 28 is present in the tune report at >IO% relative to mass 69 then an air leak is present in the system. The source of the leak should be isolated and fixed before the sequenceis stated, however if a slight air leak is detected, data can be collected, analyzed, and used as long as the data quality objectives are met. 15.0 POLLUTIONPREVENTIONAND WASTE MANAGEMENT 15.1 Dispose of samplevials in low BTU and flammablesolvent in high BTU containers. Dispose of glass pipette waste in broken glass containers located in the laboratory. 16.0 RECORDS 16.1 Store chromatograms in the study folder that is labeled with the study number. Include the following information on each chromatogram either in the header or hand written on the chromatogram: injection date, analyst's initial, sample unique number, sample name, .preparation date, incubationperiod, dilutionfactor (if applicable), and instrumentname. Store a copy of the acquisitionconditionswith the chromatogram packet. 16.2 Plot the calibrationcurve by non-weightedlinear regression and store in the study/project folder. 16.3 Print the sequenceand MS tune report fiom HP Chemstation. The sequence should be initialed and dated, and stored in the run log binder. The MS tune report should be stored in the tune report file. Copy of the sequence and MS tune report should be placed in appropriate study/project folder. 16.4 Summarizedata using suitable s o h a r e and store in the study/projectfolder. 16.5 Back up electronicdata to appropriatemedium (primarily CD). Record in the study/project folder the filename and location of backup electronic data. 16.6 List the documentsand records generatedwhen performing this method and where they are to be archived. ETS-8-182.0 AnaIysis of FCs by Purge & TrapAutosampler/Concentrator/GC/MS Page 11 of 12 Page 73 of 14% BACK TO MAIN 3M Environmental Laboratory Report No. E00-2192 17.0 ATTACHMENT 17.1 None. 18.0 REFERENCES 18.1 Archon Purge and Trap AutosamplerSystemOperator's Manual, 1996,Varian. 18.2 Tekmar LSC200InstructionManual, 1996,Tekmar. 18.3 Agilent MSD HardwareManual for 5973N,1999,Agilent. 18.4 Agilent 6890 Series Gas Chromatograph,volumes 1-3, 1999,Agilent 19.0 AFFECTEDDOCUMENTS 19.1 None. 20.0 REVISIONS Revision Number. Reason For Revision - Revision Date E D - 8 - 182.0 Analysis o f F G by Purge & Trap Autosampfer/Concentrator/GC/MS Page 12 of 12 Page 74 of 148 BACK TO MAIN 3M Environmental Laboratory Report No. E00-2192 I 3M ENVIRONMENTLAALB, ORATORY Method Indirect Photolysis Screening Test in Synthetic Humic Water Method Number: ETS-8-177.0 Approved By: Adoption Date: ,./..+e Revision Effective Date: ETS-8-177.0 IndirectPhotolysis Screening Tests in Synthetic Humic Water Page 1 of 16 Page 75 of 148 BACK TO MAIN 3M Environmental Laboratory Report No. E00-2192 1.o SCOPEAND APPLICATION 1.1 Purpose. Chemicals dissolved in natural waters are subject to two types of photoreaction. In the fvst case, the chemical of interest absorbs sunlight directly and is transformed to products when unstable excited states of the molecule lead to decomposition. In the second case, reaction of dissolved chemical is the result of chemical or electronic excitation transfer tom light-absorbing species in the water. Synthetic humic water (SHW) is used for the photolytic reaction matrix because it contains dissolved organic material that absorbs sunlight and produces reactive intermediatesthat include singlet oxygen (`0,)that promotes indirect photolysis of the test substance. 1.2 The method is divided into two phases. Phase one includes the preparation of SHW. Phase Two provides a procedure to calculate solarphotolysis rate constants and halflives of test chemicals in pure water (PW) and SHW.This phase also includes parallel solar irradiation of a radiometer to calculate k,o (the indirect photolysis rate in the test vessel, e.g. 40 mL glass VOA vial) and kpE (the near-surface photolysis rate constant in natural water bodies). 1.3 CompatibleAnalytes. Chemicals that will be subjectedto this indirect photolysis screening and testing method include but are not limited to the following compounds: Comwund Acronym Compound Acronym Peduorooctanesuffonate PFOS Perfluorobutanesuifonate PFBS N-methylperfluorooctanesulfonamide N-MeFOSA N-methylperfluorobutanesulfonamide N-MeFBSA N-ethylperfluorooctanesulfonamide Z-(N-methylperfIuorooctane sulfonamido) ethyl alcohol N-EtFOSA N-MeFOSEOH N-ethylperfluorobutanesulfonamide 2-(N-methylperluorobutanesulfonamido) ethyl alcohol N-EtFBSA -~ - N-MeFBSE OH Z-(N-ethyIprrfluorooctanc su1fonamido)ethyl alcohol I I-perfluorooctene Perfluorooctanehydride N-EtFOSE-OH I -- IH,f&hy,jrjde 2-(N-ethylperfluorobutanesu1fonamido)ethyl alcohol 1 I -perfluorobutene Peffluorobutanehydride N-EtFBSE-OH -- I ...and other C4 throughC1o homologues,and polymericmaterialsbasedon the aboveaforementionedcompounds. I 1.4 Acceptable matrix. Synthetic humic water (SHW), 0.005 M pH 7.0 Phosphate Buffer. ETS-8-177.0 Indirect Photolysis Screening Tests in synthetic Humic Water Page 2 of I6 Page 76 of 148 BACK TO MAIN 3M Environmental Laboratory Report No. E00-2192 2.0 SUMMARY OF METHOD 2.1 Phase One: A solutionof standardizedsynthetichumic water is prepared by water extraction of commercialhumic material. The SHW is buffered at pH 7 with 0.005 M Phosphatebuffer to maintainpH and pre-aged inthe photoreactorto produce predictable bleaching behavior. It is then dilutedat the time of use to a W-visible absorbance typical of most surfacefresh waters (approximately0.5 AU at 370 nm). 2.2 Phase Two:Study samples (5mL aqueousmatrix) are,prepared in 40 mL glass VOA vials equippedwith screw-topcaps with septa. Test substanceis added to the vials where indicated. (See tablebelow.) Vials are placed in the photoreactor and immersedin a water bath controlled at 25 f 5 OC. Samples to be exposed are photolyzed in the photoreactor at 261 W/m2(300-800nm) for designated time intervals. A suggestedset of time intervals is listed below. Additional timepointsmay be added, if necessary,or as assigned by the Team Leader. Time 0 sampleswill be refiigerated at 1-5 "C.until all timepointshave been completed. Dark controls (unexposed)will also be prepared for each timepoint. Absorbancecontrols will be used to monitor photo-bleaching of the S H W . Exposed and unexposedabsorbancecontrolswill be prepared per timepoint. - - 2.2.1 Samplesto be prepared for each timepoint and for each exposuretype: LCWS GCMS Analysis Analysis at 370 nm + Control Mahix(#l) blank 0 0 + + Control Mabix(#l) sample 0 0 + + Control Matrix(#l) spike 0 0 + Contra\ Matrix(%) blank 0 0 Concml Matrix(#Z) ramplo 0 0 + + Control Maaix(#Z) spike 0 0 + Absorbance Control 0 0 0 0 0 + 0 0 +i- + 0 0 0 Where "+" =additionof solutionor test substance and "0" =NO addition, analysis. Time Point # of Exposed )#xoefnU Samples Samples Analysis ( Exp + Unexp) 0 8hr 16 hr 32 hr 64 hr 128 hr 0 30 (Time 0) 13 30 30 26 30 30 26 - 30 30 26 30 30 26 30 30 26 150 I80 143 A A NA A A NA A A NA A A NA A A NA A A NA A A NA A A NA A A NA A A NA A A NA A A NA A A NA NA NA A NA NA A analysisperformed,and NA =no GUMS Analysis (Exp + Unexp) 13 26. 26 26 26 26 1 43 UVNis Analysis (Exp + Unexp) 4 8 8 8 8 8 44 ETS-8-177.0 Indirect PhotorySs Screening Tests in Synthetic Humic Water Page 3 of 16 Page 77 of 148 BACK TO MAIN 3M Environmental Laboratory Report No. E00-2192 3.0 QUALITCYONTROL-DEFlNITION/FREQUENCY~ERFORMANCECRITERIA 3.1 Blanks 3.1.1 Definitions: Matrix Blank. A sample of analyte-freematrix (e.g. SHWhuffer) to which all reagents are added in the same volumes or proportions as used in sample processing. For photolysis studies, there are multipte matrix blanks to adequately represent the variables of the study with reference to the matrix (e.g. Exposed, Unexposed and Time 0). The matrix blank is carried through the sample preparation, photolytic and analytical procedures to monitor for contamination during any step. It is also used to establish a chromatographic baseline and monitor for interference or suppression of target analyte(s) from the matrix. Control Blank. A sample of analyte-freecontrol matrix (such as buffer or ASTM Type 11water) to which all reagents are added in the same volumes or proportions as used in sample processing. The control matrix serves as a monitor of the effect of the matrix on the test substance, test analytes and chromatographic behavior. For photolysis studies, there are multiple control blanks to adequately represent the v,piablesof the study with reference to the matrix (e.g. Exposed, Unexposed and Time 0 samples). The control blank is carried through the sample preparation, photolytic and analytical procedures to monitor for contamination during any step. It is also used to establish a chromatographic baseIine and monitor for interference or suppression of target analyte(s) from the control matrix. 3.1.2 FreqnencyPerformance Criteria: Listed in the following table: I MatrixID Matrix Blank (Buffer/SHW) ControlBlank #1 (BuffedPW) Matrix descriDtion 0.01 M PhosphateBuffer,pH 7: ASTM Typo II Watcr Frewency 1 Performance Criteria 1 Replicate per light and dark exposure, for each he and for ea& analytical methodology. b Y background level Of *get dp shall be less than 25% the area counts Of the LOQ. 3.2 Sample Triplicate 3.2.1 Definition: Three aliquots prepared as representatives of the same sample source (e.g. test substance) and carried through all steps of the photolytic study process and analytical procedures in an identical manner. The results from triplicate analyses are used to evaluate variance of the total method, including sample preparation, photolytic process and analysis. ETS-8-177.0 Indirect Photolysis Screening Tests in Synthetic Humic Water Page 4 of 16 Page 78 of 148 BACK TO MAIN 3M Environmental Laboratory Report No. E00-2192 3.2.2 Frequency/PerformanceCriteria: Listed in the followin&table: I Matrix Description Frequency I Test Matrix and test substance Performance Criteria The analyst shall accept %RSDs <25%. Precision must be documented and justified (if 3.3 Analytical Spike (AS) 3.3.1 Defmition: A known mass of target analyte(s) in a specified amount of a diluted andor aliquottedsample. This assumes that an independentestimate of target analyteconcentrationis available. Analytical spikes are used to evaluate the recovery efficiency of the andyte and the matrix effect. 3.3.2 Frequency/PerformanceCriteria: Listed in the followingtable: Matrix Dewriotion Test Matrix and test substance, spiked with target anaIyte(s) just prior to analysis Test Matrix with NO test substance, spiked with target analyte(s)just prior to analysis Control Matrix (#1) and test substance, spiked with target analyte(s)just priar toanalysis ControlMatrix (#2) and test substance, spiked with target analyte(s)just prior to analysis Frequency I 2 spiked samples per treatment type(onein lower half of the calibrationrange, and one in the upper halfof the calibrationrange) 1Replicate per treatment type (mid-range spike concentmtian) Performance Criteria The analyst shall accept accuracy of 100 f 25%. If accuracy is outside of this range, document and justify, if possible, the reason for the deviation.. 3.4 Control Sample 3.4.1 Definition: A h o w n matrix containing the test substance caxried through the entire sample preparation, photolytic and analytical procedure. This is used to document laboratoryperfonname by comparing recoveriesand matrix effects from the different matrices and sample types. 3.4.2 Frequency/PerformanceCriteria: Listed in the followingtable: I MoMx Description 1 Control Matrix (#1) and test substance I test substance pw I Frequency 1 Performance Criteria I I 1Replicate per lightand &k for hepobcand for each analytical me&odology The analyst shall accept accuracy of 100 f 25%. If accuracy is outside of this range, dowment and justify, if possible, the reason for the deviation. ETS-8-177.0 Indirect Photolysis Screening Tests in Synthetic Humic Water Page 5 of 16 Page 79 of 148 BACK TO MAIN 3M Environmental Laboratory Report No. E00-2192 3.5 Absorbance Control 3.5.1 Definition: An analyte-freematrix that is canied through the sampleprocessing procedure and analyzedby absorption spectroscopy at 370 nm. It is used to monitor the photo-bleaching rate of the SHW during the testing phase. 3.5.2 Frequency/Performance Criteria: Listed in the table below. Matrix Description ControlMatrix (#1) Buffer/SIW only I Frequency I 2 Replicatesper light and dark exposure, for each time point I Performance Criteria I Absorbance measured at 370 nm is between 0.01AU-0.05 AU (1 cm pathlength cell) 3.6 lntemal StandardlSurrogate 3.6.1 Internal Standard Definition (applies to LC/MS samples): A known amount of a compound similar in analytical behavior to the target analyte(s) of interest (e.g. 3,3,4,4,5,5,6,6,7,7, 8,8,8-tridecafluorooctanesulfonic acid (THPFOS) if perfluorooctanesulfonate(PFOS)were to be the target analyte), added to all samples and standards(post-irradiation),and carried through the entire analytical process. It provides a reference for evaluating and controllingthe precision and bias of the applied analyticalmethod. Samplesare to be quantified using the internal standard. 3.6.2 Surrogate Definition (applies to LC/MS and GCMS samples): A known amount of a compound similar in analytical behavior to the target analyte(s) that may be added to all samples (pre- or post-irradiation, at the discretion of the Team Leader), and carried through the remaining sample preparation and/or analyticalprocess. If added before exposure, it monitorsthe presence of vial leaks during photolysis, as well as the performance of the purge and trap autosampler and concentrator. Surrogate analysis is used to evaluate the precision and bias ofthe applied analytical method. Surrogates are not used for quantitation. 3.6.3 Frequency/PerformanceCriteria: Listed in the following table: Matrix DescriDtion Sample muted with30 mLof internal standard compound dissolved in a suitable analytical solvent Sample with surrogate compound spiked into it. _ _ ~ -~ Freauencv of Use - Every LCMS sample analyzed May be added to every L C W and GCMS sample analyzed I Performance Criteria The O/oRSDfor internal standards shall be calculated for the area response of all appropriate samplesper analyticalbatch. The analyst shall accept %RSDvalues of 4 5 % . %RSD values >15% shall be documented and justified, if possible. The % recovery of internal standards should be 100 k 25%. .Surrogates are examined for qualitative information only (Le., area response should be relatively constant). ETS-8-177.0 Indirect PhotolysisScreening Testsin Synthetic Humic Water Page 6of 16 Page 80 of 148 BACK TO MAIN 3M Environmental Laboratory Report No. E00-2192 3.7 Other Definitions. 3.7.1 Test Substanceflest Analyte: Any substance(mixture or controlled compound) added or administeredto the test system for the purpose of chemicalanalysis. 3.7.2 Degradation Product(s): Secondary analytes of interest produced as a result of chemicalreactionsduring the photolysis and monitored (qualitativelyor quantitatively)during the sample analysisprocedure. 3.7.3 Target Analyte(s): The analyte(s) singled out in the analyticalphase of the study is the target analyte. The target analyte may be identical to the test substanceused in the experimentalphase of the study, a by-product or degradationproduct that is monitored (qualitatively or quantitatively)during the sample analysis procedure. 3.7.4 Test Matrix: The physical matrix in which the study will be conducted. 3.7.5 Relative Percent Difference (RPD): A measure of precision defined as the absolutevalue of the &ferenceof the two valuesdividedby the average of the two values and multiplied by 100. 3.7.6 Relative Standard Deviation (RSD): A measure of relative precision for three or more samplereplicates; definedas the samplestandarddeviation divided by the sample average and multiplied by 100. This is expressed as a percent (%RSD). 3.7.7 Limit of Qnantitation (LOQ): The lowest concentrationthat can be reliably achieved within specified limits of precision and accuracy during routine laboratoryoperating conditions. The LOQ can be estimated as 10times the background level in the blank samples. However, it may be nominally chosen within these guidelines to simplify data reporting. For many analytes, the LOQ analyteconcentrationis selected as the lowest non-zero standardin the calibrationcurvethat is over fourtimes the background level in the blanks. Sample LOQs are highly matrix-dependent. 4.0 WARNINGS A N D CAUTIONS 4.1 Health and Safety Warnings 4.1.1 Wear the proper lab attire for all parts of these procedures. Wear gloves and eye protection at all times, 4.1.2 Handle all solvents in a hood for all parts of the described sample preparation procedure. 4.1.3 For potential hazards of each chemical used, refer to material safety data sheets, packing materials, and 3M Environmental Laboratory's Chemical Hazard Review. 4.1.4 No mouth pipetting is allowed. 4.2 Cautions 4.2.1 The photoreactors are equipped with a continuous flow of cooling water that poses a threat of electrocution when handling the photoreactor during irradiation sequences. ETS-8-177.0 Indirect Phoiolysir Screening Texts in Synthetic Humic Water Page 7 of 16 Page 81 of 148 BACK TO MAIN 3M Environmental Laboratory Report No. E00-2192 4.2.2 Wear dark protectiveeyewearwhen operatingthe reactor. Do not look directly at the activated lamp. Use caution when handling samples in the reactor; the interior walls of the reactor and exposed glass vials become extremely hot. 5.0 INTERFERENCE 5.1 Contaminantsin solvents,reagents, glassware and other sampleprocessing or analysis hardware may cause interference.To reduce the possibilityof interference,glassware in which standards are prepared should be pre-rinsed with methanol and allowed to dry before use. The routine analysis of laboratorymethod blanks must be used to demonstrate that there is no interference under the conditions of the analysis. 6.0 EQUIPMENT 6.1 Analytical balance sensitive to 0.1 mg 6.2 Photoreactor: SuntestCPSi-,XLS+, or equivalent, capableof producing 250~765 Wattdm', equipped with a xenon arclamp (e.g. 2200 W Xenon Lamp) and the appropriate filters to allow the desired wavelength (e.g. W Special Suprax" with cut-on at 290 nm, and Quartz dish with IRreflective coating), and a flowingwater bath circulatingpump or . equivalent. 6.3 Water cooler/recircdator capable of maintaining temperature at 25 "C f 5 OC 6.4 UV-Visible Spectrophotometer(W-VIS), equipped with tungsten and deuterium lamps, model 8453, or equivalent 6.4.1 Autosampler: Model G1120A,or I-cmpathlength cell holder: Model 08451- 60104, or equivalent. 6.4.1.1 1-cmpathlengthquartzspectrophotometercell, or equivalent. 6.4.2 Long Path-Length Cell Holder, Hewlett Packard part number 89076C,or equivalent 6.4.2.1 10-crnpath length quartz cell equipped with stopcocks, Hewlett Packard Part # 5061-3392, or equivalent. 6.4.3 Data acquisitionand analysis software,HP ChemStationfor UV-Visible Spectroscopy, G11IGAA Rev. B.01.02,or later. 6.5 Data System: A PC capableof controlling the W-Visible Spectrophotometersystem. 6.6 Centrifuge capable of maintaining >2000 rpm for 10 minutes at ambient temperature (2226 "C). 6.7 Radiometer, capableof detecting and recording irradiationoutput of the photoreactor for the duration of the study. 6.8 Lab Oven, capable of maintaining 70-80 "C. 7.0 SUPPLIESAND MATERIALS 7.1 40-mL amber and clear glass vials (VOA) with screw caps. 7.2 Crimp cap autovials: 1.S-mL, caps, crimper, and decapper. 7.3 Adhesive-backed labels (return address size) for labeling quartz vials and autovials. 7.4 Disposable glass graduated pipettes, 1 mL to 10 mL. ETS-8-177.0 indirect Photolysis Screening Tests in Synthetic Humic Water Page 8 of 16 Page 82 of 148 BACK TO MAIN 3M Environmental Laboratory Report No. E00-2192 7.5 DisposableglassPasteurpipettes and rubber bulbs. 7.6 Glass beakers, various sizes. 7.7 Volumetric flasks, from 10mL to 1000mL. 7.8 Hamilton Gastight@syringes (precision* 1%of the total volume), 5 pL to 1000pL. 7.9 10-mL Bottle-top dispenser. 7.10 Teflon* filters filter holder apparatus: 0.4 pm pore-size and 0.2 pm pore-size filters (47 mm diameter, Gelmanm or equivalent. 7.11 500-mL glass screw-top containers. 8.0 REAGENTASND STANDARDS 8.1 WaterRure water (PW),ASTM Type II water at a minimum 8.2 Methanol (MeOH), HPLC/SPEC/GC grade from EM Scienceor equivalent. 8.3 Acetone, HPLC/SPEC/GC grade from EM Science or equivalent. 8.4 Acetonitrile, HPLC/SPEC/GC grade from EM Science or equivalent. 8.5, Humic acid, sodium salt, fiom Aldrich or equivalent. 8.6 NaOH, reagent grade Grom EM ScienceTMor equivalent. 8.7 0.1YONaOH solution Example: Weigh approximateIy 1.O g sodium hydroxide into a weigh boat and transfer quantitatively to a 1 L volumetric flask and diluteto the mark with PW or equivalent. 8.8 Sulfuric Acid (H,SO,), reagent grade from Fisheror equivalent. 8.9 Potassium phosphate, reagent grade from JT Baker or equivalent. 8.9.1 0.005 M, pH 7.0 Phosphate Buffer. Example: Weigh 1.36 g KH,PO, into a weigh boat and transfer to a 1L volumetric flaskusing PW and dilute to the mark. Transfer the 1 L of solution to a 2 L volumetric flask. Add 600 mL of 0.1% NaOH, adjust the pH to 7.0 f 0.1 with 0.1% NaOH or diluteH2S04,and dilute to the mark with PW. 8.10 Method Blank Solutions: Method Blank h e s Matrix ID Matrix descriRtion Test Matrix Buffer/SHW Example: 1:lO Solution: Dilute 50 mL Synthetic Humic Water with 0.01 M pH 7.0 PhosphateBuffer solutionto 500 mL. ControlMatrix (#1) Buffer/PW Example: 1:lO Solution: Dilute 50 mL Pure Water (ASTMType n) with 0.01 M pH 7.0 Phosphate Buffer solutionto 500 mL. 1 Control Matrix (#2) PW I Pure Water (ASTMType II) I 8.11 Stock Solutions. Stock solutions for internal standards and spiking solutions are prepared in MeOH at concentrations of approximately 10,000pg/mL by weighing approximately 0.1 g of the appropriate substanceinto a 1O-mL volumetric flask and bringingto the mark with MeOH. Dilute to make appropriateworking solutions. 8.11.1 Diluting Solutionwith Internal Standard: The diluting solution shall contain internal standard at an arearesponse level equivaht to approximately half the ETS-8-177.0 Indirect Photolysis Screening Tests in Synthetic Humic Water Page 9 of 16 Page 83 of 148 BACK TO MAIN 3M Environmental Laboratory Report No. E00-2192 area response of the test substance's high standard in the calibration curve. Example: Internal standard solution in MeOH is prepared by diluting 50pL of internal standard stock solution (Section 8.11)to 1 L with MeOH to a nominal concentrationof 0.5 AU pg/mL,. 8.12 Test SoIutions 8.12.1 Test Substance: Prepare a solutionof the test substancein acetonitrile. Calculate the concentration so that after the test substance is added to the test vial, no more than 1% of the volume in the test vial will be solvent. (e.g. 50pL added to 5 mLof matrix = 1%v/v) Then measure the absorbance of the test substance solution diluted with bufferlwater matrix to the desired concentration, The maximum absorbance at any wavelength greater than 29Onm must be e 0.05, when measured in a standard 1-cm pathlength cell. Example: A 900 pg/mL solution of test substancein acetonitrileis prepared by weighing 90 mg of test substanceinto a 100mL volUmetric flask and diluting to the mark with acetonitrile. 9.0 SAMPLE HANDLING 9.1 Record times of initial preparation and dilution on the fluorochemical degradation (photolysis) analysis sampleprep sheet (AttachmentA). 9.2 Once the test substancesolutionhas been added, the 40mL VOA sample vials shall be stored and handled cap-side down to minimize loss of any potential volatile analytes. After the exposure period, the LCMS samples may be turned upright and stored in a cooler at 1-5"C. After the exposureperiod, GCMS samplesshall be maintained in an inverted position in a cooler at 1-5 "Cuntil they are loaded onto the autosampler. 9.3 Once the 30-mL aliquot of diluting solventhas been added to the LCMS photolysis samples, (see Section 12.0), the samples should be analyzed as soon as possible. Alternatively, the samplesmay be stored at 1-5 "C.Day 0 samples are to be stored at 1-5 "Cduring the time of sample exposure, and then diluted along with the exposed and unexposed samplesjust prior to analysis. 10.0 QUALITCYONTROL 10.1 Quality control parameters (and the fiequency of use) are included in Section 3.0. 11.0 CALIBRATIONAND STANDARDIZATION 11.1 The analytes of interestmust be standardized according to laboratoryspecifications. 11.2 AI1 equipmentused, such as the analyticalbalance, photoreactors, etc. should be calibrated prior to use (daily, weekly, etc.) as specified in its standard operating procedure. 11.3 All samples analyzed will be run against a standard curve containingvarying amounts of test substance, and a fixed amount of internal standard or surrogate compound. ETS-8-177.0 Indirect Photobsis Screening Tests in Synthetic Humic Wuter Page 10 of 16 Page 84 of 148 BACK TO MAIN 3M Environmental Laboratory Report No. E00-2192 12.0 PROCEDURES 12.1 Phase One-Preparationand standardizationof svnthetichumic water. 12.1.1 Weigh approximately2.5 g humic acid k t 0 a tared 250 mL centrifuge tube. 12.1.2. Add 0.1% NaOH solutionto 250 mL. 12.1.3 Screw-cap shut and tape the tube and place horizontally on an orbital shaker. Shake vigorously (e.g. 100-250rpm)at room temperaturefor approximatelyone hour. 12.1.4 Centrifugethe 250 mL of solutionat approximately2000 rpm for 10minutes or until solutionhas cleared, and then filter the supernatantthrough a 0.4pmfilter into a clean 500-mLglass screw-topcontainer. 12.1.5 Adjust the pH of the solutionto 7.0 with dilute H2S04or 0.1 % NaOH. 12.1.6 Filter-sterilizethe solutionthrough a 0.2pmdiameterporesize filter into a clean 500-mLglass screw-top container. 12.1.7 Seal the container and place cap-side down in the photoreactor chamber. 12.1.8 Expose the SHW 24 hours at 261 W/mzto pre-age the solution (equivalent to three day's worth of Miami, Florida sunlight). The EPA's definition of "1 Day" of irradiationis "eight hours," The irradiation intensityof 261 W/m2was chosen because it yields the equivalent average optimum natural daylight radiation for 300-400 nm (see the table below): Irradiance Source Average OptimumNatural Daylight` Atlas Photoreactor with integrated irradiance output of 261 W/m2300-800 nm using the IRReflecting and 290 cut- on filters ADDrOXimate Inteprated and Individual Irradiances in W/m2 250-300 nm 300-400nm `400-8OOnm 3 4 0 m o,o 27.8 259.0 0.30 0.08 27.8 234.36 0.24 420nm 0.67 0.71 12.1.9 Aliquot the SHW into a l-cm quam W-VIScuvette and analyzethe absorbance at 370 nm. 12.1.10 Check the pH of the solutionusing pH paper or a pH probe. Adjust the pH if necessary to 7.0 f 0.1 using a dilute&SO4 solutionor 0.1% NaOH solution. 12.1.11 Calculate the dilution factor necessary to decrease the absorbance to approximately0.5 AU (in a I-cm pathlength cell) in 1 L of SHW: where: 9.5 =L , n J 1L x the measured absorbance of the SHW at 370 nm x = the volume of S H W needed to dilute to 1 L with water. 12.1.12 Bring the solutionto the exact dilutioncalculated in 12.1.11with PW. ETS-8-177.0 Indirect Photolysis Screening T e s i~n Synthetic Humic Water Page 11 of 16 Page 85 of 148 BACK TO MAIN 3M Environmental Laboratory Report No. E00-2192 12.1.13 Verify that the absorbance is approximately 0.5 AU by aliquoting the diluted SHW into a I-cm W-VIS cuvette and taking the absorbance reading at 370 nm. 12.1.14 Transfer the SHW stock solution into an amber, or clear foil-wrapped 1 L glass storage bottle, tightly cap and refiigerate. 12.2 Phase Two 12.2.1 Fill out the "Fluorochemical Degradation (Photolysis) Sample Prep Sheet" (Attachment A) as much as possible, assigning sequentialunique ID numbers to each sampleto be prepared, 12.2.2 Obtain the appropriate number of clear and amber 40-mL glass vials with caps and cardboard boxes. Label the vial caps using a black permanent marker to distinctly identifl samples. 12.2.3 Create labels for each sample to be affixed to the 40-mL vials and the autosampler vials after photolysis is completed. The labels should include the sample number, test substance, matrix, exposure type (e.g. exposedunexposed/Time 0), date and initials of the analyst. 12.2.4 Aliquot 5.0 mL of BuffbdSHW, BufferPW and PW solutions into clear (for exposed samples) and amber (for unexposed and Time 0 samples) 40-mL glass VOA vials. Add test substanceto the appropriate vials. See the table below for list of vials, replicates, and sample types. If pre-hydrolysis surrogates are to be used, add them also at this point. 12.2.5 Create one set of samples (listed below) per time point andfor each analytical methodology. (LC/MS and GC/MS): J DescrMiption sample Rep 1 Sample Rep2 Sample Rep 3 ` SampleSpike I Sample Spike 2 Matrix Blank Matrix Blank Spike 1 C ~ n t Md abix(#I) blank ControlUatrix(#l) sample Control Mabix(#l) spike Conml Mabix(#2) blank Contml Uabix(#2) sample Control Mahix(#2) spike Sample Rep 1 Sample Rep 2 Sample Rep 3 Sample Spike 1 Sample Spike 2 Test Matrix Blank Test Matrix Blank Spike Control Matrix(#l) blank Control Matrix(#l) sample Control Matrix(#l) d k e Control Matrix(#2) blank Control hIabix(32) sample Control hlatrix(32) spike a t (Buffer+/SHW) + + + -?. + + 0 0 0 0 0 0 + + + + + + + 0 0 0 0 0 0 r (Buffer/PW) 0 0 0 0 0 0 0 + + + 0 0 0 0 0 0 0 0 0 + 0 + + 0 0 0 i x 2 (PW 0 0 0 0 0 0 0 0 0 0 + + + 0 0 0 0 0 0 0 0 0 + 0 + + Test Substance + + + + + 0 0 + 0 + + 0 + + + + + + 0 0 0 + + 0 + +. C1earlExpose.d Clearkposed Cleafiposcd Clearkposed Clear/Exposed ClearExposed Clearfixposed ClearExposed CleadExposed Clearnzxposed C!ear/Exposcd Clear/Exposed CleadEXposed AmberAJnexposed ArnberNnexposed AmberiUnexposed AmbcriUnexposed AmberiUnexposed AmberNnexposed AmberiUnexposcd AmbnNnexposed AmberNnexposed AmberNnexposed AmberNnexposcd AmbcrAJnexposed ArnberNnexposed ETS-8-177.0 Indirect PhotolysisScreening Tests in Qnthetic Humic Wafer Page 12 of 16 Page 86 of 148 BACK TO MAIN 3M Environmental Laboratory Report No. E00-2192 Control Matrix(#l)= SHwIBuffer 1:9 v/v Control Matrix(#2)= PWBuffer 1:9v/v Create one set of samples (listed below) for each time point for WMS analysis: 12.2.6 Store the "Time 0" vials in a labeled box at 1-5 "C. 12.2.7 Place all the vials that will go into the photoreactorinto an oven set to 70-80"C. for 5-10 minutes to acclimate the vials, liquid and headspace to photoreactor conditions. Upon removingthe vials h m the oven, immediatelyre-tighten the caps and proceed to load the reactor. 12.2.8 Place the amber "unexposed"vials in plastic bags and arrange on the bottom of the photolysis tray (make sure that they don't float once the tray is filled with water). The "unexposed" vials will remain submerged in the cooling water (25 f 5 "C) during the exposure. (The vials are exposure- and temperature-controlled.) 12.2.9 Place the clear "exposed" vials in the rack in thephotoreactortray cap-side down, and install the rack so that the VOA vial caps will be submerged throughout the duration of exposure. 12.2.10 Prepare the radiometerto read intensityof irradianceover the duration of the exposure. See SOP ETS-9-50.0 for operation of radiometer. 12.2.11 Expose the samples for the designated time intervals at 261 W/m*. See SOP ETS-9-44.0 for operation of the photoreactor. 12.2.12 Following each exposure interval, remove vials fromthe photoreactor and store inverted in a cooler at 1-5 "C.After all exposureshave been completed,remove all samplevials as well as the "Time 0"vials from the cooler and analyze as a single batch for each instrument. 12.2.13 W - V I S absorbancecontrol analysis 12.2.13.1 Analyze the pH 7.0 SHWhufferabsorbance controls by WNisible absorbance spectroscopyat 370nm by aliquotingthe test solution directly into a 1-cm or greater pathlength quartz cuvette and obtaining the spectra, , See SOP ETS-9-46.0for operation of the WNIS instrument,The resultantpeak at 370 nm will be analyzed to determinethe change in absorbancebetween the Time 0, exposed and unexposed samples. 12.2.14 LC/MS sample analysis 12.2.15 Dilute the exposed and unexposed samples for all timepoints with 30 mL internal standard solutionin methanol(Section 8.11.1). Add spiking solutionto the appropriatevials. Invert each vial severaltimes to mix. 12.2.16 Transfer aliquots of LC/MS samples into autovials and then place them in the autosampler for analysis of the parent compound and possible degradation products. Analyze accordingto ETS-8-181.O. 12.2.17 GCMS sample analysis ETS-8-177.0 Indirect Photolysis Screening Tests in Synthetic Humic Water Page 13 of 16 Page 87 of 148 BACK TO MAIN 3M Environmental Laboratory Report No. E00-2192 12.2.17.1 12.2.17.2 Analyze the exposed and unexposed samples for all timepoints as-is by purge and trap GCMS. Add spiking and surrogate solutions, as required, to the appropriatevials. Analyze according to ETS-8-182.0. Important: Maintainvials in the inverted position until they can be placed in the autosampler. 13.0 DATAA N f i Y S I S AND CALCULATIONS 13.1 Not applicable, as this is a samplepreparation and analysis method. Consult the appropriate analyticalprotocol for guidanceregarding data analysis and calculations. 14.0 METHOPDERFORMANCE 14.1 Not applicable. 15.0 POLLUTIOPNREVENTIOANNDWASTMEANAGEMENT 15.1 Dispose of samplewaste'byplacing in high or low BTU (British Thermal Unit) waste containers as appropriate. Use broken glass containers to dispose of glass pipettes. 16.0 RECORDS 16.1 Print out hard copiesof all graphics and data analysis summariesfor archiving. 16.2 Sign and date all graphics and label with instrument ID. 16.3 Fill out the samplepreparationworksheet(s)documents completely,making sure to includa all initials and dates. 16.4 Archive electronic datato compact disc media. 17.0 ATTACHMENTS 17.1 "FluorochemicalDegradation (photolysis)Sample Prep Sheet" 18.0 REFERENCES 18.1 Interpersonalconversationwith CarrieO'Connor, Optical SystemsEngineer, Atlas Electric Devices. 18.2 "Suntest CPS/CPS+ SpectralIrradianceDistribution," table distributedby Atlas EIectric Devices Company, sent via fax by Richard Sherwin, Sales Representative, 26 July, 2000. 18.3 "Atlas Xenon Filter Combination and Sunlight Measurements," information generated by Atlas Electric Devices Company sent via fax by Richard Sherwin, Sales Representative, 26 July, 2000. 18.4 OPPTS 835.5270, Indirect Photolysis Screening Test: Sunlight photolysis in water containing dissolved humic substances. ETS-8-177.0 Indirect PhotolysisScreening Tests in Synthetic Humic Water Page 14 of 16 Page 88 of 148 19.0 AFFECTED OCUMENTS 19.1 None 20.0 Revisions Revision Number. Reason For Revision BACK TO MAIN 3M Environmental Laboratory Report No. E00-2192 - Revision Date ETS-8-177.0 Indirect Photolysis Screening Tests in Synthetic Humic Water Page 15 of 16 Page 89 of 148 BACK TO MAIN 0v 3 v- 0 . rco 0 W a 0 0 Z BACK TO MAIN 3M EnvironmentalLaboratoryReport No. E00-2192 3M ENVIRONMENTAL LABORATORY EQUIPMENPTROCEDURE OPERATIONAND MAINTENANCOEF THE HEWLETPTACKARD 8453 W-VISIBLE SPECTROPHOTOMETER Procedure Number: ETS-9-46.0 Approved by: Laboratory Management Adoption Date: /o/zJbr7 Revision Effective Date: /A/*/" ' Date ETS-9-46.0 Operationand Maintenance of the HP8453 W-Vis Spectrophotometer Page I of 9 Page 91 of 148 BACK TO MAIN 3M Environmental Laboratory Report No. E00-2192 1.0 SCOPE AND APPLICATION 1.1 This equipmentprocedure describesthe operation,cleaning, and maintenance of the Hewlett-Packard 8453 UV-Visible Spectroscopy System. 2.0 DEFINITIONS 2.1 Absorbance: Measure of concentration of material present: expressed as product of molar extinction coefficient (E), pathlength (b), and concentration (c), wriien as A = E b c (also known as Beer's Law). 2.2 Cuvette or flow cell: Transparentreceptacle in which sample solutions are introduced into the light path of spectrometers. Usually, two sides are equal (e.g. 1 cm x 1 cm) while the third dimension is elongated, possibly as long as 15 cm. For W work, the material is quartz.Visible work permits the use of glass or plastic cuvettes. 2.3 Pathlength: The distance the light passes through the sample in its holder. In practical terms, the inside dimension of the cuvette (usually 1 cm). 2.4 Slit width: Size of opening through which light from cuvette emerges. Choice of slit width depends on wavelength range, separation ability of wavelength selector, and desired isolation of specific wavelength. Slit width is often fixed or automatically programmed. 2.5 Solvent Cutoff: The wavelength at which the solvent absorbs a significantportion of the light, causing a loss of signal. In other words, the solvent becomes opaque to the wavelengths being used. This is common in the ultraviolet, rare in the visible. 2.6 Transmittance: Ratio of the radiant power transmitted by a sample to the radiant power transmitted by a blank in an equivalent cell or by some other means of compensationfor solvent absorption, reflection losses, etc. 2.7 Visible: The portion of the electromagnetic spectrum, from 400to 800nm,detectable by human eyes. 2.8 Ultra-violet (UV):The portion of the invisisbleelectromagneticspectrumcomposed of wavelengthsof 10400 nm. In U V spectrometrywe are primarily interested in the nearW (quartz) region extending from 200 to 380 nm. 2.9 UV Spectrum: a plot of wavelength (or fiequency)of absorption versus the absorption intensity (absorbance or transmittance). 3.0 DESCRIPTION 3.1 The HP 8453 spectrophotometer is a single-beam, microprocessor-controlled, UV-visible spectrophotometerwith collimatingoptics. The ChemStationBfor W-Visible spectroscopysoftwarerunning on a PC with Microsof@ NT operating system provides instrumentcontrol, data acquisition,and data evaluation. 4.0 IDENTIFICATION 4.1 Hewlett Packard G1103A SerialNo. CN93500458 4.2 HewlettPackard 89Q9QASerialNo. DE14300757 5.0 WARNINGS AND CAUTlONS 5.1 Health and Safety Warnings: ETS-9-46.0 Operation and Maintenance ofthe HP8453 UV-VisSpectrophotometer Page 2 of 9 Page 92 of 148 BACK TO MAIN 3M Environmental Laboratory Report No. E00-2192 5.1.1 Eye damagemay result fromdirectly viewing light produced by deuteriumlamps used in detectors and spectrophotometers. Always turn off the deuterium lamp before opening the lamp door on the instrument. 5.1.2 Some adjustmentsdescribed in the service manual are made with power supplied to the instrument, and protective covers removed. Electricity and heat available at many points may, if contacted, result in personal injury. 5.1.3 Capacitorsinside the instrumentmay still be charged, even though the instrument has been disconnected from its source of supply. Dangerous voltages, capable of causing serious personal injury, are present in this instrument. Use extreme caution when handling, testing, and adjusting. 5.2 Cautions: 5.2.1 Never touch the quartz envelope of the deuterium lamp with your fingers. Fingerprintsabsorb W light and may be burnt in, thus reducing lifetime of the lamp. 5.2.2 Quartz sample cells or sample cells with quartz faceplates are required if you want to use the full 190to 1100nm wavelength range of the spectrophotometer.Good quality glass cells may be used when working above 350 nm. Disposableplastic sample cells are not recommended for use. 5.2.3 For high precision measurements, wait until the spectrophotometerand the lamps have reached thermal equilibrium. The time required is a function of environmental conditions but the instrument should be ready after 45 minutes. To determine if the spectrophotometeris in stable working condi.tion,the HP 8453 Self- test may be performed. (See section 13.1) 5.2.4 Ensure cell windows are free of fingerprintsand other contamination. 5.2.5 Avoid the use of alkaline solutions(pH> 9.5) which can attack quartz and thus impair the optical properties of the flow cells. 5.2.6 Solution in cell should be free of floating particles. 5.2.7 Solution in cell and cell walls should be fiee of bubbles. 5.2.8 Ensure that solution in cell is homogeneous by thoroughly mixing before measurement. 5.2.9 Blank is measured on the same solvent as sample. 5.2.10 Blank measurement should show a flat baseline. 5.2.11 Cell orientation of blank and sample measurements should be the same. 5.2.12 Ideally, the cell is not removed between sample measurements, which means the cell is filledrjnsed using a pipette or a flow cell is used. 5.2.13 Time between blank and sample measurements should be short. 6.0 SPECIALINSTRUCTIONS 6.1 None. 7.0 RESPONSIBILITY 7.1 The operator is responsiblefor routine maintenance and cleaning. ETS-9-46.0 Operationand Maintenanceof the HP8453 UV-VisSpectrophotometer Page 3 of 9 Page 93 of 148 BACK TO MAIN 3M Environmental Laboratory Report No. E00-2192 7.2 The person responsible for the equipment (and an alternate) will be identified in the front of the equipmentlogbook, and are responsiblefor all routine and non-routine maintenance and associated documentation. 8.0 SUPPLIES AND MATERIALS 8.1 Pozidriv screwdriver 8.2 Isopropanol, reagent grade 8.3 Canister of compressed oil-free air. 8.4 Surgical cotton swabs, lint-free. 8.5 Deuterium lamp assembly, Agilent 8453 (Part No. 2140-0605). . 8.6 Lamp, Tungsten G1315A, Agilent 8453A (PartNo. G1103-60001). 9.0 INSTRUMENT CLEANING PROCEDURES 9.1 Cleaning the Stray Light Filter. (Recommendedat one-yearly intervals or more frequentlywhen operating the spectrophotometerin a particularly dirty environment.) 9.1.1 Turn off the instr&en<and d&,connect the power cord. Take the plastic and sheet metal rear covers off, see "Removing and Replacing Covers" on page 109of the HP 8453 Service Manual. 9.1.2 Remove any accessoryboard or MI0 board that m a y be plugged in from the rear side of the instrument. 9.1.3 Remove the upper rear foam block. 9.1.4 Disconnectthe shutter cable fromthe SPM board. Open the screw that fixes the shutter assembly to the optical unit and remove the shutter assembly. 9.1.5 Dampen a lint-free, surgical cotton swab with reagent grade isopropanol and gently swab the surface of the stray light filter. Repeat several times with clean swabs and alcohol each time, 9.1.6 Use a canister of compressed oil-free air to further clean the stray light filter. 9.1.7 Position the shutter assembly above the source lens and fix the screw that holds it at the optical unit, see Figure 39 on page 124of the Servicemanual. Connect the shutter cable to the SPM board. 9.1.8 Replace the upper rear and upper fkont foam blocks. 9.1.9 If available,replace any accessoryboard or MI0 board (plugged in from the rear side of the instrument). 9.1.10 Replace the plastic and sheet metal rear covers. Push the plastic rear cover down so that it locates on both sides, see "Removing and Replacing Covers" on page 109of the HP 8453 Service Manual. 9J.11 Reconnectthe line power and turnon the instrument.Check that the spectrophotometerpasses the self-test, this means that the green light on the front panel comes on and that you can do a blank measurement from the s o h a r e . 9.2 Cleaningthe SourceLens fromthe Sample Compartment Side. (Recommended at oneyearly intervals or more frequently when operating the spectrophotometerin a particularly dirty environment.) 9.2.1 Turn off the instrumentand disconnectthe power cord. 9.2.2 Remove any cuvette holder from the sample compartment. ETS-9-46.0 Operationand Maintenance of the HPS453 W-Vis Spectrophotometer Page 4 of 9 Page 94 of 148 BACK TO MAIN 3M Environmental Laboratory Report No. E00-2192 9.2.3 To have better access you may want to take the plastic and sheet metal rear covers off,see "Removing and Replacing Covers" on page 109 of the HP 8453 Service Manual. 9.2.4 Dampen a lint-free, surgical cotton swab with reagent grade isopropanol and gently swab the surface of the source lens. Repeat several times With clean swabs and alcohol each time. 9.2.5 Use a canister of compressedoil-free air to M e r clean the source lens. 9.2.6 If you have taken the covers off,replace them. 9.2.7 Replace the cuvette holder: Reconnect line power and turn on the instrument. Check that the spectrophotometerpasses the self-test, this means that the green Iight on the front panel comes on and that you can do a blank measurementfrom the software. 9.3 Cleaning the SpectrographLens. (Recommendedat one-yearly intervals or more hquently when operatingthe spectrophotometerin a particularly dirty environment.) 9.3.1 Turn off the instrumentand disconnect the power cord. 9.3.2 Remove any cuvette holder from the sample compartment. 9.3.3 To have better access you may want to take the plastic and sheetmetal rear covers off, see "Removing and Replacing Covers" on page 109of the HP 8453 Service Manual. 9.3.4 Dampen a lint-free, surgical cotton swab with reagent grade isopropanol and gently swab the surface of the spectrographlens. Repeat several times with clean swabs and alcohol each time. 9.3.5 Use a canister of compressedoil-free air to m e r clean the spectrographlens, 9.3.6 If you have taken the covers off,replacethem. Replace the cell holder in the sample compartment. 9.3.7 Reconnect line power and turnon the instrument. Checkthat the spectrophotometerpasses the self-test, this means that the green light on the front panel comes on and that you can do a blank measurement from the software. 10.0 MAINTENANCPEROCEDURES 10.1 Routine maintenance. 10.1.1 Cleaning the stray light filter. Indicators for a dirty stray light filter include: 10.1.1.1 After exchanging the lamps, the intensitytest executedby the ChemStation softwarestill falls below the specified level. 10.1.1.2 One of the stray light tests fails. 10.1.1.3 The photometricaccuracytest fails. 10.1.2 Cleaningthe lenses that are accessible from the sample compartmentside. An indicationfor dirty lenses is when, after exchanging the lamps,the intensity test executedby the ChemStation softwarestill falls below the specified level. 10.2 Non-routine: Document any non-routine maintenance. 10.2.1 Exchange the deuterium or the tungsten lamp when the intensity test, which is executedthrough the ChemStation software,fallsbelow the specified level or when one of the lamps no longer ignites. See HP 8453 Service Manual for lamp replacement procedure (p.96). ETS-9-46.0 Operation and Maintenance of the HP8453 UV-VisSpectrophotometer Page 5 of 9 Page 95 of 148 BACK TO MAIN 3M Environmental Laboratory Report No. E00-2192 11.0 OPERATINPGROCEDURES 11.1 Powering Up the HP 8453'W-VisibleSpectrophotometerand PC controller. 11.1.1 Switch on the PC and boot the PC operating system. 11.1.2 Switch on the spectrophotometerand wait until the spectrophotometer's indicator light turns green. Thisprocess includesthe spectrophotometer's self test and takes about one minute. 11.1.3 Launch a measurement session by pressing the operating system's "Start" button and select"Programs", "HP W-Visible ChemStatiom", "spectrometer 1 onlne" 11.1.4 The system is ready to use if the blue "busy" status display on the system's bottom message line turns off. Note: For high precision measurementswait until the spectrophotometerand the lamps have reached thermal equilibrium.The time required is a function of environmental conditionsbut should be ready after 45 minutes. 11.1.5 The first measurement to perform is a reference measurement. After this alignment you are ready to measure absorbance data and spectra 11.2 Inserting a Cell. 11.2.1 The HP 8453 is shipped with the standard single-cellholder which accommodates standard cells or flow cells. 11.2.2 Move the locking lever to its up position. 11.2.3 Insert the sample cell, making sure you orient it correctly. The frosted (non-clear) sides of the sample cell shouldnot be in the path of the light beam. 11.2.4 Lock the sample cell in place by pushing the locking lever back down. 11.2.5 Small volume flow cells and particularly any cells With less than a 2 mm aperture may require use of the optionaladjustablecell holder. This device helps you ensure the cells are properly centered in the light path. 11.3 Entering a Cell's Path Length. 11.3.1 Click "Setup" on the InstrumentPanel. 11.3.2 Type the path length in cm in the "Setup Manual" dialog box. 11.3.3 Click "OK" to set the specifiedpath length. 11.4 Starting a Measurement Session, 11.4.1 Start a measurement session by selecting Instrument I online fiom the menu. 11.4.2 Perform a reference measurement.Typically the cell containingthe solvent used with your samples is put in the measurement position and a blank measurement performed. To start this measurement, click the "Blank" button on the Instrument Panel or press the spectrophotometer's"Blank"button, 11.4.3 Perform a sample measurement. To get the most precise results, use the same cell in the same orientationto the measurementbeam. Flush the cell about three times with the sample solution and start the measurementby clickingthe Instnunent Panel's "Sample" button or by pressing the spectrophotometer's "Sample" button. 11.5 Setting up a Method for Single Component Analysis. 11.5.1 Choose the "Quantification" task from the data analysis panel. 11.5.2 Enter the used wavelength in the input fields. ETS-9-46.0 Operation and Maintenance of the HP8453 W-Vis Spectrophotometer Page 6 of 9 Page 96 of 148 BACK TO MAIN 3M Environmental Laboratory Report No. E00-2192 11.53 If background correctionis desired, select "Single ReferenceWavelength", "Subtract Average Over a Range" or "Three-point Drop Line" from the background correction combo box. 11.5.3.1 "Single Reference Wavelength"requiresthe input of one wavelength in the adjacentwavelength edit field on the right side of the combo box. 11.5.3.2 For "Subtract Average Over a Range" or "Three-point Drop Line" you must define the rangehaseline by entering the start and end wavelengths in the two adjacent wavelength edit field on the right side of the combo box. 11.5.4 Specify a name for the analyte. 11.5.5 Choose "Concentration" to enter the analyte concentrationdirectly or "Weight & Volume" to have the ChemStation calculate the concentration. Enter the units for the concentrationor the weight and volume. 11.5.6 If you want to be prompted for the concentrationof the standardsduring measurement, select "Prompt for StandardInformation". In the combo box you can select whether the prompt asks you for the concentration, or calculates the concentrationbased on volume, weight and purity. 11.5.7 If you have diluted samples and want to correct for dilution, select "Prompt for Dilution Factor" of sample. 11.5.8 Choose the desired calibration curve type. 11.5.9 Select the desired data type and display range of the spectra in the graphical window. 11.5.10 Choose "OK" to close the dialog box. 11.5.11 Perform the following steps ifyou want to calibratethe method. 11.5.11.1 Measure a blank on the solvent if necessary using the "Blank" button in the instrumentpanel. 11.5.11.2 Measure the standardsusing the "Standard"button in the instrumentpanel. If you have selected one of the prompts, the appropriate values will be requested in a diaIog box. The spectrum is displayed automatically in the "Standard Spectra" window as they are measured. Note: There is no fixed limit to the number of calibration standardsthat can be incorporated into a calibration. However, each of the calibration curve types requires a minimum number of standardsof differentconcentrations, which can be found in Table 7, page 45 of the HP Manual: UnderstandingYour UV- Visible SpectroscopySystem. The ChemStation@s o h a r e calibrates automaticallywhen at least the minimum number of standardshas been measured. A table with the used standards and values as well as calibration curve is displayed. 11.5.11.3 If the calibrationis successfitl,the calibrationcurve icon of the data analysis panel changes from red to green. 11.6 Measuring and Displaying an Absorbance Spectrum 11.6.1 Select the "Clear" icon using the Toolbar, to deleteany spectral data that you do not wish to keep. 11.6.2 Select the "Spectrum/Peaks"task from the Method menu or data analysis panel. 11.4.3 Select the boxes or "PeaWVdley Find" if necessary. ETS-9-46.0 Operation and Maintenance of the HP8453 UV-Vis Spectrophotometer Page 7 of 9 Page 97 of 148 BACK TO MAIN 3M Environmental Laboratory Report No. E00-2192 11.6.4 Select "Absorbance" as data type. 11.6.5 Set the display range you want to see in the graphical window. 11.6.6 Choose "OK" to close the "Spectrum/PeaksParameters" dialog box. 11.6.7 Measure a Blank on the solvent if necessary using the "Blank"button in the instrument panel. 11.6.8 Measure all the samples using the "Sample" button in the instrument panel. The spectra are displayed automatically in the "Sample Spectra" window as they are measured and depending on the selected parameters you will get a table of results. 11.7 Loading Spectra: 11.7.1 Choose "Load"from the "File" menu, then choose the type of spectrathat you want to load (Samplesor Standards)from the submenuto display the "Load Spectra'' dialog box. 11.7.2 If the spectra you wish to load are not in the "File Name" list, select a different directory from the "Directories" list. 11.73 Select the spectra you wish to load from the File Name list and choose OK to close the dialog box. 11.8 Saving Spectra: 11.8.1 Choose "Save" from the "File" menu, then choose the type of spectra that you want to save (Samples, Standardsor Selected Spectra)fiom the submenuto display the "Save SpectraAs" dialog box. 11.8.2 If you wish to save the spectra in a directory other than the current one, seIect the new directory from the "Directories" list. 11.8.3 Type the name you wish to save the spectra as in the "File Name" field and choose "OK" to close the dialog box. 11.8.3.1 A valid file name consist of eight dphanumeric charactersand the file extension .sd or .std. Usually, the extension .std is used for standards only. 11.8.4 You can also save spectrausing the ToolBar. 12.0 RECOROS 12.1 Document all cleaning and maintenance performed on the instrument in the maintenance or dmaintenance logbook.Include a descriptionofthe procedure(s) performed, name of person who performed procedure@),any unusual observations, parts replaced or needing replacement, and whether the procedure was routine or non-routine. Logbooks are archived when complete. 13.0 TESTING, CALIBRATIONAND/ORSTANDARDIZATIONPROCEDURES 13.1 HP 8453 Self-Test: 13.1.1 Make sure that you are in the "Verification and Diagnostics"mode. The mode is indicated on the tool bar of the HP ChemStationa session. 13.1.2 Select the "Self-Test" task in the analysis panel's selection box. 13.1.3 Choose "Self-Test". Start from the "Task"menu or click "Start"to startthe self- test. 13.1.4 The self-test results will be displayed in a window with passlfail criteria. 13.2 Calibrating for a single component analysis. ETS-9-46.0 OperationandMaintenance of the HP8453 UV-Vis Spectrophotometer Page 8 o f 9 Page 98 of 148 . `C BACK TO MAIN 3M Environmental Laboratory Report No. E00-2192 13.2.1 Calibration for single component analysis is based on the measurement of standard sampleswith known concentrations. During the calibrationprocess, the software calculatesthe calibrationcoefficients,which are then used for the quantificationof unknown samples. 13.2.2 The status for calibration can be seen in the data analysis panel: 13.2.2.1 Uncalibrated: RED dashed calibration curve icon. 13.2.2.2 Calibrated: GREEN continuouscalibration curve icon. 13.2.3 To calibrate for single component anaIysis: 13.23.1 Load or set up a method for the "Quantification" task. 13.2.3.2 If the "Standard" spectrawindow is not displayed, choose "Show" standardsin the data analysis panel. 13.2.33 You can either load the standardsfrom file or measure them. 13.2.3.4 To measure standards: 13.2.3.4.1 Measure a bank on the solvent if necessary using the "Blank" button in the instrumentpanel. 13.2.3.4.2 Measure the standards using the "Standard" button in the instrument panel. If you have selected one of the prompts in the method, the appropriatevalues will be requested in a dialog box. 13.2.4 The spectraare displayedautomaticallyin the "Standard Spectra"window as the standards are measured. A minimum number of standards is required, depending on the selected calibrationcurve. The ChemStationmsoftwae calibrates automatically when at least the minimum number of standardshave been measured. A table with the used standards and values as well as a calibration curve is displayed. 13.2.5 If the calibrationis successfil, the calibrationcurve icon of the data analysispanel changes &om red to green. 14.0 REFERENCES 14.1 Defhtions obtained from www.spectroscopymag.com. 14.2 HP Manual: Understanding Your W-Visible Spectroscopy System, Hewlett-Packard: Wilmington, DE, 1997. Part No. G1115-90005. 14.3 HI' 8453 W-Visible Spectrophotometer Operator's Manual, Hewlett-Packard: Wilmington, DE, 2000. PartNo.G1115-90012. 14.4 HP 8453 W-Visible Spectrophotometer Service Manual, Hewlett-Packard: Wilmington, DE, 1998. PartNo. G111S-90003. 15.0 AFFECTEDDOCUMENTS 15.1 None. 16.0 REVISIONS Revision Number. Reason For Revision - Revision Date ETS-9-46.0 Operation and Maintenance of the HP8453 UV-VisSpectrophotometer Page 9 of 9 Page 99 of 14% BACK TO MAIN 3M Environmental Laboratory Report No. E00-2192 3M ENVIRONMENTAL LABORATORY --- EQUIPMENPTROCEDURE ROUTINEMAXBTENANCE OF h C H O N PURGE AND TRAPAUTOSAMPLER, TEKMARPURGEAND TRAPCONCENTRATAONRD AGILENGTAS CHROMATOGRAPH/MSAPSESCTROMETER Procedure Number: ETS-9-49.0 Adoption Date: ,c/!z+. Approved by: Laboratory Manager Date ETS-9-49.0 Routine Maintenance of the Purge & Trap Autosantpler/Concentrutor/GC/MS Page 100 of 148 BACK TO MAIN 3M Environmental Laboratory Report No. E00-2192 1.0 SCOPEAND APPLICATION (VSE NUMBERETDIER I) 1.1 This equipmentprocedure describesthe maintenancerequired for optimal operation of the Archon Purge and Trap Autosampler, Telanar Purge and Trap Concentratorand Agilent gas chromatograph/ mass spectrometer(GCMS) system. Specificitems requiring routine maintenance include occasional tightening vial escalator's nuts and refilling the StandardVial and water bottle in the Archon autosampler and periodic cleaning of the mass spectrometer ion source. 2.0 DEFINITIONS 2.1 None. 3.0 DESCRIPTION 3.1 Archon purge and trap autosampler equipped with Tekmar purge and trap concentrator and Agilent gas chromatograph and mass spectrometer. 4.0 IDENTIFICATION 4.1 System : "Rufus".(An equivalent systemmay be used). 4.1.1 Autosampler: serialnumber 13006,Varian, Archon 4.1.2 Concentrator: serial number 90297002,LSC2000,Tekmar 4.1.3 GC: serial number US00034972,6890 G1530A, Agilent ' 4.1.4 MS:serial number US01180105,5973NG2589A, Agilent 4.1.5 PC: serial number US94850812, D6720T,HP Kayak XA 5.0 WARNINGS AND CAUTIONS 5.1 'Health and Safety Warnings: 5.1.1 Coolingthe Telanar before removingthe side cover for maintenanceprevents contact bums. 5.1.2 Turning offpower sourcefor Tekmarbefore removing the side cover will prevent electric shock. 5.2 Cautions: 5.2.1 It is recommended that a grounded antistatic wrist strap be worn while disconnectingall wires, contacts, or cableswhich are connected to printed circuit boards within Archon autosampler, Tekmar concentrator or MS analyzer. 5.2.2 To prevent the breakage of the Standard Vial on Archon autosampler, during the refill, do not use any tool and do not overtighten the thumbnut. 5.2.3 Never add oil while the foreline pump is on. 6.0 SPECIAL INSTRUCTIONS 6.1 Not applicable. ETS-9-49.0 Routine Maintenance of the Purge & TrapAutosampler/Concentrator/GC/MS Page 2 of 5 Page 101 of 148 BACK TO MAIN 3M Environmental Laboratory Report No. E00-2192 7.0 RESPONSIBILITY 7.1 Routine maintenanceproceduresmay be performed by a primary custodian, and by any analyst who has been trained to perform these maintenance procedures by a primary custodian. 8.0 SUPPLIESAND MATERIALS 8.1 Graphite Ferrules, 0.4 mm I.D. for 0.25 mm columns 8.2 Abrasive paper, Hewlett-Packard, part no. 5061-5896 8.3 Alumina abrasive powder, Hewlett-Packard, part no. 8660-0791 8.4 Acetone, reagent grade 8.5 Dichloromethane, reagent grade 8.6 Methanol, purge and trap grade 8.7 Gloves (clean, lint-free, cotton), Hewlett-Packard, part no. 8650-0030(large); 8650-0029 (small) 8.8 Cotton swabs 8.9 Chem-wipes 8.10 Glass beakers 8.11 Sonicator 8.12 Base deactivated 2 mm ID gooseneck splitless injection port liners, Restek Corporation, part #20796-210.5, or equivalent 8.13 11mm diameter Themogreen LB2 septa, Supelco, part #23163, or equivalent 8.14 Viton injection port O-rings, Restek Corporation,part #20377, or equivalent 8.15 Septum wrench, Hewlett-Packard, part #19251-00100 8.16 Tweezers 9.0 CLEANINPGROCEDURES NIA 10.0 MAlNTENANCE PROCEDURES 10.1 Routine: Tighten the elevator`s assembly nuts when Archon autosampler displays error message I' Elevator not homed position `I. 10.1.1 Stop autosamplerrunby pressing STOP button on the front display twice. 10.1.2 Open the back cover of autosampler 10.1.3 Tighten top and bottom nuts on the elevator's assembly, do not over tighten them, 10.1.4 Close the back cover of autosampler 10.2 Routine: Fill the water bottle, empty the waste bottle. 10.3 Routine: If internal standards or surrogates are to be used, be certain the Standard Vial is filled with the required internal standard or surrogate. 10.3.1 Turn thehelium gas "OFF"with the toggle switch. 10.3.2 Push "System" key, choose Maintenance, Standard Control,Front Park. 10.3.3 Grasp the vial and loosen the black thumbnut. SIide the Vial down. ETS-949.0 Routine Maintenance of the Purge & Trap AutosampIer/Concenhtor/GC/MS Page 3 of5 Page 102 of 148 BACK TO MAIN 3M Environmental Laboratory Report No. E00-2192 10.3.4 Clean the vial with methanol, dry it thoroughly and fill the vial with approximately 5 ml of standard or s m g a t e 10.3.5 Slide the vial back up into standardmount. Finger-tightenthumbnut until it is snug. Do not use any tool and do not overthighten. 10.3.6 Turn the helium gas into ON position. Prime Standard Loop. 10.4 Routine: GCMS forelhe pump maintenance. 10.4.1 Examine the oil level window daily. If the oil level is near or below the lower line then add foreline pump oil. Never add oil while the foreline pump is on. 10.4.1.1 Vent the MSD accordingto the MSD HardwareManual. 10.4.1.2 Remove the fill cap. 10.4.1.3 Add pump fluid until the oil level in the window is near, but not above, the upper line. 10.4.1.4 Reinstall the fill cap. 10.4.1.5 Pump down the MSD according to the MSD Hardware Manual 10.4.2 Change forelinepump oil every 6-12 months accordingto the MSD Hardware I manual. 10.5 Nonroutine: Document any nonroutine mahtenance in the instrument's maintenance logbook. 11.O OPERATINPGROCEDURES 11.1 For operating procedures, refer to an appropriate analytical method, or to the Archon Purge and Trap Autosampler System Operator's Manual,Tekmar LSCZOO Instruction Manual and the Hewlett-PackardMSD HardwareManual for HP 5973N & HP 6890 SeriesMass SelectiveDetectors. I 12.0 RECORDS 12.1 Document any maintenance performed on the instrument in the maintenance or dmaintenance logbook. Jnclude. a description ofthe procedure(s) performed,any unusual observations, parts replaced or needing replacement, and whether the procedure was routine or non-routine. Be sure to date and initial the entry. Logbooks are archived when complete. 13.0 TESTINGC,ALIBRATIOANND/ORSTANDARDIZATPIROONCEDURES 13.1 After cleanhg the sourceand allowing sufficienttime for the vacuum to pump down and the mass spectrometerto equilibrateto operationtemperature, run an autotune; check for improved performance and for the presence or absence of air leaks. A tune report can also be used to check for leaks afterperforminginjection port maintenance. 14.0 REFERENCES 14.1 Archon Purge and Trap Autosampler System Operator's Manual 14.2 Tekmar LSC200InstructionManual ETS-9-49.0 Routine Maintenance of the Purge & TrapAutosampler/Concenttor/GC/MS Page 4 of 5 Page 103 of 148 BACK TO MAIN 3M Environmental Laboratory Report No. E00-2192 14.3 HewIett-Packard MSD Hardware Manual for Hp 5973N & HP 6890 Series Mass Selective Detectors. 15.0 AFFECTEDDOCUMENTS 15.2 None. 16.0 REVISIONS Revision Number. Reason For Revision Revision ETS-949.0 RoutineMaintenance of the Purge & TrapAutosampler/Concentrator/GC/MS Page 5 of 5 Page 104 of 148 BACK TO MAIN 3M Environmental Laboratory Report No. E00-2192 Appendix B: Chemical Characterization This appendix includes chemical characterization information for both reference substances and control substances. Page 105 of 148 BACK TO MAIN 3M Environmental Laboratory Report No. E00-2192 Chemical Characterization I Substance IUPAC Name I PFOA Perfluorooctanoic acid, ammonium salt I PF'HpA Pertluoroheptanoicacid Chemical Formula CsFisO2NH4 C7F1102H Identifier I Source Expiration Date 3825-26-1* I 3M Saecialtv Chemicals I 2002 375-85-9* Aldrich ~ ~ 2005 Storage Conditions Frozen Frozen Chemical Lot Number 332 TCR-9913 1-25 Physical Description White wax or powder Clear Crystals Purity Substance 95% I I C7Perfluoroheptenes(90/10 mix) I i 98%1 C, Hydride IUPAC Name 10% 2-Perfluoroheptene, 90% Perfluoroheptene 1,1,2,2,3,3,4,4,5,5,6,6,7,7,7 pentadecafluoroheptane I Chemical Formula I Identifier Source Expiration Date I C4F&F=C7F5. C,FIICF=CF, I I 355-63-5* I I ~ ~~ Lancaster Synthesis 2005 C,F I 272 13-61-2* ~~ ~~ Lancaster Synthesis 2005 I Storage Conditions I Frozen I Frozen Chemical Lot Number 90004250, TNA 3025 9005911, TNA-3026 Physical Description Clear ambient liquid Clear ambient liquid Purity 100% 97% PFPA I Perfluoropentanoicacid 2706-90-3* I Aldrich Frozen SD-043 I Clear Liquid 95%1 C6Hydride I 355-37-3* Lancaster Synthesis Frozen I 98% I Page 106 of 148 BACK TO MAIN 3M Environmental Laboratory Report No. E00-2192 Reference Substances (continued) Reference Substance Cs Hydride/Olefin Mix Cs Terminal Hydride C4Terminal Hydride IUPAC Name 1,1,1,2,2,3,3,4,4,5,5,6,6,7,8,8,8 pentadecafluorooctane, 2- perfluorooctene 1'1'2'2'3'3' '4' ' '6,6' ' ' ' ' heptadecafluorooctane 1,1,1,2,3,3,4,4,4 nonafluorobutane Chemical Formula C6F13CFHCF3'C6F13CF=CF2 C8F17H CP9H Identifier TCR-99030-18 335-65-9* 375-17-7* Source I Exairation Date ~~ ~ Storage Conditions 3M Specialtv Chemicals I 6/6/99 I Frozen Aldrich Chemical 2002 Frozen Crescent Chemical I 2002 ~ Frozen Chemical Lot Number 1 04307PN, TNA-2983 6A-46, TNA-3997 Physical Description Purity I Reference Substance IUPAC Name Clear ambient liquid I 85% Cs Hydride, 15% Cs Olefin I C4Interior Olefin I 2-Perfluorobutene Clear ambient liquid 99% C3Terminal Hydride 1,1,2,2,3,3,3 heptafluoropropane Clear ambient liquid 99% C2Terminal Hydride 1,1,2,2,2 pentafluoroethane Chemical Formula Identifier Source C4FS I 360-89-4* I Lancaster Synthesis C3F7H 2252-84-4* Lancaster Synthesis 354-33-6* Lancaster Synthesis I Extiration Date I ~~ Storage Conditions I Chemical Lot Number I 2002 I I I Frozen I 2010 1 2010 ~~ Flammable Flammable I G00195. TNA-4298 I G0062B. TNA-4294 I G00492. TNA-3021 ~~ ~~ Physical Description Clear ambient liquid Gas Gas Purity 97% 97% 99% Page 107 of 148 BACK TO MAIN 3M EnvironmentalLaboratory Report No. E00-2192 Control Substances structure IUPAC Name Use Source Expiration Date Storage Conditions Chemical Lot Number I Physical Description Purity I Control Substances I structure IUPAC Name Use Source Expiration Date Storage Conditions I Chemical Lot Number Physical Description Purity I Control Substances Structure IUPAC Name Use Some Expiration Date Storage Conditions Chemical Lot Number Physical Description Purity *CAS Number PFCH C&IZ Perfluorocyclo-hexane Surrogate Standard For GC/MS analysis Aldrich Chemical 2005 Frozen 01911AU I Colorless Moist Solid 97% I Chlorobenzene-& PFBS Pentafluorobenzene Perfluorobutane-sulfonate, potassium salt C&FS C4FWzK Pentafluorobenzene Internal Standard for LC/MS analysis Instrumental Surrogate Standard For GCIMS analysis 3M Specialtv Chemicals 2002 Restek Corn. ~~ 612002 Frozen Frozen TCR-99030-028 A013256 I White Powder I Methanol solution 97%< 99% (2500 p g i d i0.2%) I Toluene-& I Dibromofluoromethane C&IDs Chlorobenzene-d5 c7 D8 Toluene-d8 ' CHBrzF Dibromofluoromethane Instrumental Surrogate Standard For GCMS analysis Restek Corp. 612002 Frozen I A013256 Methanol solution 99% (2500 p g / d & 0.2%) I 1,4 Difluorobenzene Instrm Standard Eor CIL/IW~ analysis analysis Restek Corp. Restek Corp. 212002 212002 Frozen Frozen I A012973 I A012973 ~ I Methanol solution 99% (2500 p g / d F0.2%) I 4-Bromofluoro-benzene I Methanol solution 99% (2500 pglmL 0.2%) I 1,4-Dichlorobenzene-d., c6 H4FZ 1,4 Difluorobenzene C6HdBrF 4-Bromofluoro-benzene Instrumental Surrogate Standard For GCIMS analysis Instrumental Surrogate Standard For GCIMS analysis Restek Corp. 612002 Frozen A013256 Methanol solution 99% (2500 pdmL k 0.2%) Restek Corp. I 212002 Frozen A012973 . Methanol solution 99% (2500 ~g/rnL 0.2%) C6C12D4 1,4-Dichlorobenzene-d4 Instrumental Surrogate Standard For GCIMS analv& ~ 612002 Frozen A013256 Methanol solution 99% (2500 DglrnL k 0.2%) Page 108 of 148 BACK TO MAIN 3M EnvironmentalLaboratory Report No. E00-2192 ~ Appendix C: Kinetics Model and Kinetics Calculations This appendix presents the mathematicaldescriptionof the kinetics model employed in this study and the application of this model in the determination of the estimated half-lives presented. Page 109 of 148 BACK TO MAIN 3M Environmental Laboratory Report No. E00-2192 Kinetics Model C1. Reaction Components and Rates The arguments below are based on the following idealized set of reactions representing the photodegradation of a parent compound P and its products A,, which number N. The actual reactions that occur are subsumed in these equations, and are assumed to proceed with pseudo-first order rates k,, (for the parent) and k,, (for the products). P + photon k Prn +n,A,+Y, (m=ltoN) A, +photon +k h YmZ (m= 1toN) where "photon may either represent a photon of light or it may represent some other species in solution that reacted with a photon to produce a new reactive species and the general symbolsY,, and YmZrepresent all the other hydrolysis products. C2. Parent Compound Concentrations Equation C1 indicates that the pseudo-first order differential change in the parent concentration P at a constant flux of light or a constant concentration of radicals is given by which is equivalent to the separable differential equation gP = - [ zn, kpm]dt Equation C4 may be directly integratedto obtain the general solution [-c ) In[P]= nmk,, t + C my1 With the initial condition P(t = 0) = Po,the specific solution to EquationC4 is using the additional definition of the total parent photolysis rate Page 110 of 148 BACK TO MAIN 3M Environmental Laboratory Report No. E00-2192 -cN k, n, k,, . m=l Equation C6 can be re-written in a form that allows a least-squares estimate of the total parent hydrolysis rate: k,t =-In [i] Using the initial(t = 0) measuredvalue of the parent concentration Poand later values P measured at later times t , one can calculate and plot the (linear) quantity [- In (P/Po)] versus c, time and obtain a least -squares estimate of the slope of the line. The resulting slope is the least-squares estimate of the total parent photolysis rate. Equation C6 indicates that over a period of time TI': (the parent half-life) the parent concentration P is reduced through hydrolysis by a factor of two, where A least squares estimate of the parent photolysis half-life is therefore available from C3. Product Compound Concentrations The pseudo-first order differential changes in the product concentrations &, (using Equations C2 and C6)are dA, = ( n,kpmP- k,,A,)dt = ( n,k,,Po e-kp* - kAmA,)dt (CIV and the (first order, non-separable) differential equation governing the product concentrations is %+ k,A, = n,kp,Po e-kpt dt The "standard form" of Equation C12 is Page 111 of 148 BACK TO MAIN 3M Environmental Laboratory Report No. E00-2192 A: + S (t) A, = Q(t) where the "function" S (t) is actually a constant: (t>= kAm and Q(t) =n,kp,Po e-kpt . The general solution A, to Equation C12 is contained in where and There are two cases of Equation C18 to consider. In the circumstance that kArn= k, ,which occurs only when the rate of the mthproduct is identical to the total parent photolysis rate, the general solution to Equation 818 is (for k, = k,) A, e k p=t nmkPmPtO+ C and, using the initial conditionA ,(t = 0)= A, ,the specific solution to Equation18 is (for k, = k, ) A, = (n,k,,Po t +A, ) e-kp . Page 112 of 148 BACK TO MAIN 3M Environmental Laboratory Report No. E00-2192 We note that when ,k = k, = 0 (that is, when both the parent and potential product are photolytically stable), Equation C7 requires (also) that kp, = 0, so Equation C20 becomes A, =A, indicating, as required, that the product concentration does not change with time. The circumstance k,, = k, is highly improbable, and is neglected in the remainder of this discussion. However, the reader should bear in mind that the expressions derived below do not hold when the parent photolysis rate k, and the product photolysis ratek, approach each other. In the more probable case, for which k,, # k, (Le. that the rate of the mthproduct is different from the total parent rate), the general solution to Equation C18 is and the specific solution to Equation C18 with the initialcondition A,(t = 0)= A,, is nmkPmPO kP -kAm 1e-k, t - nmkPmPO e-kp t kP -kAm Of greatest interest here is the case in which the product compounds are known to be photolytically stable, that is, when ,k =0 for all m. In this case, Equation C23 becomes (for stable products) A, =A,, + nmkPmPO kP (1- e-kp t ) C4. Relationships Between the Parent and Compound Concentrations Equations C7 and C24 can be combined to obtain (for stable products) Page 113 of 148 BACK TO MAIN 3M Environmental Laboratory Report No. E00-2192 so that or (for stable products) (for stable products) If the changes in the product concentrations are all small compared to the original parent concentration, that is, if we may use the expression (valid for -1 IX 5 1 ) ln(l+X)=X- -1x2 +-1x3--1x4 +..... L 3 4 and Equation B23 becomes (for stable products and or Page 114 of 148 BACK TO MAIN 3M Environmental Laboratory Report No. E00-2192 (for stable products and cm Am-Amo << Po) C5. Parent Half-Life Estimates Based on Limits of Quantification of the Products In every experimental determinationof k, ,there is some set of values A;Q (the "limits of quantitation") below which the product concentrations A, cannot be reliably measured. If during an experiment carried out over the period of timed t all the product concentrations A, remain below their limits of quantitation, then the maximum possible value of the rate k, is obtained by assuming (for all the products) that 1) A,, = 0 and 2) at time t = A t , the product concentrations have increased to the values A, = A:Q. With these assumptions, the experimental data indicate that the reaction rate k, is less than some maximum value (kP),, as follows: (for photolytically stable products at concentrations below the limits of quantitation) vi) Under the same circumstances and assumptions, the experimental data indicatethat the parent half-life TI': (see Equation C9)is greater than the value (T . as follows: mm (for photolytically stable products at concentrations below the limits of quantitation) The reader should note that Equations C32 and C33 are valid only when both 1) the products are stable and 2)the concentrations of all the potential products are measured. Otherwise, the quantity (k,), in Equation C32 may not actually represent the maximum possible value of the rate constant k, ,and the related result in Equation C33 for (Tv:) . is also questionable. mm Page 115 of 148 BACK TO MAIN 3M Environmental Laboratory Report No. E00-2192 C6. Parent Half-Life Estimates Based on Limits of Quantification and Experimental Precision of Product Concentrations In certain experiments, some products are present at quantifiable but essentially constant concentrationsover the time (A t ) of the experiment. In this case, it is the experimental precision of the measured product concentrations, rather than the limits of quantitation, which contribute to the estimate of the maximum value of the parent hydrolysis rate k, . If the set of concentrationsmeasured for the mthproduct have the mean value p, and standard deviation 0, , the data do not exclude the possibility that the product concentration increased from the initialvalue 0, -pm to the value (T, + p, at time t = A t . Taking this possibility to be the actual case for the measured products, the maximumvalue of the quantity (A, -Am,) is 2 0 , . This reasoning suggests that the following estimate of the maximum parent photolysis rate is appropriate: (for stable products at either 1) constant measured concentrationswith standard deviation omor 2) concentrations below the limits of quantitation) -1 corn]. k, 5 (k,)- r 1 = 1 0' A AZQ+ BelowLOQ Cons tan t Under these circumstances and assumptions, the experimental data indicate that the parent half-life T1'i is greater than the value (T v;) . as follows: mm (for stable products at either 1) constant measured concentrations with standard deviation omor 2) concentrations below the limits of quantitation) The reader should note that Equations C34 and C35 are valid only when both 1) the products are photolytically stable and 2) the concentrations of all the potential products are measured. C7. Parent Half-Life Estimates Based on the Experimental Precision of Parent Concentrations In certain experiments, the concentration of the parent remains essentially constant over the time (A t ) of the experiment. In this case, it is the experimental precision of the measured parent concentrations that determines the maximumvalue of the parent hydrolysis rate k, . If the set of concentrations measuredfor the parent have the mean value ppand standard deviation 0,,the data do not exclude the possibility that the product concentration increased Page 116 of 148 BACK TO MAIN 3M Environmental Laboratory Report No. E00-2192 from the initialvalue - pp CY to,the value pp +CYa,t time t = A t . This reasoning suggests that the following estimate of the maximum parent photolysis rate is appropriate: (for essentially constant parent concentrations with mean value p, and standard deviation 0,) Under these circumstances and assumptions, the experimental data indicate that the parent half-life T1'i is greater than the value (Ty;)minas follows: (for essentially constant parent concentrations with mean value ppand standard deviationCYp ) References to Appendix C: I. N Levine, "Physical Chemistry," McGraw-Hill (New York), pp. 498-501 (1978). c2 F. Daniels, et al., "Experimental Physical Chemistry", McGraw Hill (New York), p.131 (1962). Kinetic Calculations - Indirect Photolysis Only two values of the parent concentration were recorded (a,'nd P ) which represent the values before and after the exposure period of length At. In this case, no least squares regression is possible to determine the rate k, in Equation C8: k,t =-In [g] The measured values of for Po and P are 1427 nglml and 1432 ng/ml, respectively. Equation C39 is appropriate: Page 117 of 148 BACK TO MAIN 3M EnvironmentalLaboratory Report No. E00-2192 The observed rate using At = 69.5 hours, &, = 1478nglm1,and O,,= 33.2 ng/ml is k, = 6.46 x I O 4hours". The rate of photolysis in the reactor k , is related to the actinic rate of photolysis kACTby kACT =kP(y) where I,, = 261 w/m2is the actinic solar intensity (at 45" south latitude) and the measured reactor intensity is I, = 680 w/m2. This gives k, = 6 . 4 6 ~ 1 0h-r~-'[;26 ;:I= 2.48~10-4hr-' For samples under constant illumination,the reaction rate and half-life are related by Equation C9: However, the actinic half-life is three times larger, according the standard eight-hour exposure day. This leads to - (indirect photolysis) TA$!=3w2) = 349 days, k ACT Page 118 of 148 BACK TO MAIN 3M Environmental Laboratory Report No. E00-2192 ~ ~ Appendix D: Representative Chromatograms Chromatograms from the present study are included in this appendix. Page I 1 9 of 148 BACK TO MAIN 3M Environmental Laboratory Report No. E00-2192 Batch Run # 2 of 62 Data File C:\HPCHEM\1\DATA\R0518OOB\rushOOO2.D Sample Name: MeOH blank E===E======III=====PEP==I==~===========~=~=~============~~========------ Injection Date : 5/18/00 3:07:45 PM Seq. Line : Sample Name : MeOH blank Vial : Acq. Operator : kej Inj : Acq. Instrument : Rush Acq. Method : C:\HPCHEM\l\METHODS\PFOA516.M. Last changed : 5/18/00 11:35:03 AM by kej Analysis Method : C:\HPCHEM\l\METHODS\R0518AX.M Last changed : 7/10/00 9:43:20 AM by kej (modified after loading) (Results are from SIM Analysis (ES-) f o r PFOS/PFBS/PFOA using Dionex IonPac NG1 2 99 1 a previously saved column, 4 ~ 3 5 m . MSDI 263. EIC=2627:263.7 (RO518LXlBlRUSHooo2.D) API-ES Negative MeOH Solvent Blank =L-+L^^^^ m 3Mx) I " 0 2 4 6 a 10 mi MSDI 383, EICP3627:363.7(ROSIaooBRU.SHWJ2.D) APES Negatlve 0 2 4 6 a 10 mil MSD1299, EIC=296.7:299.7 (RO516OOB~USHo00Z.D)API-ES Nqathn, Instrument 1 7 / 1 0 / 0 0 9:43:20 AM kej Page 1 of 2 Page 120 of 148 BACK TO MAIN 3M Environmental Laboratory Report No. E00-2192 Batch Run # 3 of 62 Data File C:\HPCHEM\1\DATA\R0518OOB\rushOOO3.D Sample Name: 1:7 MilliQ/MeOH ==============3=======~-====~=-======~ Injection Date : 5/18/00 3:26:02 PM Seq. Line : 3 Sample Name : 1:7 MilliQ/MeOH Vial : 98 Acq. Operator : kej Inj : 1 Acq. Instrument : Rush Inj Volume : 5 pl Acq. Method : C:\KPCHEM\l\METHODS\PFOA516.M Last changed : 5/18/00 11:35:03 AM by kej Analysis Method : C:\HPCH!3l\l\METHODS\R0518AX.M Last changed : 7/1Q/OO 9:43:24 AM by kej (modified after loading) SlM Analysis (ES-) for PFOS/PFBS/PFOA using Dionex IonPac NG1 column, 4x35mm. MSDlZ63, EIC=2&1.7Z63.7(RO518WElvtUSHooo3.D) API-ES NPgative 9ooo1 Bwo Control Blank .. ', 0 2 4 6 a. m MSD1363.ElC=362.7363.7 (RG518OOBRUSHwoJ.D) API-ES N W 0 2 4 i 6 MSDl299, ElC=298.7:299.7 (R051BOOB\RUSHMx)3.D) API-ES Negatlve . , .i. i -11- Bow i 0 2 4 ti MSDI 413, lC=412.7:413.7 (ROSl8OOB!RUSHooo3.Ll) API-ES Negative 55M) lb C 0 2 4 i rb C Instrument 1 7/10/00 9:43:25 AM kej Page 1 of 2 Page 121 of 148 BACK TO MAIN 3M Environmental Laboratory Report No. E00-2192 Batch Run # 4 of 62 Data File C:\HPCHEM\1\DATA\ROS18OOB\rushOOO4.D Sample Name: 00028-37-00 .--.--.-.--.--.-.--.--.-.--.--.-.--.--.-.--.--.-.--.-.--.--.-.--.--.-.--.--.-.--.--.-.--.--.=.=.=.=..=.=.=.=.=.=.=............ Injection Date ! 5/18/00 3:44:20 PM Seq. Line : Sample Name : 00028-37-00 Vial : Acq. Operator : k e j Acq. Instrument : Rush Inj : Acq. Method : C:\HPCHEM\l\METHODS\PFOA516.M Last changed : 5/18/00 11:35:03 AM by kej Analysis Method : C:\HPCHEM\l\METHODS\RO518AX.M Last changed : 7/10/00 9:43:28 AM by kej (modified after loading) (Results are from SIM Analysis (ES-) for PFOS/PFBS/PFOA using Dionex IonPac NG1 4 1 1 a previously saved column, 4x35m. 9060 8ooo Matrix Blank 7ow &.n 6000 540W0a0 -4 fLJ7P.r I " . I . . . I . . . l . . I ( . . 0 2 4 6 8 10 MSDi 363,EiC=362.7:363.7 (RO51800BRUSHWO4.0) API-ES Negatlve BWO 5wOL A F 4oOoi \ J - " w A J L + ~ ~ w / r , ' , , , , , I,. , . I , , . 1. min ( .. . i 50000 25w 0 ---, 0 2 4 6 8 10 min MSDi 413, ElC=412.7:413.7(Rffi1800B\RUSHW.D) API-ES Negative Instrument 1 7/10/00 9:43:28 AM kej Page 1 of 2 Page 122 of 148 BACK TO MAIN 3M EnvironmentalLaboratory Report No. E00-2192 Batch Run # 5 of 62 Data File C:\HPCHEM\1\DATA\R051800~\rush0005.D Sample Name: 00028-37-01 ..................................................................... Injection Date : 5/18/00 4:02:35 PM Seq. Line : 5 Sample Name : 00028-37-01 Vial : 2 Acq. Operator : kej Inj : 1 Acq. Instrument : Rush Inj Volume : 5 pl Acq. Method : C:\HPCHEM\l\METHoDS\PFOA516.M Last changed : 5/18/00 11:35:03 AM by k e j Analysis Method : C:\HPCHEM\~\METHODS\RO~~~AX.M Last changed : 7/10/00 9:43:32 AM by k e j (modified after loading) SIM Analysis (ES-) for PFOS/PFBS/PFOA using Dionex IonPac NG1 column, 4x35m. MSDI 363,EICm382.7383.7 (Rffi18WB\RUSHM)05.D) API-ES NegalNa/ 5WW 25Mx) 0 ~~~. - - - - I _ _ . - 0MSD1 413, EiC1412.7:42113.7 . (R, ffi180. 08\RUSHM4KI 15.D)' - API-ES NagaIl~6eI 8 10 mil A Instrument 1 7/10/00 9:43:32 AM kej Page 1 of 2 Page 123 of 148 BACK TO MAIN 3M Environmental Laboratory Report No. E00-2192 Batch Run # 6 of 62 Data File C:\HPCHEM\1\DATA\R0518OOB\rushOOO6.D Sample Name: 00028-37-02 ...................................................................... Injection Date : 5/18/00 4:20:50 PM Seq. Line : 6 Sample Name : 00028-37-02 Vial : 3 Acq. Operator : kej Inj : 1 Acq. Instrument : Rush Inj Volume : 5 pl Acq. Method : C:\HPCHEM\l\METHODS\PFOA516.M Last changed : 5/18/00 11:35:03 AM by kej Analysis Method : C:\HPCHEM\l\METHODs\RO518AX.M Last changed : 7/10/00 9:43:36 AM by kej (modified after loading) SIM Analysis (ES-) for PFOS/PFBS/PFOA using Dionex IonPac NG1 column, 4x35m. MSDl 263,EiC1262.7263.7(RO518WE\RUSHO~.D)API-ES Negatii I I 9ooo -ZBMX) h/-- Calibration Std 2 A -d%-.JL-& I . . " " ~ 1 ,b I sow0 25wo 0 -- 1__--..--__5 8 1I0 , , mip 0MSD1 413, EIC.412 7 4213 7 (ROSlsoOBRUSHO4W6.D) API-ES Negabv6~ Instrument 1 7/10/00 9:43:36 AM kej Page 1 of 2 Page 124 of 148 BACK TO MAIN 3M Environmental Laboratory Report No. E00-2192 Batch Run # 13 of 62 Data File C:\Hi?CHEM\1\DATA\R0518OOB\rushOOl3.D Sample Name: 00028-37-09 =I==P=l==========r=s==-=P IE=P====fl====-P=====PI=I=====EPS==============P== Injection Date : 5/18/00 6:28:34 PM Seq. Line : 13 Sample Name : 00028-37-09 Vial : 10 Acq. Operator : kej Inj : 1 Acq. Instrument : Rush Inj Volume : 5 pl Acq. Method : C:\HPCHEM\l\METHODS\PFOA516.M Last changed : 5/18/00 11:35:03 AM by kej Analysis Method : C:\HPCHEM\l\METHODS\R0518AX.M Last changed : 7/10/00 9:44:04 AM by kej (modified after loading) SIM Analysis (ES-) for PFOS/PFBS/PFOA using Dionex IonPac NG1 column, 4x35~. lmm{ - 8 MSDl 263,ElC=2627:263.(7ROslsOOEWUSHWl3.D)API-ESNegatlvc Calibration Std 9 , ~ " ~ " ' I ' ' ' , ~ ~ ~ I 0 2 4 6 8 10 m MSD13W.EIC1.352.7363.7(R051800BWUSHW13D) A P E S Negative 2oowo I " ' I ) . . I ' ' . , 0 2 4 6 8 MSDl 299,ElC=298.7:299.7(R051EWBWJSHW13.D)API-ES NegaWe 10 m I " . I . ' 0 2 4 6 8 10 MSDl 413,ElC=412.7:413.7(ROslBWBWUSH0013.D)A P E S Negative Instrument 1 1/10/00 9:44:04 AM kej Page 1 of 2 Page 125 of 148 BACK TO MAIN 3M Environmental Laboratory Report No. E00-2192 Batch Run # 29 of 62 Data File C:\HPCHEM\l\DATA\R0518OOB\rush0029.D Sample Name: 0515-PFOAfe-11 ===19=1=======1======E=I==I===~=========-===~~=====~===================~== Injection Date : 5/18/00 11:20:33 PM Seq. Line : 29 Sample Name : 0515-PFOAfe-11 Vial : 21 Acq. Operator : kej Inj : 1 Acq. Instrument : Rush Inj Volume : 5 pl Acq. Method : C:\HPCHEM\l\METHODS\PFOA516.M Last changed : 5/19/00 11:35:03 AM by kej Analysis Method : C:\HPCHEM\l\METHODS\RO51BAX.M Last changed : 7/10/00 9:45:05 AM by kej (modified after loading) SIM Analysis (ES-) for PFOS/PFBS/PFOA using Dionex IonPac NG1 column, 4x35mm. MSDI 263. EIC+282.7:283.7 (RaSl8OOEvlUSHPms.D) APCES Negative :I0 2 4 6 MSDl 383,EIC=362.7:363.7 (RaSl8WBWUSHomS.D)API-ESNegative 3m --LA/ IO mip t - - 0 2 4 6 a 10 mh MSDl 299. EiC~296.72997 (Ro518wBvlUSHoo29.0) APCES Negative - , , , _.-_ 0 2 4 6 8 10 MSD1 413, ElC-412.7'413.7 (RO518OOBvlUSHomS.D)API-ES Negative Q 2 4 6 B mid Instrument 1 7/10/00 9:45:05 AM kej Page 1 of 2 Page 126 of 148 BACK TO MAIN 3M Environmental Laboratory Report No. E00-2192 Batch Run # 30 of 62 Data File C:\HPCHEM\l\DATA\R051800B\rushO03O.D Sample Name: 0515-PFOAfe-12 ========33=====5=== ..=.= .= .- ..-........................................ Injection Date : 5/18/00 11:38:48 PM Seq. Line : 30 Sample Name : 0515-PFOAfe-12 Vial : 22 Acq. Operator : kej Inj : 1 Acq. Instrument : Rush Inj Volume : 5 pl A c q . Method : C:\HPCHEM\l\METHODS\PFOA516.M Last changed : 5/18/00 11:35:03 AM by kej Analysis Method : C:\HPCHEM\l\METHODs\RO518AX.M Last changed : 7/10/00 9:45:09 AM by k e j (modified after loading) SIM Analysis (ES-) for PFOS/PFBS/PFOA using Dionex IonPac NG1 column, 4x35~. ' 4 I 1 125ooo 1M)Ow 25Mx) I . . . , ' . . , . . . I . , 2 4 6 8 . , . ._ l _ 10 mir ~li.::i).*, 175wo soOoo 25wo . . . 0 - 0MSD1 413, EIC.412.7:421I3 7 (R. ffilBW, EWUSH040I 30 0)' API-EI S Ne, gative61 . ' 8 10 1 . rnin Insteument 1 7 1 ' 1 0 / 0 0 9:45:10 AM kej Page 1 of 2 Page 127 of 148 BACK TO MAIN 3M Environmental Laboratory Report No. E00-2192 Batch Run # 31 of 62 Data File C:\HPCHEM\l\DATA\R0518OOB\rushO03l.D Sample Name: 0515-PFOAfe-13 ............................................................................ Injection Date : 5/18/00 11:57:01 PM Seq. Line : 31 Sample Name : 0515-PFOAfe-13 Vial : 23 Acq. Operator : kej Inj : 1 Acq. Instrument : Rush Inj Volume : 5 pl Acq. Method : C:\HPCHE!M\l\METHODS\PFOA516.M Last changed : 5/18/00 11:35:03 AM by kej Analysis Method : C:\HPCHEM\l\METHODS\R0518AX.M Last changed : 7/10/00 9:45:13 AM by kej (modified after loading) SIM Analysis (ES-) for PFOS/PFBS/PFOA using Dionex IonPac 'NG1 column, 4x35~. MSDl 263, EIC1282.7:203.7(RO5laoOBvlUSHoo31.D) API-ES N W t h - Exposed 72hrs sample Fe203 NoPcmxide I M I 0 2 I " ' I " ' I " ' 4 6 a 10 mln MSDl 363.EIC=38273363.7 (RO518MlBlRUSHW3l.D) API-ES Negative 14ooo 12m low0 8wo 6wo 'm Imo',--.- - - f / . . . l . . , , . ../----a- 0 2 4 6 6 10 min MSOl 299. EIC=Z98.7:299.7(R051aoOBvlUSH0031D)API-ES Negative I " ' I . . 0 2 4 6 MSDI 413. EICn41Z.f:413.7 (ROSl~BWUSHGO31.0) API-ES NeOallW ISMKXIO 125wM, lMxxxM 75m 50oooO 250000 0, I . ) ' I E ' . 8 1 ' , 10 ' , ' . . I , ~ ~ mlr , Instrument 1 7/10/00 9:45:14 AM kej Page 1 of 2 Page 128 of 148 BACK TO MAIN 3M Environmental Laboratory Report No. E00-2192 Batch Run # 31 of 62 Data File C:\HPCHEM\1\DATA\R051800B\rush0037.D Sample Name: 0515-PFOAfe-19 =======S=IPflP-===CI*=~-========~=-==-~==~==-========~======~=~====~= Injection Date : 5/19/00 1:46:30 AM Seq. Line : 37 Sample Name : 0515-PFOAfe-19 Vial : 29 Acq. O p e r a t o r : kej Inj : 1 Acq. InstrLment : Rush Inj Volume : 5 1.11 Acq. Method : C:\HPCHEM\l\METHODS\PFOA516-M L a s t changed : 5/18/00 11:35:03 AM by kej Analysis Method : C:\HPCHEM\l\METHODS\ROSlllAX.M L a s t changed : 7/10/00 9:45:36 AM by kej (modified after loading) SIM Ana1ysi.s (ES-) f o r PFOS/PFBS/PFOA using DiOneX IonPac NG1 column, 4~35m. MSDl 263, EIC=262.7263.7(R05f&3JBWUSHW37.!3) API-ESNegative II - Enposed 72hB Control MilliQ NOPeroxide 0 2 4 MSDl 383.EIC-362 7 3837 (ROWeOO8WUSHCQ370) AP1-ES N@IW 12000 8 10 ml 2w0 C 2 4 6 8 10 rn~ MSDl299. EIC=2987299 7 (ROWsOa~WUSUCU307) APCES N e g a h 25000 . . - I ' " I ' ' ' I ' ' I , , 0 2 4 6 8 10 m MSDl 413, IC~41274137(R~~eOOB\RUSHW37A0P) I-ESNegak Instrument 1 7/10/00 9:45:36 AM kej Page 1 of 2 Page 129 of 148 BACK TO MAIN 3M Environmental Laboratory Report No. E00-2192 Batch Run # 40 of 61 Data File C:\HPCHEM\1\DATA\RO5180OB\rushOO91.D ______----------_-______-_--_-_--_--___--_----- -------------------------------p===-------------------====- Sample Name: 0515-PFOAfe-51 -=---_-_-_-___________ ____ Injection Date : 5/19/00 6:13:39 PM Seq. Line : Sample Name : 0515-PFOAfe-$1 Vial : Acq. Operator : kej Acq. Instrument : Rush Inj : Acq. Method : C:\HPCHEM\l\METHODS\PFOA516.M Last changed : 5/18/00 11:35:03 AM by kej Analysis Method : C:\HPCHEM\l\METHODS\R0518BX.M Last changed : 7/10/00 9:16:40 AM by kej (modified after loading) (Results are from SIM Analysis (ES-) for PFOS/PFBS/PFOA using Dionex IonPac NG1 91 61 1 a previously saved column, 4 x 3 5 m . 7000 6000 Day 0 Blank Fe203 No Pemxtde Instrument 1 7/10/00 9:16:40 AM kej Page 1 of 2 Page 130 of 148 BACK TO MAIN 3M Environmental Laboratory Report No. E00-2192 Batch Run # 41 of 61 Data File C:\HPCHEM\1\DATA\R0518OOB\rushOO92.D Sample Name: 0515-PFOAfe-52 =1=1=3==.==1===59~=====~========~~==*--===~==========-===~=======~=== Injection Date : 5/19/00 6:31:53 PM Seq. Line : 92 Sample Name : 0515-PFOAfe-52 Vial : 62 Acq. Operator : kej Inj : 1 Acq. Instrument : Rush Inj Volume : 5 pl Acq. Method : C:\HPCHEM\l\METHoDS\PFOA516.M Last changed : 5/18/00 11:35:03 AM by kej Analysis Method : C:\HPCHEM\l\METHODS\RO518BX.M Last changed : 7/10/00 9:16:44 AM by kej (modified after loading) SIM Analysis (ES-) for PFOS/PFBS/PFOA using Dionex IonPac NG1 column, 4x35m. k Spiked Fez03 No Peroxide Instrument 1 7/10/00 9:16:44 AM kej Page 1 of 2 Page 131 of 148 BACK TO MAIN 3M Environmental Laboratory Report No. E00-2192 Batch Run # 42 of 61 Data File C:\HPCHEM\1\DATA\R0518OOB\rushOO93.D Sample Name: 0515-PFOAfe-53 =======iE=============ii.Ci=-~===~==-~=~==~=~===~====~=============----- Injection Date : 5/19/00 6:50:09 PM Seq. Line : 93 Sample Name : 0515-PFOAfe-53 Acq. Operator : kej Acq. Instrument : Rush Vial .: 63 Inj : 1 Inj Volume : 5 p1 Acq. Method : C:\HPCHEM\l\METHODS\PFOASl6.M Last changed : 5/18/00 11:35:03 AM by kej Analysis Method : C:\HPCHEM\l\METHODS\R0518BX.M Last changed : 7/10/00 9:16:48 AM by kej (modified after loading) SIM Analysis (ES-) for PFOS/PFBS/PFOA using Dionex IonPac NG1 column, 4x35mm. MSD1 28, ElC=2627263.7 (R051N10B~lJSHW93.0A) PI-ES Negath'e Day 0 Sample Fe203 NoPemxide 5Mx) 12ooo loo00 Bwo 6003 4MM zwo ------ -- I I ' . l . . , , . 4 --A+, Instrument 1 7/10/00 9:16:48 AM kej Page 1 of 2 Page 132 of 148 BACK TO MAIN 3M EnvironmentalLaboratory Report No. E00-2192 Batch Run # 47 of 61 Data File C:\HPCHEM\1\DATA\R0518OOB\rushOO98.D Sample Name: 0515-PFOAfe-58 ======i========il==Il=====IiE.=fil====3~=-==~======================= Injection Date : 5/19/00 8:21:32 PM Seq. Line : 98 Sample Name : 0515-PFOAfe-58 Vial : 68 Acq. Operator : kej Inj : 1 Acq. Instrument : Rush Inj Volume : 5 p1 Acq. Method : C:\HPCHF,M\l\METHODS\PFOA516.M Last changed : 5/18/00 11:35:03 AM by kej Analysis Method : C:\HPCHEM\l\METHODS\RO518BX.M Last changed : 7/10/00 9:16:48 AM by kej (modified after loading) SIM Analysis (ES-) f o r PFOS/PFBS/PFOA using Dionex IonPac NG1 column, 4x35m. MSDl 263, EIC.zL62.72S3.7(R05I@OOBWUSHWW.D)API-ES Negative ml Control Millip No Peroxide Dayo a 2 4 6 MSDl 363,ElC.382.7383.7 (R051800BWUSHW98.D) APCES Negative 6 b 2 4 MSDl 299, EIC=298.7299.7 (R0518WSWUSH0098.D) API-ES Negathw ~~1 5 m 25000 0--, , 0 2 l ' * ' I4 " ' I .6 ' MSD1 413, ElC=412.7:413.7(RC51800B\RUSH~.D)API-ES Negafive 10 mi I ti mi L-_ 8 10 ; , mi XXXXX] 2m 0- . , ~~~ 0 2 4 6 0 I r 10 , ' rniD Instrument 1 7/10/00 9:17:10 AM kej Page 1 of 2 Page 133 of 148 BACK TO MAIN 3M EnvironmentalLaboratory Report No. E00-2192 Batch Run # 14 of 61 Data File C:\HPCHEM\1\DATA\RO51800B\rush0065.D Sample Name: 0515-PFOAfe-31 =i==^=====IL==~===l==il=3==F==O=C.====E=== Injection Date : 5/19/00 10:17:53 AM Seq, Line : 65 Sample Name : 0515-PFOAfe-31 Vial : 41 Acq. Operator : kej Inj : 1 Acq. Instrument : Rush Inj Volume : 5 p1 Acq. Method : C:\HPCHEM\l\METHODS\PFOA516.M Last changed : 5/18/00 11:35:03 AM by kej Analysis Method : C:\HPCHEM\l\METHODS\R0518BX.M Last changed : 7/10/00 9:15:03 A M by kej (modified after loading) (Results are from a previously saved SIM Analysis (ES-) for PFOS/PFBS/PFOA using Dionex IonPac NG1 column, 4x35mm. 'I Instrument 1 7/10/00 9:15:03 AM kej Page 1 of 2 Page 134 of 148 BACK TO MAIN 3M Environmental Laboratory Report No. E00-2192 Batch Run # 15 of 61 Data File C:\HPCHEM\~\DATA\R 5 800B\rush00 6.D Sample Name: 0515-PFOAfe-32 ====i=====E=3=ii==iEf==l===l=====iS=E===iir===================i=---- ------ Injection Date : 5/19/00 10:36:09 AM Seq. Line : 66 Sample Name : 0515-PFOAfe-32 Vial : 4 2 A c q . 0pera:or : kej Inj : 1 Acq. Instrument : Rush Inj Volume : 5 p l Acq. Method : C:\HPCHEM\l\METHODS\PFOA516.M Last changed : 5/18/00 11:35:03 AM by kej Analysis Method : C:\HPCHEM\l\METHODS\R0518BX.M Last changed : 7/10/00 9:15:07 AM by kej (modified after loading) SIM Analysis (ES-) for PFOS/PFBS/PFOA using Dionex IonPac NG1 calm, 4x35m MSDl 263,EIC=282.7=.7 (RO518WBRUSHCO66.D)API-ES N-W a. - Unexpnscd 72hn Blank Spiked FcZ03 No Peroxide 0 2 , , , I - - I - - 4, 6 ~ " L .MSDl 363,ElC6627363.7(RoS18ooEWJSH~.D)API-ES N@~w 525woMo0o) 0 ' 2 I ' . ' 4 I ' ' . I 8 10 d;_ ' a4' 10 MSD1299, ElC=298.7:290.7 (RWl8OOB\RUsHOO66.D) APKS N e ~ a t i i ~ % I ~ ' SWOD 25ooo 0 0MSDl 413, ElC41' 2.7421I3.7 ( ,R ~ l ~" ~ \ R U S H4Io o S 'eA. DP )K, S ; Neg1aUvs6 8 ~0- I " , I . . . I . . . t , 2 4 6 8 10 A,,1I0 - Instrument 1 7/10/00 9:15:07 AM kej Page 1 of 2 Page 135 of 148 BACK TO MAIN 3M EnvironmentalLaboratory Report No. E00-2192 Batch Run # 16 of 61 Data File C:\HPCHEM\1\DATA\R0518OOB\rushOO67.D Sample Name: 0515-PFOAfe-33 ===========--=..ii~e===m==-Eiil=iD====-=*~===~=============-============~~========= Injection Date : 5/19/00 10:54:22 AM Seq. Line : Sample Name : 0515-PFOAfe-33 Vial : Acq. Operator : kej Inj : Acq. Instrnment : Rush Acq. Method : C:\HPCHE&l\l\METHODS\PFOA516 .M Last changed : 5/18/00 11:35:03 AM by kej Analysis Method : C:\HPCHEM\l\METHODS\R0518BX.M Last changed : 7/10/00 9:15:10 AM by kej (modified after loading) (Results are from SIM Analysis (ES-) for PFOS/PFBS/PFOA using Dionex IonPac NG1 67 43 1 a previously saved column, 4 ~ 3 5 m . 7W4 - Unexposed 72hn sample Fez03 Noperoxide r, t - - . ' " . . . , . . . , . . . , . , I . ' . , 0 2 4 8 8 MSDl 333,EIC-362.7J8.7 (RO518WBWJSHMwr.D) APCES Negatlve 10 mi 0 2 4 6 E r'o mi MSDl 299. EICE298.7:299.7(R0518M)B\RUSHWW.D) API-ES Negallve I1woW 75000 5oMx) 25ooo 0- -__.-- 0 2 4 5 8 10 mi MSDl 413, ElC42.7:413.7 (ROSl800B\RUSHOOW.D)APES NqsUVe . . . . . , 0 - 0 2 I , , , . . , 7--- 4 8 8 10 mil Instrument 1 7/10/00 9:15:11 AM kej Page 1 of 2 Page 136 of 148 BACK TO MAIN 3M Environmental Laboratory Report No. E00-2192 Batch Run # 21 of 61 Data File C:\HPCHEM\l\DATA\R0518OOB\rush0072.D Sample Name: 0515-PFOAfe-38 - - ---- -------------_---_*===~=~~-====~=~====-------- ---- ----- -----------------i___ Injection Date : 5/19/00 12:26:11 PM Seq. Line : 1 2 Sample Name : 0515-PFOAfe-38 Vial : 4 8 ' Acq. Operator : kej Inj : 1 Acq. Instrument : Rush Acq. Method : C:\HPCHW\l\METHODS\PFOA516.M Last changed : 5/18/00 11:35:03 AM by kej Analysis Method : C:\HPCHEM\l\METHODS\RO518BX.M Last changed : 7/10/00 9:15:29 AM by kej (modified after loading) (Results are from a previously saved SIM Analysis (ES-) for PFOS/PFBS/PFOA using Dionex IonPac NG1 column, 4x35mm. MSDl 263.ElC=262.7263.7 (RffilBWS\RUSHW72.D) API-ES N @ b 0 i 4 6 a MSDI 363, ElCW2.7369.7 (R0518WBWJSHW72.D)API-ES N W i I k w.3 0 2 4 6 6 MSDsDt 299,E I C ~ W . 7 2 9 9 .(7ROSlBM)B\RUSHW72.0) API-ES Negdive 10 mil 10 rnl lsMxyxl 125Mwo SMXWX) 2 4 6 a fo rn Instrument 17/10/00 9:15:29 AM kej Page 1 of 2 Page 137 of 148 BACK TO MAIN 3M EnvironmentalLaboratory Report No. E00-2192 __~ - Appendix E: Soil Types and Characterizations This appendix presents the physical descriptionsand chemical characterizationsof the three soils used in the present investigation Page 138 of 148 BACK TO MAIN 3M EnvironmentalLaboratory Report No. E00-2192 STANDARD LABORATORY SQiLS STcmlxEo, y MOR? COWA U EPkSSM s3 22000 <to <.?IO . 0.6 3000 4.5 8 36 12 20000 ' 0.04 I' 2mo MK) !j2 120 18 620 40 900 d9 U 40000 <lo ?7 4.5 3oOo co.5 5 41 8.5 22wo 0.1 1 1500 120 84 M 14 150 40 400 47 4 48000 ' no loa 0.6 . 86000 4.5 , 6 2J 13 18000 0.02 3OOOO . .. f10 92 220 13 7lO 40 em 47 8.14 3.50 0.68 ' 0.10 297 0.43 0.03 0.02 42 18 28.3 22.0 0.1 1 0.09 0.04 0.05 26.1 0.18 3.58 0.08 , lo0 21.3 0.20 0.05 61 5 15 2.00 0.25 1.80 84 14 6.0 1470 280 2s 1.79 3.09 0.277 0.478 OM 0.805 1S.f 22.3 16.0 s.7 .4.8 7.7 5.7 4.5 7.5 1.8 1.1) NONE 0.98 0.32 0.68 22 44 34 LOAM BDL BO1 26 36 38 CLAY LOAM BDL BDL 22 26 52 SANDY CLAY LOAM BM BDL .- Page 139 of 148 BACK TO MAIN 3M Environmental Laboratory Report No. E00-2192 Appendix F: Light Intensity Measurements at 45" South Latitude (Miami FL) Page 140 of 148 BACK TO MAIN 3M .EnvironmentalLaboratory Report No. E00-2192 .I. 'da;, . I I I' I .CInA : I.. I . . *Small variationsare possible, depending un condition oflamp andfilters. Page 141 of 148 BACK TO MAIN 3M Environmental Laboratory Report No. E00-2192 Appendix G: Characteristics of the Spectral Output of the Suntest Instruments This appendix contains an Excel spreadsheet of the characteristics of the spectral output of the Suntest Photoreactors used in the present investigation. Page 142 of 148 BACK TO MAIN 3M Environmental Laboratory Report No. E00-2192 Suntest Irradiance in W/mA2*nm Assuming the use of 300-800nm Global Sensor Only Filters Used Wavelength nm 250 252 254 256 258 260 262 264 266 268 270 272 274 276 278 280 282 284 286 288 290 292 294 296 298 300 302 304 306 308 310 312 314 316 318 320 322 324 326 328 IR QlSuprax (UV) 0.001 0 0 0 0.001 0 0 0 0 0 0 0 0 0 0 0 0 0 0.003 0.005 0.009 0.014 0.021 0.028 0.045 0.054 0.07 0.085 0.116 0.138 0.151 0.175 0.21 0.24 0.263 0.279 0.329 0.352 0.369 0.4 Irradiances factored to yield 680 W/mA2in 300-800nm band IR QlSuDrax IUV) 0.001 119 0 0 0 0.0011I 9 0 0 0 0 0 0 0 0 0 0 0 0 0 0.003357 0.005595 0.010071 0.015666 0.023499 0.031332 0.050355 0.060426 0.07833 0.0951 15 0.129804 0.154422 0.168969 0.195825 0.23499 0.26856 0.294297 0.312201 0.368151 0.393888 0.412911 0.4476 Page 143 of 148 BACK TO MAIN 3M Environmental Laboratory Report No. E00-2192 330 0.431 0.482289 332 0.449 0.502431 334 0.475 0.531525 336 0.495 0.553905 338 0.525 0.587475 340 0.549 0.614331 342 0.565 0.632235 344 0.566 0.633354 346 0.587 0.656853 348 0.614 0.687066 350 0.61 0.68259 352 0.635 0.710565 354 0.656 0.734064 356 0.685 0.76651 5 358 0.662 0.740778 360 0.675 0.755325 362 0.719 0.804561 364 0.714 0.798966 366 0.73 0.81687 368 0.813 0.909747 370 0.858 0.9601 02 372 0.767 0.858273 374 0.8 0.8952 376 0.827 0.925413 378 0.864 0.966816 380 0.962 1.076478 382 0.992 1.I10048 384 0.974 I.089906 386 0.996 1.I14524 388 1.028 I.150332 390 1.111 1.243209 392 1.126 1.259994 394 1.227 1.373013 396 1.642 1.837398 398 I.552 1.736688 400 1.243 1.390917 402 1.228 1.374132 404 1.241 1.388679 406 I.284 1.436796 408 1.473 1.648287 410 1.395 1.561005 412 1.551 1.735569 414 1.41 6 1.584504 416 1.369 1.531911 418 I.426 1.595694 420 1.644 1.839636 422 1.453 1.625907 424 I.472 1.647 168 426 I.462 1.635978 428 1.466 I.640454 Page 144 of 148 430 432 434 436 438 440 442 444 446 448 450 452 454 456 458 460 462 464 466 468 470 472 474 476 478 480 482 484 486 488 490 492 494 496 498 500 502 504 506 508 510 512 514 516 518 520 522 524 526 528 1.466 1.487 1.5 1.566 1.714 1.616 1.616 1.57 1.563 1.573 2.267 2.031 1.796 1.811 2.127 1.835 3.267 2.476 2.541 5.277 2.487 1.922 2.924 1.837 1.813 2.289 2.516 2.651 1.952 1.842 1.898 3.012 2.089 1.871 1.888 1.898 I.973 2.005 1.94 1.927 1.934 I.963 2.013 2.031 2.021 I.995 1.971 1.98 1.966 1.978 BACK TO MAIN 3M Environmental Laboratory Report No. E00-2192 1.640454 1.663953 I I.6785 1.752354 1.917966 1.808304 1.808304 1.75683 1.748997 1.760187 2.536773 2.272689 2.009724 2.026509 2.380113 2.053365 3.655773 2.770644 2.843379 5.904963 2.782953 2.1 50718 3.271956 2.055603 2.028747 2.561391 2.8 I5404 2.966469 2.184288 2.061 198 2.123862 3.370428 2.337591 2.093649 2.1 12672 2.123862 2.207787 2.243595 2.1 7086 2.1 56313 2.164146 2.196597 2.252547 2.272689 2.261499 2.232405 2.205549 2.21562 2.199954 2.213382 Page 145 of 148 BACK TO MAIN 3M Environmental Laboratory Report No. E00-2192 530 I.954 2.186526 532 I.932 2.161908 534 1.942 2.173098 536 2.008 2.246952 538 2.014 2.253666 540 2.113 2.364447 542 1.996 2.233524 544 1.977 2.21 2263 546 1.962 2.195478 548 1.921 2.149599 550 1.876 2.099244 552 1.84 2.05896 554 1.938 2.168622 556 2.17 2.42823 558 2.106 2.356614 560 1.936 2.166384 562 1.912 2.139528 564 1.749 1.957131 566 1.706 1.go9014 568 1.77 1.98063 570 1.997 2.234643 572 2.032 2.273808 574 1.802 2.016438 576 1.624 1.817256 578 1.572 1.759068 580 1.654 1.850826 582 2.215 2.478585 584 2.034 2.276046 586 1.738 I.944822 588 2.118 2.370042 590 2.159 2.415921 592 1.996 2.233524 594 2.185 2.445015 596 1.607 I.798233 598 1.492 1.669548 600 1.471 1.646049 602 I.37 1.53303 604 1.263 I.413297 606 1.207 1.350633 608 1.184 1.324896 610 1.292 1.445748 612 1.494 1.671786 614 1.31 1.46589 616 1.631 1.825089 618 2.672 2.989968 620 2.172 2.430468 622 1.416 I.584504 624 1.181 1.321539 626 1.256 1.405464 628 1.251 1.399869 Page 146 of 148 BACK TO MAIN 3M Environmental Laboratory Report No. E00-2192 630 1.51 I.68969 632 2.325 2.601675 634 1.246 1.394274 636 0.959 1.073121 638 0.927 1.037313 640 0.834 0.933246 642 0.856 0.957864 644 0.876 0.980244 646 1.013 I.I33547 648 1.571 1.757949 650 1.431 1.601 289 652 1.12 1.25328 654 1.071 1.I98449 656 0.86 0.96234 658 0.801 0.896319 660 1.103 1.234257 662 0.763 0.853797 664 0.762 0.852678 666 0.855 0.956745 668 1.037 I.160403 670 0.575 0.643425 672 0.682 0.763158 674 0.912 1.020528 676 0.526 0.588594 678 0.567 0.634473 680 0.514 0.575166 682 0.738 0.825822 684 1.065 1.I91735 686 1.214 1.358466 688 2.331 2.608389 690 1.16 1.29804 692 0.73 0.81687 694 0.603 0.674757 696 0.432 0.483408 698 0.688 0.769872 700 0.347 0.388293 702 0.327 0.365913 704 0.298 0.333462 706 0.31 0.34689 708 0.275 0.307725 710 0.424 0.474456 712 2.069 2.31521 1 714 0.594 0.664686 716 0.302 0.337938 718 0.289 0.323391 720 0.254 0.284226 722 0.297 0.332343 724 0.384 0.429696 726 0.592 0.662448 728 0.817 0.9 14223 Page 147 of 148 BACK TO MAIN 3M Environmental Laboratory Report No. E00-2192 730 0.593 732 0.634 734 0.472 736 0.316 738 0.375 740 1.097 742 0.368 744 0.272 746 0.264 748 0.439 750 0.356 752 0.231 754 0.273 756 0.406 758 0.823 760 1.344 762 0.554 764 1.555 766 1.114 768 0.388 770 0.194 772 0.152 774 0.188 776 0.21 778 0.247 780 0.388 782 0.327 784 0.225 786 0.171 788 0.335 790 0.693 792 0.137 794 0.18 796 0.326 798 0.632 800 0.233 Total Integrated irradiance in 300-800nm Wavelength Band 607.6 W/mA2 0.663567 0.709446 0.528168 0.353604 0.419625 I.227543 0.41 1792 0.304368 0.295416 0.491241 0.398364 0.258489 0.305487 0.454314 0.920937 1.503936 0.619926 1.740045 1.246566 0.434172 0.21 7086 0.170088 0.210372 0.23499 0.276393 0.4341 72 0.365913 0.251 775 0.191 349 0.374865 0.775467 0.153303 0.20142 0.364794 0.707208 0.260727 680.0 W/mA2 Page 148 of 148 1__