Document Vj9yNXMZ2wZwxwrBGbxBDVJLj

DATA SUMMARY REPORT 2012 DATA SUMMARY REPORT MISSISSIPPI RIVER - POOL 2 AND ADJACENT LOCATIONS Prepared for Brewer Attorneys and Counselors Dallas, Texas Prepared by Anchor QEA, LLC 4300 Route 50, Suite 202 Saratoga Springs, New York 12866 April 2016 2012 DATA SUMMARY REPORT MISSISSIPPI RIVER - POOL 2 AND ADJACENT LOCATIONS Prepared for Brewer Attorneys and Counselors Dallas, Texas Prepared by Anchor QEA, LLC 4300 Route 50, Suite 202 Saratoga Springs, New York 12866 April 2016 TABLE OF CONTENTS 1 INTRODUCTION ................................................................................................................1 2 METHODS ...........................................................................................................................2 2.1 Water Sample Locations ..................................................................................................2 2.2 Water Sampling................................................................................................................2 2.2.1 Water Sampling Procedures ......................................................................................2 2.2.2 Laboratory Analyses ...................................................................................................3 2.3 Quality Assurance/Quality Control ................................................................................3 3 RESULTS ..............................................................................................................................4 3.1 Mississippi River Flow .....................................................................................................4 3.2 Analytical Results.............................................................................................................4 3.3 Data Validation.................................................................................................................4 3.4 Laboratory Data Reports ..................................................................................................4 4 REFERENCES ......................................................................................................................5 List of Tables Table 1 Summary of Sampling Locations Table 2 2012 Surface Water Results List of Figures Figure 1 Locations of 2012 Surface Water Samples Figure 2 Mississippi Hydrograph with Sampling Events List of Appendices Appendix A Data Validation Reports 2012 Data Summary Report Mississippi River - Pool 2 i April 2016 160945-01.02 ACRONYMS AND ABBREVIATIONS Anchor QEA Anchor QEA, LLC cfs cubic feet per second DSR Data Summary Report PFAS perfluoroalkyl substance PFBA Perfluorobutanoate PFBS Perfluorobutanesulfonate PFDA Perfluorodecanoate PFDoA Perfluorododecanoate PFHpA Perfluoroheptanoate PFHxA Perfluorohexanoate PFHxS Perfluorohexanesulfonate PFNA Perfluorononanoate PFOA Perfluorooctanoate PFOS Perfluorooctanesulfonate PFOSA Perfluorooctane sulfonamide PFPeA Perfluoropentanoate PFUnA Perfluoroundecanoate QA/QC quality assurance/quality control QAPP Quality Assurance Project Plan SAP Sampling and Analysis Plan USGS United States Geological Survey 2012 Data Summary Report Mississippi River - Pool 2 i April 2016 160945-01.02 1 INTRODUCTION This Data Summary Report (DSR) has been developed by Anchor QEA, LLC, on behalf of Brewer Attorneys and Counselors, to present the results of sampling and analysis activities performed to measure the water concentrations of perfluoroalkyl substances (PFASs) in Pool 2 of the Mississippi River in 2012 and additional nearby locations as documented in the 2012 Sampling and Analysis Plan (SAP; Anchor QEA 2012). The objective of this DSR is to describe the methods, summarize the data, and present the results of the applicable data quality assessments associated with the 2012 sampling and analysis activities. 2012 Data Summary Report Mississippi River - Pool 2 1 April 2016 160945-01.02 2 METHODS 2.1 Water Sample Locations A total of 19 sampling locations were identified in the SAP. In the Mississippi River, seven locations were sampled from the centroid of the river. Cross-channel transects containing between three to five sampling nodes were sampled at five locations. An additional seven samples were collected from the Minnehaha Creek (1 sample), Minnesota River (1 sample), Lake Calhoun (2 samples), and Pigs Eye Lake (3 samples). Three rounds of sampling were conducted targeting a low, moderate, and high flow to the extent possible. Accordingly, the targeted flow regimes were the 25, 50, and 75 percentile flow for the historical record (5,900 cubic feet per second [cfs], 10,400 cfs, and 20,400 cfs, respectively), as measured at the United States Geological Survey (USGS) Mississippi River gaging station (station number - 5331000) located in Saint Paul, Minnesota (Figure 1). A summary of the sampling locations is provided in Table 1. 2.2 Water Sampling 2.2.1 Water Sampling Procedures Sampling was performed at all locations specified in Table 1 and shown in Figure 1. Each location was sampled three times to capture a range of flow conditions. The sampling methods are presented in detail in Standard Operating Procedure for Water Sampling, included as Attachment 1 of the SAP (Anchor QEA 2012), and described below. Water sampling was conducted using a stainless steel Kemmerer sampler. At locations where the water depth was greater than or equal to 10 feet, subsamples were collected at 20% and 80% of the water depth and combined to form a single sample. At locations where the water depth was less than 10 feet, the samples were collected at 60% of the water depth. Samples were transferred from the stainless steel sampler to sample bottles supplied by the laboratory. The samples were kept on ice prior to shipment to the analytical laboratories. Water quality parameters, including temperature, pH, turbidity, and conductivity, were measured in the field at each sampling station using a YSI 6920 multiparameter probe. In 2012 Data Summary Report Mississippi River - Pool 2 2 April 2016 160945-01.02 Methods addition, the actual field coordinates of the locations occupied during sample collection were recorded using a Trimble GeoXT GPS unit. 2.2.2 Laboratory Analyses Water samples collected during the program were submitted to AXYS Analytical Laboratory for PFAS analysis including the following compounds: Perfluorobutanesulfonate (PFBS) Perfluorobutanoate (PFBA) Perfluorodecanoate (PFDA) Perfluorododecanoate (PFDoA) Perfluoroheptanoate (PFHpA) Perfluorohexanesulfonate (PFHxS) Perfluorohexanoate (PFHxA) Perfluorononanoate (PFNA) Perfluorooctane sulfonamide (PFOSA) Perfluorooctanesulfonate (PFOS) Perfluorooctanoate (PFOA) Perfluoropentanoate (PFPeA) Perfluoroundecanoate (PFUnA) Samples were also submitted to Pace Analytical for total organic carbon, total dissolved solids, and total suspended solids analysis. 2.3 Quality Assurance/Quality Control Quality assurance/quality control (QA/QC) procedures presented in a quality assurance project plan (QAPP) for an earlier study (2011 Cardno ENTRIX Quality Assurance Project Plan; [Cardno ENTRIX 2011]) were adopted and followed for this sampling effort. Sampling and analytical activities were consistent with the methodologies presented in the QAPP, and included the collection of appropriate additional QA/QC samples, including equipment rinse blanks, matrix spike samples, and duplicate samples. A summary of field QA/QC samples collected is presented in the QAPP. 2012 Data Summary Report Mississippi River - Pool 2 3 April 2016 160945-01.02 3 RESULTS 3.1 Mississippi River Flow Three rounds of sampling were conducted during July and August 2012. The first sampling round was conducted during July 11 through 14, 2012, to capture the high flow regime. The average daily flow as measured at the Mississippi River gaging station located in Saint Paul (USGS gage 5331000) was 24,200 cfs. The second round of sampling was conducted from July 30 through August 1, 2012, when the average daily flow was 14,600 cfs. The low flow event was conducted when the river flows were averaging 5,500 cfs from August 27 through August 28, 2012 (Figure 2). The observed flows were relatively close to those targeted and referenced in Section 2.1. 3.2 Analytical Results A total of 108 environmental samples were submitted for analysis for PFASs, total organic carbon, total dissolved solids, and total suspended solids. In addition, five field blanks and six field duplicates were submitted as QA/QC samples. The results for the sampling are presented in Table 2. 3.3 Data Validation A United States Environmental Protection Agency Stage 2A data validation review of the analytical results was conducted for each sampling round. The final validation reports for the surface water samples are included as Appendix A. 3.4 Laboratory Data Reports Due to the file size, the laboratory data reports are not included in this electronic data summary report. The laboratory data reports can be provided upon request. 2012 Data Summary Report Mississippi River - Pool 2 4 April 2016 160945-01.02 4 REFERENCES Anchor QEA, 2012. Sampling and Analysis Plan - Mississippi Pool 2. Prepared for Faegre, Baker and Daniels, LLP. July 2012. Cardno ENTRIX, 2011. Quality Assurance Project Plan. Prepared by Cardno ENTRIX for the 3M Company. June 2011. 2012 Data Summary Report Mississippi River - Pool 2 5 April 2016 160945-01.02 TABLES River Mile Mississippi River RM 847.3 Lake Calhoun and Minnehaha Creek (approximate RM 847) Mississippi River RM 844.1 Minnesota River RM 0 Mississippi River RM 841 Mississippi River RM 836.3 Mississippi River RM 835.2 Pigs Eye Lake (approximate RM 833.4) Mississippi River RM 831 Mississippi River RM 829 Mississippi River RM 826 Mississippi River RM 818.5 Mississippi River RM 817.2 Mississippi River RM 815.8 Mississippi River RM814 Note: RM = river mile Table 1 Summary of Sampling Locations Type Location Centroid 2 Locations Centroid Upstream Section of Pool 2 North end of Lake Calhoun South end of Lake Calhoun Confluence with Mississippi River Centroid Near Minneapolis-Saint Paul Airport, upstream of confluence with Minnesota River Centroid Minnesota River above confluence Centroid Centroid 4 Node Transect 3 Locations Centroid Centroid Downstream of confluence of Mississippi River and Minnesota Rivers Upstream of Metropolitan Council Environmental Services Metro treatment plant Downstream of Metropolitan Council Environmental Services Metro treatment plant North end of Pigs Eye Lake South end of Pigs Eye Lake Outfall of Pigs Eye Lake at Mississippi confluence Upstream of Northern Tier Energy's Saint Paul Park Refinery Downstream of Northern Tier Energy's Saint Paul Park Refinery Centroid Upstream of Spring Lake 5 Node Transect Upstream of 3M Cottage Grove facility 5 Node Transect Downstream of East Cove 5 Node Transect End of Pool 2 3 Node Transect Downstream of Lock and Dam No. 2 (Pool 3) 2012 Data Summary Report Mississippi River - Pool 2 1 April 2016 160945-01.02 Sample Name LKCALHOUN-N-201207140945 LKCALHOUN-N-201208010841 LKCALHOUN-N-201208291121 LKCALHOUN-S-201207141017 LKCALHOUN-S-201208010821 LKCALHOUN-S-201208291224 MINNE-RM847.0-C-201207111323 MINNE-RM847.0-C-201207301237 MINNE-RM847.0-C-201208271213 MIN-RM0.0-C-201207111444 MIN-RM0.0-C-201207301321 MIN-RM0.0-C-201208271234 MISS-RM814.3-1-201207130838 MISS-RM814.3-1-201207311537 MISS-RM814.3-1-201207311537DUP MISS-RM814.3-1-201207311537MS MISS-RM814.3-1-201208281339 MISS-RM814.3-2-201207130848 MISS-RM814.3-2-201207311544 MISS-RM814.3-2-201208281344 MISS-RM814.3-3-201207130900 MISS-RM814.3-3-201207130900DUP MISS-RM814.3-3-201207130900MS MISS-RM814.3-3-201207130900MSD MISS-RM814.3-3-201207311720 MISS-RM814.3-3-201208281352 MISS-RM815.8-1-201207131043 MISS-RM815.8-1-201207311443 MISS-RM815.8-1-201208281200 MISS-RM815.8-2-201207131028 MISS-RM815.8-2-201207311430 MISS-RM815.8-2-201208281216 MISS-RM815.8-3-201207131014 MISS-RM815.8-3-201207311412 MISS-RM815.8-3-201207311412DUP MISS-RM815.8-3-201207311412MS MISS-RM815.8-3-201208281230 MISS-RM815.8-4-201207130945 MISS-RM815.8-4-201207311403 MISS-RM815.8-4-201208281237 MISS-RM815.8-5-201207131000 MISS-RM815.8-5-201207311352 MISS-RM815.8-5-201208281245 MISS-RM817.2-1-201207121340 MISS-RM817.2-1-201207311246 MISS-RM817.2-1-201208281137 MISS-RM817.2-1-201208281137DUP MISS-RM817.2-1-201208281137MS MISS-RM817.2-2-201207121400 MISS-RM817.2-2-201207311236 MISS-RM817.2-2-201208281126 MISS-RM817.2-3-201207121416 MISS-RM817.2-3-201207311226 MISS-RM817.2-3-201208281117 MISS-RM817.2-4-201207121428 MISS-RM817.2-4-201207311213 MISS-RM817.2-4-201208281106 MISS-RM817.2-5-201207121453 MISS-RM817.2-5-201207311158 MISS-RM817.2-5-201208281059 MISS-RM818.5-1-201207121304 MISS-RM818.5-1-201207311304 Sample Date 7/14/2012 8/1/2012 8/29/2012 7/14/2012 8/1/2012 8/29/2012 7/11/2012 7/30/2012 8/27/2012 7/11/2012 7/30/2012 8/27/2012 7/13/2012 7/31/2012 7/31/2012 7/31/2012 8/28/2012 7/13/2012 7/31/2012 8/28/2012 7/13/2012 7/13/2012 7/13/2012 7/13/2012 7/31/2012 8/28/2012 7/13/2012 7/31/2012 8/28/2012 7/13/2012 7/31/2012 8/28/2012 7/13/2012 7/31/2012 7/31/2012 7/31/2012 8/28/2012 7/13/2012 7/31/2012 8/28/2012 7/13/2012 7/31/2012 8/28/2012 7/12/2012 7/31/2012 8/28/2012 8/28/2012 8/28/2012 7/12/2012 7/31/2012 8/28/2012 7/12/2012 7/31/2012 8/28/2012 7/12/2012 7/31/2012 8/28/2012 7/12/2012 7/31/2012 8/28/2012 7/12/2012 7/31/2012 Sample Time 9:45:00 AM 8:41:00 AM 11:21:00 AM 10:17:00 AM 8:21:00 AM 12:24:00 PM 1:23:00 PM 12:37:00 PM 12:13:00 PM 2:44:00 PM 1:21:00 PM 12:34:00 PM 8:38:00 AM 3:37:00 PM 3:37:00 PM 3:37:00 PM 1:39:00 PM 8:48:00 AM 3:44:00 PM 1:44:00 PM 9:00:00 AM 9:00:00 AM 9:00:00 AM 9:00:00 AM 5:20:00 PM 1:52:00 PM 10:43:00 AM 2:43:00 PM 12:00:00 PM 10:28:00 AM 2:30:00 PM 12:16:00 PM 10:14:00 AM 2:12:00 PM 2:12:00 PM 2:12:00 PM 12:30:00 PM 9:45:00 AM 2:03:00 PM 12:37:00 PM 10:00:00 AM 1:52:00 PM 12:45:00 PM 1:40:00 PM 12:46:00 PM 11:37:00 AM 11:37:00 AM 11:37:00 AM 2:00:00 PM 12:36:00 PM 11:26:00 AM 2:16:00 PM 12:26:00 PM 11:17:00 AM 2:28:00 PM 12:13:00 PM 11:06:00 AM 2:53:00 PM 11:58:00 AM 10:59:00 AM 1:04:00 PM 1:04:00 PM Parent Location LKCALHOUN-N LKCALHOUN-N LKCALHOUN-N LKCALHOUN-S LKCALHOUN-S LKCALHOUN-S MINNE-RM847.0-C MINNE-RM847.0-C MINNE-RM847.0-C MIN-RM0.0-C MIN-RM0.0-C MIN-RM0.0-C MISS-RM814.3-1 MISS-RM814.3-1 MISS-RM814.3-1 -MISS-RM814.3-1 MISS-RM814.3-2 MISS-RM814.3-2 MISS-RM814.3-2 MISS-RM814.3-3 MISS-RM814.3-3 --MISS-RM814.3-3 MISS-RM814.3-3 MISS-RM815.8-1 MISS-RM815.8-1 MISS-RM815.8-1 MISS-RM815.8.2 MISS-RM815.8.2 MISS-RM815.8.2 MISS-RM815.8-3 MISS-RM815.8-3 MISS-RM815.8-3 -MISS-RM815.8-3 MISS-RM815.8-4 MISS-RM815.8-4 MISS-RM815.8-4 MISS-RM815.8-5 MISS-RM815.8-5 MISS-RM815.8-5 MISS-RM817.2-1 MISS-RM817.2-1 MISS-RM817.2-1 MISS-RM817.2-1 -MISS-RM817.2-2 MISS-RM817.2-2 MISS-RM817.2-2 MISS-RM817.2-3 MISS-RM817.2-3 MISS-RM817.2-3 MISS-RM817.2-4 MISS-RM817.2-4 MISS-RM817.2-4 MISS-RM817.2-5 MISS-RM817.2-5 MISS-RM817.2-5 MISS-RM818.5-1 MISS-RM818.5-1 Sample Type N N N N N N N N N N N N N N LR MS N N N N N LR MS MSD N N N N N N N N N N LR MS N N N N N N N N N N LR MS N N N N N N N N N N N N N N PFBA (ng/L) 16.3 21 20.7 16.2 20.4 18.4 23.7 16.6 22.1 9.05 9.37 8.38 18.2 22.4 20.6 600 64.1 36.2 44.2 70.2 37.7 33.6 426 475 43.5 68.6 29.8 19.2 34 19.9 15.6 30.3 19.8 17.8 19.9 372 28.5 18.4 17.9 27 16.9 19.1 53.3 20.6 18.2 31.9 31.1 447 19.1 J 17.7 26.9 19.7 J 16 23.8 16.4 J 26.6 30.6 23.4 J 24.8 31.6 21.2 J 16 Table 2 2012 Surface Water Results PFBS PFDA PFDoA PFHpA (ng/L) (ng/L) (ng/L) (ng/L) < 2.53 < 1.27 < 1.27 3.88 < 1.94 < 0.969 < 0.969 3.99 < 1.91 1.04 < 0.957 4.62 < 2.48 1.86 < 1.24 4.47 < 1.96 < 0.981 < 0.981 4.3 < 2.1 1.17 < 0.897 4.44 < 1.8 < 0.902 < 0.902 2.25 < 1.78 < 0.889 < 0.889 2.38 < 2.11 < 0.974 < 0.974 2.62 < 1.87 < 0.933 < 0.933 < 0.933 < 1.92 < 0.96 < 0.96 1.35 < 2.01 < 1 < 1 2.26 < 1.94 < 0.972 < 0.972 < 1.12 < 1.94 J < 0.968 < 0.968 < 2.9 < 1.83 < 0.915 < 0.915 < 2.75 684 552 514 832 21.8 < 0.962 < 0.962 3.98 < 2.05 < 1.03 < 1.03 < 1.36 3.55 < 0.979 < 0.979 < 1.95 26.9 < 1.02 < 1.02 4.67 3.2 < 1.01 < 1.01 < 1.3 3.75 < 0.987 < 0.987 < 1.68 727 475 454 665 734 584 473 676 2.57 < 1.03 < 1.03 < 3.08 15.7 < 0.965 < 0.965 4.97 < 1.98 < 0.989 < 0.989 < 1.42 < 1.99 < 0.994 < 0.994 3.25 < 1.93 < 0.966 < 0.966 4.2 < 2 < 1 < 1 < 2.02 < 2 < 0.999 < 0.999 < 3 < 1.91 < 0.955 < 0.955 3.98 < 2.26 < 1.13 < 1.13 < 1.69 < 2.15 J < 1.07 < 1.07 < 1.24 < 1.94 < 0.969 < 0.969 < 1.86 533 396 413 535 < 2.05 < 1.02 < 1.02 2.94 < 2.14 < 1.07 < 1.07 < 1.15 < 1.98 < 0.988 < 0.988 < 2.97 < 2.1 < 1.05 < 1.05 < 3.08 < 2.17 < 1.08 < 1.08 < 1.59 < 2.03 < 1.01 < 1.01 < 3.04 22.7 < 0.966 < 0.966 4.69 < 1.97 < 0.985 < 0.985 < 1.52 < 1.9 < 0.949 < 0.949 2.33 2.19 < 1 < 1 3.43 2.74 < 1.05 < 1.05 2.94 726 451 449 622 < 2.03 < 1.01 < 1.01 < 1.45 < 1.98 < 0.989 < 0.989 1.97 2.58 < 1.03 < 1.03 4.16 < 1.95 < 0.975 < 0.975 < 2.03 < 1.97 < 0.984 < 0.984 < 1.53 2.25 < 0.982 < 0.982 4.15 2.09 < 0.94 < 0.94 < 2.15 < 1.89 < 0.945 < 0.945 < 2.13 2.67 < 0.931 < 0.931 2.82 2.91 < 1.02 < 1.02 < 1.59 < 1.82 < 0.912 < 0.912 < 2.11 4.3 < 0.991 < 0.991 5.13 < 1.96 < 0.982 < 0.982 < 1.35 < 1.94 < 0.971 < 0.971 < 0.971 PFHxA (ng/L) 5.38 6.33 10.9 6.1 6.11 7.79 2.23 2.31 5.87 < 0.947 1.89 5.31 1.36 < 2.9 < 2.75 632 7.07 < 1.41 2.72 10 3.19 2.45 536 556 3.34 8.25 < 1.11 < 2.98 4.31 < 1 < 3 4.43 < 1.13 < 1.07 < 0.969 427 3.74 < 1.08 < 2.97 5.11 < 1.08 < 3.04 6.53 < 0.985 2.31 3.61 4.05 480 < 1.3 < 1.57 5.12 < 0.975 2 4.56 < 1.44 2.4 4.56 < 2.04 1.34 5.28 < 1.52 < 0.971 PFHxS (ng/L) 3.85 2.06 3.09 3.49 2.38 2.41 1.99 < 1.78 3.72 < 1.87 < 1.92 < 2.01 < 1.94 < 1.94 < 1.83 1050 5.06 < 2.05 2.24 7.08 < 2.01 2.54 952 974 < 2.05 4.32 < 1.98 < 1.99 2.37 < 2 < 2 2.15 < 2.26 < 2.15 J < 1.94 794 < 2.05 < 2.14 < 1.98 2.28 < 2.17 < 2.03 3.3 < 1.97 < 1.9 < 2 < 2.11 951 < 2.03 < 1.98 < 2.06 < 1.95 < 1.97 J 2.71 < 1.88 < 1.89 J 2.01 < 2.05 < 1.82 J 2.88 < 1.96 < 1.94 J PFNA (ng/L) < 1.27 < 0.969 1.64 1.64 1.16 1.35 < 0.902 < 0.889 1.55 < 0.933 < 0.96 < 1 < 0.972 < 0.968 < 1.27 536 < 0.962 < 1.03 < 0.979 < 1.02 < 1.01 < 0.987 472 530 < 1.03 < 0.965 < 0.989 < 0.994 < 0.966 < 1 < 0.999 < 0.955 < 1.13 < 1.07 < 0.969 452 < 1.02 < 1.07 < 0.988 < 1.05 < 1.08 < 1.01 < 0.966 < 0.985 < 0.949 < 1 < 1.05 486 < 1.01 < 0.989 < 1.03 < 0.975 < 0.984 < 0.982 < 0.94 < 0.945 < 0.931 < 1.02 < 0.912 < 0.991 < 0.982 < 0.971 PFOA (ng/L) 14.5 14.2 19.2 13.9 14.3 15.9 5.62 6.8 7.29 1.58 3.05 4.59 2.69 3.99 4.42 538 16.6 6.86 9.88 20.4 7.59 7.22 456 519 11.2 18.7 1.3 2.95 6.07 1.73 2.35 5.61 2.15 2.22 3.12 390 6.45 1.4 1.8 6.12 2.49 3.04 15.7 2.17 1.5 4.87 5.12 506 2.03 2.1 4.93 1.87 3.62 5.48 1.84 6.71 8.86 5.99 6.13 10.5 1.77 1.7 PFOS (ng/L) 42.5 32 46.8 77.8 42.4 49.8 6.68 9.31 8.82 < 1.87 J 1.733 J 1.995 J 2.12 2.64 1.84 1050 5.32 3.87 5.69 8.3 4.16 5.19 960 1050 5.73 8.75 < 1.98 J 1.347 J 2.25 < 2 J 1.821 J 2.53 1.061 J 1.415 J 1.002 797 2.9 < 2.14 J < 1.98 J 2.22 1.537 J 1.506 J 8.94 < 1.97 J 1.646 J 2.03 1.989 J 874 1.653 J < 1.98 J 2.83 < 1.95 J 1.503 J 3.92 0.893 J 1.793 J 3.56 7.28 3.49 J 4.94 < 1.96 J 1.431 J PFOSA (ng/L) < 1.27 < 0.969 < 0.957 < 1.24 < 0.981 < 0.897 < 0.902 < 0.889 < 0.974 < 0.933 < 0.96 < 1 < 0.972 < 0.968 < 0.915 610 < 0.962 < 1.03 < 0.979 < 1.02 < 1.01 < 0.987 515 558 < 1.03 < 0.965 < 0.989 < 0.994 < 0.966 < 1 < 0.999 < 0.955 < 1.13 < 1.07 < 0.969 463 < 1.02 < 1.07 < 0.988 < 1.05 < 1.08 < 1.01 < 0.966 < 0.985 < 0.949 < 1 < 1.05 503 < 1.01 < 0.989 < 1.03 < 0.975 < 0.984 < 0.982 < 0.94 < 0.945 < 0.931 < 1.02 < 0.912 < 0.991 < 0.982 < 0.971 PFPeA (ng/L) 3.99 3.75 8.92 3.41 < 3.05 3.91 < 1.53 < 3.39 < 1.97 < 1.45 3.09 3.32 < 1.88 < 3.03 < 4.15 429 9.31 < 2.01 3.38 10.4 < 1.9 3.1 416 428 4.19 8.42 < 1.39 < 2.98 4.29 < 1.42 < 3.51 3.47 < 1.54 < 2.7 J < 1.11 322 4.58 < 2.31 3.71 4.61 < 1.67 3.24 7.14 < 1.85 < 1.73 3.03 3.92 368 < 1.74 < 2.26 4.54 < 1.72 < 3.26 3.6 < 2.42 2.95 5.28 < 1.7 2.96 5.21 < 2.12 < 2.87 PFUnA (ng/L) < 1.27 < 0.969 < 0.957 < 1.24 < 0.981 < 0.897 < 0.902 < 0.889 < 0.974 < 0.933 < 0.96 < 1 < 0.972 < 0.968 < 0.915 580 < 0.962 < 1.03 < 0.979 < 1.02 < 1.01 < 0.987 463 571 < 1.03 < 0.965 < 0.989 < 0.994 < 0.966 < 1 < 0.999 < 0.955 < 1.13 < 1.07 < 0.969 431 < 1.02 < 1.07 < 0.988 < 1.05 < 1.08 < 1.01 < 0.966 < 0.985 < 0.949 < 1 < 1.05 470 < 1.01 < 0.989 < 1.03 < 0.975 < 0.984 < 0.982 < 0.94 < 0.945 < 0.931 < 1.02 < 0.912 < 0.991 < 0.982 < 0.971 TDS (mg/L) 316 321 320 298 294 320 287 241 313 456 465 534 230 214 --292 230 211 334 230 214 --226 327 232 214 335 ---240 221 --327 230 218 335 248 232 336 250 222 322 323 -254 241 318 255 233 326 253 234 330 244 246 331 254 256 TOC (mg/L) 1.9 2.3 4.0 1.4 3.0 1.6 6.4 4.4 2.7 10.6 6.7 3.3 16.5 19.0 --10.4 16.7 14.5 10.5 17.1 ---14.0 10.6 16.2 13.7 10.2 ---16.2 14.2 --10.5 16.3 13.6 10 16.9 14.1 10.3 16.3 14.0 11.1 --16.2 14.8 10.4 16.1 13.9 10.4 16.5 14.0 10.4 16.2 13.7 10.4 15.7 13.6 TSS (mg/L) < 10 < 10 < 10 11.6 < 10 < 10 10.1 < 10 < 10 39.3 31.4 23.2 41.2 30.8 --31.8 38.4 20.7 26.0 25.6 27.5 --21.7 32.1 45.6 29.2 43.2 ---58.0 43.3 --46.0 48.8 47.2 41.1 28.7 24.7 23.2 37.3 24.9 27.5 30.4 -30.2 27.5 20.5 51.6 42.4 24.1 37.0 31.6 22.3 30.6 28.6 18.0 46.5 41.1 2012 Data Summary Report Mississippi River - Pool 2 1 of 3 April 2016 160945-01.02 Sample Name MISS-RM818.5-1-201208280915 MISS-RM818.5-2-201207121311 MISS-RM818.5-2-201207311313 MISS-RM818.5-2-201208280932 MISS-RM818.5-3-201207121225 MISS-RM818.5-3-201207311325 MISS-RM818.5-3-201208280939 MISS-RM818.5-4-201207121242 MISS-RM818.5-4-201207311342 MISS-RM818.5-4-201208280952 MISS-RM818.5-5-201207121258 MISS-RM818.5-5-201207121258MS MISS-RM818.5-5-201207311047 MISS-RM818.5-5-201207311047DUP MISS-RM818.5-5-201207311047MS MISS-RM818.5-5-201208281015 MISS-RM826.0-C-201207121120 MISS-RM826.0-C-201207311002 MISS-RM826.0-C-201208280842 MISS-RM829.0-C-201207121058 MISS-RM829.0-C-201207310938 MISS-RM829.0-C-201208280818 MISS-RM831.0-C-201207121030 MISS-RM831.0-C-201207301603 MISS-RM831.0-C-201208271545 MISS-RM835.2-1-201207111639 MISS-RM835.2-1-201207301438 MISS-RM835.2-1-201208271339 MISS-RM835.2-2-201207111628 MISS-RM835.2-2-201207301343 MISS-RM835.2-2-201208271358 MISS-RM835.2-3-201207111628 MISS-RM835.2-3-201207301347 MISS-RM835.2-3-201208271402 MISS-RM835.2-4-201207111616 MISS-RM835.2-4-201207301351 MISS-RM835.2-4-201208271410 MISS-RM836.3-C-201207111553 MISS-RM836.3-C-201207301334 MISS-RM836.3-C-201208271329 MISS-RM841.0-C-201207111530 MISS-RM841.0-C-201207301337 MISS-RM841.0-C-201208271243 MISS-RM844.1-C-201207110244 MISS-RM844.1-C-201207301300 MISS-RM844.1-C-201208271224 MISS-RM847.3-C-201207111400 MISS-RM847.3-C-201207301213 MISS-RM847.3-C-201208271151 PIGLK-N-201207120915 PIGLK-N-201207310857 PIGLK-N-201208271513 PIGLK-OF-201207121000 PIGLK-OF-201207301518 PIGLK-OF-201208271425 PIGLK-S-201207120930 PIGLK-S-201207301457 PIGLK-S-201208271453 WS-FB-20120730 WS-FB-20120731 WS-FB-20120828 WS-FB-20120829 Sample Date 8/28/2012 7/12/2012 7/31/2012 8/28/2012 7/12/2012 7/31/2012 8/28/2012 7/12/2012 7/31/2012 8/28/2012 7/12/2012 7/12/2012 7/31/2012 7/31/2012 7/31/2012 8/28/2012 7/12/2012 7/31/2012 8/28/2012 7/12/2012 7/31/2012 8/28/2012 7/12/2012 7/30/2012 8/27/2012 7/11/2012 7/30/2012 8/27/2012 7/11/2012 7/30/2012 8/27/2012 7/11/2012 7/30/2012 8/27/2012 7/11/2012 7/30/2012 8/27/2012 7/11/2012 7/30/2012 8/27/2012 7/11/2012 7/30/2012 8/27/2012 7/11/2012 7/30/2012 8/27/2012 7/11/2012 7/30/2012 8/27/2012 7/12/2012 7/31/2012 8/27/2012 7/12/2012 7/30/2012 8/27/2012 7/12/2012 7/30/2012 8/27/2012 7/30/2012 7/31/2012 8/28/2012 8/29/2012 Sample Time 9:15:00 AM 1:11:00 PM 1:13:00 PM 9:32:00 AM 12:25:00 PM 1:25:00 PM 9:39:00 AM 12:42:00 PM 1:42:00 PM 9:52:00 AM 12:58:00 PM 12:58:00 PM 10:47:00 AM 10:47:00 AM 10:47:00 AM 10:15:00 AM 11:20:00 AM 10:02:00 AM 8:42:00 AM 10:58:00 AM 9:38:00 AM 8:18:00 AM 10:30:00 AM 4:03:00 PM 3:45:00 PM 4:39:00 PM 2:38:00 PM 1:39:00 PM 4:28:00 PM 1:43:00 PM 1:58:00 PM 4:20:00 PM 1:47:00 PM 2:02:00 PM 4:16:00 PM 1:51:00 PM 2:10:00 PM 3:53:00 PM 1:34:00 PM 1:29:00 PM 3:30:00 PM 1:37:00 PM 12:43:00 PM 2:26:00 PM 1:00:00 PM 12:24:00 PM 2:00:00 PM 12:13:00 PM 11:51:00 AM 9:15:00 AM 8:57:00 AM 3:13:00 PM 10:00:00 AM 3:18:00 PM 2:25:00 PM 9:30:00 AM 2:57:00 PM 2:53:00 PM 11:41:00 AM 2:49:00 PM 4:00:00 PM 11:00:00 AM Parent Location MISS-RM818.5-1 MISS-RM818.5-2 MISS-RM818.5-2 MISS-RM818.5-2 MISS-RM818.5-3 MISS-RM818.5-3 MISS-RM818.5-3 MISS-RM818.5-4 MISS-RM818.5-4 MISS-RM818.5-4 MISS-RM818.5-5 -MISS-RM818.5-5 MISS-RM818.5-5 -MISS-RM818.5-5 MISS-RM826.0-C MISS-RM826.0-C MISS-RM826.0-C MISS-RM829.0-C MISS-RM829.0-C MISS-RM829.0-C MISS-RM831.0-C MISS-RM831.0-C MISS-RM831.0-C MISS-RM835.2-1 MISS-RM835.2-1 MISS-RM835.2-1 MISS-RM835.2-2 MISS-RM835.2-2 MISS-RM835.2-2 MISS-RM835.2-3 MISS-RM835.2-3 MISS-RM835.2-3 MISS-RM835.2-4 MISS-RM835.2-4 MISS-RM835.2-4 MISS-RM836.3-C MISS-RM836.3-C MISS-RM836.3-C MISS-RM841.0-C MISS-RM841.0-C MISS-RM841.0-C MISS-RM844.1-C MISS-RM844.1-C MISS-RM844.1-C MISS-RM847.3-C MISS-RM847.3-C MISS-RM847.3-C PIGLK-N PIGLK-N PIGLK-N PIGLK-OF PIGLK-OF PIGLK-OF PIGLK-S PIGLK-S PIGLK-S ----- Sample Type N N N N N N N N N N N MS N LR MS N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N FB FB FB FB PFBA (ng/L) 27.8 R 16.9 21.2 19 J 16.2 21.9 R 13.7 22.3 R -24.2 20.5 544 21 14 J 21.6 14.8 R 18.2 14.7 18 J 16.8 14.1 13.4 J 10.9 12 14.6 9.83 12 12.7 11.9 11.7 11 12.5 18.9 12.7 10.8 11.9 11.3 10.3 9.94 12.9 11.8 10.7 10.9 11.9 10.7 74.8 157 158 26.9 39.4 45 36 110 172 < 0.991 < 1.06 < 1.12 < 1.08 Table 2 2012 Surface Water Results PFBS (ng/L) PFDA (ng/L) PFDoA (ng/L) PFHpA (ng/L) < 1.93 < 1.88 < 1.94 < 1.89 < 2.12 < 2.05 2.22 < 1.98 < 2.01 < 1.94 2.01 J 590 < 1.97 J < 1.93 597 < 2.24 < 1.73 < 1.81 < 2.24 < 1.88 < 1.85 < 1.99 < 1.82 < 2.21 < 2.18 < 2.09 < 2.1 < 2.17 < 1.9 < 2.04 < 2.11 < 2.05 < 1.72 < 1.97 < 1.84 < 1.88 < 1.93 < 2.09 < 2.04 < 2.17 < 1.42 < 1.86 < 1.95 < 1.8 < 2.01 < 1.91 < 1.74 < 2 < 2.11 5.11 2.29 6.77 9.74 < 1.96 2.11 6.45 < 2.04 5.68 < 1.98 < 2.12 < 2.24 < 2.16 < 0.964 < 0.939 < 0.972 < 0.943 < 1.06 < 1.03 < 0.966 < 0.991 < 1.01 < 0.971 < 0.996 419 < 0.985 < 0.966 559 < 1.12 < 0.863 < 0.907 < 1.12 < 0.942 < 0.927 < 0.996 < 0.911 < 1.1 < 1.09 < 1.05 < 1.05 < 1.08 < 0.949 < 1.02 < 1.05 < 1.03 < 0.858 < 0.987 < 0.921 < 0.941 < 0.963 < 1.04 < 1.02 < 1.09 < 0.708 < 0.93 < 0.976 < 0.902 < 1.01 < 0.957 < 0.872 < 1 < 1.05 < 0.983 < 0.999 < 1.08 < 0.782 < 0.98 < 0.965 < 0.894 < 1.02 < 1.08 < 0.991 < 1.06 < 1.12 < 1.08 < 0.964 < 0.939 < 0.972 < 0.943 < 1.06 < 1.03 < 0.966 < 0.991 < 1.01 < 0.971 < 0.996 438 < 0.985 < 0.966 478 < 1.12 < 0.863 < 0.907 < 1.12 < 0.942 < 0.927 < 0.996 < 0.911 < 1.1 < 1.09 < 1.05 < 1.05 < 1.08 < 0.949 < 1.02 < 1.05 < 1.03 < 0.858 < 0.987 < 0.921 < 0.941 < 0.963 < 1.04 < 1.02 < 1.09 < 0.708 < 0.93 < 0.976 < 0.902 < 1.01 < 0.957 < 0.872 < 1 < 1.05 < 0.983 < 0.999 < 1.08 < 0.782 < 0.98 < 0.965 < 0.894 < 1.02 < 1.08 < 0.991 < 1.06 < 1.12 < 1.08 3 < 0.939 < 2.06 3.14 < 1.79 < 2.07 4.22 < 1.9 < 1.24 3.19 < 1.04 518 < 2.95 < 2.9 640 1.77 < 0.909 < 1.28 2.13 < 2.02 < 1.8 1.86 < 1.27 < 1.48 2.01 < 1.05 < 2.47 2.87 < 1.8 < 1.57 1.95 < 1.03 < 2.84 1.94 < 2.11 < 1.8 2.13 < 1.32 < 3.07 1.49 < 0.74 < 2.82 < 1.11 < 1.25 < 1.24 1.24 < 1.04 < 2.91 < 1.12 3.01 9.25 7.93 < 1.88 < 2.94 3.53 2.88 5.3 8.82 < 0.991 < 1.06 < 1.12 < 1.08 PFHxA (ng/L) 4.38 < 1.24 < 0.972 3.04 < 1.23 < 1.03 3.43 < 0.991 < 1.01 2.49 1.16 417 < 3.38 < 2.9 528 3.08 < 0.863 < 0.907 2.46 < 0.942 < 0.927 2.1 < 0.911 < 1.34 2.3 < 1.05 < 1.05 1.42 < 0.949 < 1.56 < 1.05 < 1.03 < 2.57 1.55 < 0.921 < 1.06 3.33 < 1.04 < 3.07 2.1 < 0.708 < 2.79 1.11 < 0.902 < 1.01 < 0.957 < 0.872 < 1.14 < 1.05 5.43 14.1 15.4 2.01 4.19 6.64 3.25 12.9 19.7 < 0.991 < 1.06 < 1.12 < 1.08 PFHxS (ng/L) 4.26 < 1.88 < 1.94 J 2.1 < 2.12 < 2.05 J 2.9 < 1.98 < 2.01 J < 1.94 < 1.99 786 < 1.97 < 1.93 917 < 2.24 < 1.73 < 1.81 J < 2.24 < 1.88 < 1.85 J < 1.99 < 1.82 < 2.21 J < 2.18 < 2.09 < 2.1 J < 2.17 < 1.9 < 2.04 J < 2.11 < 2.05 < 1.72 < 1.97 < 1.84 < 1.88 1.98 < 2.09 < 2.04 < 2.17 < 1.42 < 1.86 < 1.95 < 1.8 < 2.01 < 1.91 < 1.74 < 2 < 2.11 2.68 5.99 5.76 < 1.57 2.36 2.81 1.88 4.07 4.9 < 1.98 < 2.12 < 2.24 < 2.16 PFNA (ng/L) < 0.964 < 0.939 < 0.972 < 0.943 < 1.06 < 1.03 < 0.966 < 0.991 < 1.01 < 0.971 < 0.996 412 < 0.985 < 0.996 460 < 1.12 < 0.863 < 0.907 < 1.12 < 0.942 < 0.927 < 0.996 < 0.911 < 1.1 < 1.09 < 1.05 < 1.05 < 1.08 < 0.949 < 1.02 < 1.05 < 1.03 < 0.858 < 0.987 < 0.921 < 0.941 0.995 < 1.04 < 1.02 < 1.09 < 0.708 < 0.93 < 0.976 < 0.902 < 1.01 < 0.957 < 0.872 < 1 < 1.05 < 0.983 < 0.999 < 1.08 < 0.782 < 0.98 < 0.965 < 0.894 < 1.02 < 1.08 < 0.991 < 1.06 < 1.12 < 1.08 PFOA (ng/L) 5.58 1.82 2.96 4.65 1.98 2.07 5.02 1.59 2.42 4.95 3.16 397 3.96 4.04 503 5.03 1.88 1.97 4.18 1.62 2.45 4.15 1.69 2.68 4.62 < 1.05 < 1.05 2.3 < 0.949 1.69 2.23 < 1.03 1.98 3.65 1.25 2.06 5.73 2 1.2 3.09 1.57 1.41 2.25 < 0.902 1.3 2.5 0.948 1.09 1.71 84.7 189 214 16.6 25.1 51.5 41.3 110 212 < 0.991 < 1.06 < 1.12 < 1.08 PFOS (ng/L) 2.93 < 1.88 J 0.919 J 2.7 1.482 J 1.096 J 4 < 1.98 J 1.807 J 1.446 J 1.374 J 828 2.03 1.97 878 2.088 J < 1.73 J 1.549 J 1.091 J < 1.88 J < 1.85 J 1.593 J 0.993 J < 2.21 J < 2.18 J < 2.09 J < 2.1 J < 2.17 J < 1.9 J 1.217 J 1.207 J < 2.05 J < 1.72 J < 1.97 J < 1.84 J 1.738 J 2.59 < 2.09 J < 2.04 J 1.833 J 0.805 J < 1.86 J < 1.95 J < 1.8 J < 2.01 J 2.21 < 1.74 J < 2 J 1.459 J 11.1 26.9 18.5 3.68 4.96 4.14 6.04 14.4 15.7 < 1.98 J < 2.12 J < 2.24 J < 2.16 J PFOSA (ng/L) < 0.964 < 0.939 < 0.972 < 0.943 < 1.06 < 1.03 < 0.966 < 0.991 < 1.01 < 0.971 < 0.996 467 < 0.985 < 0.966 533 < 1.12 < 0.863 < 0.907 < 1.12 < 0.942 < 0.927 < 0.996 < 0.911 < 1.1 < 1.09 < 1.05 < 1.05 < 1.08 < 0.949 < 1.02 < 1.05 < 1.03 < 0.858 < 0.987 < 0.921 < 0.941 < 0.963 < 1.04 < 1.02 < 1.09 < 0.708 < 0.93 < 0.976 < 0.902 < 1.01 < 0.957 < 0.872 < 1 < 1.05 < 0.983 < 0.999 < 1.08 < 0.782 < 0.98 < 0.965 < 0.894 < 1.02 < 1.08 < 0.991 < 1.06 < 1.12 < 1.08 PFPeA (ng/L) 5.06 < 2.57 < 2.16 4.37 < 1.95 < 1.81 2.71 < 1.23 < 2.06 2.53 < 2.39 J 301 < 2.95 < 2.9 384 2.67 < 2.41 < 1.45 2.61 < 1.59 1.61 1.79 < 2.33 < 2.63 < 1.56 < 1.6 < 2.89 1.1 < 2.02 < 2.71 < 1.43 < 1.11 < 2.76 2.19 < 2.19 < 2 3.04 < 2.08 < 3.07 2.1 < 1.97 < 2.79 1.64 < 1.21 < 3.63 1.14 < 1.69 < 2.22 < 1.27 < 2.61 3.92 6.18 < 1.83 < 2.94 3.08 < 2.4 < 4.05 5.78 < 0.991 < 1.06 < 1.12 < 1.08 PFUnA (ng/L) < 0.964 < 0.939 < 0.972 < 0.943 < 1.06 < 1.03 < 0.966 < 0.991 < 1.01 < 0.971 < 0.996 425 < 0.985 < 0.966 609 < 1.12 < 0.863 < 0.907 < 1.12 < 0.942 < 0.927 < 0.996 < 0.911 < 1.1 < 1.09 < 1.05 < 1.05 < 1.08 < 0.949 < 1.02 < 1.05 < 1.03 < 0.858 < 0.987 < 0.921 < 0.941 < 0.963 < 1.04 < 1.02 < 1.09 < 0.708 < 0.93 < 0.976 < 0.902 < 1.01 < 0.957 < 0.872 < 1 < 1.05 < 0.983 < 0.999 < 1.08 < 0.782 < 0.98 < 0.965 < 0.894 < 1.02 < 1.08 < 0.991 < 1.06 < 1.12 < 1.08 TDS (mg/L) 321 255 230 305 247 240 309 240 226 307 251 -238 --307 246 245 313 248 235 302 238 223 327 261 232 318 254 229 276 235 211 285 260 214 324 245 218 282 227 219 288 182 169 220 181 171 216 256 275 325 246 244 324 249 245 328 --< 10.0 < 10.0 TOC (mg/L) 10.3 16.1 13.6 11.1 16.1 13.8 11.4 16.2 13.7 9.8 J 16.7 -14.1 --9.9 J 16.3 14.7 J 11.3 J 16.4 14.9 9.4 J 17.5 14.8 10.6 J 17.1 14.8 10.8 J 17.6 14.9 11.1 J 17.3 J 15.0 10.1 J 17.5 15.1 10.3 J 17.3 15.1 10.8 J 18.0 15.0 10.7 J 18.7 16.4 11.4 J 18.7 16.4 11.6 J 13.9 12.3 12.2 J 15.7 13.5 10.8 J 15.8 12.7 11.6 J < 0.5 < 0.5 < 0.5 < 0.5 TSS (mg/L) 19.1 29.6 33.1 18.0 67.8 34.2 16.8 24.2 16.1 14.8 29.3 -23.7 --26.3 32.3 26.2 15.8 35.6 25.7 15.9 29.1 19.2 14.8 28.6 20.6 27.7 27.2 17.5 17.0 28.8 17.2 16.4 29.0 13.2 15.5 25.6 19.7 16.0 25.5 19.2 13.1 20.6 15.6 12.7 22.4 17.2 10.3 42.1 46.9 34.7 32.3 51.8 42.2 34.1 75.0 54.8 --< 10 < 10 2012 Data Summary Report Mississippi River - Pool 2 2 of 3 April 2016 160945-01.02 Sample Name Sample Date Sample Time WS-FD-20120711 7/11/2012 4:39:00 PM WS-FD-20120712 7/12/2012 2:16:00 PM WS-FD-20120730 7/30/2012 1:51:00 PM WS-FD-20120731 7/31/2012 11:58:00 AM WS-FD-20120827 8/27/2012 3:45:00 PM WS-FD-20120828 WS-RB-20120714 8/28/2012 7/14/2012 1:44:00 PM 9:12:00 AM Notes: All non-detect results are reported at the reporting limit. -- = results not reported or not applicable < = compound analyzed, but not detected above reporting limit FB = field blank FD = field duplicate J = estimated value LR = lab replicate MS = matrix spike MSD = matrix spike duplicate mg/L = milligrams per liter ng/L = nanogram per liter Parent Location MISS-RM835.2-1 MISS-RM817.2-3 MISS-RM835.2-4 MISS-RM817.2-5 MISS-RM831.0-C MISS-RM814.3-2 -- Sample Type FD FD FD FD FD FD RB N = environmental sample PFBA = Perfluorobutanoate PFBS = Perfluorobutanesulfonate PFDA = Perfluorodecanoate PFDoA = Perfluorododecanoate PFHpA = Perfluoroheptanoate PFHxA = Perfluorohexanoate PFHxS = Perfluorohexanesulfonate PFNA = Perfluorononanoate PFOA = Perfluorooctanoate PFBA (ng/L) 12.9 14.5 11.4 27.6 14.2 79.8 1.22 Table 2 2012 Surface Water Results PFBS (ng/L) PFDA (ng/L) PFDoA (ng/L) PFHpA (ng/L) < 1.73 < 3.09 < 1.8 < 2.18 < 2.24 24.4 < 1.83 < 0.863 < 1.54 < 0.898 < 1.09 < 1.12 < 0.913 < 0.916 < 0.863 < 1.54 < 0.898 < 1.09 < 1.12 < 0.913 < 0.916 < 1.83 < 1.54 2.02 < 3.26 1.2 3.74 < 0.916 PFHxA (ng/L) < 0.863 < 1.54 0.962 < 3.26 1.94 7.21 < 0.916 PFOS = Perfluorooctanesulfonate PFOSA = Perfluorooctane sulfonamide PFPeA = Perfluoropentanoate PFUnA = Perfluoroundecanoate R = compound analyzed, but rejected RB = rinse blank TDS = total dissolved solids TOC = total organic carbon TSS = total suspended solids WS = water sample PFHxS (ng/L) < 1.73 < 3.09 < 1.8 < 2.18 < 2.24 4.77 < 1.83 PFNA (ng/L) < 0.863 < 1.54 < 1.07 < 1.37 < 1.12 1.12 < 0.916 PFOA (ng/L) 1.24 2.25 1.21 6.8 5.01 19.7 < 0.916 PFOS (ng/L) < 1.73 J < 3.09 J < 1.8 J 3.27 2.4 6.09 < 1.83 J PFOSA (ng/L) < 0.863 < 1.54 < 0.898 < 1.09 < 1.12 < 0.913 < 0.916 PFPeA (ng/L) 1.51 < 1.55 < 1.8 < 3.26 2.27 9 < 0.916 PFUnA (ng/L) < 0.863 < 1.54 < 0.898 < 1.09 < 1.12 < 0.913 < 0.916 TDS (mg/L) 258 239 206 248 335 318 -- TOC (mg/L) < 0.5 < 0.5 < 0.5 < 0.5 < 0.5 < 0.5 < 0.5 TSS (mg/L) 30.4 31.2 13.4 26.5 15.0 25.7 -- 2012 Data Summary Report Mississippi River - Pool 2 3 of 3 April 2016 160945-01.02 FIGURES P:\Projects\3M\Minnesota_PFC_Litigation\GIS\mxd\Water\Locations of 2012 Surface Water Samples_for_DSR_032316.mxd rconstant 4/7/2016 2:42:13 PM Minnesot a River Lake Calhoun 853 852 851 850 849 Minnehaha Creek 848847 MSP Airport 846 845 1 2 3 4 5 6 Seneca 7 WWTP 8 9 10 11 12 842 843 844 839 838 840 841 Holman Field Airport 837 Metro WWTP 836 835 Pigs Eye Lake 834 833 832 831 St. Paul Refinery 830 829 828 827 826 Flint Hills Refinery 825 824 823 822 Legend 2012 Sampling Points Possible PFAS Sources Lakes Calhoun Roads Locks and Dams Mississippi River Stream Network Eagles Point WWTP 819 3M WWTP 820 821 818 817 816 815 814 Figure 1 Feet Locations of 2012 Surface Water Samples 0 15,000 30,000 2012 Data Summary Report Mississippi River - Pool 2 1105 8104 cfs cfs 0 0 cfs plin2g420 plin1g460 plin5g500 Samw = Samw = Samw = WaAtevgr Flo WaAtevgr Flo WaAtvegr Flo Mississippi River Flow (cfs) 6104 4104 2104 0 Jan Feb Mar Apr May Jun Jul Aug Sep Oct Nov Dec 2012 2012 Flow Median Flow 1990-2016 Water Sampling Event Figure 2 Mississippi River Hydrograph with Sampling Events 2012 Data Summary Report Mississippi River - Pool 2 Flow from USGS gage 5331000 - Mississippi River at St. Paul, MN. SLL - \\Saratoga1\Saratoga\Projects\3M\Minnesota_PFC_Litigation\Analysis\PFOS_water_analyses\Hydrographs\IDL\Plot_MR_Flow_2012_AQsampling.pro Wed Mar 23 16:45:41 2016 APPENDIX A DATA VALIDATION REPORTS 720 Olive Way, Suite 1900 Seattle, Washington 98101 Phone 206.287.9130 Fax 206.287.9131 www.anchorqea.com DATA VALIDATION REVIEW REPORT - USEPA STAGE 2A Project: Mississippi River Pool 2 Surface Water Sampling: Round 1 Project Number: 110800-01.01 Date: January 17, 2013 This report summarizes the review of analytical results for 36 water samples, one field blank and two field duplicates collected July 12 - 14, 2012. The samples were collected by Anchor QEA, LLC, and submitted to Axys Analytical Services, Ltd. (Axys) in Sidney, British Columbia and Pace Analytical Services, Inc. (Pace) in Minneapolis, Minnesota. The samples were analyzed for the following parameters: Total dissolved solids (TDS) by Standard Method (SM) 2540C Total suspended solids (TSS) by SM 2540D Total organic carbon (TOC) by U.S. Environmental Protection Agency (USEPA) method 9060 Perfluorinated organic compounds (PFCs) by Axys method MLA-060, Revision 10 Pace SDG number 10198875 and Axys sample data group (SDG) number L18218 and were reviewed in this report. Axys SDG L18218 consists of individual reports for batches WG40629, WG40630, and WG40640. Samples reviewed in this report are presented in Table 1. Sample ID LKCALHOUN-N-201207140945 LKCALHOUN-S-201207141017 MIN-RM0.0-C-201207111444 MINNE-RM847.0-C-201207111323 MISS-RM814.3-1-201207130838 MISS-RM814.3-2-201207130848 MISS-RM814.3-3-201207130900 MISS-RM815.8-1-201207131043 MISS-RM815.8-3-201207131014 MISS-RM815.8-4-201207130945 Table 1 Samples Reviewed Pace Lab ID 10198875001 10198875002 10198875003 10198875004 10198875005 10198875006 10198875007 10198875008 10198875009 10198875010 Axys Lab ID L18218-1 L18218-2 L18218-3 L18218-4 L18218-5 L18218-6 L18218-7 L18218-8 L18218-9 L18218-10 Matrix Water Water Water Water Water Water Water Water Water Water Analyses Requested PFCs, TDS, TSS, TOC PFCs, TDS, TSS, TOC PFCs, TDS, TSS, TOC PFCs, TDS, TSS, TOC PFCs, TDS, TSS, TOC PFCs, TDS, TSS, TOC PFCs, TDS, TSS, TOC PFCs, TDS, TSS, TOC PFCs, TDS, TSS, TOC PFCs, TDS, TSS, TOC Sample ID MISS-RM815.8-5-201207131000 MISS-RM815.8.2-201207131028 MISS-RM817.2-1-201207121340 MISS-RM817.2-2-201207121400 MISS-RM817.2-3-201207121416 MISS-RM817.2-4-201207121428 MISS-RM817.2-5-201207121453 MISS-RM818.5-1-201207121304 MISS-RM818.5-2-201207121311 MISS-RM818.5-3-201207121225 MISS-RM818.5-4-201207121242 MISS-RM818.5-5-201207121258 MISS-RM826.0-C-201207121120 MISS-RM829.0-C-201207121058 MISS-RM831.0-C-201207121030 MISS-RM835.2-1-201207111639 MISS-RM835.2-2-201207111628 MISS-RM835.2-3-201207111628 MISS-RM835.2-4-201207111616 MISS-RM836.3-C-201207111553 MISS-RM841.0-C-201207111530 MISS-RM844.1-C-201207110244 MISS-RM847.3-C-201207111400 PIGLK-N-201207120915 PIGLK-OF-201207121000 PIGLK-S-201207120930 WS-FD-20120711 WS-FD-20120712 WS-RB-20120714 TOC BLANK-20120716 Pace Lab ID 10198875011 10198875012 10198875013 10198875014 10198875015 10198875016 10198875017 10198875018 10198875019 10198875020 10198875021 10198875022 10198875023 10198875024 10198875025 10198875026 10198875027 10198875028 10198875029 10198875030 10198875031 10198875032 10198875033 10198875034 10198875035 10198875036 10198875037 10198875038 10198875039 10198875040 Axys Lab ID L18218-11 L18218-12 L18218-13 L18218-14 L18218-15 L18218-16 L18218-17 L18218-18 L18218-19 L18218-20 L18218-21 L18218-22 L18218-23 L18218-24 L18218-25 L18218-26 L18218-27 L18218-28 L18218-29 L18218-30 L18218-31 L18218-32 L18218-33 L18218-34 L18218-35 L18218-36 L18218-37 L18218-38 L18218-39 Matrix Water Water Water Water Water Water Water Water Water Water Water Water Water Water Water Water Water Water Water Water Water Water Water Water Water Water Water Water Water Water Mississippi Pool 2 January 17, 2013 Page 2 Analyses Requested PFCs, TDS, TSS, TOC PFCs, TDS, TSS, TOC PFCs, TDS, TSS, TOC PFCs, TDS, TSS, TOC PFCs, TDS, TSS, TOC PFCs, TDS, TSS, TOC PFCs, TDS, TSS, TOC PFCs, TDS, TSS, TOC PFCs, TDS, TSS, TOC PFCs, TDS, TSS, TOC PFCs, TDS, TSS, TOC PFCs, TDS, TSS, TOC PFCs, TDS, TSS, TOC PFCs, TDS, TSS, TOC PFCs, TDS, TSS, TOC PFCs, TDS, TSS, TOC PFCs, TDS, TSS, TOC PFCs, TDS, TSS, TOC PFCs, TDS, TSS, TOC PFCs, TDS, TSS, TOC PFCs, TDS, TSS, TOC PFCs, TDS, TSS, TOC PFCs, TDS, TSS, TOC PFCs, TDS, TSS, TOC PFCs, TDS, TSS, TOC PFCs, TDS, TSS, TOC PFCs, TDS, TSS, TOC PFCs, TDS, TSS, TOC PFCs, TDS, TSS, TOC TOC Data Validation and Qualifications The following comments refer to the laboratory's performance in meeting the quality assurance/quality control (QA/QC) guidelines outlined in the analytical procedures and data quality objective sections of the Quality Assurance Project Plan (QAPP). Laboratory results were reviewed using the following guidelines: USEPA Contract Laboratory Program National Functional Guidelines for Inorganic Data Review (USEPA 2004) USEPA Contract Laboratory Program National Functional Guidelines for Organic Data Review (USEPA 1999) Mississippi Pool 2 January 17, 2013 Page 3 USEPA Contract Laboratory Program National Functional Guidelines for Superfund Organic Methods Data Review (USEPA 2008) Laboratory and method QC criteria were also used as stated in USEPA 1986 (SW-846, Third Edition), Test Methods for Evaluating Solid Waste: Physical/Chemical Methods, update 1, August 1993; update II, January 1995; update IIA, February 1994; update IIB, August 1995; update III, June 1997; update IIIA, May 1999; update IIIB, June 2008; update IVA and IVB, January 2008. Unless noted in this report, laboratory results for the samples listed above were within QC criteria. Field Documentation Field documentation was checked for completeness and accuracy. The chain-of-custody forms were signed by Pace and Axys at the time of sample receipt; the samples were received in good condition. Coolers received at Pace were within the recommended temperature range of 4.02.0C, with the exception of one cooler that was received at ambient temperature; however, the samples were delivered on the day of collection so data are not expected to be affected. All coolers received at Axys were above 10C. The laboratory indicated that this does not significantly impact data accuracy, so data are not expected to be affected. Holding Times, Sample Containers and Sample Preservation Samples were appropriately preserved and analyzed within holding times. The laboratory provided polyethylene bottles for TOC sample collection by mistake, instead of the amber glass bottles recommended by the method. However, EPA method 9060 allows for conventional polyethylene as long as the containers do not contribute any contaminating organics to the sample. A TOC bottle blank (TOC Blank) was analyzed; no TOC was detected in the blank. Laboratory Method Blanks Laboratory method blanks were analyzed at the required frequencies. All method blanks were free of target analytes. Field Quality Control Mississippi Pool 2 January 17, 2013 Page 4 Field Blanks One field blank was collected in association with this sample set for PFCs. Perfluorobutanoate (PFBA) was detected in the field blank at a level above the reporting limit (RL). PFBA results in most samples were greater than ten times (10x) the concentration in the field blank; however, the following four samples contained PFBA at a level less than 10x: MIN-RM0.0-C-201207111444, MISS-RM835.2-4-201207111616, MISS-RM841.0-C201207111530 and MISS-RM847.3-C-201207111400. No data were qualified based on field blank results. Field Duplicates Two field duplicates were collected in association with this sample set. Detected results are summarized in Table 2. Table 2 Field Duplicate Summary Analyte Perfluorobutanoate (PFBA) Perfluorooctanoate (PFOA) TDS TSS TOC MISS-RM817.2-3-201207121416 WS-FD-20120712 RPD 19.7 ng/L 14.5 ng/L 30% 1.87 ng/L 2.25 ng/L 18% 255 mg/L 239 mg/L 6% 51.6 mg/L 31.2 mg/L 49% 16.1 mg/L 16.9 mg/L 5% Analyte Perfluorobutanoate (PFBA) Perfluorooctanoate (PFOA) Perfluoropentanoate (PFPeA) TDS TSS TOC MISS-RM835.2-1-201207111639 13.4 ng/L 1.05U ng/L 1.6U ng/L 261 mg/L 28.6 mg/L 17.1 mg/L WS-FD-20120711 12.9 ng/L 1.24 ng/L 1.51 ng/L 258 mg/L 30.4 mg/L 17.0 mg/L RPD 4% 200% 200% 1% 6% 1% Results at or near the reporting limit (RL) may have exaggerated relative percent difference (RPD) values. The PFBA and TSS RPD values for sample MISS-RM817.2-3-201207121416 exceeded the QAPP's 20% advisory limit for field duplicates. No data were qualified based on field duplicate results. Labeled Compound Recoveries Mississippi Pool 2 January 17, 2013 Page 5 Labeled compound recoveries were below the laboratory control limit for perfluorohexanoate (PFHxA) and/or perfluorobutanoate (PFBA) in several samples. Because final target sample concentrations are corrected using the labeled compound recoveries, no data were qualified unless the labeled compound was not quantifiable (NQ). In these cases, sample results have not been reported. PFHxA and PFBA were also below the control limit in the MSD performed on sample MISS-RM814.3-3-201207130900, however the target analyte %R values were within control limits, so data are not expected to be affected. All other labeled compound recoveries were within the laboratory control limits. See Table 3 for qualified data. Laboratory Control Sample and Laboratory Control Sample Duplicate Laboratory control samples (LCS) and laboratory control sample duplicates (LCSD) were analyzed at the required frequencies. All LCS/LCSD analyses yielded percent recovery (%R) and/or RPD values within laboratory control limits. Matrix Spike and Matrix Spike Duplicate Matrix spike (MS) and matrix spike duplicate (MSD) samples were analyzed at required frequencies. All MS/MSD analyses yielded %R and/or RPD values within laboratory control limits with the following exceptions: - SDG 10198875 TOC: The MS and/or MSD %R values for two of the replicates of samples LKCALHOUN-N-201207140945 and MISS-RM835.2-2-201207111628 were outside of the laboratory control limit. However, since the %R values were in control for the reported mean TOC value, no data were qualified. The TOC mean %R value for the MSD in sample MISS-RM835.2-3-201207111628 was above the control limit. Only the parent sample was qualified as potentially biased high, since the MS/MSDs performed on other samples resulted in %R values that were within control limits. - SDG L18218/Batch WG40629 PFCs: The %R values for the MS/MSD performed on sample MISS-RM814.3-3-201207130900 were above the project control limit for perfluoroheptanoate (PFHpA). No data were qualified since this compound was not detected in the parent sample. Mississippi Pool 2 January 17, 2013 Page 6 - SDG L18218/Batch WG40630 PFCs: The %R values for perfluoropentanoate (PFPeA) and perfluorobutanesulfonate (PFBS) were below the project control limit, and PFBA was not quantifiable in the MS performed on sample MISSRM818.5-5-201207121258. Associated results were qualified "J" or "UJ" to indicate a potentially low bias. See Table 3 for qualified data. Laboratory Replicates Laboratory replicates were analyzed for PFCs, TDS and TSS; results were within laboratory control limits. Precision was assessed for TOC using the MSD RPD values. Sample Analyses PFBA was not quantifiable in four samples, due to no %R for the associated labeled compound. Sample results were rejected and are not usable for any purpose. See Table 3 for qualified data. Method Reporting Limits and Method Detection Limits Most reporting limits were deemed acceptable as reported. Values for PFOS-1 were reported to the sample adjusted method detection limit (MDL). MDL values were determined using the laboratory's most recent MDL study and then adjusting for sample volume, final extract volume, and sample dilutions. Results detected above the MDL and below the method reporting limit (MRL), with a signal to noise ratio greater than 3, were qualified with a "J" to indicate that the results are estimated. Non-detected results were reported to the MDL and qualified with a "UJ" to indicate that the non-detected value is estimated. Results (detects and non-detects) for other compounds were reported to the sample adjusted MRL. Overall Assessment This evaluation determined that the laboratory followed the specified analytical methods and all requested sample analyses were completed. Accuracy was acceptable as demonstrated by the surrogate, LCS and MS/MSD %R values, with the exceptions noted above. Precision was Mississippi Pool 2 January 17, 2013 Page 7 also acceptable as demonstrated by the laboratory duplicates and MS/MSD RPD values. Most data were deemed acceptable as reported; all other data are acceptable as qualified. Table 3 summarizes the qualifiers applied to samples reviewed in this report. Data Qualifier Definitions U J UJ R DNR Indicates the compound or analyte was analyzed for but not detected at or above the specified limit. Indicates an estimated value. Indicates the compound or analyte was analyzed for but not detected and the specified limit reported is estimated Indicates data is rejected and unusable Do not report Sample ID MIN-RM0.0-C201207111444 MISS-RM815.8.2201207131028 MISS-RM815.8-1201207131043 MISS-RM815.8-3201207131014 MISS-RM815.8-4201207130945 MISS-RM815.8-5201207131000 MISS-RM817.2-1201207121340 MISS-RM817.2-2201207121400 MISS-RM817.2-3- Table 3 Data Qualification Summary Parameter Analyte Reported Result PFCs Perfluorooctanesulfonate (PFOS) 1.87U ng/L PFCs Perfluorooctanesulfonate (PFOS) 2.00U ng/L PFCs Perfluorooctanesulfonate (PFOS) 1.98U ng/L PFCs Perfluorooctanesulfonate (PFOS) 2.26U ng/L PFCs Perfluorooctanesulfonate (PFOS) 2.14U ng/L PFCs Perfluorooctanesulfonate (PFOS) 2.17U ng/L PFCs PFCs PFCs Perfluorooctanesulfonate (PFOS) Perfluorobutanoate (PFBA) Perfluorooctanesulfonate (PFOS) Perfluorobutanoate 1.97U ng/L 19.1 ng/L 2.03U ng/L 19.7 ng/L Qualified Result 0.84UJ ng/L 0.90UJ ng/L 0.89UJ ng/L 1.061J ng/L 0.96UJ ng/L 1.537J ng/L 0.89UJ ng/L 19.1J ng/L 1.653J ng/L 19.7J Reason Result reported to MDL Result reported to MDL Result reported to MDL Result detected below MRL Result reported to MDL Result detected below MRL Result reported to MDL No MS %R Result detected below MRL No MS %R Sample ID 201207121416 MISS-RM817.2-4201207121428 MISS-RM817.2-5201207121453 MISS-RM818.5-1201207121304 MISS-RM818.5-2201207121311 MISS-RM818.5-3201207121225 MISS-RM818.5-4201207121242 MISS-RM818.5-5201207121258 MISS-RM826.0-C201207121120 MISS-RM829.0-C201207121058 MISS-RM831.0-C- Parameter PFCs PFCs PFCs PFCs PFCs PFCs PFCs PFCs PFCs PFCs Analyte (PFBA) Perfluorooctanesulfonate (PFOS) Perfluorobutanoate (PFBA) Perfluorooctanesulfonate (PFOS) Perfluorobutanoate (PFBA) Perfluorobutanoate (PFBA) Perfluorooctanesulfonate (PFOS) Perfluorobutanoate (PFBA) Perfluorooctanesulfonate (PFOS) Perfluorobutanoate (PFBA) Perfluorooctanesulfonate (PFOS) Perfluorobutanoate (PFBA) Perfluorooctanesulfonate (PFOS) Perfluorobutanesulfonate (PFBS) Perfluorobutanoate (PFBA) Perfluoropentanoate (PFPeA) Perfluorooctanesulfonate (PFOS) Perfluorobutanoate (PFBA) Perfluorooctanesulfonate (PFOS) Perfluorobutanoate (PFBA) Perfluorooctanesulfonate (PFOS) Perfluorobutanoate Reported Result 1.95U ng/L 16.4 ng/L 1.88U ng/L 23.4 ng/L 21.2 ng/L 1.96U ng/L NQ 1.88U ng/L 19 ng/L 2.12U ng/L NQ 1.98U ng/L 2.01 ng/L NQ 2.39U ng/L 1.99U ng/L 14 ng/L 1.73U ng/L NQ 1.88U ng/L 18 ng/L Mississippi Pool 2 January 17, 2013 Page 8 Qualified Result ng/L 0.88UJ ng/L 16.4J ng/L 0.893J ng/L 23.4J ng/L 21.2J ng/L 0.88UJ ng/L R 0.84UJ ng/L Reason Result reported to MDL No MS %R Result detected below MRL No MS %R No MS %R Result reported to MDL Not quantifiable Result reported to MDL 19J ng/L No MS %R 1.482J ng/L R 0.89UJ ng/L 2.01J ng/L R 2.39UJ ng/L 1.374J ng/J Result detected below MRL Not quantifiable Result reported to MDL Low MS %R Not quantifiable Low MS %R Result detected below MRL 14J ng/L No MS %R 0.78UJ ng/L R 0.85UJ ng/L 18J ng/L Result reported to MDL Not quantifiable Result reported to MDL No MS %R Sample ID 201207121030 MISS-RM835.2-1201207111639 MISS-RM835.2-2201207111628 MISS-RM835.2-3201207111628 MISS-RM835.2-4201207111616 MISS-RM836.3-C201207111553 MISS-RM841.0-C201207111530 MISS-RM844.1-C201207110244 MISS-RM847.3-C201207111400 WS-FD-20120711 WS-FD-20120712 WS-RB-20120714 Parameter PFCs PFCs Conventionals PFCs PFCs PFCs PFCs PFCs PFCs PFCs PFCs PFCs Analyte (PFBA) Perfluorooctanesulfonate (PFOS) Perfluorobutanoate (PFBA) Perfluorooctanesulfonate (PFOS) Perfluorooctanesulfonate (PFOS) Total organic carbon Perfluorooctanesulfonate (PFOS) Perfluorooctanesulfonate (PFOS) Perfluorooctanesulfonate (PFOS) Perfluorooctanesulfonate (PFOS) Perfluorooctanesulfonate (PFOS) Perfluorooctanesulfonate (PFOS) Perfluorooctanesulfonate (PFOS) Perfluorooctanesulfonate (PFOS) Perfluorooctanesulfonate (PFOS) Reported Result 1.82U ng/L 13.4 ng/L 2.09U ng/L 1.90U ng/L 17.3 mg/L 2.05U ng/L 1.84U ng/L 2.09U ng/L 1.42U ng/L 1.80U ng/L 1.74U ng/L 1.73U ng/L 3.09U ng/L 1.83U ng/L Mississippi Pool 2 January 17, 2013 Page 9 Qualified Result Reason 0.993J ng/L 13.4J ng/L 0.94UJ ng/L 0.85UJ ng/L 17.3J mg/L 0.92UJ ng/L 0.83UJ ng/L 0.94UJ ng/L 0.805J ng/L 0.81UJ ng/L 0.79UJ ng/L 0.78UJ ng/L 1.39UJ ng/L 0.82UJ ng/L Result detected below MRL No MS %R Result reported to MDL Result reported to MDL High MSD %R value Result reported to MDL Result reported to MDL Result reported to MDL Result detected below MRL Result reported to MDL Result reported to MDL Result reported to MDL Result reported to MDL Result reported to MDL REFERENCES Cardno Entrix, 2011. Quality Assurance Project Plan; In Support of 2011 Fish and Water Collection from Mississippi River Pool 2. June 2011. Mississippi Pool 2 January 17, 2013 Page 10 USEPA (U.S. Environmental Protection Agency), 1986. Test methods for Evaluating Solid Waste: Physical/Chemical Methods. U.S. Environmental Protection Agency, Office of Solid Waste and Emergency Response. EPA 530/SW-846. USEPA, 2004. USEPA Contract Laboratory Program National Functional Guidelines for Inorganic Data Review. U.S. Environmental Protection Agency, Office of Superfund Remediation and Technology Innovation (OSRTI). EPA 540-R-04-004. October. USEPA, 1999. USEPA Contract Laboratory Program National Functional Guidelines for Organic Data Review. U.S. Environmental Protection Agency, Office of Emergency and Remedial Response. USEPA 540/R-99/008. October. USEPA, 2008. USEPA Contract Laboratory Program National Functional Guidelines for Superfund Organic Methods Data Review. U.S. Environmental Protection Agency, Office of Superfund Remediation and Technology Innovation. USEPA 540-R-08-01. June. 720 Olive Way, Suite 1900 Seattle, Washington 98101 Phone 206.287.9130 Fax 206.287.9131 www.anchorqea.com DATA VALIDATION REVIEW REPORT - USEPA STAGE 2A Project: Mississippi River Pool 2 Surface Water Sampling: Round 2 Project Number: 110800-01.01 Date: January 17, 2013 This report summarizes the review of analytical results for 36 water samples, two field blanks and two field duplicates collected July 30 - August 1, 2012. The samples were collected by Anchor QEA, LLC, and submitted to Axys Analytical Services, Ltd. (Axys) in Sidney, British Columbia and Pace Analytical Services, Inc. (Pace) in Minneapolis, Minnesota. The samples were analyzed for the following parameters: Total dissolved solids (TDS) by Standard Method (SM) 2540C Total suspended solids (TSS) by SM 2540D Total organic carbon (TOC) by U.S. Environmental Protection Agency (USEPA) method 9060 Perfluorinated organic compounds (PFCs) by Axys method MLA-060, Revision 10 Pace SDG number 10200857 and Axys sample data group (SDG) number L18315 and were reviewed in this report. Axys SDG L18315 consists of individual reports for batches WG40822, WG40823, WG40824. Samples reviewed in this report are presented in Table 1. Table 1 Samples Reviewed Sample ID LKCALHOUN-N-201208010841 LKCALHOUN-S-201208010821 MINNE-RM847.0-C-201207301237 MIN-RM0.0-C-201207301321 MISS-RM814.3-1-201207311537 MISS-RM814.3-2-201207311544 MISS-RM814.3-3-201207311720 MISS-RM815.8.2-201207311430 Pace Lab ID Axys Lab ID Matrix Analyses Requested 10200857001 10200857002 10200857004 10200857003 10200857005 10200857006 10200857007 10200857011 L18315-1 L18315-2 L18315-4 L18315-3 L18315-5 L18315-6 L18315-7 L18315-12 Water Water Water Water Water Water Water Water PFCs, TDS, TSS, TOC PFCs, TDS, TSS, TOC PFCs, TDS, TSS, TOC PFCs, TDS, TSS, TOC PFCs, TDS, TSS, TOC PFCs, TDS, TSS, TOC PFCs, TDS, TSS, TOC PFCs, TDS, TSS, TOC Sample ID MISS-RM815.8-1-201207311443 MISS-RM815.8-3-201207311412 MISS-RM815.8-4-201207311403 MISS-RM815.8-5-201207311352 MISS-RM817.2-1-201207311246 MISS-RM817.2-2-201207311236 MISS-RM817.2-3-201207311226 MISS-RM817.2-4-201207311213 MISS-RM817.2-5-201207311158 MISS-RM818.5-1-201207311304 MISS-RM818.5-2-201207311313 MISS-RM818.5-3-201207311325 MISS-RM818.5-4-201207311342 MISS-RM818.5-5-201207311047 MISS-RM826.0-C-201207311002 MISS-RM829.0-C-201207310938 MISS-RM831.0-C-201207301603 MISS-RM835.2-1-201207301438 MISS-RM835.2-2-201207301343 MISS-RM835.2-3-201207301347 MISS-RM835.2-4-201207301351 MISS-RM836.3-C-201207301334 MISS-RM841.0-C-201207301337 MISS-RM844.1-C-201207301300 MISS-RM847.3-C-201207301213 PIGLK-N-201207310857 PIGLK-OF-201207301518 PIGLK-S-201207301457 WS-FB-20120730 WS-FB-20120731 WS-FD-20120730 WS-FD-20120731 Mississippi Pool 2 - Round 2 January 17, 2013 Page 2 Pace Lab ID Axys Lab ID Matrix Analyses Requested 10200857008 10200857009 10200857010 10200857040 10200857012 10200857013 10200857014 10200857015 10200857016 10200857017 10200857018 10200857019 10200857020 10200857021 10200857022 10200857023 10200857024 10200857025 10200857026 10200857027 10200857028 10200857029 10200857030 10200857031 10200857032 10200857033 10200857034 10200857035 10200857036 10200857037 10200857038 10200857039 L18315-8 L18315-9 L18315-10 L18315-11 L18315-13 L18315-14 L18315-15 L18315-16 L18315-17 L18315-18 L18315-19 L18315-20 L18315-21 L18315-22 L18315-23 L18315-24 L18315-25 L18315-26 L18315-27 L18315-28 L18315-29 L18315-30 L18315-31 L18315-32 L18315-33 L18315-34 L18315-35 L18315-36 L18315-37 L18315-38 L18315-39 L18315-40 Water Water Water Water Water Water Water Water Water Water Water Water Water Water Water Water Water Water Water Water Water Water Water Water Water Water Water Water Water Water Water Water PFCs, TDS, TSS, TOC PFCs, TDS, TSS, TOC PFCs, TDS, TSS, TOC PFCs, TDS, TSS, TOC PFCs, TDS, TSS, TOC PFCs, TDS, TSS, TOC PFCs, TDS, TSS, TOC PFCs, TDS, TSS, TOC PFCs, TDS, TSS, TOC PFCs, TDS, TSS, TOC PFCs, TDS, TSS, TOC PFCs, TDS, TSS, TOC PFCs, TDS, TSS, TOC PFCs, TDS, TSS, TOC PFCs, TDS, TSS, TOC PFCs, TDS, TSS, TOC PFCs, TDS, TSS, TOC PFCs, TDS, TSS, TOC PFCs, TDS, TSS, TOC PFCs, TDS, TSS, TOC PFCs, TDS, TSS, TOC PFCs, TDS, TSS, TOC PFCs, TDS, TSS, TOC PFCs, TDS, TSS, TOC PFCs, TDS, TSS, TOC PFCs, TDS, TSS, TOC PFCs, TDS, TSS, TOC PFCs, TDS, TSS, TOC PFCs, TDS, TSS, TOC PFCs, TDS, TSS, TOC PFCs, TDS, TSS, TOC PFCs, TDS, TSS, TOC Data Validation and Qualifications The following comments refer to the laboratory's performance in meeting the quality assurance/quality control (QA/QC) guidelines outlined in the analytical procedures and data quality objective sections of the Quality Assurance Project Plan (QAPP). Laboratory results were reviewed using the following guidelines: Mississippi Pool 2 - Round 2 January 17, 2013 Page 3 USEPA Contract Laboratory Program National Functional Guidelines for Inorganic Data Review (USEPA 2004) USEPA Contract Laboratory Program National Functional Guidelines for Organic Data Review (USEPA 1999) USEPA Contract Laboratory Program National Functional Guidelines for Superfund Organic Methods Data Review (USEPA 2008) Laboratory and method QC criteria were also used as stated in USEPA 1986 (SW-846, Third Edition), Test Methods for Evaluating Solid Waste: Physical/Chemical Methods, update 1, August 1993; update II, January 1995; update IIA, February 1994; update IIB, August 1995; update III, June 1997; update IIIA, May 1999; update IIIB, June 2008; update IVA and IVB, January 2008. Unless noted in this report, laboratory results for the samples listed above were within QC criteria. Field Documentation Field documentation was checked for completeness and accuracy. The chain-of-custody forms were signed by Pace and Axys at the time of sample receipt; the samples were received in good condition. Coolers received at Pace were within the recommended temperature range of 4.02.0C. All coolers received at Axys were above the recommended temperature range, but less than or equal to 10C. The laboratory indicated that this does not significantly impact data accuracy. Holding Times, Sample Containers and Sample Preservation Samples were appropriately preserved and analyzed within holding times. Laboratory Method Blanks Laboratory method blanks were analyzed at the required frequencies. All method blanks were free of target analytes. Field Quality Control Field Blanks Two field blanks were collected in association with this sample set for TOC and PFCs, and were both free of target analytes. Field Duplicates Mississippi Pool 2 - Round 2 January 17, 2013 Page 4 Two field duplicates were collected in association with this sample set. Detected results are summarized in Table 2. Table 2 Field Duplicate Summary Analyte Perfluorobutanoate (PFBA) Perfluoroheptanoate (PFHpA) Perfluorohexanoate (PFHxA) Perfluorooctanoate (PFOA) Total dissolved solids Total organic carbon Total suspended solids MISS-RM835.2-4-201207301351 12.5 ng/L 1.80U ng/L 1.06U ng/L 2.06 ng/L 214 mg/L 15.1 mg/L 13.2 mg/L WS-FD-20120730 11.4 ng/L 2.02 ng/L 0.962 ng/L 1.21 ng/L 206 mg/L 14.9 mg/L 13.4 mg/L RPD 9% 200% 200% 52% 4% 1% 2% Analyte Perfluorobutanoate (PFBA) Perfluorohexanoate (PFHxA) Perfluorooctanesulfonate (PFOS) Perfluorooctanoate (PFOA) Perfluoropentanoate (PFPeA) Total dissolved solids Total organic carbon Total suspended solids MISS-RM817.2-5-201207311158 24.8 ng/L 1.34 ng/L 3.49 ng/L 6.13 ng/L 2.96 ng/L 246 mg/L 13.7 mg/L 28.6 mg/L WS-FD-20120731 27.6 ng/L 3.26U ng/L 3.27 ng/L 6.80 ng/L 3.26U ng/L 248 mg/L 13.5 mg/L 26.5 mg/L RPD 11% 200% 7% 10% 200% 1% 1% 8% Results at or near the reporting limit (RL) may have exaggerated relative percent difference (RPD) values. The PFOA RPD values for sample MISS-RM835.2-4-201207301351 exceeded the QAPP's 20% advisory limit for field duplicates. No data were qualified based on field duplicate results. Labeled Compound Recoveries Labeled compound recoveries were within the laboratory control limits. Laboratory Control Sample Laboratory control samples (LCS) or ongoing precision and recovery standard (OPR) were analyzed at the required frequencies. All LCS analyses yielded percent recovery (%R) values within laboratory control limits, with the exception of two PFC compounds in SDG L18315, batch WG40823. The percent recovery (%R) values for perfluorooctanesulfonate (PFOS) and perfluorohexanesulfonate (PFHxS) in the ongoing precision and recovery standard were Mississippi Pool 2 - Round 2 January 17, 2013 Page 5 below the project control limit. Associated sample results have been qualified "J" or "UJ" to indicate a potentially low bias. See Table 3 for qualified data. Matrix Spike and Matrix Spike Duplicate Matrix spike (MS) and matrix spike duplicate (MSD) samples were analyzed at required frequencies. All MS/MSD analyses yielded %R and/or RPD values within laboratory control limits with the following exceptions: - SDG 10198875 TOC: The MSD %R values for one of the replicates and for the TOC mean of sample MISS-RM826.0-C-201207311002 were above the laboratory control limit. Only the parent sample was qualified as potentially biased high, since the MS/MSDs performed on other samples resulted in %R values that were within control limits. - SDG L18315/Batch WG40822 PFCs: In the MS performed on sample MISSRM814.3-1-201207311537, the %R value for perfluoroheptanoate (PFHpA) was above the project control limit. The data were not qualified because PFHpA was not detected in the sample. The MS %R value for perfluorobutanesulfonate (PFBS) was below the project control limit. The parent sample result was qualified "UJ" to indicate a potentially low bias. - SDG L18315/Batch WG40823 PFCs: In the MS performed on sample MISSRM815.8-3-201207311412, the %R values for perfluoropentanoate (PFPeA) and PFBS were below the project control limit. The parent sample results were qualified "UJ" to indicate a potentially low bias. - SDG L18315/Batch WG40824 PFCs: In the MS performed on sample MISSRM818.5-5-201207311047, the %R value for PFBS was below the project control limit. The parent sample result was qualified "UJ" to indicate a potentially low bias. See Table 3 for qualified data. Laboratory Replicates Laboratory replicates were analyzed for PFCs, TDS and TSS; results were within laboratory control limits. Precision was assessed for TOC using the MSD RPD values. Mississippi Pool 2 - Round 2 January 17, 2013 Page 6 Method Reporting Limits and Method Detection Limits Most reporting limits were deemed acceptable as reported. Values for PFOS-1 were reported to the sample adjusted method detection limit (MDL). MDL values were determined using the laboratory's most recent MDL study and then adjusting for sample volume, final extract volume, and sample dilutions. Results detected above the MDL and below the method reporting limit (MRL), with a signal to noise ratio greater than 3, were qualified with a "J" to indicate that the results are estimated. Non-detected results were reported to the MDL and qualified with a "UJ" to indicate that the non-detected value is estimated. Results (detects and non-detects) for other compounds were reported to the sample adjusted MRL. Overall Assessment This evaluation determined that the laboratory followed the specified analytical methods and all requested sample analyses were completed. Accuracy was acceptable as demonstrated by the surrogate, LCS and MS/MSD %R values, with the exceptions noted above. Precision was also acceptable as demonstrated by the laboratory duplicates and MS/MSD RPD values. Most data were deemed acceptable as reported; all other data are acceptable as qualified. Table 3 summarizes the qualifiers applied to samples reviewed in this report. Data Qualifier Definitions U Indicates the compound or analyte was analyzed for but not detected at or above the specified limit. J Indicates an estimated value. UJ Indicates the compound or analyte was analyzed for but not detected and the specified limit reported is estimated R Indicates data is rejected and unusable DNR Do not report Sample ID MIN-RM0.0-C201207301321 Table 3 Data Qualification Summary Parameter Analyte Reported Result Qualified Result PFCs Perfluorooctanesulfonate 1.92U 1.733J (PFOS) ng/L ng/L Reason Result detected below MRL Sample ID MISS-RM814.3-1- 201207311537 MISS-RM815.8-1- 201207311443 MISS-RM815.8-2201207311430 MISS-RM815.8-3201207311412 MISS-RM815.8-4201207311403 MISS-RM815.8-5201207311352 MISS-RM817.2-1201207311246 MISS-RM817.2-2201207311236 MISS-RM817.2-3201207311226 MISS-RM817.2-4201207311213 Parameter PFCs PFCs PFCs PFCs PFCs PFCs PFCs PFCs PFCs PFCs Analyte Perfluorobutanesulfonate (PFBS) Perfluorooctanesulfonate (PFOS) Perfluorooctanesulfonate (PFOS) Perfluoropentanoate (PFPeA) Perfluorobutanesulfonate (PFBS) Perfluorohexanesulfonate (PFHxS) Perfluorooctanesulfonate (PFOS) Perfluorooctanesulfonate (PFOS) Perfluorooctanesulfonate (PFOS) Perfluorooctanesulfonate (PFOS) Perfluorooctanesulfonate (PFOS) Perfluorohexanesulfonate (PFHxS) Perfluorooctanesulfonate (PFOS) Perfluorohexanesulfonate (PFHxS) Perfluorooctanesulfonate (PFOS) Mississippi Pool 2 - Round 2 January 17, 2013 Page 7 Reported Result 1.94U ng/L 1.99U ng/L 2.00U ng/L 2.70U ng/L 2.15U ng/L 2.15U ng/L 2.15U ng/L 1.98U ng/L 2.03U ng/L 1.90U ng/L 1.98U ng/L 1.97U ng/L 1.97U ng/L 1.89U ng/L 1.89U ng/L Qualified Result 1.94UJ ng/L 1.347J ng/L 1.821J ng/L 2.70UJ ng/L 2.15UJ ng/L 2.15UJ ng/L 1.415J ng/L 0.89UJ ng/L 1.506J ng/L 1.646J ng/L 0.89UJ ng/L 1.97UJ ng/L 1.503J ng/L 1.89UJ ng/L 1.793J ng/L Reason Low MS %R Result detected below MRL Result detected below MRL Low MS %R Low LCS %R Low LCS %R; Result detected below MRL Result reported to MDL Result detected below MRL Result detected below MRL Result reported to MDL Low LCS %R Low LCS %R; Result detected below MRL Low LCS %R Low LCS %R; Result detected below Sample ID MISS-RM817.2-5201207311158 MISS-RM818.5-1201207311304 MISS-RM818.5-2201207311313 MISS-RM818.5-3201207311325 MISS-RM818.5-4201207311342 MISS-RM818.5-5201207311047 MISS-RM826.0-C201207311002 MISS-RM829.0-C201207310938 Parameter PFCs PFCs PFCs PFCs PFCs PFCs PFCs Conventionals PFCs Analyte Perfluorohexanesulfonate (PFHxS) Perfluorooctanesulfonate (PFOS) Perfluorohexanesulfonate (PFHxS) Perfluorooctanesulfonate (PFOS) Perfluorohexanesulfonate (PFHxS) Perfluorooctanesulfonate (PFOS) Perfluorohexanesulfonate (PFHxS) Perfluorooctanesulfonate (PFOS) Perfluorohexanesulfonate (PFHxS) Perfluorooctanesulfonate (PFOS) Perfluorobutanesulfonate (PFBS) Perfluorohexanesulfonate (PFHxS) Perfluorooctanesulfonate (PFOS) Total organic carbon Perfluorohexanesulfonate (PFHxS) Perfluorooctanesulfonate (PFOS) Mississippi Pool 2 - Round 2 January 17, 2013 Page 8 Reported Result 1.82U ng/L 3.49 ng/L 1.94U ng/L 1.94U ng/L 1.94U ng/L 1.94U ng/L 2.05U ng/L 2.05U ng/L 2.01U ng/L 2.01U ng/L 1.97U ng/L 1.81U ng/L 1.81U ng/L 14.7 mg/L 1.85U ng/L 1.85U ng/L Qualified Result 1.82UJ ng/L 3.49J ng/L 1.94UJ ng/L 1.431J ng/L 1.94UJ ng/L 0.919J ng/L 2.05UJ ng/L 1.096J ng/L 2.01UJ ng/L 1.807J ng/L 1.97UJ ng/L 1.81UJ ng/L 1.549J ng/L 14.7J mg/L 1.85UJ ng/L 0.83UJ ng/L Reason MRL Low LCS %R Low LCS %R Low LCS %R; Result detected below MRL Low LCS %R Low LCS %R; Result detected below MRL Low LCS %R Low LCS %R; Result detected below MRL Low LCS %R Low LCS %R; Result detected below MRL Low MS %R Low LCS %R Low LCS %R; Result detected below MRL High MS %R Low LCS %R Low LCS %R; Result Sample ID MISS-RM831.0-C201207301603 MISS-RM835.2-1201207301438 MISS-RM835.2-2201207301343 MISS-RM835.2-3201207301347 MISS-RM835.2-4201207301351 MISS-RM836.3-C201207301334 MISS-RM841.0-C201207301337 MISS-RM844.1-C201207301300 MISS-RM847.3-C201207301213 WS-FB-20120730 WS-FB-20120731 WS-FD-20120730 Parameter PFCs PFCs PFCs PFCs PFCs PFCs PFCs PFCs PFCs PFCs PFCs PFCs Analyte Perfluorohexanesulfonate (PFHxS) Perfluorooctanesulfonate (PFOS) Perfluorohexanesulfonate (PFHxS) Perfluorooctanesulfonate (PFOS) Perfluorohexanesulfonate (PFHxS) Perfluorooctanesulfonate (PFOS) Perfluorooctanesulfonate (PFOS) Perfluorooctanesulfonate (PFOS) Perfluorooctanesulfonate (PFOS) Perfluorooctanesulfonate (PFOS) Perfluorooctanesulfonate (PFOS) Perfluorooctanesulfonate (PFOS) Perfluorooctanesulfonate (PFOS) Perfluorooctanesulfonate (PFOS) Perfluorooctanesulfonate (PFOS) Mississippi Pool 2 - Round 2 January 17, 2013 Page 9 Reported Result 2.21U ng/L 2.21U ng/L 2.1U ng/L 2.1U ng/L 2.04U ng/L 2.04U ng/L 1.72U ng/L 1.88U ng/L 2.04U ng/L 1.86U ng/L 2.01U ng/L 2.00U ng/L 1.98U ng/L 2.12U ng/L 1.8U ng/L Qualified Result 2.21UJ ng/L 0.99UJ ng/L 2.1UJ ng/L 0.95UJ ng/L 2.04UJ ng/L 1.217J ng/L 0.77UJ ng/L 1.738J ng/L 0.92UJ ng/L 0.84UJ ng/L 0.91UJ ng/L 0.90UJ ng/L 0.89UJ ng/L 0.95UJ ng/L 0.81UJ ng/L Reason reported to MDL Low LCS %R Low LCS %R; Result reported to MDL Low LCS %R Low LCS %R; Result reported to MDL Low LCS %R Low LCS %R; Result detected below MRL Result reported to MDL Result detected below MRL Result reported to MDL Result reported to MDL Result reported to MDL Result reported to MDL Result reported to MDL Result reported to MDL Result reported Sample ID Parameter Analyte Mississippi Pool 2 - Round 2 January 17, 2013 Page 10 Reported Qualified Result Result Reason to MDL REFERENCES Cardno Entrix, 2011. Quality Assurance Project Plan; In Support of 2011 Fish and Water Collection from Mississippi River Pool 2. June 2011. USEPA (U.S. Environmental Protection Agency), 1986. Test methods for Evaluating Solid Waste: Physical/Chemical Methods. U.S. Environmental Protection Agency, Office of Solid Waste and Emergency Response. EPA 530/SW-846. USEPA, 1999. USEPA Contract Laboratory Program National Functional Guidelines for Organic Data Review. U.S. Environmental Protection Agency, Office of Emergency and Remedial Response. USEPA 540/R-99/008. October. USEPA, 2004. USEPA Contract Laboratory Program National Functional Guidelines for Inorganic Data Review. U.S. Environmental Protection Agency, Office of Superfund Remediation and Technology Innovation (OSRTI). EPA 540-R-04-004. October. USEPA, 2008. USEPA Contract Laboratory Program National Functional Guidelines for Superfund Organic Methods Data Review. U.S. Environmental Protection Agency, Office of Superfund Remediation and Technology Innovation. USEPA 540-R-08-01. June. 720 Olive Way, Suite 1900 Seattle, Washington 98101 Phone 206.287.9130 Fax 206.287.9131 www.anchorqea.com DATA VALIDATION REVIEW REPORT - USEPA STAGE 2A Project: Mississippi River Pool 2 Surface Water Sampling: Round 3 Project Number: Date: 110800-01.01 January 17, 2013 This report summarizes the review of analytical results for 36 water samples, two field blanks and two field duplicates collected August 27 through 29, 2012. The samples were collected by Anchor QEA, LLC, and submitted to Axys Analytical Services, Ltd. (Axys) in Sidney, British Columbia and Pace Analytical Services, Inc. (Pace) in Minneapolis, Minnesota. The samples were analyzed for the following parameters: Total dissolved solids (TDS) by Standard Method (SM) 2540C Total suspended solids (TSS) by SM 2540D Total organic carbon (TOC) by U.S. Environmental Protection Agency (USEPA) method 9060 Perfluorinated organic compounds (PFCs) by Axys method MLA-060, Revision 10 Pace SDG number 10203837 and Axys sample data group (SDG) number L18486 were reviewed in this report. Axys SDG L18486 consists of individual reports for batches WG41168 and WG41317. Samples reviewed in this report are presented in Table 1. Table 1 Samples Reviewed Sample ID LKCALHOUN-N-201208291121 LKCALHOUN-S-201208291224 MIN-RM0.0-C-201208271234 MINNE-RM847.0-C-201208271213 MISS-RM814.3-1-201208281339 MISS-RM814.3-2-201208281344 MISS-RM814.3-3-201208281352 MISS-RM815.8-1-201208281200 Pace Lab ID Axys Lab ID Matrix Analyses Requested 10203837001 10203837002 10203837003 10203837004 10203837005 10203837006 10203837007 10203837008 L18486-1 L18486-2 L18486-3 L18486-4 L18486-5 L18486-6 L18486-7 L18486-8 Water Water Water Water Water Water Water Water PFCs, TDS, TSS, TOC PFCs, TDS, TSS, TOC PFCs, TDS, TSS, TOC PFCs, TDS, TSS, TOC PFCs, TDS, TSS, TOC PFCs, TDS, TSS, TOC PFCs, TDS, TSS, TOC PFCs, TDS, TSS, TOC Mississippi Pool 2 - Round 3 January 17, 2013 Page 2 Sample ID MISS-RM815.8-3-201208281230 MISS-RM815.8-4-201208281237 MISS-RM815.8-5-201208281245 MISS-RM815.8.2-201208281216 MISS-RM817.2-1-201208281137 MISS-RM817.2-2-201208281126 MISS-RM817.2-3-20120828111 MISS-RM817.2-4-201208281106 MISS-RM817.2-5-201208281059 MISS-RM818.5-1-201208280915 MISS-RM818.5-2-201208280932 MISS-RM818.5-3-201208280939 MISS-RM818.5-4-201208280952 MISS-RM818.5-5-201208281015 MISS-RM826.0-C-201208280842 MISS-RM829.0-C-201208280818 MISS-RM831.0-C-201208271545 MISS-RM835.2-1-201208271339 MISS-RM835.2-2-201208271358 MISS-RM835.2-3-201208271402 MISS-RM835.2-4-201208271410 MISS-RM836.3-C-201208271329 MISS-RM841.0-C-201208271243 MISS-RM844.1-C-201208271224 MISS-RM847.3-C-201208271151 PIGLK-N-201208271513 PIGLK-OF-201208271425 PIGLK-S-201208271453 WS-FB-20120828 WS-FB-20120829 WS-FD-20120827 WS-FD-20120828 Pace Lab ID Axys Lab ID Matrix Analyses Requested 10203837009 10203837010 10203837011 10203837012 10203837013 10203837014 10203837015 10203837016 10203837017 10203837018 10203837019 10203837020 10203837021 10203837022 10203837023 10203837024 10203837025 10203837026 10203837027 10203837028 10203837029 10203837030 10203837031 10203837032 10203837033 10203837034 10203837035 10203837036 10203837037 10203837038 10203837039 10203837040 L18486-9 L18486-10 L18486-11 L18486-12 L18486-13 L18486-14 L18486-15 L18486-16 L18486-17 L18486-18 L18486-19 L18486-20 L18486-21 L18486-22 L18486-23 L18486-24 L18486-25 L18486-26 L18486-27 L18486-28 L18486-29 L18486-30 L18486-31 L18486-32 L18486-33 L18486-34 L18486-35 L18486-36 L18486-37 L18486-38 L18486-39 L18486-40 Water Water Water Water Water Water Water Water Water Water Water Water Water Water Water Water Water Water Water Water Water Water Water Water Water Water Water Water Water Water Water Water PFCs, TDS, TSS, TOC PFCs, TDS, TSS, TOC PFCs, TDS, TSS, TOC PFCs, TDS, TSS, TOC PFCs, TDS, TSS, TOC PFCs, TDS, TSS, TOC PFCs, TDS, TSS, TOC PFCs, TDS, TSS, TOC PFCs, TDS, TSS, TOC PFCs, TDS, TSS, TOC PFCs, TDS, TSS, TOC PFCs, TDS, TSS, TOC PFCs, TDS, TSS, TOC PFCs, TDS, TSS, TOC PFCs, TDS, TSS, TOC PFCs, TDS, TSS, TOC PFCs, TDS, TSS, TOC PFCs, TDS, TSS, TOC PFCs, TDS, TSS, TOC PFCs, TDS, TSS, TOC PFCs, TDS, TSS, TOC PFCs, TDS, TSS, TOC PFCs, TDS, TSS, TOC PFCs, TDS, TSS, TOC PFCs, TDS, TSS, TOC PFCs, TDS, TSS, TOC PFCs, TDS, TSS, TOC PFCs, TDS, TSS, TOC PFCs, TDS, TSS, TOC PFCs, TDS, TSS, TOC PFCs, TDS, TSS, TOC PFCs, TDS, TSS, TOC Data Validation and Qualifications The following comments refer to the laboratory's performance in meeting the quality assurance/quality control (QA/QC) guidelines outlined in the analytical procedures and data quality objective sections of the Quality Assurance Project Plan (QAPP). Laboratory results were reviewed using the following guidelines: Mississippi Pool 2 - Round 3 January 17, 2013 Page 3 USEPA Contract Laboratory Program National Functional Guidelines for Inorganic Data Review (USEPA 2004) USEPA Contract Laboratory Program National Functional Guidelines for Organic Data Review (USEPA 1999) USEPA Contract Laboratory Program National Functional Guidelines for Superfund Organic Methods Data Review (USEPA 2008) Laboratory and method QC criteria were also used as stated in USEPA 1986 (SW-846, Third Edition), Test Methods for Evaluating Solid Waste: Physical/Chemical Methods, update 1, August 1993; update II, January 1995; update IIA, February 1994; update IIB, August 1995; update III, June 1997; update IIIA, May 1999; update IIIB, June 2008; update IVA and IVB, January 2008. Unless noted in this report, laboratory results for the samples listed above were within QC criteria. Field Documentation Field documentation was checked for completeness and accuracy. The chain-of-custody forms were signed by Pace and Axys at the time of sample receipt; the samples were received in good condition. Four coolers received at Pace were above the recommended temperature range of 4.02.0C, but below 10C. One cooler was received at 10.2C. Data is not expected to be affected since the samples were preserved at the time of collection. Two coolers received at Axys were above the recommended temperature range, but less than or equal to 10C; two other coolers were above 10C. The laboratory indicated that this does not significantly impact data accuracy, so data were not qualified. Holding Times, Sample Containers and Sample Preservation Samples were appropriately preserved and analyzed within holding times. Laboratory Method Blanks Laboratory method blanks were analyzed at the required frequencies. All method blanks were free of target analytes. Field Quality Control Mississippi Pool 2 - Round 3 January 17, 2013 Page 4 Field Blanks Two field blanks were collected in association with this sample set for TDS, TSS, TOC and PFCs, and were free of target analytes. Field Duplicates Two field duplicates were collected in association with this sample set. Detected results are summarized in Table 2. Table 2 Field Duplicate Summary Analyte Perfluorobutanoate (PFBA) Perfluoroheptanoate (PFHpA) Perfluorohexanoate (PFHxA) Perfluorooctanesulfonate (PFOS) Perfluorooctanoate (PFOA) Perfluoropentanoate (PFPeA) Total dissolved solids Total organic carbon Total suspended solids MISS-RM831.0-C-201208271545 14.1 ng/L 2.01 ng/L 2.30 ng/L 2.18U ng/L 4.62 ng/L 1.56U ng/L 327 mg/L 10.6 mg/L 14.8 mg/L WS-FD-20120827 14.2 ng/L 1.20 ng/L 1.94 ng/L 2.40 ng/L 5.01 ng/L 2.27 ng/L 335 mg/L 10.1 mg/L 15.0 mg/L RPD 1% 50% 17% 200% 8% 200% 2% 5% 1% Analyte Perfluorobutanesulfonate (PFBS) Perfluorobutanoate (PFBA) Perfluoroheptanoate (PFHpA) Perfluorohexanesulfonate (PFHxS) Perfluorohexanoate (PFHxA) Perfluorononanoate (PFNA) Perfluorooctanesulfonate (PFOS) Perfluorooctanoate (PFOA) Perfluoropentanoate (PFPeA) Total dissolved solids Total suspended solids Total organic carbon MISS-RM814.3-2-201208281344 26.9 ng/L 70.2 ng/L 4.67 ng/L 7.08 ng/L 10.0 ng/L 1.02U ng/L 8.30 ng/L 20.4 ng/L 10.4 ng/L 334 mg/L 26.0 mg/L 10.5 mg/L WS-FD-20120828 24.4 ng/L 79.8 ng/L 3.74 ng/L 4.77 ng/L 7.21 ng/L 1.12 ng/L 6.09 ng/L 19.7 ng/L 9.00 ng/L 318 mg/L 25.7 mg/L 10.2 mg/L RPD 10% 13% 22% 39% 32% 200% 31% 3% 14% 5% 1% 3% Results at or near the reporting limit (RL) may have exaggerated relative percent difference (RPD) values. Results below detection were treated as a zero concentration when calculating RPD values. Three PFCs had RPD values that exceeded the QAPP's 20% advisory limit for field duplicates in sample MISS-RM831.0-C-201208271545. Five PFCs had RPD values that Mississippi Pool 2 - Round 3 January 17, 2013 Page 5 exceeded the advisory limit in sample MISS-RM814.3-2-201208281344. No data were qualified based on field duplicate results. Labeled Compound Recoveries Labeled compound recoveries were within the laboratory control limits with one exception. The compound 13C2-Perfluorocaproic acid (13C2-PFHxA) in sample PIGLK-N-201208271513 recovered below method control limits. Because final target sample concentrations are corrected using the labeled compound recoveries, no data were qualified. Laboratory Control Sample Laboratory control samples (LCS) or ongoing precision and recovery standard (OPR) were analyzed at the required frequencies. All LCS and OPR analyses yielded percent recovery (%R) values within laboratory control limits. Matrix Spike and Matrix Spike Duplicate Matrix spike (MS) and matrix spike duplicate (MSD) samples were analyzed at required frequencies. All MS/MSD analyses yielded %R and/or RPD values within laboratory control limits with the following exceptions: - SDG 10203837 TOC: The MS and/or the MSD %R values for several of the replicates and for the TOC mean of samples MISS-RM818.5-4-201208280952 and MISS-RM826.0-C-201208280842 were above the laboratory control limit. Associated detected results were qualified "J" to indicate a potentially high bias. See Table 3 for qualified data. Laboratory Replicates Laboratory replicates were analyzed for PFCs, TDS and TSS; results were within laboratory control limits. Precision was assessed for TOC using the MSD RPD values. Method Reporting Limits and Method Detection Limits Most reporting limits were deemed acceptable as reported. Values for PFOS-1 were reported to the sample adjusted method detection limit (MDL). MDL values were determined using the laboratory's most recent MDL study and then adjusting for sample volume, final extract volume, and sample dilutions. Results detected above the MDL and below the method reporting limit (MRL), with a signal to noise ratio greater than 3, were qualified with a "J" to Mississippi Pool 2 - Round 3 January 17, 2013 Page 6 indicate that the results are estimated. Non-detected results were reported to the MDL and qualified with a "UJ" to indicate that the non-detected value is estimated. Results (detects and non-detects) for other compounds were reported to the sample adjusted MRL. Overall Assessment This evaluation determined that the laboratory followed the specified analytical methods and all requested sample analyses were completed. Accuracy was acceptable as demonstrated by the surrogate, LCS, OPR and MS/MSD %R values, with the exceptions noted above. Precision was also acceptable as demonstrated by the laboratory duplicates and MS/MSD RPD values. Most data were deemed acceptable as reported; all other data are acceptable as qualified. Table 3 summarizes the qualifiers applied to samples reviewed in this report. Data Qualifier Definitions U J UJ R DNR Indicates the compound or analyte was analyzed for but not detected at or above the specified limit. Indicates an estimated value. Indicates the compound or analyte was analyzed for but not detected and the specified limit reported is estimated Indicates data is rejected and unusable Do not report Sample ID MIN-RM0.0-C201208271234 MISS-RM818.5-4201208280952 MISS-RM818.5-5201208281015 MISS-RM826.0-C201208280842 Parameter PFCs PFCs Conventionals PFCs Conventionals PFCs Conventionals Table 3 Data Qualification Summary Analyte Perfluorooctanesulfonate (PFOS) Perfluorooctanesulfonate (PFOS) TOC Perfluorooctanesulfonate (PFOS) TOC Perfluorooctanesulfonate (PFOS) TOC Reported Result 2.01U ng/L 1.94U ng/L 9.8 mg/L 2.24U ng/L 9.9 mg/L 2.24U ng/L 11.3 mg/L Qualified Result 1.995J ng/L 1.446J ng/L 9.8J mg/L 2.088J ng/L 9.9J mg/L 1.091J ng/L 11.3J mg/L Reason Result detected below MRL Result detected below MRL High MS and/or MSD %R Result detected below MRL High MS and/or MSD %R Result detected below MRL High MS and/or MSD %R Sample ID MISS-RM829.0-C201208280818 MISS-RM831.0-C201208271545 MISS-RM835.2-1201208271339 MISS-RM835.2-2201208271358 MISS-RM835.2-3201208271402 MISS-RM835.2-4201208271410 MISS-RM836.3-C201208271329 MISS-RM841.0-C201208271243 MISS-RM844.1-C201208271224 MISS-RM847.3-C201208271151 PIGLK-N201208271513 PIGLK-OF201208271425 PIGLK-S201208271453 WS-FB-20120828 WS-FB-20120829 WS-FD-20120827 Parameter PFCs Conventionals PFCs Conventionals PFCs Conventionals PFCs Conventionals PFCs Conventionals Conventionals PFCs Conventionals PFCs Conventionals Conventionals PFCs Conventionals Conventionals Conventionals Conventionals PFCs PFCs Conventionals Analyte Perfluorooctanesulfonate (PFOS) TOC Perfluorooctanesulfonate (PFOS) TOC Perfluorooctanesulfonate (PFOS) TOC Perfluorooctanesulfonate (PFOS) TOC Perfluorooctanesulfonate (PFOS) TOC TOC Perfluorooctanesulfonate (PFOS) TOC Perfluorooctanesulfonate (PFOS) TOC TOC Perfluorooctanesulfonate (PFOS) TOC TOC TOC TOC Perfluorooctanesulfonate (PFOS) Perfluorooctanesulfonate (PFOS) TOC Reported Result 1.99U ng/L 9.4 mg/L 2.18U ng/L 10.6 mg/L 2.17U ng/L 10.8 mg/L 2.11U ng/L 11.1 mg/L 1.97U ng/L 10.1 mg/L 10.3 mg/L 2.17U ng/L 10.8 mg/L 1.95U ng/L 10.7 mg/L 11.4 mg/L 2.11U ng/L 11.6 mg/L 12.2 mg/L 10.8 mg/L 11.6 mg/L 2.24U ng/L 2.16U ng/L 10.1 mg/L Mississippi Pool 2 - Round 3 January 17, 2013 Page 7 Qualified Result 1.593J ng/L 9.4J mg/L 0.98UJ ng/L 10.6J mg/L 0.98UJ ng/L 10.8J mg/L 1.207J ng/L 11.1J mg/L 0.89UJ ng/L 10.1J mg/L 10.3J mg/L 1.833J ng/L 10.8J mg/L 0.88UJ ng/L 10.7J mg/L 11.4J mg/L 1.459J ng/L 11.6J mg/L 12.2J mg/L 10.8J mg/L 11.6J mg/L 1.01UJ ng/L 0.97UJ ng/L 10.1J mg/L Reason Result detected below MRL High MS and/or MSD %R Result reported to MDL High MS and/or MSD %R Result reported to MDL High MS and/or MSD %R Result detected below MRL High MS and/or MSD %R Result reported to MDL High MS and/or MSD %R High MS and/or MSD %R Result detected below MRL High MS and/or MSD %R Result reported down to MDL High MS and/or MSD %R High MS and/or MSD %R Result detected below MRL High MS and/or MSD %R High MS and/or MSD %R High MS and/or MSD %R High MS and/or MSD %R Result reported down to MDL Result reported down to MDL High MS and/or MSD %R Sample ID Parameter WS-FD-20120828 Conventionals Analyte TOC Reported Result 10.2 mg/L Mississippi Pool 2 - Round 3 January 17, 2013 Page 8 Qualified Result 10.2J mg/L Reason High MS and/or MSD %R REFERENCES Cardno Entrix, 2011. Quality Assurance Project Plan; In Support of 2011 Fish and Water Collection from Mississippi River Pool 2. June 2011. USEPA (U.S. Environmental Protection Agency), 1986. Test methods for Evaluating Solid Waste: Physical/Chemical Methods. U.S. Environmental Protection Agency, Office of Solid Waste and Emergency Response. EPA 530/SW-846. USEPA, 1999. USEPA Contract Laboratory Program National Functional Guidelines for Organic Data Review. U.S. Environmental Protection Agency, Office of Emergency and Remedial Response. USEPA 540/R-99/008. October. USEPA, 2004. USEPA Contract Laboratory Program National Functional Guidelines for Inorganic Data Review. U.S. Environmental Protection Agency, Office of Superfund Remediation and Technology Innovation (OSRTI). EPA 540-R-04-004. October. USEPA, 2008. USEPA Contract Laboratory Program National Functional Guidelines for Superfund Organic Methods Data Review. U.S. Environmental Protection Agency, Office of Superfund Remediation and Technology Innovation. USEPA 540-R-08-01. June.