reached. To display the total time and irradiance, press "Enter". Record exposure time 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'. 12.5.12 The SUNTEST@ will shut off automatically when the switch off criteria are ETS 944.0 Page 6 of 8 Equipment Procedure for the AtIa SUNTESTStinlight Exposure System Page 60 of 148 BACK TO MAIN 3M Environmental Laboratory Report 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 equipment must include the dates of the operation, whether the operations followed the 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 performing the maintenance. Maintenance by outside contractors should include their name and company affiliation. Run Log: Record each experiment in the appropriate instrument logbook. Enter the operators initials, 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. SUNTEST" Data Output Log: XENOVIEW@ 2.2 Storage Sohare 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 instruction manual for details on how to operate software. Any printouts of program or other data should be initialed and dated prior to adding to the study file. 13.1.2 13.1.3 13.2 1dentification. records for each system include equipment ID, manufacturer, model number, and serial number of each individual component. In addition, if components are removed or added, the above information must be written in the logbook including the 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 00 Rev. 0 12/ 98 Atlas 14.2 14.3 14.4 14.5 14.6 14.7 14.8 14.9 Electric Devices Company. SUNTEST@ CPS/ CPS+ Operating Manual, 6/ 97 Atlas Company. SUNTEST@ XLS+ Immersion Device Operating Manual, 2/ 99 Atlas Company. SUNTEST@ CPS+/ XLS+ Software Documentation 1.4 Atlas Company. XENOVmV 2.2 Storage Software operating Instructions. ETS 9 50.0, Operation and Maintenance of Radiometer and Detector. *` SUNTEST% adiance in W/ m2* nm". Tables finished by Atlas Company, "Atlas Xenon Filter Combination". Table furnished by Atlas Company. "SUNEST" CPS/ CPS+ Spectral Irradiance Distribution". Table furnished by Atlas Company.

ETS 94.0 Page 7 of 8 Equipment Procedure for the Atlas SUNTEST Sunlight Exposure Systein Page 61 of 148 BACK TO MAIN 3M Environmental Laboratory Report No. E00 2192 15.0 AFFECTED DOCUMENTS 15.1 None.

16.0 REVISIONS Revision Revision Number. Reason For Revision  Date ETS 944.0 Page 8 of 8 Equipment Procedure for the Atlas SUNTEST Sunlight Exposure System Page 62 of 148 BACK TO MAIN 3M Environmental Laboratory Report No. E00 2192 3M ENVIRONMENTAL LABORATORY ANALYSIS OF FLUOROCHEMICALS BY ARCHON PURGE AND TRAP AUTOSAMPLER, TEKMAR PURGE AND TRAP CONCENTRATOR AND AGILENT GAS ,

CHROMATOGRAPHBV~ ASS SPECTROMETER Procedure Number: ETS 3 1820 Exact Copy of Original Initial Date "r sizz+ Adoption Date: 2a 00 11 Revision Date:

Approved by:

T ,h/&/ Ud Laboratoj Manager Date ETS 8 182.0 Analysis of FCs by Purge & Trap Autosampler/ Concentrator/ GC/ MS Page 63 of 148 BACK TO MAIN 3M Environmental Laboratory Report No. E00 2192 1.0 SCOPE AND APPLICATION 1.1 Scope. This method is used for the analysis of selected hydrolysis and photolysis samples for the presence of degradation products such as olefins and hydrides using gas chromatographylmass spectrometry in a full scan 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. Applicable compounds. Compounds that may be analyzed by this method are listed below. Other fluorochemicals may be detected by monitoring mass spectra and running library comparison. Compounds that are detected but do not have appropriate standards, will be quantified relative to structurally similar standard 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) 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 Sample Surrogate compounds. May be added at the time of sample preparation. 1 A. 1 Perfluorocyclohexane 1.2 1.3 1.4 2.0 SUMMARY OF METHOD 2.1 A dynamic purge and trap system (autosampler and concentrator) is coupled to a temperature programmed 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 flows in opposite direction and temperature of 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 sample vial, allowing low level detection of fluorochemicals.

ETS 8 182.0 Page 2 of 12 Analysis of FCs by Purge & Trap Autosampler/ Concentrator/ GC/ MS 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, intermediate or 3.2 3.3 3.4 3.5 3.6 3.7 3.8 3.9 purchased standard to achieve standard soIutions in a concentration range of interest, Calibration Curve. The graphical relationship between known values, such as concentration of a series of calibration standards and their instrumental response. External Standard Quantification. Process of establishing the concentration of 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 unknown concentrations by comparing the area response of target analyte( s) to the area response and corresponding analyte amount on the appropriate analyte's calibration curve. 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. Instrument Surrogate. An organic compound similar to the target analyte( s) in behavior in the analytical process, but is not normally found in the sample( s). A surrogate may be added to sample vial during instrument analysis. Sample Surrogate. An organic compound similar to the target analyte( s) in chemical composition and behavior in the analytical process, but is not normally found in the sample( s). A surrogate may be added to sample triplicates and matrix spike samples along with the test analyte (pre photolysis). Continuing Calibration Verification (CCV). Standards analyzed during an analytical nm to verify the continued accuracy of the calibration curve. This solution may or may not be prepared from a different source or lot number than the calibration curve standards. Solvent Blank. A sample of analyte free medium that is not taken through the sample preparation process. This blank is used to evaluate instrument contamination. Blank, For photolysis studies, there are multiple blanks to adequately represent the variables of the study (Exposed, Unexposed and Day 0 samples witldwithout peroxide 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 chromatographic baselinehackground and monitor for analytical interference or 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 sample processing. It is used to document the test system without test analyte. 3.9.2 Control Blank: A sample of analyte flee matrix (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 & Trap AutosampIer/ Concentrator/ GC/ MS Page 3 of 12 Page 65 of 148 BACK TO MAIN 3M Environmental Laboratory Report No. E00 2192 3.10 3.11 3.12 3.13 3.14 3.15 4.0 background levels, interferences or suppression of target analytgs) from the matrix. Limit of Quantitation (LOQ). The lowest concentration that 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 simplify data reporting. For many analytes, the LOQ is selected as the lowest non; BO standard in the calibration curve that is greater than 4 times the level of the matrix blank. Sample Triplicates. Three samples taken from and representative of the same sample source. These are prepared separately and canied through all steps of the exposure, extraction and analytical procedures in an identical manner. There are multiple sets of triplicate samples to adequately represent the photolytic variables 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. 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)). Analytical Spike. Prepared by adding a known mass of target anaIyte( s) to a specified mount of a sample or control matrix prior to analysis. This assumes that an independent estimate of target analyte concentration is available. Matrix spikes are used to determine the effect of the matrix on method recovery efficiency. Accuracy. The closeness of agreement between an experimentally determined 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 acceptance criterion is 75% to 125% of the nominal value, 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 calibration standards below the geometric mean shall equal the number of calibration standards above the geometric mean. Having equal distribution of calibration standards above and below the geometric mean when analyzing and reprocessing data, effectively weights the curve such that both the high and low ends of the curve are given equivalent significance.

WARNINGS AND CAUTIONS 4.1 Health and Safety Warnings: 4.1.1 The operator must be familiar with the purge and trap autosampler/ concentrator/ GC/ MS system and associated hazards, such as high temperature, effluent venting, solvent use, and low pressure vacuum system. See instrument manuals ETS 8 182.0 Page 4 of 12 Analysis of FCs by Purge & Trap Autosampler/ Concen# rator/ GU~ S 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 spectrometer pump exhaust must be connected to the laboratory vent system to keep potentially hazardous effluent from mixing with laboratory air.

It is recommended that a grounded antistatic Wrist strap be worn while disconnecting al1 wires, contacts, or cables which 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 overtighten the thumbnut. 4.2 Cautions: 4.2.1 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 SUPPLKES AND 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 8.2 Methanol, Purge and Trap grade or equivalent Standards. Typically a minimurn of five calibration standards, ranging fiom 1 ng/ ml to 20 ng/ ml are prepared. This concentration range should bracket the concentration of samples and matrix spikes; if the analyte concentration exceeds this range, then the calibration range should be increased, Instrument Surrogates. Used only to monitor performance ofpurge and trap autosampler and concentrator and not for quantitation. Sample Surrogates. May be used to monitor sample preparation, photolytic exposure and analytical perfonnance. 8.3 8.4 9.0 SAMPLE HANDLING 9.1 Store standards and samples in the refrigerator at 4 ' C 5 3 C until analysis time.

Page 5 of 12 ETS 8 182.0 Analysis of FCS by Purge & Trap Autosampler/ Concenhator/ GC/ MS 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 QUALITY CONTROL 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 sufficient to encompass the expected concentrations of the study samples. In general, a minimum of live calibration standards is required for fit of linear regression.

Continuing Calibration Verification (0 . Analyze a mid range calibration standard after a maximum of every fifteen samples.

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. Acceptable values 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. Sample Triplicates. hepare and analyze all samples in triplicate to provide a measure of the precision of analysis. 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 should be analyzed periodically to measure the precision associated with the analysis. The analyst shall accept percent spike recoveries of 100 f 25%. Spike recoveries outside of this range should be noted and used with other criteria to evaluate the condition of the analytical run. Consult with the Team Leader or designee for direction and final acceptance or rejection of the anaIytica1 run. 10.2 10.3 10.4 10.5 11.0 CALIBRATION AND STANDARDIZATION 113.1 Analyze standards prior to each set of samples. The linear regression will be calculated from the plot of all individual calibration points, without including or not forcing through zero, using Target NT Software. A minimum of five calibration standards is required to generate. linear regression for target analyte( s). If the calibration curve residuals are greater than 25% deviation from the theoretical value, quadratic curve fitting andor dropping lowhigh curve points may be required if data review shows this to be a consistent and more accurate representation of the instrument response. Document in the raw data the technical justification for any deviation and consult with the team leader or designee for direction and for final acceptance or rejection of the data. If the curve does not meet requirements perform routine maintenance or prepare a new standard curve (if necessary) and reanalyze 11.2 ETS 8 182.0 Analysis of FCs by Purge & Trap Autosampler/ 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 Standby Pol CLOSED DesDrn Pol CLOSED STOP Pol. CLOSED Gripper Closed 999 Equilb. Count 0 Equilb. Time 0 Needle Sparge? YES Ign. Vial Type? YES Ignore No Vial? NO HotWater Rinse? NO Vial Checks? YES Beep on Error? YES 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 12.1.2 Archon System Options Barcode Scanner NO 12.1.3 Archon Method Soil Purge Flow 40mVmin Soil Purge Pressure 2Opsi ETS 8 182.0 Analysis of FCS by Purge & Trap Autosumpler/ 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 Purge Dry Purge Desorb Preheat Desorb Bake BGB BGB Auto VaIve Line Mount Runs per Sample 40° C (30° C by purge) 20.0omin 2.0Omin 245° C 0.5Omin at 250° C 1 O. OOrnin at 26OOC OFF Delay Osec Drain ON 180° C 180° C 100° C 1 Purge Flow 4OmLlmin Purge Pressure 2Opsi Trap 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 Final time: 1O. Oomin 12.3.2 Front Inlet: Mode: Split Initial temp: 180 OC Pressure: 8.5Opsi (on) Split ratio: 10.7 : 1 Split flow: 16.1 mYmh Total flow: 20.6 mumin to 28OoC 12.4 Set MS conditions 12.4.1 Adjust conditions as needed to optimize system performance and document operating conditions in the instrument run log. 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 & Trap Autosampler/ Concentrator/ GCLMS Page 8 of 12 Page 70 of 148 BACK TO MAIN 3M Environmental Laboratory Report No. E00 2192 Reviewcode M1 12.5 Set up the instrument acquisition method. Name the sequence. The sequence includes a sample list documenting the method used and datafiles created. The sequence should be documented n the run files.

12.6.1 Set up autosampler and concentrator methods. Bring samples to room 12.6 Sample analysis.

temperature ( 22 C), spike them and place them on autosampler. Generate a mass spectrometer tune report and review. Operating conditions provided 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.

version 4.0 for processing. ' 12.6.2 When data acquisition is complete, data files shouId be transferred to Target Explanation Peak was not automatically integrated by Target, therefore, integrated manuallv 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 integration of 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.

 _

M 2 M3 M 4 M5 ___~ _.___

Peak was automatically integrated; was reintegrated manually to improve sample to sample integration consistency. Incorrect quantification ion 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, summarize the data using an appropriate form. 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:

(observed concentration  background concentration) ' x 100 expected concentration %Recovery =

14.0 METHOD PERFORMANCE 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 Page 9 of 12 ETS 8 182.0 Analysis of FCs by Purge & Trap AutosmpIerlConcentraior/ CC/ MS Page 71 of 148 BACK TO MAIN 3M Environmental Laboratory Report No. E00 2192 14.2 14.3 14.4 14.5 14.6 14.7 14.8 14.9 linearity and intercept, particularly for accuracy of quantitation at the low and high ends of the curve. Consult with the Team Leader or designee for direction and for final acceptance or rejection for the data. Calibration Standards. The acceptance criterion for the calibration standards is that the accuracy of each standard is 75% to 125% (A 25 % difference) of the nominal value. Calibration standards outside this range are to be noted. Document in the raw data the technical justification for deviations. Consult with the Team Leader or designee for direction and for final acceptance or rejection for the data. Instrument Surrogate. Review of the instrument surrogate performance is performed by monitoring instrument surrogate recoveries throughout the run. Inconsistencies in 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. Sample Surrogate. Sample surrogate performance is evaluated by averaging the area response throughout the analytical run and calculating %RSD. Inconsistencies in the surrogate peak 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. 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 should be consulted. Only those samples analyzed before the last acceptable calibration check standard will be used. Consult with the Team Leader or designee for direction and for final acceptance or rejection for the data. Solvent Blanks. Solvent blanks should show no more than a 5% carryover from a high standard or calibration check standard. If so, two sequential solvent blanks may be necessary to rule out instrumental contamination Matrix Blanks. Matrix blanks are the basis for determining the LOQ. and are monitored at various times in the analytical run. Peaks with greater than 25% of the peak area of the 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. 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. Limit of Quantitation (LOQ). The LOQ is equal to the lowest acceptable standard (i. e. % accuracy is f; 25 % nominal value) in the calibration curve that is greater than 4 times 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 final report that is deemed out of control will be ETS 8 182.0 Page 10 of 12 Anahsir of FCs by Purge & Trap Autosampler/ Concentrator/ GCYMS Page 72 of 148 BACK TO MAIN 3M Environmental Laboratory Report No. E00 2192 required to have technical justification 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 acceptance or rejection of the data.

14.11 Analytical Spikes. The analyst shall accept percent spike recovery values of 100 f 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 that are 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.

14.12 System Suitability.

14.12.1 Tuning: A mass spectrometer tune report shall be generated before starting each analytical sequence. If the tune parameters do not meet the criteria suggested by 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 sequence is 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 POLLUTION PREVENTION AND WASTE MANAGEMENT 15.1 Dispose of sample vials in low BTU and flammable solvent 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, incubation period, dilution factor (if applicable), and instrument name. Store a copy of the acquisition conditions with the chromatogram packet. Plot the calibration curve by non weighted linear regression and store in the study/ project folder. Print the sequence and 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. Summarize data using suitable sohare and store in the study/ project folder. Back up electronic data to appropriate medium (primarily CD). Record in the study/ project folder the filename and location of backup electronic data. List the documents and records generated when performing this method and where they are to be archived. 16.2 16.3 16.4 16.5 16.6 ETS 8 182.0 Page 11 of 12 AnaIysis of FCs by Purge & Trap Autosampler/ Concentrator/ GC/ MS 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 18.2 18.3 18.4 Archon Purge and Trap Autosampler System Operator's Manual, 1996, Varian. Tekmar LSC200 Instruction Manual, 1996, Tekmar. Agilent MSD Hardware Manual for 5973N, 1999, Agilent. Agilent 6890 Series Gas Chromatograph, volumes 1 3, 1999, Agilent 19.0 AFFECTED DOCUMENTS 19.1 None.

20.0 REVISIONS Revision Revision Number. Reason For Revision  Date ED 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 ENVIRONMENTAL, LABORATORY Method Indirect Photolysis Screening Test in Synthetic Humic Water Method Number: ETS 8 177.0 Adoption Date: ,./..+ e Revision Effective Date:

Approved By:

ETS 8 177.0 Indirect Photolysis Screening Tests in Synthetic Humic Water Page 1 of 16 Page 75 of 148 BACK TO MAIN 3M Environmental Laboratory Report No. E00 2192 Comwund 1 .o SCOPE AND APPLICATION 1.1 Purpose. Chemicals dissolved in natural waters are subject to two types of Acronym Compound Acronym 1.2 1.3 Peduorooctanesuf fonate 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 intermediates that include singlet oxygen (` 0,) that promotes indirect photolysis of the test substance. The method is divided into two phases. Phase one includes the preparation of SHW. Phase Two provides a procedure to calculate solar photolysis rate constants and half lives 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). Compatible Analytes. Chemicals that will be subjected to this indirect photolysis screening and testing method include but are not limited to the following compounds:

PFOS Perfluorobutanesuifonate PFBS N methylperfluorooctanesulfonamide N ethylperfluorooctanesulfonamide N MeFOSA N methylperfluorobutanesulfonamide N MeFBSA N EtFOSA N ethylperfluorobutanesul fonamide N EtFBSA Z( N methylperfIuorooctane sulfonamido) ethyl alcohol su1fonamido) ethyl alcohol I perfluorooctene Z( N ethyIprrfluorooctanc ~

N MeFOSEOH 2( N methylper€ luorobutanesulfonamido) ethyl N MeFBSE alcohol OH N EtFOSE OH 2( N ethylperfluorobutanesu1fonamido) ethyl N EtFBSE OH alcohol  I perfluorobutene  I Perfluorooctanehydride I IH, f& hy, jrjde 1 Peffluorobutanehydride I ... and other C4 through C1o homologues, and polymeric materials based on the above aforementioned compounds. 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 solution of standardized synthetic humic water is prepared by water extraction of commercial humic material. The SHW is buffered at pH 7 with 0.005 M Phosphate buffer to maintain pH and pre aged in the photoreactor to produce predictable bleaching behavior. It is then diluted at the time of use to a W visible absorbance typical of most surface fresh waters (approximately 0.5 AU at 370 nm). Phase Two: Study samples (5mL aqueous matrix) are, prepared in 40 mL glass VOA vials equipped with screw top caps with septa. Test substance is added to the vials where indicated. (See table below.) Vials are placed in the photoreactor and immersed in a water bath controlled at 25 f 5 OC. Samples to be exposed are photolyzed in the photoreactor at 261 W/ m2 (300 800 nm) for designated time intervals. A suggested set of time intervals is listed below. Additional timepoints may be added, if necessary, or as assigned by the Team Leader. Time 0 samples will be refiigerated at 1 5 "C. until all timepoints have been completed. Dark controls (unexposed) will also be prepared for each timepoint. Absorbance controls will be used to monitor photo bleaching of the SHW. Exposed and unexposedabsorbance controls will be prepared per timepoint. 2.2 2.2.1 Samples to be prepared for each timepoint and for each exposure type:

Control Mahix(# l) blank 0 + 0 0 0 Control Mabix(# l) sample 0 + 0 + 0 Control Matrix(# l) spike 0 + 0 + + Contra\ Matrix(%) blank 0 0 + 0 0 Concml Matrix(# Z) ramplo 0 0 + i 0 Control Maaix(# Z) spike 0 0 + + + Absorbance Control + 0 0 0 0 Where "+" = addition of solution or test substance and "0" =NO addition,  LCWS Analysis A A A A A A A A A A A A A NA  GCMS Analysis A A A A A A A A A A A A A NA at 370 nm NA N A N A N A N A N A NA NA N A NA N A NA N A A N A N A A analysis performed, and NA = no analysis. Time Point # of Exposed # of Unex) Samples Samples Analysis GUMS Analysis UVNis Analysis ( Exp + Unexp) (Exp + Unexp) (Exp + Unexp) 0 0 30 (Time 0) 13 13 4 8hr 30 30 26 26. 8 16 hr 30 30 26 26 8 32 hr 30 30 26 26 8 64 hr 30 30 26 26 8 128 hr 30 30 26 26 8 150 I80 143 1 43 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 0.01 M Phosphate Buffer, pH 7: 1 Replicate per light and dark exposure, for each he and for ea& analytical methodology. ASTM Typo II Watcr 3.0 QUALITY CONTROL DEFlNITION/ FREQUENCY~ ERFORMANCE CRITERIA 3.1 Blanks 3.1.1 Definitions: Matrix Blank. A sample of analyte free matrix (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 free control matrix (such as buffer or ASTM Type 11 water) 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, piables of 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:

b Y background level Of *get dp shall be less than 25% the area counts Of the LOQ. I MatrixID Matrix Blank (Buffer/ SHW)

ControlBlank #1 (BuffedPW) Frewency Performance 1 Criteria Matrix descriDtion 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 Matrix Description I Frequency I 3.2.2 Frequency/ Performance Criteria: Listed in the followin& table:

Performance Criteria test substance lightand &k for he pobc and for each analytical test substance me& odology The analyst shall accept %RSDs <25%. Precision Test Matrix and test substance must be documented and justified (if 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. 3.3 Analytical Spike (AS) 3.3.1 Defmition: A known mass of target analyte( s) in a specified amount of a diluted andor aliquotted sample. This assumes that an independent estimate of target analyte concentration is available. Analytical spikes are used to evaluate the recovery efficiency of the andyte and the matrix effect. Frequency/ Performance Criteria: Listed in the following table: 3.3.2 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 Control Matrix (# 1) and test substance, spiked with target analyte( s) just priar to analysis Control Matrix (# 2) and test substance, spiked with target analyte( s) just prior to analysis to analysis Frequency I 2 spiked samples per treatment type (one in lower half of the calibration range, and one in the upper half of the calibration range)

1 Replicate 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: Ahown matrix containing the test substance caxried through the entire sample preparation, photolytic and analytical procedure. This is used to document laboratory perfonname by comparing recoveries and matrix effects from the different matrices and sample types. Frequency/ Performance Criteria: Listed in the following table: 3.4.2 I MoMx Description I Frequency 1 Performance Criteria 1 Control Matrix (# 1) and I 1 Replicate per I I pw Page 5 of 16 ETS 8 177.0 Indirect Photolysis Screening Tests in Synthetic Humic Water Page 79 of 148 BACK TO MAIN 3M Environmental Laboratory Report No. E00 2192 Control Matrix (# 1) Buffer/ S€ IW only 3.5 Absorbance Control 3.5.1 Definition: An analyte free matrix that is canied through the sample processing procedure and analyzed by absorption spectroscopy at 370 nm. It is used to monitor the photo bleaching rate of the SHW during the testing phase. Frequency/ Performance Criteria: Listed in the table below. 3.5.2 2 Replicates per light and dark exposure, for each time point pathlength cell) Absorbance measured at 370 nm is between 0.01AU 0.05 AU (1 cm Matrix Description I Frequency I Performance Criteria I I 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 tridecafluorooctane sulfonic acid (THPFOS) if perfluorooctane sulfonate (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 controlling the precision and bias of the applied analytical method. Samples are to be quantified using the internal standard. 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 analytical process. If added before exposure, it monitors the 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 of the applied analytical method. Surrogates are not used for quantitation. Frequency/ Performance Criteria: Listed in the following table: 3.6.2 3.6.3 Matrix DescriDtion Sample muted with 30 mL of internal standard compound dissolved in a suitable analytical solvent Sample with surrogate compound spiked into it. __~ ~

Freauencv of Use I Performance Criteria

Every LCMS sample analyzed May be added to every L C W and GCMS sample analyzed The O/ oRSD for internal standards shall be calculated for the area response of all appropriate samples per analytical batch. The analyst shall accept %RSD values of 45%. %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 Page 6 of 16 Indirect Photolysis Screening Tests in Synthetic Humic Water Page 80 of 148 BACK TO MAIN 3M Environmental Laboratory Report No. E00 2192 3.7 Other Definitions. 3.7.1 3.7.2 3.7.3 3.7.4 3.7.5 3.7.6 3.7.7 Test Substanceflest Analyte: Any substance (mixture or controlled compound) added or administered to the test system for the purpose of chemical analysis. Degradation Product( s): Secondary analytes of interest produced as a result of chemical reactions during the photolysis and monitored (qualitatively or quantitatively) during the sample analysis procedure. Target Analyte( s): The analyte( s) singled out in the analytical phase of the study is the target analyte. The target analyte may be identical to the test substance used in the experimental phase of the study, a by product or degradation product that is monitored (qualitatively or quantitatively) during the sample analysis procedure. Test Matrix: The physical matrix in which the study will be conducted. Relative Percent Difference (RPD): A measure of precision defined as the absolute value of the &f€ erence of the two values divided by the average of the two values and multiplied by 100. 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 a percent (% RSD). Limit of Qnantitation (LOQ): The lowest concentration that can be reliably achieved within specified limits of precision and accuracy during routine laboratory operating conditions. The LOQ can be estimated as 10 times 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 analyte concentration is selected as the lowest non zero standard in the calibration curve that is over four times the background level in the blanks. Sample LOQs are highly matrix dependent.

4.0 WARNINGS AND CAUTIONS 4.1 Health and Safety Warnings 4.1.1 4.1.2 4.1.3 Wear the proper lab attire for all parts of these procedures. Wear gloves and eye protection at all times, Handle all solvents in a hood for all parts of the described sample preparation procedure. For potential hazards of each chemical used, refer to material safety data sheets, packing materials, and 3M Environmental Laboratory's Chemical Hazard Review. No mouth pipetting is allowed.

The photoreactors are equipped with a continuous flow of cooling water that poses a threat of electrocution when handling the photoreactor during irradiation sequences. 4.1.4 4.2.1 4.2 Cautions 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 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 Contaminants in solvents, reagents, glassware and other sample processing or analysis hardware may cause interference. To reduce the possibility of interference, glassware in which standards are prepared should be pre rinsed with methanol and allowed to dry before use. The routine analysis of laboratory method blanks must be used to demonstrate that there is no interference under the conditions of the analysis.

6.0 EQUIPMENT 6.1 6.2 Analytical balance sensitive to 0.1 mg Photoreactor: Suntest CPSi, XLS+, or equivalent, capable of 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 IR reflective coating), and a flowing water bath circulating pump or Water cooler/ recircdator capable of maintaining temperature at 25 "C f 5 OC . UV Visible Spectrophotometer (W VIS), equipped with tungsten and deuterium lamps, model 8453, or equivalent 6.4.1 equivalent. 6.3 6.4 Autosampler: Model G1120A, or I cm pathlength cell holder: Model 08451 60104, or equivalent. 1 cm pathlength quartz spectrophotometer cell, or equivalent. Long Path Length Cell Holder, Hewlett Packard part number 89076C, or equivalent <IP_ADDRESS> 6.4.2 <IP_ADDRESS> 10 crn path length quartz cell equipped with stopcocks, Hewlett Packard Part # 5061 3392, or equivalent. 6.4.3 Data System: A PC capable of controlling the W Visible Spectrophotometer system. Centrifuge capable of maintaining >2000 rpm for 10 minutes at ambient temperature (22 26 "C). Radiometer, capable of detecting and recording irradiation output of the photoreactor for the duration of the study. Lab Oven, capable of maintaining 70 80 "C. Data acquisition and analysis software, HP ChemStation for UV Visible Spectroscopy, G11 IGAA Rev. B. 01.02, or later. 6.5 6.6 6.7 6.8 7.0 SUPPLIES AND MATERIALS 7.1 7.2 7.3 7.4 40 mL amber and clear glass vials (VOA) with screw caps. Crimp cap autovials: 1 .S mL, caps, crimper, and decapper. Adhesive backed labels (return address size) for labeling quartz vials and autovials. 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 7.6 Glass beakers, various sizes. 7.7 7.8 7.9 1 0 mL Bottle top dispenser. 7.10 7.11 500 mL glass screw top containers. Disposable glass Pasteur pipettes and rubber bulbs.

Volumetric flasks, from 10 mL to 1000 mL. Hamilton Gastight@ syringes (precision* 1% of the total volume), 5 pL to 1000 pL.

Teflon* filters filter holder apparatus: 0.4 pm pore size and 0.2 pm pore size filters (47 mm diameter, Gelmanm or equivalent.

8.0 REAGENTS AND STANDARDS 8.1 WaterRure water (PW), ASTM Type II water at a minimum 8.2 8.3 8.4 8.5, 8.6 8.7 8.8 8.9 8.10 Methanol (MeOH), HPLC/ SPEC/ GC grade from EM Science or equivalent. Acetone, HPLC/ SPEC/ GC grade from EM Science or equivalent. Acetonitrile, HPLC/ SPEC/ GC grade from EM Science or equivalent. Humic acid, sodium salt, fiom Aldrich or equivalent. NaOH, reagent grade Grom EM ScienceTM or equivalent. 0.1 YO NaOH solution Example: Weigh approximateIy 1 .O g sodium hydroxide into a weigh boat and transfer quantitatively to a 1 L volumetric flask and dilute to the mark with PW or equivalent. Sulfuric Acid (H, SO,), reagent grade from Fisher or equivalent. 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 1 L volumetric flask using 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 dilute H2S04, and dilute to the mark with PW. Method Blank Solutions:

Method Blank h e s Matrix ID Test Matrix Buffer/ SHW Control Matrix (# 1) Buffer/ PW Matrix descriRtion Example: 1: lO Solution: Dilute 50 mL Synthetic Humic Water with 0.01 M pH 7.0 Phosphate Buffer solution to 500 mL.

Example: 1: lO Solution: Dilute 50 mL Pure Water (ASTM Type n) with 0.01 M pH 7.0 Phosphate Buffer solution to 500 mL.

1 Control Matrix (# 2) PW I Pure Water (ASTM Type II) I 8.11 Stock Solutions. Stock solutions for internal standards and spiking solutions are prepared in MeOH at concentrations of approximately 10,000 pg/ mL by weighing approximately 0.1 g of the appropriate substance into a 1 O mL volumetric flask and bringing to the mark with MeOH. Dilute to make appropriate working solutions. 8.11.1 Diluting Solution with Internal Standard: The diluting solution shall contain internal standard at an area response 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 8.12 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 8.1 1) to 1 L with MeOH to a nominal concentration of 0.5 AU pg/ mL,. Test SoIutions 8.12.1 Test Substance: Prepare a solution of the test substance in 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 mL of 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 substance in acetonitrile is prepared by weighing 90 mg of test substance into a 100 mL volUmetric flask and diluting to the mark with acetonitrile.

9.0 SAMPLE HANDLING 9.1 9.2 Record times of initial preparation and dilution on the fluorochemical degradation (photolysis) analysis sample prep sheet (Attachment A). Once the test substance solution has been added, the 40 mL 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 exposure period, GCMS samples shall be maintained in an inverted position in a cooler at 1 5 "C until they are loaded onto the autosampler. Once the 30 mL aliquot of diluting solvent has been added to the LCMS photolysis samples, (see Section 12.0), the samples should be analyzed as soon as possible. Alternatively, the samples may be stored at 1 5 "C. Day 0 samples are to be stored at 1 5 "C during the time of sample exposure, and then diluted along with the exposed and unexposed samples just prior to analysis. 9.3 10.0 QUALITY CONTROL 10.1 Quality control parameters (and the fiequency of use) are included in Section 3.0.

11.0 CALIBRATION AND STANDARDIZATION 11.1 11.2 The analytes of interest must be standardized according to laboratory specifications. AI1 equipment used, such as the analytical balance, photoreactors, etc. should be calibrated prior to use (daily, weekly, etc.) as specified in its standard operating procedure. All samples analyzed will be run against a standard curve containing varying amounts of test substance, and a fixed amount of internal standard or surrogate compound. 11.3 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 Irradiance Source Average Optimum Natural Daylight`

Atlas Photoreactor with integrated irradiance output of 261 W/ m2 300 800 nm using the IR Reflecting and 290 cut on filters 12.0 PROCEDURES 12.1 Phase One Preparation and standardization of svnthetic humic water.

ADDrOXimate Inteprated and Individual Irradiances in W/ m2 250 300 nm 300 400nm `400 8OOnm 340m 420nm o, o 27.8 259.0 0.30 0.67 0.08 27.8 234.36 0.24 0.71 12.1.1 12.1.2. 12.1.3 12.1.4 12.1.5 12.1.6 12.1.7 12.1.8 Weigh approximately 2.5 g humic acid kt0 a tared 250 mL centrifuge tube. Add 0.1% NaOH solution to 250 mL. Screw cap shut and tape the tube and place horizontally on an orbital shaker. Shake vigorously (e. g. 100 250 rpm) at room temperature for approximately one hour. Centrifuge the 250 mL of solution at approximately 2000 rpm for 10 minutes or until solution has cleared, and then filter the supernatant through a 0.4pm filter into a clean 500 mL glass screw top container. Adjust the pH of the solution to 7.0 with dilute H2S04 or 0.1 % NaOH. Filter sterilize the solution through a 0.2pm diameter poresize filter into a clean 500 mL glass screw top container. Seal the container and place cap side down in the photoreactor chamber. Expose the SHW 24 hours at 261 W/ mz to pre age the solution (equivalent to three day's worth of Miami, Florida sunlight). The EPA's definition of "1 Day" of irradiation is "eight hours," The irradiation intensity of 261 W/ m2 was chosen because it yields the equivalent average optimum natural daylight radiation for 300 400 nm (see the table below):

12.1.9 Aliquot the SHW into a l cm quam W VIS cuvette and analyze the absorbance at 370 nm. 12.1.10 Check the pH of the solution using pH paper or a pH probe. Adjust the pH if necessary to 7.0 f 0.1 using a dilute &SO4 solution or 0.1% NaOH solution. 12.1.11 Calculate the dilution factor necessary to decrease the absorbance to approximately 0.5 AU (in a I cm pathlength cell) in 1 L of SHW:

9.5 = L ,n J 1L x where: the measured absorbance of the SHW at 370 nm x = the volume of SHW needed to dilute to 1 L with water.

12.1.12 Bring the solution to the exact dilution calculated in 12.1.11 with PW.

Page 11 of 16 ETS 8 177.0 Indirect Photolysis Screening T e s ~ in Synthetic Humic Water 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 12.1.14 Transfer the SHW stock solution into an amber, or clear foil wrapped 1 L glass SHW into a I cm W VIS cuvette and taking the absorbance reading at 370 nm.

storage bottle, tightly cap and refiigerate. 12.2 Phase Two 12.2.1 12.2.2 12.2.3 12.2.4 12.2.5 Fill out the "Fluorochemical Degradation (Photolysis) Sample Prep Sheet" (Attachment A) as much as possible, assigning sequential unique ID numbers to each sample to be prepared, 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. 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. 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 substance to 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. Create one set of samples (listed below) per time point andfor each analytical methodology. (LC/ MS and GC/ MS):

J M a t r i x Description 2 Test Substance + C1earlExpose. d sample Rep 1 + 0 0 Sample Rep 2 + Sample Rep 3 + 0 0 + Cleafiposcd Sample Spike I + Sample Spike 2 ?. 0 0 + Clear/ Exposed 1 C ~n t d Mabix(# I) blank 0 0 0 Control Mabix(# l) spike 0 0 Clearnzxposed (Buffer/ SHW) (Buffer/ PW) (PW + 0 0 Clearkposed 0 0 + Clearkposed Matrix Blank + 0 0 0 ClearExposed + + + 0 0 CleadExposed Control Uatrix(# l) sample + + + 0 0 0 C! ear/ Exposcd Conml Mabix(# 2) blank + + Contml Uabix(# 2) sample 0 0 Clear/ Exposed + Control Mahix(# 2) spike 0 0 + CleadEXposed ` Matrix Blank Spike + 0 0 0 Clearfixposed ClearExposed 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 + + + + + + + 0 0 0 0 0 0 0 0 0 0 0 0 + + + 0 0 0 0 0 0 0 0 0 0 0 0 + + + + + + + 0 0 0 + + 0 + AmberAJnexposed ArnberNnexposed AmberiUnexposed AmbcriUnexposed AmberiUnexposed AmberNnexposed AmberiUnexposcd AmbnNnexposed AmberNnexposed AmberNnexposed AmberNnexposcd AmbcrAJnexposed Control hlatrix( 32) spike 0 0 + +. ArnberNnexposed ETS 8 177.0 Indirect Photolysis Screening 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 :9 v/ v Create one set of samples (listed below) for each time point for WMS analysis:

12.2.6 12.2.7 12.2.8 12.2.9 Store the "Time 0" vials in a labeled box at 1 5 "C. Place all the vials that will go into the photoreactor into an oven set to 70 80 "C. for 5 10 minutes to acclimate the vials, liquid and headspace to photoreactor conditions. Upon removing the vials h m the oven, immediately re tighten the caps and proceed to load the reactor. 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.) Place the clear "exposed" vials in the rack in the photoreactor tray 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 radiometer to read intensity of irradiance over 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 from the photoreactor and store inverted in a cooler at 1 5 "C. After all exposures have been completed, remove all sample vials 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 absorbance control analysis <IP_ADDRESS> Analyze the pH 7.0 SHWhuffer absorbance controls by WNisible absorbance spectroscopy at 370 nm by aliquoting the test solution directly into a 1 cm or greater pathlength quartz cuvette and obtaining the spectra,

, See SOP ETS 9 46.0 for operation of the WNIS instrument, The resultant peak at 370 nm will be analyzed to determine the change in absorbance between 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 solution in methanol (Section 8.1 1.1). Add spiking solution to the appropriate vials. Invert each vial several times to mix.

autosampler for analysis of the parent compound and possible degradation products. Analyze according to ETS 8 18 1 .O. 12.2.16 Transfer aliquots of LC/ MS samples into autovials and then place them in the 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 <IP_ADDRESS> 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 appropriate vials. Analyze according to ETS 8 182.0. <IP_ADDRESS> Important: Maintain vials in the inverted position until they can be placed in the autosampler.

13.0 DATA A N f i Y S I S AND CALCULATIONS 13.1 Not applicable, as this is a sample preparation and analysis method. Consult the appropriate analytical protocol for guidance regarding data analysis and calculations.

14.0 METHOD PERFORMANCE 14.1 Not applicable.

15.0 15.1 POLLUTION PREVENTION AND WASTE MANAGEMENT Dispose of sample waste'by placing 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 16.2 16.3 16.4 Print out hard copies of all graphics and data analysis summaries for archiving. Sign and date all graphics and label with instrument ID. Fill out the sample preparation worksheet( s) documents completely, making sure to includa all initials and dates. Archive electronic data to compact disc media.

17.0 ATTACHMENTS 17.1 "Fluorochemical Degradation (photolysis) Sample Prep Sheet"

18.0 REFERENCES 18.1 18.2 18.3 Interpersonal conversation with Carrie O'Connor, Optical Systems Engineer, Atlas Electric Devices. "Suntest CPS/ CPS+ Spectral Irradiance Distribution," table distributed by Atlas EIectric Devices Company, sent via fax by Richard Sherwin, Sales Representative, 26 July, 2000. "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. OPPTS 835.5270, Indirect Photolysis Screening Test: Sunlight photolysis in water containing dissolved humic substances. 18.4 ETS 8 177.0 Indirect Photolysis Screening Tests in Synthetic Humic Water Page 14 of 16 Page 88 of 148 BACK TO MAIN 3M Environmental Laboratory Report No. E00 2192 19.0 AFFECTED DOCUMENTS 19.1 None 20.0 Revisions Revision Revision Number. Reason For 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 0 0 W 0 Z 03 v .o 0 a v rc BACK TO MAIN 3M Environmental Laboratory Report No. E00 2192 3M ENVIRONMENTAL LABORATORY EQUIPMENT PROCEDURE OPERATION AND MAINTENANCE OF THE HEWLETT PACKARD 8453 W VISIBLE SPECTROPHOTOMETER Procedure Number: ETS 9 46.0 Adoption Date: /o/ zJbr7 Revision Effective Date:

Approved by:

/A/*/" Laboratory Management ' Date Page I of 9 ETS 9 46.0 Operation and Maintenance of the HP8453 W Vis Spectrophotometer Page 91 of 148 BACK TO MAIN 3M Environmental Laboratory Report No. E00 2192 1.0 SCOPE AND APPLICATION 1.1 This equipment procedure describes the 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 2.2 2.3 2.4 2.5 2.6 2.7 2.8 2.9 molar extinction coefficient (E), pathlength (b), and concentration (c), wriien as A = E b c (also known as Beer's Law). Cuvette or flow cell: Transparent receptacle 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. Pathlength: The distance the light passes through the sample in its holder. In practical terms, the inside dimension of the cuvette (usually 1 cm). 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. Solvent Cutoff: The wavelength at which the solvent absorbs a significant portion 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. 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 compensation for solvent absorption, reflection losses, etc. Visible: The portion of the electromagnetic spectrum, from 400 to 800 nm, detectable by human eyes. Ultra violet (UV): The portion of the invisisble electromagnetic spectrum composed of wavelengths of 10400 nm. In UV spectrometry we are primarily interested in the near W (quartz) region extending from 200 to 380 nm. 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 spectrophotometer with collimating optics. The ChemStationB for W Visible spectroscopy software running on a PC with Microsof@ NT operating system provides instrument control, data acquisition, and data evaluation.

4.0 IDENTIFICATION 4.1 Hewlett Packard G1103A Serial No. CN93500458 4.2 Hewlett Packard 89Q9QA Serial No. DE14300757 5.0 WARNINGS AND CAUTlONS 5.1 Health and Safety Warnings:

ETS 9 46.0 Page 2 of 9 Operation and Maintenance ofthe HP8453 UV Vis Spectrophotometer Page 92 of 148 BACK TO MAIN 3M Environmental Laboratory Report No. E00 2192 5.1.1 Eye damage may result from directly viewing light produced by deuterium lamps used in detectors and spectrophotometers. Always turn off the deuterium lamp before opening the lamp door on the instrument. 5.1.2 Some adjustments described 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 Capacitors inside the instrument may 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.

5.2.1 Never touch the quartz envelope of the deuterium lamp with your fingers. Fingerprints absorb 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 190 to 1 100 nm wavelength range of the spectrophotometer. Good quality glass cells may be used when working above 3 50 nm. Disposable plastic sample cells are not recommended for use. 5.2.3 For high precision measurements, wait until the spectrophotometer and 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 spectrophotometer is 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 fingerprints and 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. 5.2 Cautions:

6.0 SPECIAL INSTRUCTIONS 6.1 None.

7.0 RESPONSIBILITY 7.1 The operator is responsible for routine maintenance and cleaning.

ETS 9 46.0 Page 3 of 9 Operation and Maintenance of the HP8453 UV Vis Spectrophotometer 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 equipment logbook, and are responsible for 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 8.4 Surgical cotton swabs, lint free. 8.5 Deuterium lamp assembly, Agilent 8453 (Part No. 2140 0605). . 8.6 Canister of compressed oil free air.

Lamp, Tungsten G1315A, Agilent 8453A (Part No. G1103 60001).

9.0 INSTRUMENT CLEANING PROCEDURES 9.1 Cleaning the Stray Light Filter. (Recommended at one yearly intervals or more frequently when operating the spectrophotometer in a particularly dirty environment.) 9.1.1 9.1.2 9.1.3 9.1.4 9.1.5 9.1.6 9.1.7 9.1.8 9.1.9 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 109 of the HP 8453 Service Manual. Remove any accessory board or MI0 board that may be plugged in from the rear side of the instrument. Remove the upper rear foam block. Disconnect the shutter cable from the SPM board. Open the screw that fixes the shutter assembly to the optical unit and remove the shutter assembly. 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, Use a canister of compressed oil free air to further clean the stray light filter. Position the shutter assembly above the source lens and fix the screw that holds it at the optical unit, see Figure 39 on page 124 of the Service manual. Connect the shutter cable to the SPM board. Replace the upper rear and upper fkont foam blocks. If available, replace any accessory board 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 109 of the HP 8453 Service Manual.

spectrophotometer passes 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 sohare. 9J. 11 Reconnect the line power and turn on the instrument. Check that the 9.2 Cleaning the Source Lens from the Sample Compartment Side. (Recommended at one yearly intervals or more frequently when operating the spectrophotometer in a particularly dirty environment.) 9.2.1 Turn off the instrument and disconnect the power cord. 9.2.2 Remove any cuvette holder from the sample compartment.

ETS 9 46.0 Page 4 of 9 Operation and Maintenance of the HPS453 W Vis Spectrophotometer Page 94 of 148 BACK TO MAIN 3M Environmental Laboratory Report No. E00 2192 9.2.3 9.2.4 9.2.5 9.2.6 9.2.7 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. 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. Use a canister of compressed oil free air to M e r clean the source lens. If you have taken the covers off, replace them. Replace the cuvette holder: Reconnect line power and turn on the instrument. Check that the spectrophotometer passes the self test, this means that the green Iight on the front panel comes on and that you can do a blank measurement from the software. 9.3 Cleaning the Spectrograph Lens. (Recommended at one yearly intervals or more hquently when operating the spectrophotometer in a particularly dirty environment.) 9.3.1 Turn off the instrument and 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 sheet metal rear covers off, see "Removing and Replacing Covers" on page 109 of 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 spectrograph lens. Repeat several times with clean swabs and alcohol each time. 9.3.5 Use a canister of compressed oil free air to m e r clean the spectrograph lens, 9.3.6 If you have taken the covers off, replace them. Replace the cell holder in the sample compartment. 9.3.7 Reconnect line power and turn on the instrument. Check that the spectrophotometer passes 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 MAINTENANCE PROCEDURES 10.1 Routine maintenance.

<IP_ADDRESS> <IP_ADDRESS> <IP_ADDRESS> 10.1.1 Cleaning the stray light filter. Indicators for a dirty stray light filter include: After exchanging the lamps, the intensity test executed by the ChemStation software still falls below the specified level. One of the stray light tests fails. The photometric accuracy test fails. 10.1.2 Cleaning the lenses that are accessible from the sample compartment side. An indication for dirty lenses is when, after exchanging the lamps, the intensity test executed by the ChemStation software still 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 executed through the ChemStation software, falls below 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 Page 5 of 9 Operation and Maintenance of the HP8453 UV Vis Spectrophotometer Page 95 of 148 BACK TO MAIN 3M Environmental Laboratory Report No. E00 2192 11.0 OPERATING PROCEDURES 11.1 Powering Up the HP 8453'W Visible Spectrophotometer and PC controller. 11.1.1 Switch on the PC and boot the PC operating system. 11.1.2 Switch on the spectrophotometer and wait until the spectrophotometer's indicator light turns green. This process includes the 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 measurements wait until the spectrophotometer and the lamps have reached thermal equilibrium. The time required is a function of environmental conditions but 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 cell holder which accommodates 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)

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 standard cells or flow cells.

sides of the sample cell should not be in the path of the light beam.

may require use of the optional adjustable cell 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 Instrument Panel. 11.3.2 Type the path length in cm in the "Setup Manual" dialog box. 11.3.3 Click "OK" to set the specified path length.

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 containing the solvent used 11.4 Starting a Measurement Session,

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 orientation to the measurement beam. Flush the cell about three times with the sample solution and start the measurement by clicking the 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 Page 6 of 9 Operation and Maintenance of the HP8453 W Vis Spectrophotometer Page 96 of 148 BACK TO MAIN 3M Environmental Laboratory Report No. E00 2192 11.53 If background correction is desired, select "Single Reference Wavelength", "Subtract Average Over a Range" or "Three point Drop Line" from the background correction combo box. <IP_ADDRESS> <IP_ADDRESS> "Single Reference Wavelength" requires the input of one wavelength in the adjacent wavelength edit field on the right side of the combo box. 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 concentration directly or "Weight & Volume" to have the ChemStation calculate the concentration. Enter the units for the concentration or the weight and volume.

measurement, select "Prompt for Standard Information". In the combo box you can select whether the prompt asks you for the concentration, or calculates the concentration based on volume, weight and purity.

Dilution Factor" of sample. 11.5.6 If you want to be prompted for the concentration of the standards during 11.5.7 If you have diluted samples and want to correct for dilution, select "Prompt for 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 11.5.10 Choose "OK" to close the dialog box. 11.5.11 Perform the following steps ifyou want to calibrate the method. window.

<IP_ADDRESS> Measure a blank on the solvent if necessary using the "Blank" button in the instrument panel. <IP_ADDRESS> Measure the standards using the "Standard" button in the instrument panel. 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 standards that can be incorporated into a calibration. However, each of the calibration curve types requires a minimum number of standards of different concentrations, which can be found in Table 7, page 45 of the HP Manual: Understanding Your UV Visible Spectroscopy System. The ChemStation@ s o h a r e calibrates automatically when at least the minimum number of standards has been measured. A table with the used standards and values as well as calibration curve is displayed. <IP_ADDRESS> If the calibration is successfitl, the calibration curve 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 delete any spectral data that you do 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. not wish to keep.

ETS 9 46.0 Page 7 of 9 Operation and Maintenance of the HP8453 UV Vis Spectrophotometer 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/ Peaks Parameters" 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 spectra that you want to load (Samples or Standards) from the submenu to display the "Load Spectra'' dialog box.

directory from the "Directories" list.

close the dialog box. 11.7.2 If the spectra you wish to load are not in the "File Name" list, select a different 11.73 Select the spectra you wish to load from the File Name list and choose OK to 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, Standards or Selected Spectra) fiom the submenu to display the "Save Spectra As" 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. <IP_ADDRESS> A valid file name consist of eight dphanumeric characters and the file extension .sd or .std. Usually, the extension .std is used for standards only. 11.8.4 You can also save spectra using the ToolBar.

12.0 RECOROS 12.1 Document all cleaning and maintenance performed on the instrument in the maintenance or dmaintenance logbook. Include a description of the 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, CALIBRATION AND/ OR STANDARDIZATION PROCEDURES 13.1.1 Make sure that you are in the "Verification and Diagnostics" mode. The mode is 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 start the self

13.1.4 The self test results will be displayed in a window with passlfail criteria. Calibrating for a single component analysis. 13.1 HP 8453 Self Test:

indicated on the tool bar of the HP ChemStationa session.

test.

13.2 ETS 9 46.0 Page 8 of9 Operation and Maintenance of the HP8453 UV Vis Spectrophotometer Page 98 of 148 BACK TO MAIN 3M Environmental Laboratory Report No. E00 2192 . `C 13.2.1 Calibration for single component analysis is based on the measurement of standard samples with known concentrations. During the calibration process, the software calculates the calibration coefficients, which are then used for the quantification of unknown samples. 13.2.2 The status for calibration can be seen in the data analysis panel: <IP_ADDRESS> Uncalibrated: RED dashed calibration curve icon. <IP_ADDRESS> Calibrated: GREEN continuous calibration curve icon.

13.23.1 Load or set up a method for the "Quantification" task. <IP_ADDRESS> If the "Standard" spectra window is not displayed, choose "Show" standards in the data analysis panel. 13.2.33 You can either load the standards from file or measure them. <IP_ADDRESS> To measure standards: 13.2.3 To calibrate for single component anaIysis:

<IP_ADDRESS>.1 Measure a bank on the solvent if necessary using the "Blank" button in <IP_ADDRESS>.2 Measure the standards using the "Standard" button in the instrument the instrument panel.

panel. If you have selected one of the prompts in the method, the appropriate values will be requested in a dialog box. 13.2.4 The spectra are displayed automatically in the "Standard Spectra" window as the standards are measured. A minimum number of standards is required, depending on the selected calibration curve. The ChemStationm softwae calibrates automatically when at least the minimum number of standards have been measured. A table with the used standards and values as well as a calibration curve is displayed. 13.2.5 If the calibration is successfil, the calibration curve icon of the data analysis panel 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. Part No. G1115 90012. 14.4 HP 8453 W Visible Spectrophotometer Service Manual, Hewlett Packard: Wilmington, DE, 1998. PartNo. G111S 90003.

15.0 AFFECTED DOCUMENTS 15.1 None.

16.0 REVISIONS Revision Revision Number. Reason For Revision  Date ETS 9 46.0 Page 9 of 9 Operation and Maintenance of the HP8453 UV Vis Spectrophotometer Page 99 of 14% BACK TO MAIN 3M Environmental Laboratory Report No. E00 2192 3M ENVIRONMENTAL LABORATORY

EQUIPMENT PROCEDURE TEKMAR PURGE AND TRAP CONCENTRATOR AND AGILENT GAS CHROMATOGRAPH/ MASS SPECTROMETER ROUTINE MAXBTENANCE OF hCHON PURGE AND TRAP AUTOSAMPLER,

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 SCOPE AND APPLICATION (VSE NUMBERED TIER I) This equipment procedure describes the maintenance required for optimal operation of the Archon Purge and Trap Autosampler, Telanar Purge and Trap Concentrator and Agilent gas chromatograph / mass spectrometer (GCMS) system. Specific items requiring routine maintenance include occasional tightening vial escalator's nuts and refilling the Standard Vial and water bottle in the Archon autosampler and periodic cleaning of the mass spectrometer ion source. 1.1 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 system may be used). 4.1.1 Autosampler: serial number 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 US01180105,5973N G2589A, 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 Cooling the Telanar before removing the side cover for maintenance prevents contact bums. 5.1.2 Turning off power source for Tekmar before removing the side cover will prevent electric shock.

5.2.1 It is recommended that a grounded antistatic wrist strap be worn while disconnecting all wires, contacts, or cables which 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. 5.2 Cautions:

6.0 SPECIAL INSTRUCTIONS 6.1 Not applicable.

ETS 9 49.0 Page 2 of 5 Routine Maintenance of the Purge & Trap Autosampler/ Concentrator/ GC/ MS Page 101 of 148 BACK TO MAIN 3M Environmental Laboratory Report No. E00 2192 7.0 RESPONSIBILITY 7.1 Routine maintenance procedures may 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 8.1 8.2 8.3 8.4 8.5 8.6 8.7 8.8 8.9 8.10 8.11 8.12 8.13 8.14 8.15 8.16 SUPPLIES AND MATERIALS Graphite Ferrules, 0.4 mm I. D. for 0.25 mm columns Abrasive paper, Hewlett Packard, part no. 5061 5896 Alumina abrasive powder, Hewlett Packard, part no. 8660 079 1 Acetone, reagent grade Dichloromethane, reagent grade Methanol, purge and trap grade Gloves (clean, lint free, cotton), Hewlett Packard, part no. 8650 0030 (large); 8650 0029 Cotton swabs Chem wipes Glass beakers Sonicator Base deactivated 2 mm ID gooseneck splitless injection port liners, Restek Corporation, part #20796 210.5, or equivalent 1 1 mm diameter Themogreen LB2 septa, Supelco, part #23 163, or equivalent Viton injection port O rings, Restek Corporation, part #20377, or equivalent Septum wrench, Hewlett Packard, part #19251 00100 Tweezers (small)

9.0 CLEANING PROCEDURES NIA 10.0 MAlNTENANCE PROCEDURES 10.1 Routine: Tighten the elevator` s assembly nuts when Archon autosampler displays error 10.2 10.3 message I' Elevator not homed position `I.

10.1.1 Stop autosampler run by 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 Routine: Fill the water bottle, empty the waste bottle. 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 the helium 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 Page 3 of5 Routine Maintenance of the Purge & Trap AutosampIer/ Concenhtor/ GC/ MS 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 10.3.5 Slide the vial back up into standard mount. Finger tighten thumbnut until it is 10.3.6 Turn the helium gas into ON position. Prime Standard Loop. Routine: GCMS forelhe pump maintenance. 10.4.1 Examine the oil level window daily. If the oil level is near or below the lower <IP_ADDRESS> Vent the MSD according to the MSD Hardware Manual. <IP_ADDRESS> Remove the fill cap. <IP_ADDRESS> Add pump fluid until the oil level in the window is near, but not above, the upper line. <IP_ADDRESS> Reinstall the fill cap. <IP_ADDRESS> Pump down the MSD according to the MSD Hardware Manual approximately 5 ml of standard or smgate snug. Do not use any tool and do not overthighten.

10.4 line then add foreline pump oil. Never add oil while the foreline pump is on.

10.4.2 Change foreline pump oil every 6 12 months according to the MSD Hardware I Nonroutine: Document any nonroutine mahtenance in the instrument's maintenance logbook. manual. 10.5 11 .O OPERATING PROCEDURES 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 Packard MSD Hardware Manual for HP 5973N & HP 6890 Series Mass Selective Detectors. I 12.0 RECORDS 12.1 Document any maintenance performed on the instrument in the maintenance or dmaintenance logbook. Jnclude. a description of the 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 TESTING, CALIBRATION AND/ OR STANDARDIZATION PROCEDURES 13.1 After cleanhg the source and allowing sufficient time for the vacuum to pump down and the mass spectrometer to equilibrate to operation temperature, 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 after performing injection port maintenance.

14.0 REFERENCES 14.1 14.2 Tekmar LSC200 Instruction Manual Archon Purge and Trap Autosampler System Operator's Manual ETS 9 49.0 Page 4 of 5 Routine Maintenance of the Purge & Trap Autosampler/ Concenttor/ GC/ MS 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 AFFECTED DOCUMENTS 15.2 None.

16.0 REVISIONS Revision Revision Number. Reason For Revision ETS 949.0 Page 5 of 5 Routine Maintenance of the Purge & Trap Autosampler/ Concentrator/ GC/ MS 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 IUPAC Name Chemical Characterization I I I Substance PFOA PF'HpA Perfluorooctanoic acid, ammonium salt Pertluoroheptanoic acid Chemical Formula CsFisO2NH4 C7F1102H I Source I 3M Saecialtv Chemicals I Aldrich Identifier 3825 26 1* 375 85 9*

Expiration Date Storage Conditions Chemical Lot Number Substance ~ ~

2002 2005 Frozen Frozen 332 TCR 9913 1 25 C, Hydride I C7 Perfluoroheptenes (90/ 10 I mix) Physical Description Purity White wax or powder Clear Crystals 95% 98% 1 I i I Chemical Formula I C4F& F= C7F5. C, FIICF= CF, I C, F I 10% 2 Perfluoroheptene, 90% Perfluoroheptene IUPAC Name I Identifier I 355 63 5* I 272 13 61 2* 1,1,2,2,3,3,4,4,5,5,6,6,7,7,7 pentadecafluoroheptane ~

I ~~

Source Lancaster Synthesis Expiration Date 2005 I Storage Conditions I Frozen I Frozen ~~ ~~

Lancaster Synthesis 2005 Chemical Lot Number Physical Description Purity PFPA I 90004250, TNA 3025 900591 1, TNA 3026 Clear ambient liquid Clear ambient liquid 100% 97% Perfluoropentanoic acid 2706 90 3* I Aldrich Frozen SD 043 I Clear Liquid 95% 1 I C6 Hydride 355 37 3* Lancaster Synthesis Frozen I 98% I Page 106 of 148 BACK TO MAIN 3M Environmental Laboratory Report No. E00 2192 Reference Substance IUPAC Name Chemical Formula Identifier Source Reference Substances (continued)

Cs Hydride/ Olefin Mix Cs Terminal Hydride C4 Terminal Hydride 1,1,1,2,3,3,4,4,4 heptadecafluorooctane nonafluorobut ane 1,1,1,2,2,3,3,4,4,5,5,6,6,7,8,8,8 1 1 2 2 3 3 4 6,6 pentadecafluorooctane, 2 perfluorooctene ' ' ' ' ' ' ' ' ' ' ' ' ' ' '

C6F 13CFHCF3' C6F 13CF= CF2 C8F17H CP9H TCR 99030 18 335 65 9* 375 17 7*

3M Specialtv Chemicals Aldrich Chemical Crescent Chemical ~~ ~

Storage Conditions Chemical Lot Number I Exairation Date I 6/ 6/ 99 I 2002 I 2002 ~

Frozen Frozen Frozen 1 04307PN, TNA 2983 6A 46, TNA 3997 Physical Description Clear ambient liquid Clear ambient liquid Clear ambient liquid Purity Chemical Formula I 85% Cs Hydride, 15% Cs Olefin C4FS C3F7H 99%

Identifier 99%

360 89 4* 2252 84 4* I 354 33 6* I I I Reference Substance C4 Interior Olefin C3 Terminal Hydride C2 Terminal Hydride Source 1,1,2,2,2 pentafluoroethane 1,1,2,2,3,3,3 hepta fluoropropane 2 Perfluorobutene IUPAC Name Lancaster Synthesis I Lancaster Synthesis Lancaster Synthesis ~~ ~~

Physical Description Purity Clear ambient liquid Gas Gas 97% 97% 99% I Extiration Date I 2002 I 2010 1 2010 ~~

I Storage Conditions I Frozen I Flammable I Flammable ~~

I Chemical Lot Number I G00195. TNA 4298 I G0062B. TNA 4294 I G00492. TNA 3021 Page 107 of 148 BACK TO MAIN 3M Environmental Laboratory Report No. E00 2192 Control Substances PFCH PFBS Pentafluorobenzene structure Perfluorobutane sulfonate, potassium salt C& FS C& IZ IUPAC Name Perfluorocyclo hexane C4FWzK Pentafluorobenzene I Physical Description I Colorless Moist Solid I White Powder I Methanol solution Use Source Instrumental Surrogate Standard For GCIMS analysis Surrogate Standard For GC/ MS Internal Standard for LC/ MS analysis analysis Aldrich Chemical 3M Specialtv Chemicals Restek Corn.

I Control Substances I Chlorobenzene& I Toluene& I Dibromofluoromethane Expiration Date Storage Conditions Chemical Lot Number ~~

2005 2002 612002 Frozen Frozen Frozen 01911AU TCR 99030 028 A013256 Purity 97% 97%< 99% (2500 p g i d i0.2%)

I Chemical Lot Number I A013256 I A012973 I A012973 structure C& IDs I c7 D8 I Control Substances I 1,4 Difluorobenzene I 4 Bromofluoro benzene I 1,4 Dichlorobenzene d., CHBrzF IUPAC Name Use Chlorobenzene d5 Toluene d8 ' Dibromo fluoromethane Use Source Expiration Date Storage Conditions Instrumental Surrogate Standard Instrm For GCMS analysis Standard Eor CIL/ IW~ analysis analysis Restek Corp. Restek Corp. Restek Corp. 612002 212002 212002 Frozen Frozen Frozen Physical Description  ~

Methanol solution Methanol solution Methanol solution *CAS Number Purity Page 108 of 148 99% (2500 p g /d & 0.2%) I 99% (2500 p g /d F 0.2%) I 99% (2500 pglmL 0.2%)

Structure IUPAC Name c6 H4FZ C6HdBrF C6C12D4 1,4 Difluorobenzene 4 Bromofluoro benzene 1,4 Dichlorobenzene d4 Instrumental Surrogate Standard For GCIMS analysis Instrumental Surrogate Standard For GCIMS analv& Instrumental Surrogate Standard For GCIMS analysis Some ~

Restek Corp. Restek Corp.

Expiration Date 612002 I 212002 612002 Storage Conditions Frozen Frozen Frozen Chemical Lot Number Physical Description Purity A013256 A012973 . A013256 Methanol solution Methanol solution Methanol solution 99% (2500 pdmL k 0.2%) 99% (2500 ~g/ rnL 0.2%) 99% (2500 DglrnL k 0.2%) BACK TO MAIN 3M Environmental Laboratory Report No. E00 2192 ~

Appendix C: Kinetics Model and Kinetics Calculations This appendix presents the mathematical description of 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).

k Prn P + photon +n, A,+ Y, (m= ltoN)

k h A, +photon + YmZ (m= 1 toN)

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 symbols Y,, and YmZ represent 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 g=[ z P n, kpm] dt Equation C4 may be directly integrated to obtain the general solution In[ P]= c nm k,, t +C [ my1 )

With the initial condition P( t = 0) = Po, the specific solution to Equation C4 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 N k, c 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) measured value of the parent concentration Po and later values P measured at later times t , one can calculate and plot the (linear) quantity [ In (P/ Po)] versus time and obtain a least squares estimate of the slope of the line. The resulting slope is the least squares estimate c, 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 11 1 of 148 BACK TO MAIN 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 3M Environmental Laboratory Report No. E00 2192 and There are two cases of Equation C18 to consider. In the circumstance that kArn = k, , which occurs only when the rate of the mth product is identical to the total parent photolysis rate, the general solution to Equation 818 is (for k, = k,)

A, ekpt = nmkPmPO t +C and, using the initial condition A ,( t = 0) = A, , the specific solution to Equation1 8 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 mth product is different from the total parent rate), the general solution to Equation C18 is and the specific solution to Equation C18 with the initial condition A,( t = 0)= A,, is nmkPmPO kP  kAm 1 e k, t  nmkPmPO e kp t k P  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 (1 e kp t )

k P 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 (for stable products)

or (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 I X 5 1 )

ln( l+ X)= X x2 1 + x3 1  x4 1 +..... 3 4 L 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 Am Amo c m << Po )

C5. Parent Half Life Estimates Based on Limits of Quantification of the Products In every experimental determination of 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)

Under the same circumstances and assumptions, the experimental data indicate that the parent half life TI': (see Equation C9) is greater than the value (T vi) . 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 concentrations over 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 concentrations measured for the mth product have the mean value p, and standard deviation 0, , the data do not exclude the possibility that the product concentration increased from the initial value 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 maximum value 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 concentrations with standard deviation om or 2) concentrations below the limits of quantitation)

r 1 k, 5 (k,) = 1 1 AZQ+ corn]. '0 A 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 om or 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 maximum value of the parent hydrolysis rate k, . If the set of concentrations measured for the parent have the mean value pp and 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 initial value pp  CY, to the value pp +CY, at 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;) min as follows:

(for essentially constant parent concentrations with mean value pp and standard deviation CYp )

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 (€ ', and 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 Environmental Laboratory Report No. E00 2192 The observed rate using At = 69.5 hours, &, = 1478nglm1, and O,, = 33.2 ng/ ml is k, = 6.46 x IO4 hours".

The rate of photolysis in the reactor k, is related to the actinic rate of photolysis kACT by kACT = kP( y)

where I,, = 261 w/ m2 is 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 0 ~ hr ' [ 62;; ;;;: I= 2.48~ 10 4 hr '

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 3w 2) k ACT (indirect photolysis) TA$!=  = 349 days,

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 I19 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 : 2 Sample Name : MeOH blank Vial : 99 Acq. Operator : kej Inj : 1 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 SIM Analysis (ES) f o r PFOS/ PFBS/ PFOA using Dionex IonPac NG1 column, 4 ~3 5 m . (modified after loading) (Results are from a previously saved MSDI 263. EIC= 2627: 263.7 (RO518LXlBlRUSHooo2. D) API ES Negative MeOH Solvent Blank m =L+ L^^^^ 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 17/ 10/ 00 9: 43: 20 AM kej Page 1 of 2 Page 120 of 148 BACK TO MAIN 3M Environmental Laboratory Report No. E00 2192 ' , ..

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i Batch Run # 3 of 62 Data File C:\ HPCHEM\ 1\ DATA\ R0518OOB\ rushOOO3. D Sample Name: 1: 7 MilliQ/ MeOH ============== 3=======~====~=======~=====~=======~======~======

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MSDlZ63, EIC= 2& 1.7Z63.7 (RO518WElvtUSHooo3. D) API ES NPgative 9ooo1 Bwo Control Blank 0 2 4 6 a. m MSD1 363. ElC= 362.7363.7 (RG518OOBRUSHwoJ. D) API ES N W 0 2 4 i 6 MSDl299, ElC= 298.7: 299.7 (R051 BOOB\ RUSHMx) 3. D) API ES Negatlve 1

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i Matrix Blank 4 n.& fLJ7P. r I ".I ...I ...l ..I (.. Batch Run # 4 of 62 Data File C:\ HPCHEM\ 1\ DATA\ ROS18OOB\ rushOOO4. D 4 6 8 10 min 0 2 MSDi 363, EiC= 362.7: 363.7 (RO51800BRUSHWO4.0) API ES Negatlve A F ( BWO 5wOL 4oOoi \J "w A J L +~~w / r , ' , , , , , I ,. , . I ,, . 1 . Sample Name: 00028 37 00 50000 25w 0 ,

4 6 8 10 min 0 2 MSDi 413, ElC= 412.7: 413.7 (Rffi1800B\ RUSHW. D) API ES Negative .......................................................... ===========

Injection Date ! 5/ 18/ 00 3: 44: 20 PM Seq. Line : 4 Sample Name : 00028 37 00 Vial : 1 Acq. Operator : k e j Inj : 1 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\ RO518AX. M Last changed : 7/ 10/ 00 9: 43: 28 AM by kej SIM Analysis (ES) for PFOS/ PFBS/ PFOA using Dionex IonPac NG1 column, 4x35m. (modified after loading) (Results are from a previously saved Instrument 1 7/ 10/ 00 9: 43: 28 AM kej Page 1 of 2 Page 122 of 148 BACK TO MAIN 3M Environmental Laboratory 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 SIM Analysis (ES) for PFOS/ PFBS/ PFOA using Dionex IonPac NG1 column, 4x35m. (modified after loading)

MSDI 363, EICm382.7383.7 (Rffi18WB\ RUSHM) 05. D) API ES NegalNa/

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4 6 8 10 mil ~~~. 0 MSD1 413, EiC1412.7: 413.7 2 1 ,. (Rffi18008\ RUSHMK15. D) . I ' API ES NagaIl~ e  I 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 9ooo BMX)

 Batch Run # 6 of 62 Data File C:\ HPCHEM\ 1\ DATA\ R0518OOB\ rushOOO6. D Calibration Std 2 d%. JL&

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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 SIM Analysis (ES) for PFOS/ PFBS/ PFOA using Dionex IonPac NG1 column, 4x35m. (modified after loading)

I MSDl 263, EiC1262.7263.7 (RO518WE\ RUSHO~. D) API ES Negatii I I 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==

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MSDl 263, ElC= 2627: 263.7 (ROslsOOEWUSHWl3. D) API ES Negatlvc lmm{ 8 Calibration Std 9 ,~"~"' I ' ' ' ,~~~I 0 2 4 6 8 10 m MSD13W. EIC1.352.7363.7 (R051800BWUSHW13 D) APES Negative 2oowo I "' I )..I ' ' .,

0 2 4 6 8 10 m MSDl 299, ElC= 298.7: 299.7 (R051EWBWJSHW13. D) API ES NegaWe I ".I .'

0 2 4 6 8 10 MSDl 413, ElC= 412.7: 413.7 (ROslBWBWUSH0013. D) APES 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===~============~~=====~===================~==

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Injection Date : 5/ 19/ 00 1: 46: 30 AM Seq. Line : 37 Sample Name : 0515 PFOAfe 19 Vial : 29 Acq. Operator : 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 SIM Ana1ysi. s (ES) f o r PFOS/ PFBS/ PFOA using DiOneX IonPac NG1 column, 4 ~3 5 m . (modified after loading)

I MSDl 263, EIC= 262.7263.7 (R05f& 3JBWUSHW37.! 3) API ES Negative Enposed  72hB Control MilliQ NO Peroxide I 0 2 4 8 10 ml MSDl 383. EIC 362 7 383 7 (ROWeOO8WUSHCQ37 0) AP1 ES N@ IW 12000 2w0 C 2 4 6 8 10 rn~ MSDl299. EIC= 298 7299 7 (ROWsOa~ WUSUCU37 0) APCES N e g a h 25000 I ' " . I ' ' ' I ' . ' I , ,  0 2 4 6 8 10 m MSDl 413, €IC~ 41274137( R~~ eOOB\ RUSHW370) API 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 7000 6000 Batch Run # 40 of 61 Data File C:\ HPCHEM\ 1\ DATA\ RO5180OB\ rushOO91. D Sample Name: 0515 PFOAfe 51  p======= ____________________ _ =_________ _________ Injection Date : 5/ 19/ 00 6: 13: 39 PM Seq. Line : 91 Sample Name : 0515 PFOAfe$ 1 Vial : 61 Acq. Operator : kej Inj : 1 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\ R0518BX. M Last changed : 7/ 10/ 00 9: 16: 40 AM by kej SIM Analysis (ES) for PFOS/ PFBS/ PFOA using Dionex IonPac NG1 column, 4x35m. (modified after loading) (Results are from a previously saved 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 SIM Analysis (ES) for PFOS/ PFBS/ PFOA using Dionex IonPac NG1 column, 4x35m. (modified after loading)

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 12ooo loo00 B w o 6003 4MM zwo Batch Run # 42 of 61 Data File C:\ HPCHEM\ 1\ DATA\ R0518OOB\ rushOO93. D Sample Name: 0515 PFOAfe 53  A+,  I I ' .l ..,,. 4  ======= iE============= ii. Ci=~===~==~=~==~=~===~====~=============

Injection Date : 5/ 19/ 00 6: 50: 09 PM Seq. Line : 93 Sample Name : 0515 PFOAfe 53 Vial .: 63 Inj : 1 Acq. Operator : kej Acq. Instrument : Rush 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 SIM Analysis (ES) for PFOS/ PFBS/ PFOA using Dionex IonPac NG1 column, 4x35mm. (modified after loading)

MSD1 28, ElC= 2627263.7 (R051N10B~ lJSHW93.0) API ES Negath'e Day 0 Sample Fe203 NoPemxide 5Mx)

Instrument 1 7/ 10/ 00 9: 16: 48 AM kej Page 1 of 2 Page 132 of 148 BACK TO MAIN 3M Environmental Laboratory Report No. E00 2192 b 2 4 6 ti mi MSDl 299, EIC= 298.7299.7 (R0518WSWUSH0098. D) API ES Negathw _

~~ 1 0 2 l ' *' I "' I .' 4 6 L 8 10 ,; mi ~~~ 0 2 4 6 . 0 I r 10 , , ' rniD 5 m 25000 0 , ,

MSD1 413, ElC= 412.7: 413.7 (RC51800B\ RUSH~. D) API ES Negafive XXXXX]

2 m 0  Batch Run # 47 of 61 Data File C:\ HPCHEM\ 1\ DATA\ R0518OOB\ rushOO98. D Sample Name: 0515 PFOAfe 58 ======i ========i l ==I l =====I i E .=f i l ====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 SIM Analysis (ES) f o r PFOS/ PFBS/ PFOA using Dionex IonPac NG1 column, 4x35m. (modified after loading)

MSDl 263, EIC. zL62.72S3.7 (R05I@ OOBWUSHWW. D) API ES Negative Control Millip No Peroxide ml Dayo a 2 4 6 10 mi MSDl 363, ElC. 382.7383.7 (R051800BWUSHW98. D) APCES Negative I Instrument 1 7/ 10/ 00 9: 17: 10 AM kej Page 1 of 2 Page 133 of 148 BACK TO MAIN 3M Environmental Laboratory Report No. E00 2192 ' I Batch Run # 14 of 61 Data File C:\ HPCHEM\ 1\ DATA\ RO51800B\ rush0065. D Sample Name: 0515 PFOAfe 31 =i ==^=====I L ==~===l ==i l =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 AM by kej SIM Analysis (ES) for PFOS/ PFBS/ PFOA using Dionex IonPac NG1 column, 4x35mm. (modified after loading) (Results are from a previously saved Instrument 1 7/ 10/ 00 9: 15: 03 AM kej Page 1 of 2 Page 134 of 148 BACK TO MAIN Batch Run # 15 of 61 Data File C:\ HPCHEM\~\ DATA\ R 5 800B\ rush00 3M Environmental Laboratory Report No. E00 2192 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 : 42 Acq. 0pera: or : kej I n j : 1 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\ R0518BX. M Last changed : 7/ 10/ 00 9: 15: 07 AM by kej SIM Analysis (ES) for PFOS/ PFBS/ PFOA using Dionex IonPac NG1 calm, 4x35m Inj Volume : 5 p l (modified after loading)

MSDl 263, EIC= 282.7=. 7 (RO518WBRUSHCO66. D) API ES N W Unexpnscd  72hn Blank Spiked FcZ03 No Peroxide 0  I 2 I , , , 4 , 6 a. 8 10 MSDl 363, ElC6627363.7 (RoS18ooEWJSH~. D) API ES N@~ w ~" L. 5wM) 25ooo 0 0 ' 2 I ' . ' 4 I ' ' . I ' a 4 '

d;_ 10 ~%I ~' 0 MSDl 413, ElC412.7413.7 ' 2 I , (R ~l ~~\R U S H o o S e .D ) " 4 I ' , APKS NegaUvs 1 6 ; 8 10 ~ 0 2 4 6 8 A,, 10 I  MSD1 299, ElC= 298.7: 290.7 (RWl8OOB\ RUsHOO66. D) APKS N e ~a t i i SWOD 25ooo 0 I ",I ...I ...t ,

Instrument 1 7/ 10/ 00 9: 15: 07 AM kej Page 1 of 2 Page 135 of 148 BACK TO MAIN 3M Environmental Laboratory 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 : 67 Sample Name : 0515 PFOAfe 33 Vial : 43 Acq. Operator : kej Inj : 1 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 SIM Analysis (ES) for PFOS/ PFBS/ PFOA using Dionex IonPac NG1 column, 4 ~3 5 m . (modified after loading) (Results are from a previously saved Unexposed  72hn 7 W 4 sample Fez03 Noperoxide r,

"

2 4 8 8 10 mi t .' I .' ., ...,...,...,., 0 MSDl 333, EIC 362.7J8.7 (RO518WBWJSHMwr. D) APCES Negatlve 0 2 4 6 E r'o mi MSDl 299. EICE298.7: 299.7 (R0518M) B\ RUSHWW. D) API ES Negallve __.