CSO/SWO Data Validation Reports June 20, 2014

Transcription

1 CSO/SWO Data Validation Reports June 20, 2014 Transmitted Via June 20, 2014 U.S. Environmental Protection Agency, Region II Emergency and Remedial Response Division 290 Broadway, 19 th Floor, Room W-20 New York, NY Attn: Alice Yeh Re: Combined Sewer Overflow/Stormwater Outfall Investigation Data Validation Reports: Rinsate/Field Blanks collected between Event #2/Attempt#1, and Event #2/Attempt#2 Dear Ms. Yeh: In accordance with Worksheet #33 of the Combined Sewer Overflow/Stormwater Outfall (CSO/SWO) Investigation Quality Assurance Project Plan (QAPP) Revision 3, September 2013, please find enclosed Data Validation Reports for rinse/field blanks collected after Event #2/Attempt #1, and prior to Event #2/Attempt#2. CSO Rinse/Field blank samples were collected on October 11, 2013 in accordance with the CSO/SWO QAPP, at the 80 Lister Avenue facility located in Newark, NJ. The attached file contains individual Data Validation Reports corresponding to Sample Delivery Group (SDG) PR137. Analytes collected included, dioins, furans, Semivolatile Organic Compounds (SVOCs), SVOC SIM, PCBs, pesticides, Aroclor PCBs, and herbicides. The majority of the data met established acceptance criteria with only minor eceptions. Minor eceptions result in the qualification of data that are intended to inform data users of data limitations. This fulfills the data validation requirement for blanks collected between attempts #1, and #2 of Event #2. If you have any questions regarding the enclosed document please feel free to contact me at (732) Sincerely, Tierra Solutions, Inc. Brian Mikucki Environmental Scientist On behalf of Occidental Chemical Corporation (as successor to Diamond Shamrock Chemicals Company) Enclosure cc: Cliff Firstenberg, Tierra Solutions Inc. Paul Brzozowski, Tierra Solutions Inc. Diane Waldschmidt, Environmental Data Services, Ltd. Alain Hebert, ARCADIS Meredith Hayes, ARCADIS

2 DATA VALIDATION REPORT CSO/SWO Phase I TestAmerica Aroclor PCBs (Standard) and Aroclor PCBs (Concentrated Etract Analysis) SDG - PR137 Prepared by ENVIRONMENTAL DATA SERVICES, LTD. For TIERRA SOLUTIONS, INC. March 18, Oakhill Dr. Allison Park, PA I

3 DATA VALIDATION REPORT FOR AROCLOR PCBs SITE: CSO/SWO Phase I LABORATORY: TestAmerica SAMPLE DELIVERY GROUP: PR137 This sample delivery group consists of the following samples: PR109CFRB PR101HLLC The samples described above were analyzed via USEPA CLP SOM01.2 to determine the concentrations of aroclor polychlorinated biphenyls (PCBs) in water samples with modifications provided for in the Combined Sewer Overflow/Stormwater Outfall (CSO/SWO) Investigation Quality Assurance Project Plan (QAPP). Project specific quality assurance (QA) objectives, as well as the USEPA Region II SOP, Validation of Data USEPA Contract Laboratory Program Statement of Work for Organic Analysis of Low/Medium Concentration of Aroclor Organic Compounds SOM01.2 Data, HW-37 Rev. 1, August 2007, have been considered during validation of this data and its usability. Table 1 provides a summary of major and minor data quality issues identified for this data set. All data are acceptable ecept those results which have been qualified with R, rejected. Data validation and laboratory qualifiers along with associated descriptions are provided in Table 2 and Table 3 respectively. All data qualification related to this group of samples is detailed on the attached sheets. Per USEPA Region 2 Validation Guidance, All data users should note two facts. First, the "R" flag means that the associated value is unusable. In other words, due to significant quality control (QC) problems, the analysis is invalid and provides no information as to whether the compound is present or not. "R" values should not appear on data tables even as a last resort. The second, no analyte concentration, even if it has passed all QC tests, is guaranteed to be accurate. Strict QC serves to increase confidence in data but any value potentially contains error. Terri Solomon Senior Technical Specialist Date: 3/17/14

4 HOLDING TIME/SAMPLE HANDLING The amount of an analyte in a sample can change with time due to chemical instability, degradation, volatilization, etc. If the specified holding time is eceeded the data may not be valid. Proper sample handling and preservation also play a role in the chemical stability of analytes in the sample matri. If samples are not collected and stored using proper containers and/or preservatives data may not be valid. The samples in this delivery group were prepared and analyzed within the holding time specified in the validation guideline. The samples in this delivery group were received by the laboratory within the proper temperature range as specified in the validation guidance. Further, laboratory documentation indicated that sample containers and sample preservation were as specified in the CSO/SWO QAPP. BLANK CONTAMINATION Quality assurance blanks which include; method, storage, trip, field, or rinse blanks are prepared to identify any contamination which may have been introduced into the samples during laboratory preparation and analysis or field activity. Method and storage blanks measure laboratory contamination. Trip blanks measure cross contamination of samples during shipment. Field and rinse blanks measure cross contamination during field operations. Method Blank Method blanks were prepared and analyzed in association with the samples in this delivery group at the specified frequency. Upon eamination of method blank data no analyte was positively identified at a concentration equal to or above the method detection limit (MDL) in any associated method blank. Field Blank Samples PR109CFRB and PR101HLLC contained in this sample delivery group (SDG) are rinse blanks. Upon evaluation of the results reported for the rinse blanks, all target Aroclor PCBs were found to be not detected at or above the MDL. CALIBRATION Percent Relative Standard Deviation and Percent Difference Percent relative standard deviation (%RSD) is calculated from the initial calibration and is used to assess the stability of the specific compound response factor over increasing concentration. Percent difference (%D) compares the response factor (RF) of the continuing calibration check to the mean RF from the initial calibration. The %D is a measure of the instrument's daily performance. For the PCB fraction, if %RSD eceeds 20% or %D eceeds 15% for any analyte, qualify all associated positive results "J" and non-detects "UJ". If %RSD and %D grossly eceed QC criteria, non-detect data may be qualified "R". 2

5 A five-point initial calibration curve was used per USEPA CLP SOM01.2 for the Aroclors 1016, 1254, 1260, 1221, 1232, 1242, 1248, 1262 and Initial calibration standards were complete for each column. PCBs in each level of the individual mitures fell within the retention time window established during the initial calibration. The relative standard deviation values for all analytes on both analytical columns were within validation guidelines. Continuing calibrations were analyzed at the proper frequencies. Percent difference values for all target Aroclors met validation criteria in all cases. SURROGATES/SYSTEM MONITORING COMPOUNDS All samples are spiked with surrogate/system monitoring compounds (SMC) prior to sample preparation to evaluate overall laboratory performance and efficiency of the analytical technique. Surrogate recovery summaries were present for the samples in this delivery group. All observed surrogate standard recoveries for samples and method blanks reported by the validator were within validation acceptance limits. COMPOUND IDENTIFICATION PCB Fraction The retention times of positively reported compounds must fall within the calculated retention time windows for the two gas chromatographic (GC) columns. Additionally, the %D of the positive results obtained on the two GC columns should be 25%. Retention Time No target Aroclor PCBs were positively identified for any sample in this delivery group. Therefore, this evaluation was not performed. Percent Difference No target Aroclor PCBs were positively identified for any sample in this delivery group. Therefore, this evaluation was not performed. MATRIX SPIKE/MATRIX SPIKE DUPLICATE The matri spike/matri spike duplicate (MS/MSD) data are generated to determine the precision and accuracy of the analytical procedure in a given sample matri. This SDG contains rinse blanks only. Therefore a MS/MSD is not required. LABORATORY CONTROL SAMPLE Two laboratory control samples (LCSs) were processed along with the samples in this delivery group. The observed recoveries of the LCSs were within the acceptance limits of %. 3

6 REPORTING This package may contain re-etraction, re-analysis or dilution. Form 1's have been documented to clearly indicate the sample results to be reported. OTHER QUALITY CONTROL DATA OUT OF SPECIFICATION None. FIELD DUPLICATE Field duplicates are two (or more) field samples collected at the same time in the same location. Each of the samples represents the same population and is carried through all steps of the sampling and analytical procedures in an identical manner. Field duplicate results are used to assess precision of the total method including sampling, analysis, and site heterogeneity. This SDG contains rinse blanks only. Therefore a field duplicate is not required. SYSTEM PERFORMANCE AND OVERALL ASSESSMENT Overall the laboratory data generated met the project goals and quality control criteria, with the eceptions identified in this report and as summarized in Table 1. 4

7 Table 1 Review Elements Summary Were acceptance criteria met? Yes No Aroclor PCBs Major Minor Holding Time/Sample Handling Method Blanks Field Blanks Percent Relative Standard Deviation and Percent Difference Surrogates/System Monitoring Compounds PCB Fraction Retention Time Percent Difference Matri Spike/Matri Spike Duplicate NA Laboratory Control Sample Reporting Other Quality Control Data out of Specification Field Duplicate NA Major= Major data quality issue identified resulting in rejection of data. Minor= Minor data quality issue identified resulting in the qualification of data. Data qualification should be used to inform the data users of data limitations. NA = Not applicable 5

8 Table 2 Data Validation Qualifiers Qualifier Description EMPC J JH JL M NJ R U UJ UJL Estimated Maimum Possible Concentration (EMPC). Estimated value (bias undetermined) The analyte was positively identified; but the associated numerical value is the approimate concentration of the analyte in the sample. Estimated value (potential high bias) The analyte was positively identified; but the associated numerical value is the approimate concentration, with a potential high bias, of the analyte in the sample. Estimated value (potential low bias) The analyte was positively identified; but the associated numerical value is the approimate concentration, with a potential low bias, of the analyte in the sample. The analytical result reported was obtained from a sediment sample found to contain between 50 and 90 percent moisture and had no other data qualifiers added during the data validating process. The organic analysis indicates the presence of an analyte that has been tentatively identified and the associated numerical value represents its approimate concentration. The sample results are rejected. Due to a significant QA/QC problem, the analysis is invalid and provides no information as to whether the analyte is present or not. Non-detected value The result initially reported as positive by the laboratory was qualified as not detected per USEPA Region II validation guidance, due to an associated quality control failure. Estimated non-detect - The analyte was not detected above the reported sample quantitation limit. However, the reported quantitation limit is approimate and may or may not represent the actual limit of quantitation necessary to accurately and precisely measure the analyte in the sample. Estimated non-detect (potential low bias) The analyte was not detected and the report sample quantitation limit is biased low. 6

9 Laboratory Qualifiers Qualifier Description B Inorganics The reported value was obtained from an instrument reading that was less than the project quantitation limit (PQL). Organics The associated analyte was also detected in the method blank. D E The organic analyte was quantitated from a diluted analysis. Inorganics The reported value is estimated because of the presence of an interference. Organics The associated compound concentration eceeded the calibration range of the instrument. EMPC G N P U Estimated Maimum Possible Concentration (EMPC). Organic data indicated the presence of a compound that meets the identification criteria; the result is below the PQL but above the MDL. The inorganic analysis is associated with a spike sample not within control limits. The percent difference between the primary and confirmation column for gas chromatography analyses is greater than 25 percent. The analyte was analyzed for, but was not detected above the reported sample quantitation limit. * The inorganic duplicate analysis was not within the established QC limit. 7

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11 DATA VALIDATION REPORT FOR AROCLOR PCBs SITE: CSO/SWO Phase I LABORATORY: TestAmerica SAMPLE DELIVERY GROUP: PR137 (Concentrated Etract Analysis) This sample delivery group consists of the following sample: PR101HLLC The sample described above was analyzed via USEPA CLP SOM01.2 to determine the concentrations of aroclor polychlorinated biphenyls (PCBs) in water samples with modifications provided for in the Combined Sewer Overflow/Stormwater Outfall (CSO/SWO) Investigation Quality Assurance Project Plan (QAPP). Project specific quality assurance (QA) objectives, as well as the USEPA Region II SOP, Validation of Data USEPA Contract Laboratory Program Statement of Work for Organic Analysis of Low/Medium Concentration of Aroclor Organic Compounds SOM01.2 Data, HW-37 Rev. 1, August 2007, have been considered during validation of this data and its usability. Table 1 provides a summary of major and minor data quality issues identified for this data set. All data are acceptable ecept those results which have been qualified with R, rejected. Data validation and laboratory qualifiers along with associated descriptions are provided in Table 2 and Table 3 respectively. All data qualification related to this group of samples is detailed on the attached sheets. Per USEPA Region 2 Validation Guidance, All data users should note two facts. First, the "R" flag means that the associated value is unusable. In other words, due to significant quality control (QC) problems, the analysis is invalid and provides no information as to whether the compound is present or not. "R" values should not appear on data tables even as a last resort. The second, no analyte concentration, even if it has passed all QC tests, is guaranteed to be accurate. Strict QC serves to increase confidence in data but any value potentially contains error. Terri Solomon Senior Technical Specialist Date: 3/17/14

12 HOLDING TIME/SAMPLE HANDLING The amount of an analyte in a sample can change with time due to chemical instability, degradation, volatilization, etc. If the specified holding time is eceeded the data may not be valid. Proper sample handling and preservation also play a role in the chemical stability of analytes in the sample matri. If samples are not collected and stored using proper containers and/or preservatives data may not be valid. The sample in this delivery group was prepared within the allowable holding time, but was analyzed outside the holding time specified in the validation guideline. All non-detected results were qualified estimated UJ on this basis. The samples in this delivery group were received by the laboratory within the proper temperature range as specified in the validation guidance. Further, laboratory documentation indicated that sample containers and sample preservation were as specified in the CSO/SWO QAPP. BLANK CONTAMINATION Quality assurance blanks which include; method, storage, trip, field, or rinse blanks are prepared to identify any contamination which may have been introduced into the samples during laboratory preparation and analysis or field activity. Method and storage blanks measure laboratory contamination. Trip blanks measure cross contamination of samples during shipment. Field and rinse blanks measure cross contamination during field operations. Method Blank Method blanks were prepared and analyzed in association with the sample in this delivery group at the specified frequency. Upon eamination of method blank data no analyte was positively identified at a concentration equal to or above the method detection limit (MDL) in any associated method blank. Field Blank Sample PR101HLLC contained in this sample delivery group (SDG) is a rinse blank. Upon evaluation of the results reported for the rinse blank, all target Aroclor PCBs were found to be not detected at or above the MDL. CALIBRATION Percent Relative Standard Deviation and Percent Difference Percent relative standard deviation (%RSD) is calculated from the initial calibration and is used to assess the stability of the specific compound response factor over increasing concentration. Percent difference (%D) compares the response factor (RF) of the continuing calibration check to the mean RF from the initial calibration. The %D is a measure of the instrument's daily performance. For the PCB fraction, if %RSD eceeds 20% or %D eceeds 15% for any analyte, qualify all associated positive results "J" and non-detects "UJ". If %RSD and %D grossly eceed QC criteria, non-detect data may be qualified "R". 2

13 A five-point initial calibration curve was used per USEPA CLP SOM01.2 for the Aroclors 1016, 1254, 1260, 1221, 1232, 1242, 1248, 1262 and Initial calibration standards were complete for each column. PCBs in each level of the individual mitures fell within the retention time window established during the initial calibration. The relative standard deviation values for all analytes on both analytical columns were within validation guidelines. Continuing calibrations were analyzed at the proper frequencies. Percent difference values for all target Aroclors met validation criteria in all cases with one eception. The closing calibration standard associated with the sample had %D values that eceeded the acceptance limit of +/-50% for all Aroclor 1248 peaks. The sample was previously qualified for a holding time violation. No further qualification was necessary. SURROGATES/SYSTEM MONITORING COMPOUNDS All samples are spiked with surrogate/system monitoring compounds (SMC) prior to sample preparation to evaluate overall laboratory performance and efficiency of the analytical technique. Surrogate recovery summaries were present for the sample in this delivery group. All observed surrogate standard recoveries for samples and method blanks reported by the validator were within validation acceptance limits. COMPOUND IDENTIFICATION PCB Fraction The retention times of positively reported compounds must fall within the calculated retention time windows for the two gas chromatographic (GC) columns. Additionally, the % D of the positive results obtained on the two GC columns should be 25%. Retention Time No target Aroclor PCBs were positively identified for the sample in this delivery group. Therefore, this evaluation was not performed. Percent Difference No target Aroclor PCBs were positively identified for the sample in this delivery group. Therefore, this evaluation was not performed. MATRIX SPIKE/MATRIX SPIKE DUPLICATE The matri spike/matri spike duplicate (MS/MSD) data are generated to determine the precision and accuracy of the analytical procedure in a given sample matri. This SDG contains a rinse blank only. Therefore a MS/MSD is not required. 3

14 LABORATORY CONTROL SAMPLE A laboratory control sample (LCS) was processed along with the sample in this delivery group. However, the LCS was prepared to be analyzed with the un-concentrated etract of the sample in this delivery group. These spike levels are not meaningful when analyzed after undergoing the concentration process that the sample was subjected to for this analysis as analyte concentrations would eceed the calibrated range. Therefore this evaluation was not performed. REPORTING This package may contain re-etraction, re-analysis or dilution. Form 1's have been documented to clearly indicate the sample results to be reported. OTHER QUALITY CONTROL DATA OUT OF SPECIFICATION None. FIELD DUPLICATE Field duplicates are two (or more) field samples collected at the same time in the same location. Each of the samples represents the same population and is carried through all steps of the sampling and analytical procedures in an identical manner. Field duplicate results are used to assess precision of the total method including sampling, analysis, and site heterogeneity. This SDG contains a rinse blank only. Therefore a field duplicate is not required. SYSTEM PERFORMANCE AND OVERALL ASSESSMENT Overall the laboratory data generated met the project goals and quality control criteria, with the eceptions identified in this report and as summarized in Table 1. 4

15 Table 1 Review Elements Summary Were acceptance criteria met? Yes No Aroclor PCBs Major Minor Holding Time/Sample Handling Method Blanks Field Blanks Percent Relative Standard Deviation and Percent Difference Surrogates/System Monitoring Compounds PCB Fraction Retention Time Percent Difference Matri Spike/Matri Spike Duplicate NA Laboratory Control Sample NA Reporting Other Quality Control Data out of Specification Field Duplicate NA Major= Major data quality issue identified resulting in rejection of data. Minor= Minor data quality issue identified resulting in the qualification of data. Data qualification should be used to inform the data users of data limitations. NA = Not applicable 5

16 Table 2 Data Validation Qualifiers Qualifier Description EMPC J JH JL M NJ R U UJ UJL Estimated Maimum Possible Concentration (EMPC). Estimated value (bias undetermined) The analyte was positively identified; but the associated numerical value is the approimate concentration of the analyte in the sample. Estimated value (potential high bias) The analyte was positively identified; but the associated numerical value is the approimate concentration, with a potential high bias, of the analyte in the sample. Estimated value (potential low bias) The analyte was positively identified; but the associated numerical value is the approimate concentration, with a potential low bias, of the analyte in the sample. The analytical result reported was obtained from a sediment sample found to contain between 50 and 90 percent moisture and had no other data qualifiers added during the data validating process. The organic analysis indicates the presence of an analyte that has been tentatively identified and the associated numerical value represents its approimate concentration. The sample results are rejected. Due to a significant QA/QC problem, the analysis is invalid and provides no information as to whether the analyte is present or not. Non-detected value The result initially reported as positive by the laboratory was qualified as not detected per USEPA Region II validation guidance, due to an associated quality control failure. Estimated non-detect - The analyte was not detected above the reported sample quantitation limit. However, the reported quantitation limit is approimate and may or may not represent the actual limit of quantitation necessary to accurately and precisely measure the analyte in the sample. Estimated non-detect (potential low bias) The analyte was not detected and the report sample quantitation limit is biased low. 6

17 Laboratory Qualifiers Qualifier Description B Inorganics The reported value was obtained from an instrument reading that was less than the project quantitation limit (PQL). Organics The associated analyte was also detected in the method blank. D E The organic analyte was quantitated from a diluted analysis. Inorganics The reported value is estimated because of the presence of an interference. Organics The associated compound concentration eceeded the calibration range of the instrument. EMPC G N P U Estimated Maimum Possible Concentration (EMPC). Organic data indicated the presence of a compound that meets the identification criteria; the result is below the PQL but above the MDL. The inorganic analysis is associated with a spike sample not within control limits. The percent difference between the primary and confirmation column for gas chromatography analyses is greater than 25 percent. The analyte was analyzed for, but was not detected above the reported sample quantitation limit. * The inorganic duplicate analysis was not within the established QC limit. 7

18 Validated Data Table

19 Validation Data Table CSO/SWO Investigation Phase I TestAmerica SDG PR137 - Aroclor PCBs ANALYTE UNITS PR109CFRB LQ VQ PR101HLLC LQ VQ Aroclor-1016 ug/l U U UJ Aroclor-1221 ug/l U U UJ Aroclor-1232 ug/l U U UJ Aroclor-1242 ug/l U U UJ Aroclor-1248 ug/l U U UJ Aroclor-1254 ug/l U U UJ Aroclor-1260 ug/l U U UJ Aroclor-1262 ug/l U U UJ Aroclor-1268 ug/l U U UJ LQ - Laboratory Qualifier VQ - Validation Qualifier Page 1 of 1

20 Laboratory Data With Qualifiers Added

21

22

23 DATA VALIDATION REPORT CSO/SWO Phase I Vista Analytical Dioin and Furans SDG - PR137 Prepared by ENVIRONMENTAL DATA SERVICES, LTD. For TIERRA SOLUTIONS, INC. March 12, Oakhill Dr. Allison Park, PA I

24 DATA VALIDATION REPORT FOR DIOXINS AND FURANS SITE: CSO/SWO Phase I LABORATORY: Vista Analytical Laboratory SAMPLE DELIVERY GROUP: PR137 This sample delivery group consists of the following samples: PR109CFRB PR101HLLC The samples described above were analyzed via USEPA method 1613B to determine the concentrations of 2,3,7,8-substituted polychlorinated dibenzo-p-dioins and polychlorinated dibenzo furans (PCDD/PCDFs) in water with modification for high volume sample analysis as outlined in the Combined Sewer Overflow/Stormwater Outfall (CSO/SWO) Investigation Quality Assurance Project Plan (QAPP). Project specific quality assurance (QA) objectives, as well as the USEPA Region II Data Validation SOP for EPA Method 1613, Revision B Tetra through Octa-chlorinated Dioins and Furans by Isotope Dilution (HRGC/HRMS), SOP HW-25, Rev. 3, September, 2006 were used to perform the dioin and furan data validation. Table 1 provides a summary of major and minor data quality issues identified for this data set. All data are acceptable ecept those results which have been qualified with R, rejected. Data validation and laboratory qualifiers along with associated descriptions are provided in Table 2 and Table 3 respectively. All data qualification related to this group of samples is detailed on the attached sheets. Per USEPA Region 2 Validation Guidance, All data users should note two facts. First, the "R" flag means that the associated value is unusable. In other words, due to significant quality control (QC) problems, the analysis is invalid and provides no information as to whether the compound is present or not. "R" values should not appear on data tables even as a last resort. The second, no analyte concentration, even if it has passed all QC tests, is guaranteed to be accurate. Strict QC serves to increase confidence in data but any value potentially contains error. Stephen Gordon Senior Technical Specialist Date: 3/12/14

25 HOLDING TIME/SAMPLE HANDLING The amount of an analyte in a sample can change with time due to chemical instability, degradation, volatilization, etc. If the specified holding time is eceeded the data may not be valid. Proper sample handling and preservation also play a role in the chemical stability of analytes in the sample matri. If samples are not collected and stored using proper containers and/or preservatives data may not be valid. The samples in this delivery group were prepared and analyzed within the holding time specified in the validation guideline. The samples in this delivery group were received by the laboratory within the proper temperature range as specified in the validation guidance. Further, laboratory documentation indicated that sample containers and sample preservation were as specified in the CSO/SWO QAPP. CHROMATOGRAPHIC RESOLUTION A performance check solution (Window Defining Miture/Isomer Specificity Test Standard) was analyzed at the beginning of every 12-hour analysis period (DB-5 column only). Upon evaluation of the performance check solution data, all QC criteria were met. Therefore, the data associated with these check standards were not qualified. INITIAL CALIBRATION Data were submitted representing si concentration level initial calibrations. All initial calibrations used during the analysis of samples in this delivery group were contained in the data package. The validator has evaluated the initial calibrations eamining ion ratios, signal to noise ratios, relative retention time and percent relative standard deviation criteria for all PCDD/PCDFs target analytes and their labeled analogs. Upon eamination of the initial calibration data, all of the criteria listed in method 1613B were met. ROUTINE CALIBRATION A routine calibration standard was evaluated at the beginning of each 12-hour analysis period. The validator has evaluated the routine calibration standard data submitted eamining ion ratios, relative retention time, signal to noise ratios, and concentration reported for all PCDD/PCDFs target analytes and their labeled analogs. Upon eamination of the routine calibration data, all of the criteria listed in the method 1613B were met. SAMPLE DATA Sample data are reviewed during validation to verify that all analyte specific qualitative requirements are met and that results reported are quantitatively accurate. Specific qualitative and quantitative criteria used to complete these assessments are outlined in Sections; 16.0 and 17.0 of USEPA method 1613B respectively. 2

26 Qualitative Requirements All positively reported results met the established qualitative acceptance criteria. Quantitative Requirements Sample results and internal standard concentration calculations were verified and no errors were detected. Interferences Positive PCDF values reported for the samples in this delivery group were evaluated to determine the presence of the corresponding diphenyl ether at a peak signal greater than 2.5 times that of the background noise. Upon evaluation, no chromatograms ehibited the presence of diphenyl ether (at greater than 2.5 times background) within the retention time range of the relevant polychlorinated dibenzofurans. BLANK CONTAMINATION Quality assurance blanks which include; method, storage, trip, field, or rinse blanks are prepared to identify any contamination, which may have been introduced into the samples during preparation and analysis or field activity. Method and storage blanks measure lab contamination. Trip blanks measure cross contamination during shipment. Field and rinse blanks measure cross contamination during field operations. Note, data validation qualification of sample results is based on the maimum contaminant concentration detected in all associated blanks. Method Blanks Method blanks were prepared and analyzed in association with the samples in this delivery group at the specified frequency. Upon eamination of method blank data no analyte was positively identified at a concentration at or above the estimated detection limit (EDL) in any associated method blank. Field Blanks Samples PR109CFRB and PR101HLLC contained in this sample delivery group (SDG) were rinse blanks. Upon evaluation of the results reported for the rinse blanks, all target PCDD/PCDFs were found to be not detected at or above the EDL with the eceptions summarized below: Analyte PR109CFRB pg/l LQ a 2,3,7,8-TCDD 1.42 OCDD 2.70 G 2,3,7,8-TCDF G 1,2,3,4,7,8-HCDF 2.51 G 1,2,3,6,7,8-HCDF G 2,3,4,6,7,8-HCDF G 1,2,3,4,6,7,8-HpCDF 8.23 OCDF 22.0 LQ = laboratory qualifier pg/l = picograms per liter a See Table 3 for laboratory qualifier descriptions. 3

27 FIELD DUPLICATE Field duplicates are two (or more) field samples collected at the same time in the same location. Each of the samples represents the same population and is carried through all steps of the sampling and analytical procedures in an identical manner. Field duplicate results are used to assess precision of the total method, including sampling, analysis, and site heterogeneity. This SDG contains rinse blanks only. Therefore a field duplicate is not required. MATRIX SPIKE/MATRIX SPIKE DUPLICATE The matri spike and matri spike duplicate (MS/MSD) are generated to determine the precision and accuracy of the analytical procedure in a given sample matri. This SDG contains rinse blanks only. Therefore a MS/MSD is not required. INTERNAL STANDARD Internal standards ( 13 C 12-1,2,3,4-TCDD, 13 C 12-1,2,3,4-TCDF and 13 C 12-1,2,3,7,8,9-HCDF) are added to each sample and method blank etract prior to injection. The area counts for each of the recovery standards in each sample must fall within the range +100% to 50% of that observed during the analysis of the mid-level daily calibration check standard. Upon evaluation, all internal standard responses were within acceptable limits. LABELED ANALOG STANDARDS Labeled analog standards are added to each sample prior to etraction; the recovery of these standards is evaluated during data validation. Calculated percent recoveries of labeled analog standards were within method and validation acceptance limits without eception. Also, per USEPA's request, labeled analog standard recoveries were evaluated against more stringent acceptance limits of %. The following labeled analog standard recoveries for the samples indicated do not meet the more stringent acceptance limits. Observed Recovery PR109CFRB % 13C-OCDD C-OCDF 46.3 Target analyte results associated with the labeled standards listed above have been qualified "J" or "UJ" estimated at USEPA's request. INITIAL PRECISION AND RECOVERY Initial Precision and Recovery (IPR) Studies are required per USEPA method 1613B, to establish the laboratory s ability to generate data of acceptable precision and recovery. The IPR standards were prepared and analyzed successfully by the laboratory. All observed average concentration and standard deviation values passed method defined acceptance criteria. 4

28 ONGOING PRECISION AND RECOVERY Ongoing Precision and Recovery (OPR) Standards are prepared and analyzed by the laboratory with each analytical batch to assure that the results produced by the laboratory continue to remain within the limits specified in USEPA method 1613B for precision and recovery. The OPR standards were prepared and analyzed in association with the samples in this delivery group at the required frequency. All observed percent recoveries were within criteria specified in the validation guidance. CLEAN-UP RECOVERY STANDARD A clean-up recovery standard is added to primary sample etracts prior to further clean-up steps and final concentration. The recovery of the clean-up standard is used to assess the effectiveness of the various etract clean-up processes employed and final concentration steps. The clean-up recovery standard ( 37 Cl -2,3,7,8-TCDD) was successfully recovered from the samples in the delivery group. SECOND COLUMN CONFIRMATION Any sample in which a 2,3,7,8-TCDF is identified on a DB-5 analytical column, must have a confirmation analysis per USEPA method 1613B, Section This requirement is further epanded for this project where all tetra through heachlorinated dibenzofurans are confirmed on a secondary analytical column SP No positive sample results (above the method defined minimum level) were detected for the polychlorinated dibenzofuran analytes listed below in the delivery group, therefore no second column confirmations were not necessary. 2,3,7,8-TCDF 1,2,3,7,8-PeCDF 2,3,4,7,8-PeCDF 1,2,3,4,7,8-HCDF 1,2,3,6,7,8-HCDF 2,3,4,6,7,8-HCDF 1,2,3,7,8,9-HCDF OTHER QUALITY CONTROL DATA OUT OF SPECIFICATION None. REPORTING The results on the Form 1 may represent both the initial analysis and diluted analysis when the laboratory provided more than one set of analyses for a given sample location. SYSTEM PERFORMANCE AND OVERALL ASSESSMENT Overall the laboratory data generated met the project goals and quality control criteria, with the eceptions identified in this report and as summarized in Table 1. 5

29 Table 1 Review Elements Summary Were acceptance criteria met? Yes No Dioins and Furans Major Minor Holding Time/Sample Handling Chromatographic Resolution Initial Calibration Routine Calibration Qualitative Requirements Quantitative Requirements Interferences Method Blanks Field Blanks Field Duplicate NA Matri Spike/Matri Spike Duplicate NA Internal Standard Labeled Analog Standards Initial Precision and Recovery Ongoing Precision and Recovery Clean-Up Recovery Standard Second Column Confirmation Other Quality Control Data Out of Specification Major= Major data quality issue identified resulting in rejection of data. Minor= Minor data quality issue identified resulting in the qualification of data. Data qualification should be used to inform the data users of data limitations. NA = Not applicable 6

30 Table 2 Data Validation Qualifiers Qualifier EMPC J JH JL M NJ R U UJ UJL Description Estimated Maimum Possible Concentration (EMPC). Estimated value (bias undetermined) The analyte was positively identified; but the associated numerical value is the approimate concentration of the analyte in the sample. Estimated value (potential high bias) The analyte was positively identified; but the associated numerical value is the approimate concentration, with a potential high bias, of the analyte in the sample. Estimated value (potential low bias) The analyte was positively identified; but the associated numerical value is the approimate concentration, with a potential low bias, of the analyte in the sample. The analytical result reported was obtained from a sediment sample found to contain between 50 and 90 percent moisture and had no other data qualifiers added during the data validating process. The organic analysis indicates the presence of an analyte that has been tentatively identified and the associated numerical value represents its approimate concentration. The sample results are rejected. Due to a significant QA/QC problem, the analysis is invalid and provides no information as to whether the analyte is present or not. Non-detected value - The result initially reported as positive by the laboratory was qualified as not detected per USEPA Region II validation guidance, due to an associated quality control failure. Estimated non-detect - The analyte was not detected above the reported sample quantitation limit. However, the reported quantitation limit is approimate and may or may not represent the actual limit of quantitation necessary to accurately and precisely measure the analyte in the sample. Estimated non-detect (potential low bias) The analyte was not detected and the report sample quantitation limit is biased low. 7

31 Table 3 Laboratory Qualifiers Qualifier Description B Inorganics The reported value was obtained from an instrument reading that was less than the project quantitation limit (PQL). Organics The associated analyte was also detected in the method blank. D E The organic analyte was quantitated from a diluted analysis. Inorganics The reported value is estimated because of the presence of an interference. Organics The associated compound concentration eceeded the calibration range of the instrument. EMPC G N P U Estimated Maimum Possible Concentration (EMPC). Organic data indicated the presence of a compound that meets the identification criteria; the result is below the PQL but above the MDL. The inorganic analysis is associated with a spike sample not within control limits. The percent difference between the primary and confirmation column for gas chromatography analyses is greater than 25 percent. The analyte was analyzed for, but was not detected above the reported sample quantitation limit. * The inorganic duplicate analysis was not within the established QC limit. 8

32 Validated Data Table

33 Validation Data Table CSO/SWO Investigation Phase I Vista Analytical SDG PR137 - PCDD/PCDFs ANALYTE UNITS PR109CFRB LQ VQ PR101HLLC LQ VQ 2,3,7,8-TCDD pg/l U 1,2,3,7,8-PeCDD pg/l U U 1,2,3,4,7,8-HCDD pg/l U U 1,2,3,6,7,8-HCDD pg/l U U 1,2,3,7,8,9-HCDD pg/l U U 1,2,3,4,6,7,8-HpCDD pg/l U U OCDD pg/l 2.70 G J U 2,3,7,8-TCDF pg/l G U 1,2,3,7,8-PeCDF pg/l U U 2,3,4,7,8-PeCDF pg/l EMPC U 1,2,3,4,7,8-HCDF pg/l 2.51 G U 1,2,3,6,7,8-HCDF pg/l G U 2,3,4,6,7,8-HCDF pg/l G U 1,2,3,7,8,9-HCDF pg/l U U 1,2,3,4,6,7,8-HpCDF pg/l U 1,2,3,4,7,8,9-HpCDF pg/l U U OCDF pg/l 22.0 J U LQ - Laboratory Qualifier VQ - Validation Qualifier Page 1 of 1

34 Laboratory Data With Qualifiers Added

35

36

37 DATA VALIDATION REPORT CSO/SWO Phase I TestAmerica Chlorinated Herbicides (Standard) and Chlorinated Herbicides (Concentrated Etract Analysis) SDG - PR137 Prepared by ENVIRONMENTAL DATA SERVICES, LTD. For TIERRA SOLUTIONS, INC. March 14, Oakhill Dr. Allison Park, PA I

38 DATA VALIDATION REPORT FOR CHLORINATED HERBICIDES SITE: CSO/SWO Phase I LABORATORY: TestAmerica SAMPLE DELIVERY GROUP: PR137 This sample delivery group consists of the following water samples: PR109CFRB PR101HLLC The samples described above were analyzed via USEPA SW-846 method 8151A to determine the concentrations of chlorinated herbicides in water samples with modification for high volume sample analysis as outlined in the Combined Sewer Overflow/Stormwater Outfall (CSO/SWO) Investigation Quality Assurance Project Plan (QAPP). Project specific quality assurance (QA) objectives, as well as the USEPA Region II SOP, Validating Chlorinated Herbicides, GC, SW-846, Method 8151A, HW-17 Rev. 3, July 2008; have been considered during validation of this data and its usability. Table 1 provides a summary of major and minor data quality issues identified for this data set. All data are acceptable ecept those results which have been qualified with R, rejected. Data validation and laboratory qualifiers along with associated descriptions are provided in Table 2 and Table 3 respectively. All data qualification related to this group of samples is detailed on the attached sheets. Per USEPA Region 2 Validation Guidance, All data users should note two facts. First, the "R" flag means that the associated value is unusable. In other words, due to significant quality control (QC) problems, the analysis is invalid and provides no information as to whether the compound is present or not. "R" values should not appear on data tables even as a last resort. The second, no analyte concentration, even if it has passed all QC tests, is guaranteed to be accurate. Strict QC serves to increase confidence in data but any value potentially contains error. Terri Solomon Senior Technical Specialist Date: 3/14/14

39 HOLDING TIME/SAMPLE HANDLING The amount of an analyte in a sample can change with time due to chemical instability, degradation, volatilization, etc. If the specified holding time is eceeded the data may not be valid. Proper sample handling and preservation also play a role in the chemical stability of analytes in the sample matri. If samples are not collected and stored using proper containers and/or preservatives data may not be valid. The samples in this delivery group were prepared and analyzed within the holding time specified in the validation guideline. The samples in this delivery group were received by the laboratory within the proper temperature range as specified in the validation guidance. Further, laboratory documentation indicated that sample containers and sample preservation were as specified in the CSO/SWO QAPP. BLANK CONTAMINATION Quality assurance blanks which include; method, storage, trip, field, or rinse blanks are prepared to identify any contamination which may have been introduced into the samples during laboratory preparation and analysis or field activity. Method and storage blanks measure laboratory contamination. Trip blanks measure cross contamination of samples during shipment. Field and rinse blanks measure cross contamination during field operations. Method Blanks Method blanks were prepared and analyzed in association with the samples in this delivery group at the specified frequency. Upon eamination of method blank data no analyte was positively identified at a concentration equal to or above the method detection limit (MDL) in any associated method blank with the eceptions summarized below: MB /1-A Column 1 ug/l MB /1-A Column 2 ug/l ANALYTE LQ a LQ a 2,4,5-T G G Silve (2,4,5-TP) G ,4-D G G 2,4-DB G LQ = laboratory qualifier µg/l= micrograms per liter a See Table 3 for laboratory qualifier descriptions. The samples in this delivery group are rinse blanks; therefore qualification of associated results based upon observed method blank contamination is not performed in these cases. Field Blanks Samples PR109CFRB and PR101HLLC contained in this sample delivery group (SDG) are rinse blanks. Upon evaluation of the results reported for the rinse blanks, all target herbicides were found to be not detected at or above the MDL with the eceptions summarized below: 2

40 ANALYTE PR109CFRB ug/l LQ a 2,4-D 0.12 G B 2,4-DB 0.11 G B 2,4,5-T G B LQ = laboratory qualifier µg/l = micrograms per liter a See Table 3 for laboratory qualifier descriptions. The samples in this delivery group are rinse blanks; therefore qualification of associated results based upon observed rinsate blank contamination is not performed in these cases. CALIBRATION Percent Relative Standard Deviation and Percent Difference Percent relative standard deviation (%RSD) is calculated for the initial calibration and is used to indicate the stability of the specific compound response factor over increasing concentration. Percent difference (%D) compares the response factor (RF) of the continuing calibration check to the mean RF from the initial calibration. The %D is a measure of the instrument's daily performance. The %RSD must be 20% for any analyte, while the %D values must be 25%. If %RSD and %D are grossly eceed QC criteria, non-detect data may be qualified "R". All initial calibrations associated with this sample delivery group met all %RSD criteria. A five-point initial calibration curve was used as required per SW846. Initial calibration standards were complete for each analytical column. Herbicides in each level of the initial calibration and the mid-concentration continuing calibration check standard fell within the retention time windows. All continuing calibration results had %D values within established acceptance limits. SURROGATES/SYSTEM MONITORING COMPOUNDS All samples are spiked with surrogate/system monitoring compounds (SMC) prior to sample preparation to evaluate overall laboratory performance and efficiency of the analytical technique. Surrogate recovery summaries were present for the samples in this delivery group. All observed surrogate standard recoveries for samples reported by the validator were within validation acceptance limits with one eception. Sample PR109CFRB had an observed surrogate recovery for 2,4-dichlorophenylacetic acid (138%) on column 1 that was above the established acceptance limits of %. High bias is indicated. All positive sample results were reported from column 2. Therefore no qualification is necessary on this basis. COMPOUND IDENTIFICATION The retention times of positively reported compounds must fall within the calculated retention time windows for the two gas chromatographic (GC) columns. Additionally, the %D of the positive results obtained on the two GC columns must be 25%. Retention Time Positively identified target analyte herbicides reported for the samples in this delivery group had observed instrument signals within the calculated retention time windows on each of the two GC columns. 3

41 Percent Difference All positively identified target herbicide results in this delivery group met %D criteria with the eceptions summarized below: Sample Analyte Percent Difference PR109CFRB 2,4-D 91.7% 2,4-DB 300% 2,4,5-T 336% Because significant positive interferences are present in the affected retention time window of target analytes in both chromatographic columns, professional judgment was used to report and qualify sample results. Refer to section 12.0 of the SOP Chromatogram Quality. In all cases the validator has reported results from the lower of the two analytical columns and when %Ds are greater than 25% the positive results are qualified NJ, analyte tentatively identified as an estimated concentration. MATRIX SPIKE/MATRIX SPIKE DUPLICATE The matri spike/ matri spike duplicate (MS/MSD) data are generated to determine the precision and accuracy of the analytical procedure in a given sample matri. This SDG contains rinse blanks only. Therefore a MS/MSD is not required. LABORATORY CONTROL SAMPLE Two laboratory control samples (LCSs) were processed along with the samples in this delivery group. The observed recoveries of the LCSs were within the acceptance limits of % for all target analyte and surrogate compounds with one eception. The LCS ( /2-A) had an observed recovery for 2,4,5-T (131%) that was above the acceptance limit. High bias is indicated. The result was non-detected for associated sample PR101HLLC. Therefore no qualification is necessary on this basis. FIELD DUPLICATE Field duplicates are two (or more) field samples collected at the same time in the same location. Each of the samples represents the same population and is carried through all steps of the sampling and analytical procedures in an identical manner. Field duplicate results are used to assess precision of the total method including sampling, analysis, and site heterogeneity. This SDG contains rinse blanks only. Therefore a field duplicate is not required. REPORTING All sample results for this delivery group are reported from an un-diluted analysis. Project reporting limit requirements were met. Positive results have been reported from the lower of the primary and confirmation column analyses per validation guidance. 4

42 OTHER QUALITY CONTROL DATA OUT OF SPECIFICATION None. SYSTEM PERFORMANCE AND OVERALL ASSESSMENT Overall the laboratory data generated met the project goals and quality control criteria, with the eceptions identified in this report and as summarized in Table 1. 5

43 Table 1 Review Elements Summary Were acceptance criteria met? Yes No Herbicides Major Minor Holding Time/Sample Handling Method Blanks Field Blanks Percent Relative Standard Deviation and Percent Difference Surrogates/System Monitoring Compounds Compound Identification / Retention Time Compound Identification / Percent Difference Matri Spike/Matri Spike Duplicate NA Laboratory Control Sample Field Duplicate NA Other Quality Control Data out of Specification Major= Major data quality issue identified resulting in rejection of data. Minor= Minor data quality issue identified resulting in the qualification of data. Data qualification should be used to inform the data users of data limitations. NA = Not applicable 6

44 Table 2 Data Validation Qualifiers Qualifier Description EMPC J JH JL M NJ R U UJ UJL Estimated Maimum Possible Concentration (EMPC). Estimated value (bias undetermined) The analyte was positively identified; but the associated numerical value is the approimate concentration of the analyte in the sample. Estimated value (potential high bias) The analyte was positively identified; but the associated numerical value is the approimate concentration, with a potential high bias, of the analyte in the sample. Estimated value (potential low bias) The analyte was positively identified; but the associated numerical value is the approimate concentration, with a potential low bias, of the analyte in the sample. The analytical result reported was obtained from a sediment sample found to contain between 50 and 90 percent moisture and had no other data qualifiers added during the data validating process. The organic analysis indicates the presence of an analyte that has been tentatively identified and the associated numerical value represents its approimate concentration. The sample results are rejected. Due to a significant QA/QC problem, the analysis is invalid and provides no information as to whether the analyte is present or not. Non-detected value The result initially reported as positive by the laboratory was qualified as not detected per USEPA Region II validation guidance, due to an associated quality control failure. Estimated non-detect - The analyte was not detected above the reported sample quantitation limit. However, the reported quantitation limit is approimate and may or may not represent the actual limit of quantitation necessary to accurately and precisely measure the analyte in the sample. Estimated non-detect (potential low bias) The analyte was not detected and the report sample quantitation limit is biased low. 7

45 Table 3 Laboratory Qualifiers Qualifier Description B Inorganics The reported value was obtained from an instrument reading that was less than the project quantitation limit (PQL). Organics The associated analyte was also detected in the method blank. D E The organic analyte was quantitated from a diluted analysis. Inorganics The reported value is estimated because of the presence of interference. Organics The associated compound concentration eceeded the calibration range of the instrument. EMPC G N P U Estimated Maimum Possible Concentration (EMPC). Organic data indicated the presence of a compound that meets the identification criteria; the result is below the PQL but above the MDL. The inorganic analysis is associated with a spike sample not within control limits. The percent difference between the primary and confirmation column for gas chromatography analyses is greater than 25 percent. The analyte was analyzed for, but was not detected above the reported sample quantitation limit. * The inorganic duplicate analysis was not within the established QC limit. 8

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47 DATA VALIDATION REPORT FOR CHLORINATED HERBICIDES SITE: CSO/SWO Phase I LABORATORY: TestAmerica SAMPLE DELIVERY GROUP: PR137 (Concentrated Etract Analysis) This sample delivery group consists of the following water sample: PR101HLLC The sample described above was analyzed via USEPA SW-846 method 8151A to determine the concentrations of chlorinated herbicides in water samples with modification for high volume sample analysis as outlined in the Combined Sewer Overflow/Stormwater Outfall (CSO/SWO) Investigation Quality Assurance Project Plan (QAPP). Project specific quality assurance (QA) objectives, as well as the USEPA Region II SOP, Validating Chlorinated Herbicides, GC, SW-846, Method 8151A, HW-17 Rev. 3, July 2008; have been considered during validation of this data and its usability. Table 1 provides a summary of major and minor data quality issues identified for this data set. All data are acceptable ecept those results which have been qualified with R, rejected. Data validation and laboratory qualifiers along with associated descriptions are provided in Table 2 and Table 3 respectively. All data qualification related to this group of samples is detailed on the attached sheets. Per USEPA Region 2 Validation Guidance, All data users should note two facts. First, the "R" flag means that the associated value is unusable. In other words, due to significant quality control (QC) problems, the analysis is invalid and provides no information as to whether the compound is present or not. "R" values should not appear on data tables even as a last resort. The second, no analyte concentration, even if it has passed all QC tests, is guaranteed to be accurate. Strict QC serves to increase confidence in data but any value potentially contains error. Terri Solomon Senior Technical Specialist Date: 3/14/14

48 HOLDING TIME/SAMPLE HANDLING The amount of an analyte in a sample can change with time due to chemical instability, degradation, volatilization, etc. If the specified holding time is eceeded the data may not be valid. Proper sample handling and preservation also play a role in the chemical stability of analytes in the sample matri. If samples are not collected and stored using proper containers and/or preservatives data may not be valid. The samples in this delivery group were prepared within the allowable holding time, but were analyzed outside the holding time specified in the validation guideline. All positive sample results were qualified as estimated, "J" and non-detected results were qualified estimated UJ on this basis. The samples in this delivery group were received by the laboratory within the proper temperature range as specified in the validation guidance. Further, laboratory documentation indicated that sample containers and sample preservation were as specified in the CSO/SWO QAPP. BLANK CONTAMINATION Quality assurance blanks which include; method, storage, trip, field, or rinse blanks are prepared to identify any contamination which may have been introduced into the samples during laboratory preparation and analysis or field activity. Method and storage blanks measure laboratory contamination. Trip blanks measure cross contamination of samples during shipment. Field and rinse blanks measure cross contamination during field operations. Method Blanks Method blanks were prepared and analyzed in association with the sample in this delivery group at the specified frequency. Upon eamination of method blank data no analyte was positively identified at a concentration equal to or above the method detection limit (MDL) in any associated method blank. Field Blanks Sample PR101HLLC contained in this sample delivery group (SDG) is a rinse blank. Upon evaluation of the results reported for the rinse blanks, all target herbicides were found to be not detected at or above the MDL with the eceptions summarized below: ANALYTE PR101HLLC ug/l LQ a 2,4,5-T G Silve (2,4,5-TP) G LQ = laboratory qualifier µg/l = micrograms per liter a See Table 3 for laboratory qualifier descriptions. The sample in this delivery group is a rinse blank; therefore qualification of associated results based upon observed rinsate blank contamination is not performed in these cases. 2

49 CALIBRATION Percent Relative Standard Deviation and Percent Difference Percent relative standard deviation (%RSD) is calculated for the initial calibration and is used to indicate the stability of the specific compound response factor over increasing concentration. Percent difference (%D) compares the response factor (RF) of the continuing calibration check to the mean RF from the initial calibration. The %D is a measure of the instrument's daily performance. The %RSD must be 20% for any analyte, while the %D values must be 25%. If %RSD and %D are grossly eceed QC criteria, non-detect data may be qualified "R". All initial calibrations associated with this sample delivery group met all %RSD criteria. A five-point initial calibration curve was used as required per SW846. Initial calibration standards were complete for each analytical column. Herbicides in each level of the initial calibration and the mid-concentration continuing calibration check standard fell within the retention time windows. All continuing calibration results had %D values within established acceptance limits. SURROGATES/SYSTEM MONITORING COMPOUNDS All samples are spiked with surrogate/system monitoring compounds (SMC) prior to sample preparation to evaluate overall laboratory performance and efficiency of the analytical technique. Surrogate recovery summaries were present for the sample in this delivery group. All observed surrogate standard recoveries for the sample reported by the validator were within validation acceptance limits. COMPOUND IDENTIFICATION The retention times of positively reported compounds must fall within the calculated retention time windows for the two gas chromatographic (GC) columns. Additionally, the %D of the positive results obtained on the two GC columns must be 25%. Retention Time Positively identified target analyte herbicides reported for the sample in this delivery group had observed instrument signals within the calculated retention time windows on each of the two GC columns. Percent Difference All positively identified target herbicide results in this delivery group met %D criteria with two eceptions. The %D values for 2,4,5-T and Silve (2,4,5-TP) were 78.6% and 138%. Because significant positive interferences are present in the affected retention time window of target analytes in both chromatographic columns, professional judgment was used to report and qualify sample results. Refer to section 12.0 of the SOP Chromatogram Quality. In all cases the validator has reported results from the lower of the two analytical columns and when %Ds are greater than 25% the positive results are qualified NJ, analyte tentatively identified as an estimated concentration. 3

50 MATRIX SPIKE/MATRIX SPIKE DUPLICATE The matri spike/ matri spike duplicate (MS/MSD) data are generated to determine the precision and accuracy of the analytical procedure in a given sample matri. This SDG contains a rinse blank only. Therefore a MS/MSD is not required. LABORATORY CONTROL SAMPLE A laboratory control sample (LCS) was processed along with the samples in this delivery group. However, the LCS was prepared to be analyzed with the un-concentrated etracts of the samples in this delivery group. These spike levels are not meaningful when analyzed after undergoing the concentration process that the samples were subjected to for this analysis as analyte concentrations would eceed the calibrated range. Therefore this evaluation was not performed. FIELD DUPLICATE Field duplicates are two (or more) field samples collected at the same time in the same location. Each of the samples represents the same population and is carried through all steps of the sampling and analytical procedures in an identical manner. Field duplicate results are used to assess precision of the total method including sampling, analysis, and site heterogeneity. This SDG contains a rinse blank only. Therefore a field duplicate is not required. REPORTING All sample results for this delivery group are reported from an un-diluted analysis. Project reporting limit requirements were met. Positive results have been reported from the lower of the primary and confirmation column analyses per validation guidance. OTHER QUALITY CONTROL DATA OUT OF SPECIFICATION None. SYSTEM PERFORMANCE AND OVERALL ASSESSMENT Overall the laboratory data generated met the project goals and quality control criteria, with the eceptions identified in this report and as summarized in Table 1. 4

51 Table 1 Review Elements Summary Were acceptance criteria met? Yes No Herbicides Major Minor Holding Time/Sample Handling Method Blanks Field Blanks Percent Relative Standard Deviation and Percent Difference Surrogates/System Monitoring Compounds Compound Identification / Retention Time Compound Identification / Percent Difference Matri Spike/Matri Spike Duplicate NA Laboratory Control Sample NA Field Duplicate NA Other Quality Control Data out of Specification Major= Major data quality issue identified resulting in rejection of data. Minor= Minor data quality issue identified resulting in the qualification of data. Data qualification should be used to inform the data users of data limitations. NA = Not applicable 5

52 Table 2 Data Validation Qualifiers Qualifier Description EMPC J JH JL M NJ R U UJ UJL Estimated Maimum Possible Concentration (EMPC). Estimated value (bias undetermined) The analyte was positively identified; but the associated numerical value is the approimate concentration of the analyte in the sample. Estimated value (potential high bias) The analyte was positively identified; but the associated numerical value is the approimate concentration, with a potential high bias, of the analyte in the sample. Estimated value (potential low bias) The analyte was positively identified; but the associated numerical value is the approimate concentration, with a potential low bias, of the analyte in the sample. The analytical result reported was obtained from a sediment sample found to contain between 50 and 90 percent moisture and had no other data qualifiers added during the data validating process. The organic analysis indicates the presence of an analyte that has been tentatively identified and the associated numerical value represents its approimate concentration. The sample results are rejected. Due to a significant QA/QC problem, the analysis is invalid and provides no information as to whether the analyte is present or not. Non-detected value The result initially reported as positive by the laboratory was qualified as not detected per USEPA Region II validation guidance, due to an associated quality control failure. Estimated non-detect - The analyte was not detected above the reported sample quantitation limit. However, the reported quantitation limit is approimate and may or may not represent the actual limit of quantitation necessary to accurately and precisely measure the analyte in the sample. Estimated non-detect (potential low bias) The analyte was not detected and the report sample quantitation limit is biased low. 6

53 Table 3 Laboratory Qualifiers Qualifier Description B Inorganics The reported value was obtained from an instrument reading that was less than the project quantitation limit (PQL). Organics The associated analyte was also detected in the method blank. D E The organic analyte was quantitated from a diluted analysis. Inorganics The reported value is estimated because of the presence of interference. Organics The associated compound concentration eceeded the calibration range of the instrument. EMPC G N P U Estimated Maimum Possible Concentration (EMPC). Organic data indicated the presence of a compound that meets the identification criteria; the result is below the PQL but above the MDL. The inorganic analysis is associated with a spike sample not within control limits. The percent difference between the primary and confirmation column for gas chromatography analyses is greater than 25 percent. The analyte was analyzed for, but was not detected above the reported sample quantitation limit. * The inorganic duplicate analysis was not within the established QC limit. 7

54 Validated Data Table

55 ANALYTE UNITS PR109CFRB LQ VQ PR101HLLC LQ VQ 2,4-D ug/l 0.12 G B NJ 0.19 U UJ 2,4-DB ug/l 0.11 G B NJ 0.19 U UJ 2,4,5-T ug/l G B NJ G NJ Silve (2,4,5-TP) ug/l U G NJ Validation Data Table CSO/SWO Investigation Phase I TestAmerica SDG PR137- Chlorinated Herbicides LQ - Laboratory Qualifier VQ - Validation Qualifier Page 1 of 1

56 Laboratory Data With Qualifiers Added

57

58

59

60 DATA VALIDATION REPORT CSO/SWO Phase I TestAmerica Miscellaneous SDG - PR137 Prepared by ENVIRONMENTAL DATA SERVICES, LTD. For TIERRA SOLUTIONS, INC. April 10, Oakhill Dr. Allison Park, PA I

61 DATA VALIDATION REPORT FOR MISCELLANEOUS ANALYSES SITE: CSO/SWO Phase I LABORATORY: TestAmerica SAMPLE DELIVERY GROUP: PR137 This sample delivery group consists of the following samples: PR109CFRB PR101HLLC The samples described above were analyzed for the following parameters as described in Standard Methods for the Eamination of Water and Wastewater (SM), New Jersey Department of Environmental Protection (NJDEP), United States Environmental Protection Agency (USEPA) SW846, and USEPA Contract Laboratory Program (CLP) methodologies as indicated below. Parameter Analytical Method Cyanide USEPA CLP, ISM01.2 Total Organic Carbon (TOC) (liquid) USEPA 9060 Total Etractable Petroleum Hydrocarbons (TEPH) OQA-QAM /91 Rev. 6 (4/24/06) NJDEP Total Suspended Solids (TSS) SM 2540D Total Dissolved Solids (TDS) SM 2540C Project specific quality assurance (QA) objectives, as well as the following data validation standard operating procedures (SOPs) located in Appendi C of the Combined Sewer Overflow/Stormwater Outfall (CSO/SWO), Quality Assurance Project Plan (QAPP), have been considered during validation of this data and determination of its usability. Parameter Data Validation SOP Cyanide USEPA Region 2 SOP HW-2, Revision 13 TOC (solid/liquid) EDS SOP: TOC-01 Rev. 2, 7/10 TEPH EDS SOP: TEPH-01, Rev. 3, 07/07 TSS EDS SOP: TSS by Gravimetric SM 2540D, Rev. 0, 7/10 TDS EDS SOP: TDS by Gravimetric SM 2540C, Rev. 0, 7/10 Table 1 provides a summary of major and minor data quality issues identified for this data set. All data are acceptable ecept those results which have been qualified with R, rejected. Data validation and laboratory qualifiers along with associated descriptions are provided in Table 2 and Table 3 respectively. All data qualification related to this group of samples is detailed on the attached sheets. Per USEPA Region 2 Validation Guidance, All data users should note two facts. First, the "R" flag means that the associated value is unusable. In other words, due to significant quality control (QC) problems, the analysis is invalid and provides no information as to whether the compound is present or not. "R" values should not appear on data tables even as a last resort. The second, no analyte concentration, even if it has passed all QC tests, is guaranteed to be accurate. Strict QC serves to increase confidence in data but any value potentially contains error. Terri Solomon Senior Technical Specialist Date: 4/10/14

62 TOTAL CYANIDE HOLDING TIME The amount of an analyte in a sample can change with time due to chemical instability, degradation, volatilization, etc. If the specified holding time is eceeded the data may not be valid. Proper sample handling and preservation also play a role in the chemical stability of analytes in the sample matri. If samples are not collected and stored using proper containers and/or preservatives data may not be valid. The samples in this delivery group were prepared and analyzed within the holding time specified in the validation guideline. The samples in this delivery group were received by the laboratory within the proper temperature range as specified in the validation guidance. Further, laboratory documentation indicated that sample containers and sample preservation were as specified in the CSO/SWO QAPP. CALIBRATION Initial Calibration All initial calibrations consisted of five standards and a blank. The correlation coefficients for all calibration curves were greater than All validation acceptance criteria were met. Continuing Calibration Continuing calibration standards and blanks were evaluated at the proper frequency. Upon evaluation all continuing calibration standard recoveries and blank values met validation guidelines. BLANK CONTAMINATION Quality assurance blanks which include; method, storage, trip, field, or rinse blanks are prepared to identify any contamination, which may have been introduced into the samples during laboratory preparation and analysis or field activity. Method and storage blanks measure laboratory contamination. Trip blanks measure cross contamination during shipment. Field and rinse blanks measure cross contamination during field operations. Method Blanks Method blanks were prepared and analyzed in association with the samples in this delivery group at the specified frequency. Upon eamination of method blank data cyanide was positively identified (1.39 ug/l) at a concentration equal to or above the method detection limit (MDL). The samples in this delivery group are rinse blanks; therefore qualification of associated results based upon observed method blank contamination is not performed in these cases. Field Blanks Samples PR109CFRB and PR101HLLC contained in this sample delivery group (SDG) are rinse blanks. Upon evaluation of the results reported for the rinse blanks, cyanide was found to be not detected at or above the MDL. 2

63 TOTAL CYANIDE (Continued) MATRIX SPIKE Matri spikes (MS) are generated to determine the accuracy of the analytical procedure in a given sample matri. This SDG contains rinse blanks only. Therefore a MS is not required. LABORATORY DUPLICATE Laboratory duplicates are generated to determine the precision of the analytical procedure in a given sample matri. This delivery group contains rinse blanks only. Therefore a laboratory duplicate is not required. LABORATORY CONTROL SAMPLE A laboratory control sample (LCS) was not processed along with the samples in this delivery group. This delivery group contains rinse blanks only. Therefore an LCS is not required. FIELD DUPLICATE Field duplicates are two (or more) field samples collected at the same time in the same location. Each of the samples represents the same population and is carried through all steps of the sampling and analytical procedures in an identical manner. Field duplicate results are used to assess precision of the total method including sampling, analysis, and site heterogeneity. This delivery group contains rinse blanks only. Therefore a field duplicate is not required. SYSTEM PERFORMANCE AND OVERALL ASSESSMENT Overall the laboratory data generated met the project goals and quality control criteria, with the eceptions identified in this report and as summarized in Table 1. 3

64 TOTAL ORGANIC CARBON (TOC) HOLDING TIME The amount of an analyte in a sample can change with time due to chemical instability, degradation, volatilization, etc. If the specified holding time is eceeded the data may not be valid. Proper sample handling and preservation also play a role in the chemical stability of analytes in the sample matri. If samples are not collected and stored using proper containers and/or preservatives data may not be valid. The samples in this delivery group were prepared and analyzed within the holding time specified in the validation guideline. The samples in this delivery group were received by the laboratory within the proper temperature range as specified in the validation guidance. Further, laboratory documentation indicated that sample containers and sample preservation were as specified in the CSO/SWO QAPP. CALIBRATION Initial Calibration All initial calibrations consisted of five standards and a blank. The correlation coefficients for all calibration curves were greater than All validation acceptance criteria were met. Continuing Calibration Continuing calibration standards and blanks were evaluated at the proper frequency. Upon evaluation all continuing calibration standard recoveries and blank values met validation guidelines. BLANK CONTAMINATION Quality assurance blanks which include; method, storage, trip, field, or rinse blanks are prepared to identify any contamination, which may have been introduced into the samples during laboratory preparation and analysis or field activity. Method and storage blanks measure laboratory contamination. Trip blanks measure cross contamination during shipment. Field and rinse blanks measure cross contamination during field operations. Method Blanks Method blanks were prepared and analyzed in association with the samples in this delivery group at the specified frequency. Upon eamination of method blank data no TOC was positively identified at a concentration equal to or above the method detection limit (MDL) in any associated method blank. Field Blanks Samples PR109CFRB and PR101HLLC contained in this sample delivery group (SDG) are rinse blanks. Upon evaluation of the results reported for the rinse blanks, TOC was found to be not detected at or above the MDL with one eception. TOC was detected at 3.0 mg/l in rinse blank PR109CFRB. The samples in this delivery group are rinse blanks; therefore qualification of associated results based upon observed rinse blank contamination is not performed in these cases. 4

65 TOTAL ORGANIC CARBON (TOC) (Continued) MATRIX SPIKE Matri spikes (MS) are generated to determine the accuracy of the analytical procedure in a given sample matri. This SDG contains rinse blanks only. Therefore a MS is not required. LABORATORY DUPLICATE Laboratory duplicates are generated to determine the precision of the analytical procedure in a given sample matri. This delivery group contains only rinse blanks. Therefore a laboratory duplicate is not required. LABORATORY CONTROL SAMPLE Two laboratory control samples (LCS) were processed along with the samples in this delivery group. The observed recoveries for the TOC LCS (103%,102%) were within the established acceptance limits of %. FIELD DUPLICATE Field duplicates are two (or more) field samples collected at the same time in the same location. Each of the samples represents the same population and is carried through all steps of the sampling and analytical procedures in an identical manner. Field duplicate results are used to assess precision of the total method including sampling, analysis, and site heterogeneity. This delivery group contains rinse blanks only. Therefore a field duplicate is not required. SYSTEM PERFORMANCE AND OVERALL ASSESSMENT Overall the laboratory data generated met the project goals and quality control criteria, with the eceptions identified in this report and as summarized in Table 1. 5

66 TOTAL EXTRACTABLE PETROLEUM HYDROCARBONS (TEPH) HOLDING TIME The amount of an analyte in a sample can change with time due to chemical instability, degradation, volatilization, etc. If the specified holding time is eceeded the data may not be valid. Proper sample handling and preservation also play a role in the chemical stability of analytes in the sample matri. If samples are not collected and stored using proper containers and/or preservatives data may not be valid. The samples in this delivery group were prepared and analyzed within the holding time specified in the validation guideline. The samples in this delivery group were received by the laboratory within the proper temperature range as specified in the validation guidance. Further, laboratory documentation indicated that sample containers and sample preservation were as specified in the CSO/SWO QAPP. CALIBRATION Initial Calibration All initial calibrations consisted of five standards. The percent relative standard deviation (RSD) for the initial multi-level calibration curve must be 20% or correlation coefficient greater than The initial calibration met all validation acceptance criteria. Continuing Calibration Continuing calibration standards were evaluated at the proper frequency. The percent difference (%D) for the continuing calibration must be < 20%. Upon evaluation all continuing calibrations met validation acceptance criteria. BLANK CONTAMINATION Quality assurance blanks which include; method, storage, trip, field, or rinse blanks are prepared to identify any contamination, which may have been introduced into the samples during laboratory preparation and analysis or field activity. Method and storage blanks measure laboratory contamination. Trip blanks measure cross contamination during shipment. Field and rinse blanks measure cross contamination during field operations. Method Blanks Method blanks were prepared and analyzed in association with the samples in this delivery group at the specified frequency. Upon eamination of method blank data TEPH was positively identified ( mg/l) at a concentration equal to or above the method detection limit (MDL). The samples in this delivery group are rinse blanks; therefore qualification of associated results based upon observed rinse blank contamination is not performed in these cases. Field Blanks Samples PR109CFRB and PR101HLLC contained in this sample delivery group (SDG) are rinse blanks. 6

67 TOTAL EXTRACTABLE PETROLEUM HYDROCARBONS (TEPH) (Continued) Upon evaluation of the results reported for the rinse blanks, TEPH was found to be detected at or above the MDL as indicated in the table below. PR101HLLC Analyte mg/l LQ a TEPH GB LQ = laboratory qualifier mg/l= milligrams per liter a See Table 3 for laboratory qualifier descriptions. The samples in this delivery group are rinse blanks; therefore qualification of associated results based upon observed rinse blank contamination is not performed in these cases. SURROGATE STANDARDS All samples are spiked with the surrogate compounds chlorobenzene and o-terphenyl prior to etraction. Surrogate standard control limits have been established as % recovery. All sample and method blank surrogate recoveries observed fell within established acceptance limits. The retention times for the surrogate Chlorobenzene fell outside the initial calibration retention time window for both samples while the surrogate for o-terphenyl fell within the initial calibration retention time window. The affected analyte results were qualified J, estimated or UJ, estimated non-detect. MATRIX SPIKE/MATRIX SPIKE DUPLICATE The matri spike and matri spike duplicate (MS/MSD) are generated to determine the precision and accuracy of the analytical procedure in a given sample matri. This SDG contains rinse blanks only. Therefore an MS/MSD is not required. LABORATORY CONTROL SAMPLE Two laboratory control samples (LCS) were processed along with the samples in this delivery group. The observed recoveries for the TEPH LCS (77%, 84%) were within the established acceptance limits of %. FIELD DUPLICATE Field duplicates are two (or more) field samples collected at the same time in the same location. Each of the samples represents the same population and is carried through all steps of the sampling and analytical procedures in an identical manner. Field duplicate results are used to assess precision of the total method including sampling, analysis, and site heterogeneity. This SDG contains rinse blanks only. Therefore a field duplicate is not required. SYSTEM PERFORMANCE AND OVERALL ASSESSMENT Overall the laboratory data generated met the project goals and quality control criteria, with the eceptions identified in this report and as summarized in Table 1. 7

68 TOTAL SUSPENDED SOLIDS (TSS) HOLDING TIME/SAMPLE HANDLING The amount of an analyte can change with time due to chemical instability, degradation, volatilization, etc. If the specified holding time is eceeded the data may not be valid. Proper sample handling and preservation also play a role in the chemical stability of analytes in the sample matri. If samples are not collected and stored using proper containers and/or preservatives data may not be valid. The sample in this delivery group was prepared and analyzed within the holding time specified in the validation guideline. The sample in this delivery group was received by the laboratory within the proper temperature range as specified in the validation guidance. Further, laboratory documentation indicated that sample containers and sample preservation were as specified in the CSO/SWO QAPP. BLANK CONTAMINATION Quality assurance blanks which include; method, storage, trip, field, or rinse blanks are prepared to identify any contamination, which may have been introduced into the samples during laboratory preparation and analysis or field activity. Method and storage blanks measure laboratory contamination. Trip blanks measure cross contamination during shipment. Field and rinse blanks measure cross contamination during field operations. Method Blanks Method blanks were prepared and analyzed in association with the sample in this delivery group at the specified frequency. Upon eamination of method blank data TSS was positively identified (0.533 mg/l) at a concentration equal to or above the project quantitation limit (PQL). The sample in this delivery group is a rinse blank; therefore qualification of associated result based upon observed rinse blank contamination is not performed in these cases. Field Blanks Sample PR101HLLC contained in this sample delivery group (SDG) is a rinse blank. Upon evaluation, TSS was not detected at or above the PQL in the rinse blank associated with this delivery group. LABORATORY DUPLICATE Laboratory duplicates are generated to determine the precision of the analytical procedure in a given sample matri. This SDG contains a rinse blank only. Therefore a laboratory duplicate is not required. 8

69 TOTAL SUSPENDED SOLIDS (TSS) (Continued) LABORATORY CONTROL SAMPLE A laboratory control sample (LCS) was processed along with the sample in this delivery group. The observed recovery for the TSS LCS (91%) was within the established acceptance limits of %. FIELD DUPLICATE Field duplicates are two (or more) field samples collected at the same time in the same location. Each of the samples represents the same population and is carried through all steps of the sampling and analytical procedures in an identical manner. Field duplicate results are used to assess precision of the total method including sampling, analysis, and site heterogeneity. This SDG contains a rinse blank only. Therefore a field duplicate is not required. SYSTEM PERFORMANCE AND OVERALL ASSESSMENT Overall the laboratory data generated met the project goals and quality control criteria, with the eceptions identified in this report and as summarized in Table 1. 9

70 TOTAL DISSOLVED SOLIDS (TDS) HOLDING TIME/SAMPLE HANDLING The amount of an analyte can change with time due to chemical instability, degradation, volatilization, etc. If the specified holding time is eceeded the data may not be valid. Proper sample handling and preservation also play a role in the chemical stability of analytes in the sample matri. If samples are not collected and stored using proper containers and/or preservatives data may not be valid. The sample in this delivery group was prepared and analyzed within the holding time specified in the validation guideline. The sample in this delivery group was received by the laboratory within the proper temperature range as specified in the validation guidance. Further, laboratory documentation indicated that sample containers and sample preservation were as specified in the CSO/SWO QAPP. BLANK CONTAMINATION Quality assurance blanks which include; method, storage, trip, field, or rinse blanks are prepared to identify any contamination, which may have been introduced into the samples during laboratory preparation and analysis or field activity. Method and storage blanks measure laboratory contamination. Trip blanks measure cross contamination during shipment. Field and rinse blanks measure cross contamination during field operations. Method Blanks Method blanks were prepared and analyzed in association with the samples in this delivery group at the specified frequency. Upon eamination of method blank data no TDS was positively identified at a concentration equal to or above the project quantitation limit (PQL) in any associated method blank. Field Blanks Sample PR101HLLC contained in this sample delivery group (SDG) is a rinse blank. Upon evaluation of the result reported for the rinse blank, TDS was found to be detected at or above the PQL. The sample in this delivery group is a rinse blank; therefore qualification of the associated result based upon observed rinse blank contamination is not performed in this case. LABORATORY DUPLICATE Laboratory duplicates are generated to determine the precision of the analytical procedure in a given sample matri. This SDG contains a rinse blank only. Therefore a laboratory duplicate is not required. 10

71 TOTAL DISSOLVED SOLIDS (TDS) (Continued) LABORATORY CONTROL SAMPLE A laboratory control sample (LCS) was processed along with the samples in this delivery group. The observed recovery for the TDS LCS (82%) was within the established acceptance limits of %. FIELD DUPLICATE Field duplicates are two (or more) field samples collected at the same time in the same location. Each of the samples represents the same population and is carried through all steps of the sampling and analytical procedures in an identical manner. Field duplicate results are used to assess precision of the total method including sampling, analysis, and site heterogeneity. This SDG contains a rinse blank only. Therefore a field duplicate is not required. SYSTEM PERFORMANCE AND OVERALL ASSESSMENT Overall the laboratory data generated met the project goals and quality control criteria, with the eceptions identified in this report and as summarized in Table 1. 11

72 Table 1 Review Elements Summary Were acceptance criteria met? Yes No Total Cyanide Major Minor Holding Time Initial Calibration Continuing Calibration Method Blanks Field Blanks Matri Spike NA Laboratory Duplicate NA Laboratory Control Sample NA Field Duplicate NA Total Organic Carbon Holding Time Initial Calibration Continuing Calibration Method Blanks Field Blanks Matri Spike NA Laboratory Duplicate NA Laboratory Control Sample Field Duplicate NA Total Etractable Petroleum Hydrocarbons Holding Time Initial Calibration Continuing Calibration Method Blanks Field Blanks Surrogate Standards Matri Spike/Matri Spike Duplicate NA Laboratory Control Sample Field Duplicate NA Total Suspended Solids Holding Time Method Blanks Field Blanks Laboratory Duplicate NA Laboratory Control Sample Field Duplicate NA Total Dissolved Solids Holding Time Method Blanks Field Blanks Laboratory Duplicate NA Laboratory Control Sample Field Duplicate NA Major= Major data quality issue identified resulting in rejection of data. Minor= Minor data quality issue identified resulting in the qualification of data. Data qualification should be used to inform the data users of data limitations. NA = Not applicable 12

73 Table 2 Data Validation Qualifiers Qualifier Description EMPC J JH JL M NJ R U UJ Estimated Maimum Possible Concentration (EMPC). Estimated value (bias undetermined) The analyte was positively identified; but the associated numerical value is the approimate concentration of the analyte in the sample. Estimated value (potential high bias) The analyte was positively identified; but the associated numerical value is the approimate concentration, with a potential high bias, of the analyte in the sample. Estimated value (potential low bias) The analyte was positively identified; but the associated numerical value is the approimate concentration, with a potential low bias, of the analyte in the sample. The analytical result reported was obtained from a sediment sample found to contain between 50 and 90 percent moisture and had no other data qualifiers added during the data validating process. The organic analysis indicates the presence of an analyte that has been tentatively identified and the associated numerical value represents its approimate concentration. The sample results are rejected. Due to a significant QA/QC problem, the analysis is invalid and provides no information as to whether the analyte is present or not. Non-detected value The result initially reported as positive by the laboratory was qualified as not detected per USEPA Region II validation guidance, due to an associated quality control failure. Estimated non-detect - The analyte was not detected above the reported sample quantitation limit. However, the reported quantitation limit is approimate and may or may not represent the actual limit of quantitation necessary to accurately and precisely measure the analyte in the sample. UJL Estimated non-detect (potential low bias) The analyte was not detected and the report sample quantitation limit is biased low. 13

74 Table 3 Laboratory Qualifiers Qualifier Description B Inorganics The reported value was obtained from an instrument reading that was less than the project quantitation limit (PQL). Organics The associated analyte was also detected in the method blank. D E The organic analyte was quantitated from a diluted analysis. Inorganics The reported value is estimated because of the presence of interference. Organics The associated compound concentration eceeded the calibration range of the instrument. EMPC G N P U Estimated Maimum Possible Concentration (EMPC). Organic data indicated the presence of a compound that meets the identification criteria; the result is below the PQL but above the MDL. The inorganic analysis is associated with a spike sample not within control limits. The percent difference between the primary and confirmation column for gas chromatography analyses is greater than 25 percent. The analyte was analyzed for, but was not detected above the reported sample quantitation limit. * The inorganic duplicate analysis was not within the established QC limit. 14

75 Validated Data Table

76 Validation Data Table CSO/SWO Investigation Phase I TestAmerica SDG PR137 - Miscellaneous ANALYTE UNITS PR109CFRB LQ VQ PR101HLLC LQ VQ Cyanide ug/l 10.0 U 10.0 U Total Organic Carbon mg/l U Total Dissolved Solids mg/l 23.0 Total Suspended Solids mg/l 0.47 Total Petroleum Hydrocarbons (C8-C40) mg/l 0.28 U UJ GB J LQ - Laboratory Qualifier VQ - Validation Qualifier Page 1 of 1

77 Laboratory Data With Qualifiers Added

78

79

80

81

82

83

84 DATA VALIDATION REPORT CSO/SWO Phase I Vista Analytical Polychlorinated Biphenyl (PCB) Congeners SDG - PR137 Prepared by ENVIRONMENTAL DATA SERVICES, LTD. For TIERRA SOLUTIONS, INC. April 01, Oakhill Dr. Allison Park, PA I

85 DATA VALIDATION REPORT FOR POLYCHLORINATED BIPHENYL (PCB) CONGENERS SITE: CSO/SWO Phase I LABORATORY: Vista Analytical Laboratory SAMPLE DELIVERY GROUP: PR137 This sample delivery group consists of the following samples: PR109CFRB PR101HLLC The samples described above were analyzed via USEPA method 1668A to determine the concentrations of PCB Congeners in water with modification for high volume sample analysis as outlined in the Combined Sewer Overflow/Stormwater Outfall (CSO/SWO) Investigation Quality Assurance Project Plan (QAPP). Project specific quality assurance (QA) objectives, as well as the EDS SOP: Congener PCBs (USEPA 1668A) Rev.3 7/10 were used to perform the PCB congener data validation. Table 1 provides a summary of major and minor data quality issues identified for this data set. All data are acceptable ecept those results which have been qualified with R, rejected. Data validation and laboratory qualifiers along with associated descriptions are provided in Table 2 and Table 3 respectively. All data qualification related to this group of samples is detailed on the attached sheets. Per USEPA Region 2 Validation Guidance, All data users should note two facts. First, the "R" flag means that the associated value is unusable. In other words, due to significant quality control (QC) problems, the analysis is invalid and provides no information as to whether the compound is present or not. "R" values should not appear on data tables even as a last resort. The second, no analyte concentration, even if it has passed all QC tests, is guaranteed to be accurate. Strict QC serves to increase confidence in data but any value potentially contains error. Stephen Gordon Senior Technical Specialist Date: 4/01/14

86 HOLDING TIME/SAMPLE HANDLING The amount of an analyte can change with time due to chemical instability, degradation, volatilization, etc. If the specified holding time is eceeded the data may not be valid. Proper sample handling and preservation also play a role in the chemical stability of analytes in the sample matri. If samples are not collected and stored using proper containers and/or preservatives data may not be valid. The samples in this delivery group were prepared and analyzed within the holding time specified in the validation guideline. The samples in this delivery group were received by the laboratory within the proper temperature range as specified in the validation guidance. Further, laboratory documentation indicated that sample containers and sample preservation were as specified in the CSO/SWO QAPP. CHROMATOGRAPHIC RESOLUTION A performance check solution (combined 209 congener solution) was analyzed at the beginning of every 12-hour analysis period. Upon evaluation of the performance check solution data, all QC criteria were met. Therefore, the data associated with these check standards were not qualified. INITIAL CALIBRATION Data were submitted representing si concentration level initial calibrations. All initial calibrations used during the analysis of samples in this delivery group were contained in the data package. The validator has evaluated the initial calibrations eamining ion ratios, signal to noise ratios, relative retention time and percent relative standard deviation criteria for all PCB congener target analytes and their labeled analogs. Upon eamination of the initial calibration data, all of the criteria listed in method 1668A were met. ROUTINE CALIBRATION A routine calibration standard was evaluated at the beginning of each 12-hour analysis period. The validator has evaluated the routine calibration standard data submitted eamining ion ratios, relative retention time, signal to noise ratios, and concentration reported for all PCB congener target analytes and their labeled analogs. Upon eamination of the routine calibration data, all of the criteria listed in the method 1668A were met. SAMPLE DATA Sample data are reviewed during validation to verify that all analyte specific qualitative requirements are met and that results reported are quantitatively accurate. Specific qualitative and quantitative criteria used to complete these assessments are outlined in Sections; 16.0 and 17.0 of USEPA method 1668A respectively. 2

87 Qualitative Requirements All positively reported results met the established qualitative acceptance criteria. Quantitative Requirements Sample and internal standard concentration calculations were verified and no errors were detected. BLANK CONTAMINATION Quality assurance blanks which included; method, storage, trip, field, or rinse blanks are prepared to identify any contamination, which may have been introduced into the samples during preparation and analysis or field activity. Method and storage blanks measure laboratory contamination. Trip blanks measure cross contamination during shipment. Field and rinse blanks measure cross contamination during field operations. Note, data validation qualification of sample results is based on the maimum contaminant concentration detected in all associated blanks. Method Blanks Method blanks were prepared and analyzed in association with the samples in this delivery group at the specified frequency. Upon eamination of method blank data no analyte was positively identified at a concentration above the estimated detection limit (EDL) in any associated method blank with the eceptions summarized below: ANALYTE B3K0024-BLK1 pg/l LQ a B3K0032-BLK1 pg/l LQ a PCB PCB G --- PCB-20/21/ PCB G --- PCB PCB PCB G --- PCB G --- PCB-41/64/71/ G --- PCB G --- PCB G 1.75 PCB-48/ G --- PCB-52/ PCB G --- PCB-56/ G G PCB-61/ G --- PCB G --- PCB-76/ G --- PCB G G PCB G --- PCB G --- PCB-84/ G --- PCB-90/ G --- PCB-95/98/ G --- PCB-106/ G --- PCB-107/ G --- PCB G --- PCB G --- PCB-128/ G --- PCB-132/ G 3

88 ANALYTE B3H0024-BLK1 pg/l LQ a B3K0032-BLK1 pg/l PCB-138/163/ PCB G --- PCB G --- PCB PCB-182/ G --- PCB G --- PCB G --- LQ a LQ = laboratory qualifier pg/l = picograms per liter a See Table 3 for laboratory qualifier descriptions. The samples in this delivery group are rinse blanks; therefore qualification of associated results based upon observed method blank contamination is not performed in these cases. Field Blanks Samples PR109CFRB and PR101HLLC contained in this sample delivery group (SDG) were field/rinse blanks. Upon evaluation of the results reported for the field/rinse blanks, all target PCB congeners were found to be not detected at or above the EDL with the eceptions summarized below: ANALYTE PR109CFRB pg/l LQ a PR101HLLC pg/l LQ a PCB PCB PCB PCB-5/ PCB B PCB-12/ PCB PCB-16/ PCB G PCB PCB-20/21/ PCB G PCB-24/ PCB G PCB G PCB B PCB B PCB G PCB G PCB-41/64/71/ PCB-42/ G PCB-43/ PCB PCB G G PCB B 1.62 PCB-48/ G 4

89 ANALYTE PR109CFRB pg/l LQ a PR101HLLC pg/l LQ a PCB G --- PCB-52/ PCB G G PCB-56/ G PCB-61/ PCB PCB-76/ G PCB-84/ G PCB-87/117/ G PCB-88/ G --- PCB-90/ PCB-95/98/ PCB G --- PCB G PCB G --- PCB-106/ G PCB PCB-132/ G G PCB G --- PCB-138/163/ PCB-139/ PCB G G PCB G PCB PCB G --- PCB-158/ G --- PCB G PCB G PCB G --- PCB G G PCB B PCB-182/ G PCB G PCB G --- PCB G PCB-196/ PCB G PCB G --- PCB PCB G --- PCB G --- PCB LQ = laboratory qualifier pg/l = picograms per liter a See Table 3 for laboratory qualifier descriptions. FIELD DUPLICATE Field duplicates are two (or more) field samples collected at the same time in the same location. Each of the samples represents the same population and is carried through all steps of the sampling and analytical procedures in an identical manner. Field duplicate results are used to assess precision of the total method, including sampling, analysis, and site heterogeneity. This SDG contains rinse blanks only. Therefore a field duplicate is not required. 5

90 MATRIX SPIKE/MATRIX SPIKE DUPLICATE The matri spike and matri spike duplicate (MS/MSD) are generated to determine the precision and accuracy of the analytical procedure in a given sample matri. This SDG contains rinse blanks only. Therefore a MS/MSD is not required. INTERNAL STANDARDS Internal standards representing the di, tri, tetra, penta, hea, and octa chlorination levels are added to each sample and method blank etract prior to injection. The area counts for each of the recovery standards in each sample must fall within the range +100% to 50% of that observed during the analysis of the mid-level daily calibration check standard. Upon evaluation all internal standard responses were within acceptable limits. LABELED ANALOG STANDARDS Labeled analog standards are added to each sample prior to etraction; the recovery of these standards is evaluated during data validation. Calculated percent recoveries of labeled analog standards were within method and validation acceptance limits without eception. Also, per USEPA's request, labeled analog standard recoveries were evaluated against more stringent acceptance limits of %. Recoveries evaluated met the more stringent criteria in all cases. INITIAL PRECISION AND RECOVERY Initial Precision and Recovery (IPR) Studies are required per USEPA method 1668A, to establish the laboratory s ability to generate data of acceptable precision and recovery. The IPR standards were prepared and analyzed successfully by the laboratory. All observed average concentration and standard deviation values passed method defined acceptance criteria. ONGOING PRECISION AND RECOVERY Ongoing Precision and Recovery (OPR) Standards are prepared and analyzed by the laboratory with each analytical batch to assure that the results produced by the laboratory continue to remain within the limits specified in USEPA method 1668A for precision and recovery. The OPR standards were prepared and analyzed in association with the samples in this delivery group at the required frequency. All observed percent recoveries were within criteria specified in the validation guidance. 6

91 CLEAN-UP RECOVERY STANDARDS A clean-up recovery standard is added to primary sample etracts, prior to further clean-up steps and final concentration. The recovery of the clean-up standard is used to assess the effectiveness of various etract clean-up processes employed and final concentration steps. The clean-up recovery standards ( 13 C PCB 79 and 13 C PCB 178) were successfully recovered from the samples in the delivery group. INTERFERENCES Upon evaluation no chromatographic interferences were noted. OTHER QUALITY CONTROL DATA OUT OF SPECIFICATION None. REPORTING The results on the Form 1 may represent both the initial analysis and diluted analysis when the laboratory provided more than one set of analyses for a given sample location. SYSTEM PERFORMANCE AND OVERALL ASSESSMENT Overall the laboratory data generated met the project goals and quality control criteria, with the eceptions identified in this report and as summarized in Table 1. 7

92 Table 1 Review Elements Summary Were acceptance criteria met? Yes No PCB Congeners Major Minor Holding Time/Sample Handling Chromatographic Resolution Initial Calibration Routine Calibration Qualitative Requirements Quantitative Requirements Method Blanks Field Blanks Field Duplicate NA Matri Spike/Matri Spike Duplicate NA Internal Standards Recovery Standards Labeled Analog Standards Initial Precision and Recovery Ongoing Precision and Recovery Clean-Up Recovery Standards Interferences Other Quality Control Data Out of Specification Major= Major data quality issue identified resulting in rejection of data. Minor= Minor data quality issue identified resulting in the qualification of data. Data qualification should be used to inform the data users of data limitations. NA = Not applicable 8

93 Table 2 Data Validation Qualifiers Qualifier EMPC J JH JL M NJ R U UJ UJL Description Estimated Maimum Possible Concentration (EMPC). Estimated value (bias undetermined) The analyte was positively identified; but the associated numerical value is the approimate concentration of the analyte in the sample. Estimated value (potential high bias) The analyte was positively identified; but the associated numerical value is the approimate concentration, with a potential high bias, of the analyte in the sample. Estimated value (potential low bias) The analyte was positively identified; but the associated numerical value is the approimate concentration, with a potential low bias, of the analyte in the sample. The analytical result reported was obtained from a sediment sample found to contain between 50 and 90 percent moisture and had no other data qualifiers added during the data validating process. The organic analysis indicates the presence of an analyte that has been tentatively identified and the associated numerical value represents its approimate concentration. The sample results are rejected. Due to a significant QA/QC problem, the analysis is invalid and provides no information as to whether the analyte is present or not. Non-detected value - The result initially reported as positive by the laboratory was qualified as not detected per USEPA Region II validation guidance, due to an associated quality control failure. Estimated non-detect - The analyte was not detected above the reported sample quantitation limit. However, the reported quantitation limit is approimate and may or may not represent the actual limit of quantitation necessary to accurately and precisely measure the analyte in the sample. Estimated non-detect (potential low bias) The analyte was not detected and the report sample quantitation limit is biased low. 9

94 Table 3 Laboratory Qualifiers Qualifier Description B Inorganics The reported value was obtained from an instrument reading that was less than the project quantitation limit (PQL). Organics The associated analyte was also detected in the method blank. D E The organic analyte was quantitated from a diluted analysis. Inorganics The reported value is estimated because of the presence of an interference. Organics The associated compound concentration eceeded the calibration range of the instrument. EMPC G N P U Estimated Maimum Possible Concentration (EMPC). Organic data indicated the presence of a compound that meets the identification criteria; the result is below the PQL but above the MDL. The inorganic analysis is associated with a spike sample not within control limits. The percent difference between the primary and confirmation column for gas chromatography analyses is greater than 25 percent. The analyte was analyzed for, but was not detected above the reported sample quantitation limit. * The inorganic duplicate analysis was not within the established QC limit. 10

95 Validated Data Table

96 Validation Data Table CSO/SWO Investigation Phase I Vista Analytical SDG PR137 - PCB Congeners ANALYTE UNITS PR109CFRB LQ VQ PR101HLLC LQ VQ PCB-1 pg/l U PCB-2 pg/l U PCB-3 pg/l U PCB-4/10 pg/l 2.87 U 1.51 U PCB-5/8 pg/l PCB-6 pg/l 2.44 UI 1.29 U PCB-7/9 pg/l 2.16 U 1.27 U PCB-11 pg/l B PCB-12/13 pg/l U PCB-14 pg/l 1.32 EMPC 1.20 U PCB-15 pg/l U PCB-16/32 pg/l PCB-17 pg/l G PCB-18 pg/l PCB-19 pg/l U U PCB-20/21/33 pg/l PCB-22 pg/l G PCB-23 pg/l U U PCB-24/27 pg/l U PCB-25 pg/l U G PCB-26 pg/l G PCB-28 pg/l B PCB-29 pg/l U U PCB-30 pg/l U U PCB-31 pg/l B PCB-34 pg/l U U PCB-35 pg/l U U PCB-36 pg/l U U PCB-37 pg/l G PCB-38 pg/l U U PCB-39 pg/l U U PCB-40 pg/l EMPC G PCB-41/64/71/72 pg/l 2.78 EMPC 1.20 PCB-42/59 pg/l G PCB-43/49 pg/l LQ - Laboratory Qualifier VQ - Validation Qualifier Page 1 of 5

97 Validation Data Table CSO/SWO Investigation Phase I Vista Analytical SDG PR137 - PCB Congeners ANALYTE UNITS PR109CFRB LQ VQ PR101HLLC LQ VQ PCB-44 pg/l PCB-45 pg/l G G PCB-46 pg/l U U PCB-47 pg/l 4.33 B 1.62 PCB-48/75 pg/l EMPC G PCB-50 pg/l U U PCB-51 pg/l G U PCB-52/69 pg/l PCB-53 pg/l G G PCB-54 pg/l U U PCB-55 pg/l U U PCB-56/60 pg/l G PCB-57 pg/l U U PCB-58 pg/l U U PCB-61/70 pg/l 2.48 EMPC 1.17 PCB-62 pg/l U U PCB-63 pg/l U U PCB-65 pg/l U U PCB-67 pg/l U U PCB-68 pg/l EMPC EMPC PCB-73 pg/l U U PCB-74 pg/l EMPC PCB-76/66 pg/l G PCB-77 pg/l U U PCB-78 pg/l U U PCB-79 pg/l U U PCB-80 pg/l U U PCB-81 pg/l U U PCB-82 pg/l U U PCB-83 pg/l U U PCB-84/92 pg/l G PCB-85/116 pg/l U U PCB-86 pg/l U U PCB-87/117/125 pg/l G PCB-88/91 pg/l G U LQ - Laboratory Qualifier VQ - Validation Qualifier Page 2 of 5

98 Validation Data Table CSO/SWO Investigation Phase I Vista Analytical SDG PR137 - PCB Congeners ANALYTE UNITS PR109CFRB LQ VQ PR101HLLC LQ VQ PCB-89 pg/l U U PCB-90/101 pg/l 2.66 EMPC 1.35 PCB-93 pg/l U U PCB-94 pg/l U 0.47 U PCB-95/98/102 pg/l 2.25 EMPC 1.04 PCB-96 pg/l U U PCB-97 pg/l G U PCB-99 pg/l G PCB-100 pg/l U U PCB-103 pg/l U U PCB-104 pg/l U U PCB-105 pg/l G EMPC PCB-106/118 pg/l G PCB-107/109 pg/l U U PCB-108/112 pg/l U U PCB-110 pg/l PCB-111/115 pg/l U U PCB-113 pg/l U U PCB-114 pg/l U U PCB-119 pg/l U U PCB-120 pg/l U U PCB-121 pg/l U U PCB-122 pg/l U U PCB-123 pg/l U U PCB-124 pg/l U U PCB-126 pg/l U U PCB-127 pg/l U U PCB-128/162 pg/l U U PCB-129 pg/l U U PCB-130 pg/l U U PCB-131 pg/l U U PCB-132/161 pg/l G G PCB-133/142 pg/l U U PCB-134/143 pg/l U U PCB-135 pg/l U U LQ - Laboratory Qualifier VQ - Validation Qualifier Page 3 of 5

99 Validation Data Table CSO/SWO Investigation Phase I Vista Analytical SDG PR137 - PCB Congeners ANALYTE UNITS PR109CFRB LQ VQ PR101HLLC LQ VQ PCB-136 pg/l G U PCB-137 pg/l U U PCB-138/163/164 pg/l PCB-139/149 pg/l PCB-140 pg/l U U PCB-141 pg/l G G PCB-144 pg/l U U PCB-145 pg/l U U PCB-146/165 pg/l U U PCB-147 pg/l U U PCB-148 pg/l U U PCB-150 pg/l U U PCB-151 pg/l G PCB-152 pg/l U U PCB-153 pg/l 2.38 EMPC 1.26 PCB-154 pg/l U U PCB-155 pg/l U U PCB-156 pg/l G U PCB-157 pg/l U U PCB-158/160 pg/l G U PCB-159 pg/l U U PCB-166 pg/l U U PCB-167 pg/l U U PCB-168 pg/l U U PCB-169 pg/l U U PCB-170 pg/l G PCB-171 pg/l EMPC U PCB-172 pg/l U U PCB-173 pg/l U U PCB-174 pg/l G PCB-175 pg/l U U PCB-176 pg/l U U PCB-177 pg/l G U PCB-178 pg/l U U PCB-179 pg/l G G LQ - Laboratory Qualifier VQ - Validation Qualifier Page 4 of 5

100 Validation Data Table CSO/SWO Investigation Phase I Vista Analytical SDG PR137 - PCB Congeners ANALYTE UNITS PR109CFRB LQ VQ PR101HLLC LQ VQ PCB-180 pg/l B PCB-181 pg/l U U PCB-182/187 pg/l G PCB-183 pg/l G PCB-184 pg/l U U PCB-185 pg/l EMPC U PCB-186 pg/l U U PCB-188 pg/l U U PCB-189 pg/l U U PCB-190 pg/l G U PCB-191 pg/l U U PCB-192 pg/l U U PCB-193 pg/l U U PCB-194 pg/l G PCB-195 pg/l EMPC EMPC PCB-196/203 pg/l EMPC PCB-197 pg/l U U PCB-198 pg/l U U PCB-199 pg/l 2.15 EMPC G PCB-200 pg/l G U PCB-201 pg/l U U PCB-202 pg/l U U PCB-204 pg/l U U PCB-205 pg/l U U PCB-206 pg/l U PCB-207 pg/l G U PCB-208 pg/l G U PCB-209 pg/l U LQ - Laboratory Qualifier VQ - Validation Qualifier Page 5 of 5

101 Laboratory Data With Qualifiers Added

102

103

104

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108 DATA VALIDATION REPORT CSO/SWO Phase I Vista Analytical Organochlorine Pesticides SDG - PR137 Prepared by ENVIRONMENTAL DATA SERVICES, LTD. For TIERRA SOLUTIONS, INC. February 26, Oakhill Dr. Allison Park, PA I

109 DATA VALIDATION REPORT FOR ORGANOCHLORINE PESTICIDES SITE: CSO/SWO Phase I LABORATORY: Vista Analytical Laboratory SAMPLE DELIVERY GROUP: PR137 This sample delivery group consists of the following samples: PR109CFRB PR101HLLC The samples described above were analyzed via USEPA method 1699 to determine the concentrations of organochlorine pesticides in water with modification for high volume sample analysis as outlined in the Combined Sewer Overflow/Stormwater Outfall (CSO/SWO) Investigation Quality Assurance Project Plan (QAPP). Project specific quality assurance (QA) objectives, as well as the EDS SOP: Organochlorine Pesticides by HRGC/HRMS, USEPA 1699, Rev.0 7/10 were used to perform the organochlorine pesticide data validation. Table 1 provides a summary of major and minor data quality issues identified for this data set. All data are acceptable ecept those results which have been qualified with R, rejected. Data validation and laboratory qualifiers along with associated descriptions are provided in Table 2 and Table 3 respectively. All data qualification related to this group of samples is detailed on the attached sheets. Per USEPA Region 2 Validation Guidance, All data users should note two facts. First, the "R" flag means that the associated value is unusable. In other words, due to significant quality control (QC) problems, the analysis is invalid and provides no information as to whether the compound is present or not. "R" values should not appear on data tables even as a last resort. The second, no analyte concentration, even if it has passed all QC tests, is guaranteed to be accurate. Strict QC serves to increase confidence in data but any value potentially contains error. Stephen Gordon Senior Technical Specialist Date: 2/26/14

110 HOLDING TIME/SAMPLE HANDLING The amount of an analyte can change with time due to chemical instability, degradation, volatilization, etc. If the specified holding time is eceeded the data may not be valid. Proper sample handling and preservation also play a role in the chemical stability of analytes in the sample matri. If samples are not collected and stored using proper containers and/or preservatives data may not be valid. The samples in this delivery group were prepared and analyzed within the holding time specified in the validation guideline. The samples in this delivery group were received by the laboratory within the proper temperature range as specified in the validation guidance. Further, laboratory documentation indicated that sample containers and sample preservation were as specified in the CSO/SWO QAPP. RETENTION TIME CALIBRATION Retention time criteria were evaluated based upon the absolute retention time of methoychlor as observed in the continuing calibration verifications analyzed at the beginning of every 12-hour analysis period. The absolute retention time of methoychlor must eceed 39 minutes. This criteria have been established to insure that interferences are resolved from analytes of interest in environmental samples. Upon evaluation of the continuing calibration retention time data, the observed absolute retention time of methoychlor was greater than 39 minutes in all cases. ENDRIN/4,4 -DDT BREAKDOWN A standard solution containing endrin and 4,4 -DDT is analyzed following the initial and/or continuing calibrations. The results obtained for these primary analytes and corresponding breakdown products are then evaluated to determine the percentage of decomposition of the analytes during processing through the gas chromatograph. Percent breakdown of endrin and/or 4,4-DDT must not eceed 20%. Upon evaluation of the breakdown check standard data, all of the criteria outlined above were met. INITIAL CALIBRATION Data were submitted representing si concentration level initial calibrations. All initial calibrations used during the analysis of the sample in this delivery group were contained in the data package. The validator has evaluated the initial calibrations eamining ion ratios, signal to noise ratios, relative retention time and percent relative standard deviation criteria for all organochlorine pesticide target analytes and their labeled analogs. Upon eamination of the initial calibration data, all of the criteria listed in the validation guidance were met. 2

111 ROUTINE CALIBRATION A routine calibration standard was evaluated at the beginning of each 12-hour analysis period. The validator has evaluated the routine calibration standard data submitted eamining ion ratios, relative retention time, signal to noise ratios, and concentration reported for all organochlorine pesticide target analytes and their labeled analogs. Upon eamination of the routine calibration data, all of the criteria listed in the validation guidance were met. SECOND SOURCE STANDARD EVALUATION A calibration standard obtained from an independent source from that used during instrument calibration was evaluated at the beginning of each 12-hour analysis period as required. The validator has evaluated the results of the second source standard to verify that all target analyte organochlorine pesticides are present in the standard solution and that all observed recoveries fall within the required acceptance range of %. Upon eamination of the second source standard data, all of the criteria listed above were met. SAMPLE DATA Sample data are reviewed during validation to verify that all analyte specific qualitative requirements are met and that results reported are quantitatively accurate. Specific qualitative and quantitative criteria used to complete these assessments are outlined in Sections 16.0 and 17.0 of USEPA method 1699 respectively. Qualitative Requirements All positively reported results met method established qualitative acceptance criteria, with one eception. The lock mass ion signal shows a greater than 20% peak deflection within the retention time window for 4,4 -DDE in sample PR109CFRB. The affected analyte result has been qualified "J", estimated on this basis. Quantitative Requirements Sample results and internal standard concentration calculations were verified and no errors were detected. BLANK CONTAMINATION Quality assurance blanks which include; method, storage, trip, field, or rinse blanks are prepared to identify any contamination, which may have been introduced into the samples during laboratory preparation and analysis or field activity. Method and storage blanks measure laboratory contamination. Trip blanks measure cross contamination during shipment. Field and rinse blanks measure cross contamination during field operations. 3

112 Method Blanks Method blanks were prepared and analyzed in association with the sample in this delivery group at the specified frequency. Upon eamination of method blank data no analyte was positively identified at a concentration equal to or above the estimated detection limit (EDL) in any associated method blank with the eceptions summarized below: Method Blank ANALYTE pg/l LQ a Heachlorobenzene 9.44 G LQ = laboratory qualifier pg/l = picograms per liter a See Table 3 for laboratory qualifier descriptions. The samples in this delivery group are rinse blanks; therefore qualification of associated results based upon observed method blank contamination is not performed in these cases. Field Blanks Samples PR109CFRB and PR101HLLC contained in this sample delivery group (SDG) were rinse blanks. Upon evaluation of the results reported for the rinse blanks, all target organochlorine pesticides were found to be not detected at or above the EDL with the eceptions summarized below: Analyte PR109CFRB pg/l LQ a PR101HLLC pg/l LQ a Heachlorobenzene ,4 -DDE ,4'-DDE Dieldrin 6.13 G 3.16 G 2,4'-DDD G 2,4'-DDT G 4,4'-DDD G 4,4'-DDT 3270 D --- LQ = laboratory qualifier pg/l = picograms per liter a See Table 3 for laboratory qualifier descriptions. FIELD DUPLICATE Field duplicates are two (or more) field samples collected at the same time in the same location. Each of the samples represents the same population and is carried through all steps of the sampling and analytical procedures in an identical manner. Field duplicate results are used to assess precision of the total method, including sampling, analysis, and site heterogeneity. This SDG contains rinse blanks only. Therefore a field duplicate is not required. 4

113 MATRIX SPIKE/MATRIX SPIKE DUPLICATE The matri spike and matri spike duplicate (MS/MSD) are generated to determine the precision and accuracy of the analytical procedure in a given sample matri. This SDG contains rinse blanks only. Therefore a MS/MSD is not required. INTERNAL STANDARDS Internal standards are added to each sample and method blank etract prior to injection. The area counts for each of the recovery standards in each sample must fall within the range +100% to 50% of that observed during the analysis of the mid-level daily calibration check standard. Upon evaluation, all internal standard responses were within acceptable limits. LABELED ANALOG STANDARDS Labeled analog standards are added to each sample prior to etraction; the recovery of these standards is evaluated during data validation. Calculated percent recoveries of labeled analog standards were within method and validation acceptance limits without eception. Also, per USEPA's request, labeled analog standard recoveries were evaluated against more stringent acceptance limits of %. Recoveries evaluated met the more stringent criteria with one eception. The recovery of 13C6-beta-BHC (47.2%) in sample PR109CFRB failed to meet these acceptance limits. The associated analyte was qualified UJ estimated non-detect. INITIAL PRECISION AND RECOVERY Initial Precision and Recovery (IPR) Studies are required per USEPA method 1699, to establish the laboratory s ability to generate data of acceptable precision and recovery. The IPR standards were prepared and analyzed successfully by the laboratory. All observed average concentration and standard deviation values passed method defined acceptance criteria. ONGOING PRECISION AND RECOVERY Ongoing Precision and Recovery (OPR) Standards are prepared and analyzed by the laboratory with each analytical batch to assure that the results produced by the laboratory continue to remain within the limits specified in USEPA method 1699 for precision and recovery. The OPR standards were prepared and analyzed in association with the samples in this delivery group at the required frequency. All observed percent recoveries were within criteria specified in the validation guidance. 5

114 OTHER QUALITY CONTROL DATA OUT OF SPECIFICATION None. SYSTEM PERFORMANCE AND OVERALL ASSESSMENT Overall the laboratory data generated met the project goals and quality control criteria, with the eceptions identified in this report and as summarized in Table 1. 6

115 Table 1 Review Elements Summary Were acceptance criteria met? Yes No Organochlorine Pesticides Major Minor Holding Time/Sample Handling Retention Time Calibration Endrin/4,4'-DDT Breakdown Initial Calibration Routine Calibration Second Source Standard Evaluation Qualitative Requirements Quantitative Requirements Method Blanks Field Blanks Field Duplicate NA Matri Spike/Matri Spike Duplicate NA Internal Standard Labeled Analog Standards Initial Precision and Recovery Ongoing Precision and Recovery Other Quality Control Data Out of Specification Major= Major data quality issue identified resulting in rejection of data. Minor= Minor data quality issue identified resulting in the qualification of data. Data qualification should be used to inform the data users of data limitations. NA = Not applicable 7

116 Table 2 Data Validation Qualifiers Qualifier EMPC J JH JL M NJ R U UJ UJL Description Estimated Maimum Possible Concentration (EMPC). Estimated value (bias undetermined) The analyte was positively identified; but the associated numerical value is the approimate concentration of the analyte in the sample. Estimated value (potential high bias) The analyte was positively identified; but the associated numerical value is the approimate concentration, with a potential high bias, of the analyte in the sample. Estimated value (potential low bias) The analyte was positively identified; but the associated numerical value is the approimate concentration, with a potential low bias, of the analyte in the sample. The analytical result reported was obtained from a sediment sample found to contain between 50 and 90 percent moisture and had no other data qualifiers added during the data validating process. The organic analysis indicates the presence of an analyte that has been tentatively identified and the associated numerical value represents its approimate concentration. The sample results are rejected. Due to a significant QA/QC problem, the analysis is invalid and provides no information as to whether the analyte is present or not. Non-detected value - The result initially reported as positive by the laboratory was qualified as not detected per USEPA Region II validation guidance, due to an associated quality control failure. Estimated non-detect - The analyte was not detected above the reported sample quantitation limit. However, the reported quantitation limit is approimate and may or may not represent the actual limit of quantitation necessary to accurately and precisely measure the analyte in the sample. Estimated non-detect (potential low bias) The analyte was not detected and the report sample quantitation limit is biased low. 8

117 Table 3 Laboratory Qualifiers Qualifier B Description Inorganics The reported value was obtained from an instrument reading that was less than the project quantitation limit (PQL). Organics The associated analyte was also detected in the method blank. D E The organic analyte was quantitated from a diluted analysis. Inorganics The reported value is estimated because of the presence of an interference. Organics The associated compound concentration eceeded the calibration range of the instrument. EMPC G N P U Estimated Maimum Possible Concentration (EMPC). Organic data indicated the presence of a compound that meets the identification criteria; the result is below the PQL but above the MDL. The inorganic analysis is associated with a spike sample not within control limits. The percent difference between the primary and confirmation column for gas chromatography analyses is greater than 25 percent. The analyte was analyzed for, but was not detected above the reported sample quantitation limit. * The inorganic duplicate analysis was not within the established QC limit. 9

118 Validated Data Table

119 Validation Data Table CSO/SWO Investigation Phase I Vista Analytical SDG PR137 - Organochlorine Pesticides ANALYTE UNITS PR109CFRB LQ VQ PR101HLLC LQ VQ Heachlorobenzene pg/l alpha-bhc pg/l 3.75 U 2.65 U Lindane (gamma-bhc) pg/l 4.98 U 3.41 U beta-bhc pg/l 6.04 U UJ 5.15 U delta-bhc pg/l 3.41 U 2.51 U Heptachlor pg/l 2.64 EMPC 1.45 EMPC Aldrin pg/l 2.88 U 2.87 U Oychlordane pg/l 7.45 U 6.44 U cis-heptachlor Epoide pg/l 6.59 U 5.59 U trans-chlordane (gamma) pg/l 7.85 U 6.73 U trans-nonachlor pg/l 7.27 U 6.02 U cis-chlordane (alpha) pg/l 6.95 U 5.76 U Endosulfan I (alpha) pg/l 9.95 U 9.75 U 2,4'-DDE pg/l U 4,4'-DDE pg/l 202 J 5.20 U Dieldrin pg/l 6.13 G 3.16 G Endrin pg/l 4.19 U 3.09 U cis-nonachlor pg/l 5.43 U 3.60 U Endosulfan II (beta) pg/l 14.3 U 10.5 U 2,4'-DDD pg/l G 2,4'-DDT pg/l G 4,4'-DDD pg/l G 4,4'-DDT pg/l 3270 D 37.2 EMPC Endosulfan Sulfate pg/l 15.0 U 11.3 U 4,4'-Methoychlor pg/l 8.69 UD 6.24 UD Mire pg/l 3.50 UD 1.51 U Endrin Aldehyde pg/l 18.1 U 12.3 U Endrin Ketone pg/l 7.81 UD 4.53 U LQ - Labatory Qualifier VQ - Validation Qualifier Page 1 of 1

120 Laboratory Data With Qualifiers Added

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122

123 DATA VALIDATION REPORT CSO/SWO Phase I TestAmerica Semivolatile SDG - PR137 Prepared by ENVIRONMENTAL DATA SERVICES, LTD. For TIERRA SOLUTIONS, INC. April 03, Oakhill Dr. Allison Park, PA I

124 DATA VALIDATION REPORT FOR SEMIVOLATILES SITE: CSO/SWO Phase I LABORATORY: TestAmerica SAMPLE DELIVERY GROUP: PR137 This sample delivery group consists of the following samples: PR109CFRB PR101HLLC The samples described above were analyzed via USEPA CLP SOM01.2 to determine the concentrations of semivolatile organic analytes (SVOAs) in water samples with modification for high volume sample analysis as outlined in the Combined Sewer Overflow/Stormwater Outfall (CSO/SWO) Investigation Quality Assurance Project Plan (QAPP). Project specific quality assurance (QA) objectives, as well as the USEPA Region II SOP, USEPA Contract Laboratory Program Statement of Work for Organic Analysis of Low/Medium Concentration of Semivolatile Organic Compounds SOM01.2 Data Validation, HW-35/SVOA Rev. 1, August 2007, have been considered during validation of this data and its usability. Table 1 provides a summary of major and minor data quality issues identified for this data set. All data are acceptable ecept those results which have been qualified with R, rejected. Data validation and laboratory qualifiers along with associated descriptions are provided in Table 2 and Table 3 respectively. All data qualification related to this group of samples is detailed on the attached sheets. Per USEPA Region 2 Validation Guidance, All data users should note two facts. First, the "R" flag means that the associated value is unusable. In other words, due to significant quality control (QC) problems, the analysis is invalid and provides no information as to whether the compound is present or not. "R" values should not appear on data tables even as a last resort. The second, no analyte concentration, even if it has passed all QC tests, is guaranteed to be accurate. Strict QC serves to increase confidence in data but any value potentially contains error. Elise Francken Senior Technical Specialist Date: 4/02/14

125 HOLDING TIME/SAMPLE HANDLING The amount of an analyte can change with time due to chemical instability, degradation, volatilization, etc. If the specified holding time is eceeded the data may not be valid. Proper sample handling and preservation also play a role in the chemical stability of analytes in the sample matri. If samples are not collected and stored using proper containers and/or preservatives data may not be valid. The samples in this delivery group were prepared and analyzed within the holding time specified in the validation guideline. The samples in this delivery group were received by the laboratory within the proper temperature range as specified in the validation guidance. Further, laboratory documentation indicated that sample containers and sample preservation were as specified in the CSO/SWO QAPP. BLANK CONTAMINATION Quality assurance blanks which include; method, storage, trip, field, or rinse blanks are prepared to identify any contamination, which may have been introduced into the samples during laboratory preparation and analysis or field activity. Method and storage blanks measure laboratory contamination. Trip blanks measure cross contamination during shipment. Field and rinse blanks measure cross contamination during field operations. Method Blanks Method blanks were prepared and analyzed in association with the sample in this delivery group at the specified frequency. Upon eamination of method blank data no target analyte was positively identified at a concentration equal to or above the method detection limit (MDL) in the associated method blank with the eception summarized below: Method Blank ANALYTE ug/l LQ a Bis(2-ethylheyl)phthalate G LQ = laboratory qualifier µg/l = microgram per liter a See table 3 for laboratory qualifier descriptions The samples in this delivery group are rinse blanks; therefore qualification of associated results based upon observed method blank contamination is not performed in these cases. Field Blanks Samples PR109CFRB and PR101HLLC contained in this sample delivery group (SDG) are rinse blanks. Upon evaluation of the results reported for the rinse blanks, all target semivolatiles were found to be not detected at or above the MDL with the eception summarized below: PR109CFRB PR101HLLC Analyte ug/l LQ a µg/l LQ a Bis(2-ethylheyl)phthalate 0.48 G,B 0.45 G,B LQ = laboratory qualifier µg/l = microgram per liter a See table 3 for laboratory qualifier descriptions 2

126 MASS SPECTROMETER TUNING Tuning and performance criteria are established to ensure adequate mass resolution, proper identification of compounds, and to some degree, sufficient instrument sensitivity. These criteria are not sample specific. Instrument performance is determined using standard materials. Therefore, these criteria should be met in all circumstances. The tuning standard for semivolatiles is decafluorotriphenylphosphine (DFTPP). All tunes associated with this SDG were fully compliant. CALIBRATION Satisfactory instrument calibration is established to ensure that the instrument is capable of producing acceptable quantitative results. The initial calibration curve demonstrates that the instrument is capable of giving acceptable performance at the beginning of an analytical sequence. The continuing calibration verifies that the instrument is continuing to provide satisfactory daily performance. Additionally, a continuing calibration is analyzed at the end of each 12-hour analytical sequence, denoted as a closing calibration verification and ascertains acceptable performance at the conclusion of the analytical sequence. Response Factor The relative response factor (RRF) measures the instruments responses to specific chemical compounds. The RRF factors for the base neutral acid (BNA) or semivolatile target compound list (TCL) analytes must be 0.05 or > 0.01 for poor performers in both the initial and continuing calibrations. Note analytes identified as "poor performers" per validation guidance are listed below. Additionally, the RRF in the closing continuing calibration must be A value less than the respective criteria indicates serious detection and quantitation problems. If the mean RRF of the initial calibration or the continuing calibration RRF is < 0.05 for any analyte other than the poor performers, or < 0.01 for the poor performers, or the RRF for the closing continuing calibration is < 0.01 for any analyte, those analytes detected in environmental samples will be qualified as estimated. All non-detects for those analytes will be rejected. Analytes Identified as Poor Responders 2,2'-Oybis(1-chloropropane) 4-Chloroaniline Heachlorobutadiene Heachlorocyclopentadiene 2-Nitroaniline 3-Nitroaniline 2,4'-Dinitrophenol 4-Nitrophenol Acetophenone Caprolactam Atrazine Di-n-butylphthalate Bis-2(ethylheyl)phthalate Benzaldehyde 4-Nitroaniline 4,6-Dinitro-2-methylphenol N-Nitrosodiphenylamine 3,3'Dichlorobenzidine 1,1'Biphenyl Dimethylphthalate Diethylphthalate 1,2,4,5-Tetrachlorobenzene Carbazole Butylbenzylphthalate Di-n-octylphthalate The RRF values in all initial and continuing calibrations were found to be acceptable in all cases. 3

127 Percent Relative Standard Deviation and Percent Deviation Percent relative standard deviation (%RSD) is calculated from the initial calibration and is used to indicate stability of a specific compound over the calibration range. Percent deviation (%D) compares the response factor of the continuing calibration with the mean response factor of the initial calibration. Therefore, %D is a measure of the instruments daily performance. The following QC criteria have been applied for this project: The %RSD of initial calibration must be < 20% or < 40% for poor performers. A RSD value outside the initial calibration limit indicates the potential for quantitation errors. For this reason, all positive results are qualified as estimated. Severe performance failures (RSD > 90%) require qualification of non-detected results as well. The %D for opening continuing calibration must be < 25% or < 40% for poor performers. The %D for closing calibration must be <50%. A value outside these limits indicates the potential for detection and quantitation errors. For these reasons, all positive results are qualified as estimated, and non-detects are qualified with "UJ". All initial calibration and continuing calibration %RSD and %D values were within defined QC criteria with the eceptions identified below. The %RSD for 2-chloronaphthalene (26.6%) and 4-bromophenyl-phenylether (27.0%) eceeded the above acceptance limits in the initial calibration. All samples were associated with this noncompliant calibration. Both analytes were non-detect in the associated samples, therefore per validation guidance no qualification was necessary. The opening continuing calibration standard on October 31, 2013 ehibited non-compliant %D for pentachlorophenol (-26.0%). This opening standard was associated with results reported for all samples. Pentachlorophenol was not detected in the associated samples, therefore per validation guidance the nondetected results have been qualified, UJ estimated non-detect. The closing continuing calibration standard on October 31, 2013 ehibited non-compliant %D for the following analytes. Analyte %D 2,4-Dinitrophenol Pentachlorophenol This closing standard was associated with results reported for all samples. The sample results for 2,4-Dinitrophenol have been qualified, UJ estimated non-detect. Pentachlorophenol was previously qualified due to the non-compliant opening calibration therefore no further qualification was necessary 4

128 INTERNAL STANDARDS PERFORMANCE Internal standard performance criteria are meant to ensure that the gas chromatography/mass spectrometry (GC/MS) sensitivity and response are stable during every eperimental run. The internal standard area count must not vary by more than a factor of two from the associated continuing calibration standard. The retention time of the internal standard must not vary by more than +/- 30 seconds from the associated continuing calibration standard. The area count must be within - 50% to 200% range of the associated standard. If area count is > 200% non-detected results are not qualified while positive results are qualified "J', estimated. However when an observed area count is < 50% positive results are qualified "J" estimated while non-detected results are rejected. The reported sample analysis and associated method blank had internal standard areas within QC criteria in all cases. SURROGATES All samples are spiked with surrogate compounds prior to sample preparation and analyses to evaluate overall laboratory performance and efficiency of the analytical technique. The reported sample analyses and method blank had observed surrogate recoveries within the established limits. Also, per USEPA's request, surrogate recoveries were evaluated against more stringent acceptance limits of %. The reported sample analyses and method blank had observed surrogate recoveries within these established limits with the eceptions summarized below: Sample Surrogate Affected Compounds PR109CFRB Bis(2-chloroethyl)ether-d8 Bis(2-chloroethyl)ether 2,2 Oybis(1-chloropropane) Bis(2-chloroethoy)methane PR109CFRB 2-chlorophenol-d4 2-Chlorophenol PR109CFRB 4-chloroaniline-d4 4-Chloroaniline Heachlorocyclopentadiene 3,3 Dichlorbenzidine PR109CFRB PR101HLLC PR109CFRB PR101HLLC 4-nitrophenol-d4 4,6-Dinitro-2-methylphenol-d2 2-Nitroaniline 3-Nitroaniline 2,4-Dinitrophenol 4-Nitrophenol 4-Nitroaniline 4,6-Dinitro-2-methylphenol The observed surrogate recoveries were lower than the lowest acceptance limit in all cases. All affected analyte results were non-detect, therefore affected analyte results not previously qualified have been qualified, UJL estimated non-detect potential low bias. 5

129 COMPOUND IDENTIFICATION Semivolatile The TCL compounds are identified on the GC/MS by using the analytes relative retention time (RRT) and ion spectra. For the results to be a positive hit, the sample peak must be within RRT units of the standard compound, and have ion spectra which has a ratio of the primary and secondary ion intensities within 20% of that in the standard compound. In the cases where there is not an adequate ion spectrum match, the laboratory may have provided false positive identifications. All identification criteria were met. Therefore, no analytes were qualified for compound identification. MATRIX SPIKE/MATRIX SPIKE DUPLICATE The matri spike and matri spike duplicate (MS/MSD) are generated to determine the precision and accuracy of the analytical procedure in a given sample matri. This SDG contains rinse blanks only. Therefore a MS/MSD is not required. REPORTING This package did not contain re-etraction, re-analysis or dilution. OTHER QUALITY CONTROL DATA OUT OF SPECIFICATION None. FIELD DUPLICATE Field duplicates are two (or more) field samples collected at the same time in the same location. Each of the samples represent the same population and are carried through all steps of the sampling and analytical procedures in an identical manner. Field duplicate results are used to assess precision of the total method, including sampling, analysis, and site heterogeneity. This SDG contains rinse blanks only. Therefore a field duplicate is not required. SYSTEM PERFORMANCE AND OVERALL ASSESSMENT Overall the laboratory data generated met the project goals and quality control criteria, with the eceptions identified in this report and as summarized in Table 1. 6

130 Table 1 Review Elements Summary Were acceptance criteria met? Yes No Semivolatile Organics Major Minor Holding Time/Sample Handling Method Blanks Field Blanks Mass Spectrometer Tuning Response Factor Percent Relative Standard Deviation and Percent Deviation Internal Standards Performance Surrogates Compound Identification - Semivolatile Matri Spike/Matri Spike Duplicate NA Reporting Other Quality Control Data out of Specification NA Field Duplicate NA Major= Major data quality issue identified resulting in rejection of data. Minor= Minor data quality issue identified resulting in the qualification of data. Data qualification should be used to inform the data users of data limitations. NA = Not applicable 7

131 Table 2 Data Validation Qualifiers Qualifier Description EMPC J JH JL M NJ R U UJ UJL Estimated Maimum Possible Concentration (EMPC). Estimated value (bias undetermined) The analyte was positively identified; but the associated numerical value is the approimate concentration of the analyte in the sample. Estimated value (potential high bias) The analyte was positively identified; but the associated numerical value is the approimate concentration, with a potential high bias, of the analyte in the sample. Estimated value (potential low bias) The analyte was positively identified; but the associated numerical value is the approimate concentration, with a potential low bias, of the analyte in the sample. The analytical result reported was obtained from a sediment sample found to contain between 50 and 90 percent moisture and had no other data qualifiers added during the data validating process. The organic analysis indicates the presence of an analyte that has been tentatively identified and the associated numerical value represents its approimate concentration. The sample results are rejected. Due to a significant QA/QC problem, the analysis is invalid and provides no information as to whether the analyte is present or not. Non-detected value The result initially reported as positive by the laboratory was qualified as not detected per USEPA Region II validation guidance, due to an associated quality control failure. Estimated non-detect - The analyte was not detected above the reported sample quantitation limit. However, the reported quantitation limit is approimate and may or may not represent the actual limit of quantitation necessary to accurately and precisely measure the analyte in the sample. Estimated non-detect (potential low bias) The analyte was not detected and the report sample quantitation limit is biased low. 8

132 Table 3 Laboratory Qualifiers Qualifier Description B Inorganics The reported value was obtained from an instrument reading that was less than the project quantitation limit (PQL). Organics The associated analyte was also detected in the method blank. D E The organic analyte was quantitated from a diluted analysis. Inorganics The reported value is estimated because of the presence of an interference. Organics The associated compound concentration eceeded the calibration range of the instrument. EMPC G N P U Estimated Maimum Possible Concentration (EMPC). Organic data indicated the presence of a compound that meets the identification criteria; the result is below the PQL but above the MDL. The inorganic analysis is associated with a spike sample not within control limits. The percent difference between the primary and confirmation column for gas chromatography analyses is greater than 25 percent. The analyte was analyzed for, but was not detected above the reported sample quantitation limit. * The inorganic duplicate analysis was not within the established QC limit. 9

133 Validated Data Table

134 Validation Data Table CSO/SWO Investigaiton Phase I TestAmerica SDG PR137 - Semivolatiles ANALYTE UNITS PR109CFRB LQ VQ PR101HLLC LQ VQ Benzaldehyde ug/l 0.98 U 1.0 U Phenol ug/l 0.98 U 1.0 U Bis(2-chloroethyl)ether ug/l 0.98 U UJL 1.0 U 2-Chlorophenol ug/l 0.98 U UJL 1.0 U 2-Methylphenol ug/l 0.98 U 1.0 U 2,2'-Oybis(1-chloropropane) ug/l 0.98 U UJL 1.0 U Acetophenone ug/l 0.98 U 1.0 U 4-Methylphenol ug/l 0.98 U 1.0 U N-Nitroso-di-n-propylamine ug/l 0.98 U 1.0 U Heachloroethane ug/l 0.98 U 1.0 U Nitrobenzene ug/l 0.98 U 1.0 U Isophorone ug/l 0.98 U 1.0 U 2-Nitrophenol ug/l 0.98 U 1.0 U 2,4-Dimethylphenol ug/l 0.98 U 1.0 U Bis(2-chloroethoy)methane ug/l 0.98 U UJL 1.0 U 2,4-Dichlorophenol ug/l 0.98 U 1.0 U 4-Chloroaniline ug/l 0.98 U UJL 1.0 U Heachlorobutadiene ug/l 0.98 U 1.0 U Caprolactam ug/l 0.98 U 1.0 U 4-Chloro-3-methylphenol ug/l 0.98 U 1.0 U Heachlorocyclopentadiene ug/l 0.98 U UJL 1.0 U 2,4,6-Trichlorophenol ug/l 0.98 U 1.0 U 2,4,5-Trichlorophenol ug/l 0.98 U 1.0 U 1,1'-Biphenyl ug/l 0.98 U 1.0 U 2-Chloronaphthalene ug/l 0.98 U 1.0 U 2-Nitroaniline ug/l 2.0 U UJL 2.1 U UJL Dimethylphthalate ug/l 0.98 U 1.0 U 2,6-Dinitrotoluene ug/l 0.98 U 1.0 U 3-Nitroaniline ug/l 2.0 U UJL 2.1 U UJL 2,4-Dinitrophenol ug/l 2.0 U UJ 2.1 U UJ 4-Nitrophenol ug/l 2.0 U UJL 2.1 U UJL Dibenzofuran ug/l 0.98 U 1.0 U 2,4-Dinitrotoluene ug/l 0.98 U 1.0 U LQ - Laboratory Qualifier VQ - Validation Qualifier Page 1 of 2

135 Validation Data Table CSO/SWO Investigaiton Phase I TestAmerica SDG PR137 - Semivolatiles ANALYTE UNITS PR109CFRB LQ VQ PR101HLLC LQ VQ Diethylphthalate ug/l 0.98 U 1.0 U 4-Chlorophenyl-phenylether ug/l 0.98 U 1.0 U 4-Nitroaniline ug/l 2.0 U UJL 2.1 U UJL 4,6-Dinitro-2-methylphenol ug/l 2.0 U UJL 2.1 U UJL N-Nitrosodiphenylamine ug/l 0.98 U 1.0 U 1,2,4,5-Tetrachlorobenzene ug/l 0.98 U 1.0 U 4-Bromophenyl-phenylether ug/l 0.98 U 1.0 U Heachlorobenzene ug/l 0.98 U 1.0 U Atrazine ug/l 0.98 U 1.0 U Pentachlorophenol ug/l 2.0 U UJ 2.1 U UJ Carbazole ug/l 0.98 U 1.0 U Di-n-butylphthalate ug/l 0.98 U 1.0 U Butylbenzylphthalate ug/l 0.98 U 1.0 U 3,3'-Dichlorobenzidine ug/l 0.98 U UJL 1.0 U Bis(2-ethylheyl)phthalate ug/l 0.48 G B 0.45 G B Di-n-octylphthalate ug/l 0.98 U 1.0 U 2,3,4,6-Tetrachlorophenol ug/l 0.98 U 1.0 U LQ - Laboratory Qualifier VQ - Validation Qualifier Page 2 of 2

136 Laboratory Data With Qualifiers Added

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141 DATA VALIDATION REPORT CSO/SWO Phase I TestAmerica Semivolatile Selective Ion Monitoring SDG - PR137 Prepared by ENVIRONMENTAL DATA SERVICES, LTD. For TIERRA SOLUTIONS, INC. April 01, Oakhill Dr. Allison Park, PA I