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Home My WebLink AboutNC0001422_Final CAP APPENDICES_20151103Corrective Action Plan Part 1 November 2015 L.V. Sutton Energy Complex SynTerra P:\Duke Energy Progress.1026\108. Sutton Ash Basin GW Assessment Plan\16.Corrective Action Plan\FINAL CAP REPORT\Final LV Sutton CAP Report 11-02-2015.docx APPENDIX A DUKE ENERGY BACKGROUND PRIVATE WELL DATA Sutton 2015014521 2015019168 2015019189 2015019190 2015019191 2015019214 2015022416 2015023031 2015023877 2015023981 2015023982 2015022416 2015023031 J15050353 J15060444 J15060458 J15060459 J15060461 J15060462 J15070179 J15070179 J15070616 J15070662 J15070663 J15070179 J15070179 6/26/2015 6/26/2015 6/26/2015 6/26/2015 6/26/2015 6/26/2015 7/10/2015 7/10/2015 7/24/2015 7/24/2015 7/24/2015 7/10/2015 7/10/2015 Pace Pace Pace Pace Pace Pace Pace Pace Duke Duke Duke Pace Pace Test Parameter Analytical Method Limits Source Units Column2 Column1 Anions Chloride EPA 300.0 250 2L mg/L *8.5 23 8.3 9.4 5.4 220 290 3.7 28 69 220 290 Anions Sulfate EPA 300.0 250 2L mg/L *14 14 8.2 14 8.8 16 28 < 0.1 27 15 16 28 ICP Metals Aluminum (Al)EPA 200.7 mg/L < 0.01 0.0433 < 0.01 0.0123 0.606 < 0.01 < 0.01 < 0.01 < 0.005 0.007 0.01 < 0.01 < 0.01 ICP Metals Barium (Ba)EPA 200.7 0.7 2L mg/L 0.00047 0.074 0.0213 0.0377 0.0738 0.0089 0.0036 0.002 < 0.005 0.047 0.042 0.0036 0.002 ICP Metals Boron (B)EPA 200.7 0.7 2L mg/L 0.0226 0.0097 0.0129 0.0146 0.0327 0.212 0.398 0.508 0.928 0.073 < 0.05 0.398 0.508 ICP Metals Calcium (Ca)EPA 200.7 mg/L 0.233 9.7 70.3 112 5.91 74.6 54.9 51.9 15.8 103 81.4 54.9 51.9 ICP Metals Chromium (Cr)EPA 200.7 0.01 2L mg/L < 0.0005 < 0.0005 < 0.0005 0.00099 < 0.0005 < 0.0005 < 0.0005 < 0.0005 < 0.005 < 0.005 < 0.005 < 0.0005 < 0.0005 ICP Metals Copper (Cu)EPA 200.7 1 2L mg/L 0.0013 0.0096 0.0059 0.0071 0.0026 0.0023 0.0025 < 0.001 0.009 0.006 < 0.005 0.0025 < 0.001 ICP Metals Iron (Fe)EPA 200.7 0.3 2L mg/L < 0.05 6.06 0.373 0.379 0.0536 1.6 0.311 0.241 0.013 4.56 3.08 0.311 0.241 ICP Metals Magnesium (Mg)EPA 200.7 mg/L 0.0142 2.86 1.86 2.19 1.41 5.32 17.6 19.9 13.5 1.99 5.7 17.6 19.9 ICP Metals Manganese (Mn)EPA 200.7 0.05 2L mg/L < 0.0005 0.0549 0.0064 0.0598 0.022 0.0375 0.0098 0.0078 < 0.005 0.097 0.042 0.0098 0.0078 ICP Metals Nickel (Ni)EPA 200.7 0.1 2L mg/L < 0.0005 < 0.0005 < 0.0005 0.0014 0.00057 < 0.0005 < 0.0005 < 0.0005 < 0.005 < 0.005 < 0.005 < 0.0005 < 0.0005 ICP Metals Potassium (K)EPA 200.7 mg/L 0.206 1.44 1.07 0.702 2.23 3.82 13.6 16.8 32.7 1.46 1.11 13.6 16.8 ICP Metals Sodium (Na)EPA 200.7 mg/L 125 5.27 8.38 5.07 8.32 92.5 156 200 80.2 10.8 37.3 156 200 ICP Metals Strontium (Sr)EPA 200.7 mg/L 0.00088 0.059 0.133 0.556 0.022 0.294 0.432 0.435 0.323 0.214 0.130 0.432 0.435 ICP Metals Zinc (Zn)EPA 200.7 1 2L mg/L < 0.005 0.209 0.0465 < 0.005 0.0198 0.0427 < 0.005 < 0.005 0.008 0.01 < 0.005 < 0.005 < 0.005 IMS Metals Antimony (Sb)EPA 200.8 1 (IMAC)ug/L < 0.5 0.5 0.61 0.67 < 0.5 < 0.5 < 0.5 < 0.5 1.04 1.04 1.08 < 0.5 < 0.5 IMS Metals Arsenic (As)EPA 200.8 10 2L ug/L < 0.5 0.53 0.83 < 0.5 < 0.5 < 0.5 < 0.5 < 0.5 < 1 < 1 < 1 < 0.5 < 0.5 IMS Metals Beryllium (Be)EPA 200.8 4 (IMAC)ug/L < 0.2 0.2 < 0.2 < 0.2 < 0.2 < 0.2 < 0.2 < 0.2 < 1 < 1 < 1 < 0.2 < 0.2 IMS Metals Cadmium (Cd)EPA 200.8 2 2L ug/L < 0.08 < 0.08 < 0.08 0.32 < 0.08 < 0.08 < 0.08 < 0.08 < 1 < 1 < 1 < 0.08 < 0.08 IMS Metals Cobalt (Co)EPA 200.8 1 (IMAC)ug/L < 0.5 < 0.5 < 0.5 < 0.5 0.64 < 0.5 < 0.5 < 0.5 < 1 < 1 < 1 < 0.5 < 0.5 IMS Metals Lead (Pb)EPA 200.8 15 2L ug/L < 0.1 0.74 0.25 0.89 1.1 3.2 0.36 0.12 < 1 < 1 < 1 0.36 0.12 IMS Metals Molybdenum (Mo)EPA 200.8 ug/L < 0.5 < 0.5 0.81 < 0.5 < 0.5 < 0.5 < 0.5 < 0.5 < 1 < 1 < 1 < 0.5 < 0.5 IMS Metals Selenium (Se)EPA 200.8 20 2L ug/L < 0.5 < 0.5 < 0.5 < 0.5 < 0.5 < 0.5 < 0.5 < 0.5 < 1 < 1 < 1 < 0.5 < 0.5 IMS Metals Thallium (Tl) Low Level EPA 200.8 0.2 (IMAC)ug/L < 0.1 < 0.1 < 0.1 0.18 < 0.1 < 0.1 < 0.1 < 0.1 <0.2 < 0.2 < 0.2 < 0.1 < 0.1 IMS Metals Vanadium (V) Low Level EPA 200.8 0.3 (IMAC)ug/L < 1 < 1 < 1 < 1 < 1 < 1 < 1 < 1 < 0.3 < 0.3 0.514 < 1 < 1 Wet Lab Mercury (Hg)EPA 245.1 1 2L ug/L < 0.2 < 0.2 < 0.2 < 0.2 < 0.2 < 0.2 < 0.2 < 0.2 < 0.05 < 0.05 < 0.05 < 0.2 < 0.2 Vendor Work Hexavalent Chromium (Vendor)mg/L < 0.00003 < 0.00003 < 0.00003 < 0.00003 < 0.00003 < 0.00003 < 0.00003 < 0.00003 < 0.00003 < 0.00003 < 0.00003 < 0.00003 < 0.00003 Vendor Work TDS (Vendor)500 2L mg/L 300 74 220 290 76 430 630 760 ******630 760 Vendor Work TSS (Vendor)mg/L < 5 < 5 < 5 < 5 < 5 < 5 < 5 < 5 < 5 6 8 < 5 < 5 Vendor Work pH (Vendor)SI Units 7.67 6.2 7.82 7.58 4.54 7.73 8.06 8.07 8.06 7.31 7.37 8.06 8.07 *Data Not Available (Scope Change: Paramater added for later sampling) **Data Not Available (Parameter not on COC) ***Data Not Available (Analysis not Performed) Sample ID Order ID Sample Date Laboratory Corrective Action Plan Part 1 November 2015 L.V. Sutton Energy Complex SynTerra P:\Duke Energy Progress.1026\108. Sutton Ash Basin GW Assessment Plan\16.Corrective Action Plan\FINAL CAP REPORT\Final LV Sutton CAP Report 11-02-2015.docx APPENDIX B LABORATORY REPORTS – SEPTEMBER 2015 13339 Hagers Ferry Road Huntersville, NC 28078-7929 McGuire Nuclear Complex - MG03A2 Phone: 980-875-5245 Fax: 980-875-4349 Order Summary Report Analytical Laboratory Order Number:J15090625 Project Name:SUTTON - AB GW ASSESSMENT WATER Lab Contact:Mary Ann Ogle Date:9/28/2015 Customer Address: Customer Name(s):Perry Waldrep, Tim Hunsucker,Brandon Russo, Kathy Webb, John Toepfer Phone: 980-875-5274 Report Authorized By: (Signature) Program Comments: Please contact the Program Manager (Mary Ann Ogle) with any questions regarding this report. Data Flags & Calculations: Any analytical tests or individual analytes within a test flagged with a Qualifier indicate a deviation from the method quality system or quality control requirement. The qualifier description is found at the end of the Certificate of Analysis (sample results) under the qualifiers heading. All results are reported on a dry weight basis unless otherwise noted. Subcontracted data included on the Duke Certificate of Analysis is to be used as information only. Certified vendor results can be found in the subcontracted lab final report. Duke Energy Analytical Laboratory subcontracts analyses to other vendor laboratories that have been qualified by Duke Energy to perform these analyses except where noted. Data Package: This data package includes analytical results that are applicable only to the samples described in this narrative. An estimation of the uncertainty of measurement for the results in the report is available upon request. This report shall not be reproduced, except in full, without the written consent of the Analytical Laboratory. Please contact the Analytical laboratory with any questions. The order of individual sections within this report is as follows: Job Summary Report, Sample Identification, Technical Validation of Data Package, Analytical Laboratory Certificate of Analysis, Analytical Laboratory QC Reports, Sub-contracted Laboratory Results, Customer Specific Data Sheets, Reports & Documentation, Customer Database Entries, Test Case Narratives, Chain of Custody (COC) Certification: The Analytical Laboratory holds the following State Certifications : North Carolina (DENR) Certificate #248, South Carolina (DHEC) Laboratory ID # 99005. Contact the Analytical Laboratory for definitive information about the certification status of specific methods. Mary Ann Ogle Page 1 of 22 Sample ID's & Descriptions: Sample ID Plant/Station Collection Date and Time Collected By Sample Description 2015031375 Sutton 22-Sep-15 5:46 PM ILLEGIBLE AW-7D 2015031376 Sutton 22-Sep-15 5:03 PM ILLEGIBLE AW-4C 2015031377 Sutton 22-Sep-15 4:14 PM ILLEGIBLE AW-8C 2015031378 Sutton 22-Sep-15 2:42 PM ILLEGIBLE MW-23E 2015031379 Sutton 22-Sep-15 12:31 PM ILLEGIBLE ABMW-15 2015031380 Sutton 22-Sep-15 7:25 AM ILLEGIBLE Filter Blank 2015031381 Sutton 22-Sep-15 7:25 AM ILLEGIBLE Equipment Blank 7 Total Samples Page 2 of 22 COC and .pdf report are in agreement with sample totals and analyses (compliance programs and procedures). All Results are less than the laboratory reporting limits. All laboratory QA/QC requirements are acceptable. Yes No Technical Validation Review Checklist: Yes No Yes No Report Sections Included: Job Summary Report Sub-contracted Laboratory Results Sample Identification Customer Specific Data Sheets, Reports, & Documentation Technical Validation of Data Package Customer Database Entries Analytical Laboratory Certificate of Analysis Analytical Laboratory QC Report Chain of Custody Reviewed By:DBA Account Date:9/28/2015 Electronic Data Deliverable (EDD) Sent Separately Page 3 of 22 Certificate of Laboratory Analysis This report shall not be reproduced, except in full. Order # J15090625 2015031375 Collection Date:22-Sep-15 5:46 PM Site:AW-7D Matrix:GW_WW Analyte Analysis Date/TimeMethodUnits Qualifiers RDLResult Sample #: AnalystDF MERCURY (COLD VAPOR) IN WATER Mercury (Hg)< 0.05 ug/L EPA 245.1 09/23/2015 14:26 ACPAYNE0.05 1 Mercury Dissolved (cold vapor) in Water (Filtered) Mercury (Hg)< 0.05 ug/L EPA 245.1 09/23/2015 14:45 ACPAYNE0.05 1 Mercury Dissolved (cold vapor) in Water (0.1mm FILTER) Mercury (Hg)< 0.05 ug/L EPA 245.1 09/24/2015 16:08 ACPAYNE0.05 1 DISSOLVED METALS BY ICP Aluminum (Al)0.012 mg/L EPA 200.7 09/24/2015 09:20 FCJORDA0.005 1 Barium (Ba)< 0.005 mg/L EPA 200.7 09/24/2015 09:20 FCJORDA0.005 1 Boron (B)0.813 mg/L EPA 200.7 09/24/2015 09:20 FCJORDA0.05 1 Iron (Fe)0.034 mg/L EPA 200.7 09/24/2015 09:20 FCJORDA0.01 1 Manganese (Mn)0.015 mg/L EPA 200.7 09/24/2015 09:20 FCJORDA0.005 1 Strontium (Sr)0.085 mg/L EPA 200.7 09/24/2015 09:20M1 FCJORDA0.005 1 Zinc (Zn)< 0.005 mg/L EPA 200.7 09/24/2015 09:20 FCJORDA0.005 1 DISSOLVED METALS BY ICP (0.1mm FILTER) Aluminum (Al)0.013 mg/L EPA 200.7 09/24/2015 10:02 FCJORDA0.005 1 Barium (Ba)< 0.005 mg/L EPA 200.7 09/24/2015 10:02 FCJORDA0.005 1 Boron (B)0.809 mg/L EPA 200.7 09/24/2015 10:02 FCJORDA0.05 1 Iron (Fe)0.030 mg/L EPA 200.7 09/24/2015 10:02 FCJORDA0.01 1 Manganese (Mn)0.015 mg/L EPA 200.7 09/24/2015 10:02 FCJORDA0.005 1 Strontium (Sr)0.085 mg/L EPA 200.7 09/24/2015 10:02M1 FCJORDA0.005 1 Zinc (Zn)< 0.005 mg/L EPA 200.7 09/24/2015 10:02 FCJORDA0.005 1 UNDIGESTED METALS BY ICP Calcium (Ca)11.1 mg/L EPA 200.7 09/24/2015 10:52 FCJORDA0.01 1 Magnesium (Mg)6.31 mg/L EPA 200.7 09/24/2015 10:52 FCJORDA0.005 1 Potassium (K)8.33 mg/L EPA 200.7 09/24/2015 10:52 FCJORDA0.1 1 Sodium (Na)176 mg/L EPA 200.7 09/24/2015 10:52M4 FCJORDA510 TOTAL RECOVERABLE METALS BY ICP Aluminum (Al)0.130 mg/L EPA 200.7 09/24/2015 10:36 MHH71310.005 1 Barium (Ba)< 0.005 mg/L EPA 200.7 09/24/2015 10:36 MHH71310.005 1 Boron (B)0.794 mg/L EPA 200.7 09/24/2015 10:36 MHH71310.05 1 Iron (Fe)0.225 mg/L EPA 200.7 09/24/2015 10:36 MHH71310.01 1 Manganese (Mn)0.017 mg/L EPA 200.7 09/24/2015 10:36 MHH71310.005 1 Strontium (Sr)0.082 mg/L EPA 200.7 09/24/2015 10:36 MHH71310.005 1 Zinc (Zn)< 0.005 mg/L EPA 200.7 09/24/2015 10:36 MHH71310.005 1 Page 4 of 22 Certificate of Laboratory Analysis This report shall not be reproduced, except in full. Order # J15090625 2015031375 Collection Date:22-Sep-15 5:46 PM Site:AW-7D Matrix:GW_WW Analyte Analysis Date/TimeMethodUnits Qualifiers RDLResult Sample #: AnalystDF TOTAL RECOVERABLE METALS BY ICP-MS (DISSOLVED) Antimony (Sb)< 1 ug/L EPA 200.8 09/23/2015 13:07 MHALL311 Arsenic (As)< 1 ug/L EPA 200.8 09/23/2015 13:07 MHALL311 Beryllium (Be)< 1 ug/L EPA 200.8 09/23/2015 13:07 MHALL311 Cadmium (Cd)< 1 ug/L EPA 200.8 09/23/2015 13:07 MHALL311 Chromium (Cr)< 1 ug/L EPA 200.8 09/23/2015 13:07 MHALL311 Cobalt (Co)< 1 ug/L EPA 200.8 09/23/2015 13:07 MHALL311 Copper (Cu)< 1 ug/L EPA 200.8 09/23/2015 13:07 MHALL311 Lead (Pb)< 1 ug/L EPA 200.8 09/23/2015 13:07 MHALL311 Molybdenum (Mo)6.44 ug/L EPA 200.8 09/23/2015 13:07 MHALL311 Nickel (Ni)< 1 ug/L EPA 200.8 09/23/2015 13:07 MHALL311 Selenium (Se)< 1 ug/L EPA 200.8 09/23/2015 13:07M2 MHALL311 Thallium (Tl) Low Level < 0.2 ug/L EPA 200.8 09/23/2015 13:07 MHALL30.2 1 Vanadium (V) Low Level 0.467 ug/L EPA 200.8 09/23/2015 13:07 MHALL30.3 1 Total Recoverable Metals Dissolved 0.1mm Filter Antimony (Sb)< 1 ug/L EPA 200.8 09/24/2015 13:16 MHALL311 Arsenic (As)< 1 ug/L EPA 200.8 09/24/2015 13:16 MHALL311 Beryllium (Be)< 1 ug/L EPA 200.8 09/24/2015 13:16 MHALL311 Cadmium (Cd)< 1 ug/L EPA 200.8 09/24/2015 13:16 MHALL311 Chromium (Cr)< 1 ug/L EPA 200.8 09/24/2015 13:16 MHALL311 Cobalt (Co)< 1 ug/L EPA 200.8 09/24/2015 13:16 MHALL311 Copper (Cu)< 1 ug/L EPA 200.8 09/24/2015 13:16 MHALL311 Lead (Pb)< 1 ug/L EPA 200.8 09/24/2015 13:16 MHALL311 Molybdenum (Mo)6.34 ug/L EPA 200.8 09/24/2015 13:16 MHALL311 Nickel (Ni)< 1 ug/L EPA 200.8 09/24/2015 13:16 MHALL311 Selenium (Se)< 1 ug/L EPA 200.8 09/24/2015 13:16 MHALL311 Thallium (Tl) Low Level < 0.2 ug/L EPA 200.8 09/24/2015 13:16 MHALL30.2 1 Vanadium (V) Low Level 0.370 ug/L EPA 200.8 09/24/2015 13:16 MHALL30.3 1 Page 5 of 22 Certificate of Laboratory Analysis This report shall not be reproduced, except in full. Order # J15090625 2015031375 Collection Date:22-Sep-15 5:46 PM Site:AW-7D Matrix:GW_WW Analyte Analysis Date/TimeMethodUnits Qualifiers RDLResult Sample #: AnalystDF TOTAL RECOVERABLE METALS BY ICP-MS Antimony (Sb)< 1 ug/L EPA 200.8 09/23/2015 14:19 MHALL311 Arsenic (As)< 1 ug/L EPA 200.8 09/23/2015 14:19 MHALL311 Beryllium (Be)< 1 ug/L EPA 200.8 09/23/2015 14:19 MHALL311 Cadmium (Cd)< 1 ug/L EPA 200.8 09/23/2015 14:19 MHALL311 Chromium (Cr)< 1 ug/L EPA 200.8 09/23/2015 14:19 MHALL311 Cobalt (Co)< 1 ug/L EPA 200.8 09/23/2015 14:19 MHALL311 Copper (Cu)< 1 ug/L EPA 200.8 09/23/2015 14:19 MHALL311 Lead (Pb)< 1 ug/L EPA 200.8 09/23/2015 14:19 MHALL311 Molybdenum (Mo)6.66 ug/L EPA 200.8 09/23/2015 14:19 MHALL311 Nickel (Ni)< 1 ug/L EPA 200.8 09/23/2015 14:19 MHALL311 Selenium (Se)< 1 ug/L EPA 200.8 09/23/2015 14:19M2 MHALL311 Thallium (Tl) Low Level < 0.2 ug/L EPA 200.8 09/23/2015 14:19 MHALL30.2 1 Vanadium (V) Low Level 0.785 ug/L EPA 200.8 09/23/2015 14:19 MHALL30.3 1 Page 6 of 22 Certificate of Laboratory Analysis This report shall not be reproduced, except in full. Order # J15090625 2015031376 Collection Date:22-Sep-15 5:03 PM Site:AW-4C Matrix:GW_WW Analyte Analysis Date/TimeMethodUnits Qualifiers RDLResult Sample #: AnalystDF MERCURY (COLD VAPOR) IN WATER Mercury (Hg)< 0.05 ug/L EPA 245.1 09/23/2015 14:28 ACPAYNE0.05 1 Mercury Dissolved (cold vapor) in Water (Filtered) Mercury (Hg)< 0.05 ug/L EPA 245.1 09/23/2015 14:52 ACPAYNE0.05 1 Mercury Dissolved (cold vapor) in Water (0.1mm FILTER) Mercury (Hg)< 0.05 ug/L EPA 245.1 09/24/2015 16:15 ACPAYNE0.05 1 DISSOLVED METALS BY ICP Aluminum (Al)0.041 mg/L EPA 200.7 09/24/2015 09:31 FCJORDA0.005 1 Barium (Ba)0.042 mg/L EPA 200.7 09/24/2015 09:31 FCJORDA0.005 1 Boron (B)1.32 mg/L EPA 200.7 09/24/2015 09:31 FCJORDA0.05 1 Iron (Fe)3.27 mg/L EPA 200.7 09/24/2015 09:31 FCJORDA0.01 1 Manganese (Mn)0.770 mg/L EPA 200.7 09/24/2015 09:31 FCJORDA0.005 1 Strontium (Sr)0.748 mg/L EPA 200.7 09/24/2015 09:31 FCJORDA0.005 1 Zinc (Zn)< 0.005 mg/L EPA 200.7 09/24/2015 09:31 FCJORDA0.005 1 DISSOLVED METALS BY ICP (0.1mm FILTER) Aluminum (Al)0.016 mg/L EPA 200.7 09/24/2015 10:13 FCJORDA0.005 1 Barium (Ba)0.043 mg/L EPA 200.7 09/24/2015 10:13 FCJORDA0.005 1 Boron (B)1.32 mg/L EPA 200.7 09/24/2015 10:13 FCJORDA0.05 1 Iron (Fe)3.32 mg/L EPA 200.7 09/24/2015 10:13 FCJORDA0.01 1 Manganese (Mn)0.773 mg/L EPA 200.7 09/24/2015 10:13 FCJORDA0.005 1 Strontium (Sr)0.742 mg/L EPA 200.7 09/24/2015 10:13 FCJORDA0.005 1 Zinc (Zn)0.007 mg/L EPA 200.7 09/24/2015 10:13 FCJORDA0.005 1 UNDIGESTED METALS BY ICP Calcium (Ca)41.5 mg/L EPA 200.7 09/24/2015 11:07 FCJORDA0.01 1 Magnesium (Mg)7.51 mg/L EPA 200.7 09/24/2015 11:07 FCJORDA0.005 1 Potassium (K)7.37 mg/L EPA 200.7 09/24/2015 11:07 FCJORDA0.1 1 Sodium (Na)44.6 mg/L EPA 200.7 09/24/2015 11:07 FCJORDA0.05 1 TOTAL RECOVERABLE METALS BY ICP Aluminum (Al)0.150 mg/L EPA 200.7 09/24/2015 10:10 MHH71310.005 1 Barium (Ba)0.041 mg/L EPA 200.7 09/24/2015 10:10 MHH71310.005 1 Boron (B)1.27 mg/L EPA 200.7 09/24/2015 10:10 MHH71310.05 1 Iron (Fe)4.95 mg/L EPA 200.7 09/24/2015 10:10 MHH71310.01 1 Manganese (Mn)0.801 mg/L EPA 200.7 09/24/2015 10:10 MHH71310.005 1 Strontium (Sr)0.693 mg/L EPA 200.7 09/24/2015 10:10 MHH71310.005 1 Zinc (Zn)0.008 mg/L EPA 200.7 09/24/2015 10:10 MHH71310.005 1 Page 7 of 22 Certificate of Laboratory Analysis This report shall not be reproduced, except in full. Order # J15090625 2015031376 Collection Date:22-Sep-15 5:03 PM Site:AW-4C Matrix:GW_WW Analyte Analysis Date/TimeMethodUnits Qualifiers RDLResult Sample #: AnalystDF TOTAL RECOVERABLE METALS BY ICP-MS (DISSOLVED) Antimony (Sb)< 1 ug/L EPA 200.8 09/23/2015 13:23 MHALL311 Arsenic (As)< 1 ug/L EPA 200.8 09/23/2015 13:23 MHALL311 Beryllium (Be)< 1 ug/L EPA 200.8 09/23/2015 13:23 MHALL311 Cadmium (Cd)< 1 ug/L EPA 200.8 09/23/2015 13:23 MHALL311 Chromium (Cr)< 1 ug/L EPA 200.8 09/23/2015 13:23 MHALL311 Cobalt (Co)3.01 ug/L EPA 200.8 09/23/2015 13:23 MHALL311 Copper (Cu)< 1 ug/L EPA 200.8 09/23/2015 13:23 MHALL311 Lead (Pb)< 1 ug/L EPA 200.8 09/23/2015 13:23 MHALL311 Molybdenum (Mo)< 1 ug/L EPA 200.8 09/23/2015 13:23 MHALL311 Nickel (Ni)< 1 ug/L EPA 200.8 09/23/2015 13:23 MHALL311 Selenium (Se)< 1 ug/L EPA 200.8 09/23/2015 13:23 MHALL311 Thallium (Tl) Low Level < 0.2 ug/L EPA 200.8 09/23/2015 13:23 MHALL30.2 1 Vanadium (V) Low Level 0.747 ug/L EPA 200.8 09/23/2015 13:23 MHALL30.3 1 Total Recoverable Metals Dissolved 0.1mm Filter Antimony (Sb)< 1 ug/L EPA 200.8 09/24/2015 13:21 MHALL311 Arsenic (As)< 1 ug/L EPA 200.8 09/24/2015 13:21 MHALL311 Beryllium (Be)< 1 ug/L EPA 200.8 09/24/2015 13:21 MHALL311 Cadmium (Cd)< 1 ug/L EPA 200.8 09/24/2015 13:21 MHALL311 Chromium (Cr)< 1 ug/L EPA 200.8 09/24/2015 13:21 MHALL311 Cobalt (Co)2.86 ug/L EPA 200.8 09/24/2015 13:21 MHALL311 Copper (Cu)< 1 ug/L EPA 200.8 09/24/2015 13:21 MHALL311 Lead (Pb)< 1 ug/L EPA 200.8 09/24/2015 13:21 MHALL311 Molybdenum (Mo)< 1 ug/L EPA 200.8 09/24/2015 13:21 MHALL311 Nickel (Ni)< 1 ug/L EPA 200.8 09/24/2015 13:21 MHALL311 Selenium (Se)< 1 ug/L EPA 200.8 09/24/2015 13:21 MHALL311 Thallium (Tl) Low Level < 0.2 ug/L EPA 200.8 09/24/2015 13:21 MHALL30.2 1 Vanadium (V) Low Level 0.477 ug/L EPA 200.8 09/24/2015 13:21 MHALL30.3 1 Page 8 of 22 Certificate of Laboratory Analysis This report shall not be reproduced, except in full. Order # J15090625 2015031376 Collection Date:22-Sep-15 5:03 PM Site:AW-4C Matrix:GW_WW Analyte Analysis Date/TimeMethodUnits Qualifiers RDLResult Sample #: AnalystDF TOTAL RECOVERABLE METALS BY ICP-MS Antimony (Sb)< 1 ug/L EPA 200.8 09/23/2015 14:34 MHALL311 Arsenic (As)< 1 ug/L EPA 200.8 09/23/2015 14:34 MHALL311 Beryllium (Be)< 1 ug/L EPA 200.8 09/23/2015 14:34 MHALL311 Cadmium (Cd)< 1 ug/L EPA 200.8 09/23/2015 14:34 MHALL311 Chromium (Cr)1.65 ug/L EPA 200.8 09/23/2015 14:34 MHALL311 Cobalt (Co)6.15 ug/L EPA 200.8 09/23/2015 14:34 MHALL311 Copper (Cu)< 1 ug/L EPA 200.8 09/23/2015 14:34 MHALL311 Lead (Pb)< 1 ug/L EPA 200.8 09/23/2015 14:34 MHALL311 Molybdenum (Mo)< 1 ug/L EPA 200.8 09/23/2015 14:34 MHALL311 Nickel (Ni)< 1 ug/L EPA 200.8 09/23/2015 14:34 MHALL311 Selenium (Se)< 1 ug/L EPA 200.8 09/23/2015 14:34 MHALL311 Thallium (Tl) Low Level < 0.2 ug/L EPA 200.8 09/23/2015 14:34 MHALL30.2 1 Vanadium (V) Low Level 2.04 ug/L EPA 200.8 09/23/2015 14:34 MHALL30.3 1 Page 9 of 22 Certificate of Laboratory Analysis This report shall not be reproduced, except in full. Order # J15090625 2015031377 Collection Date:22-Sep-15 4:14 PM Site:AW-8C Matrix:GW_WW Analyte Analysis Date/TimeMethodUnits Qualifiers RDLResult Sample #: AnalystDF MERCURY (COLD VAPOR) IN WATER Mercury (Hg)< 0.05 ug/L EPA 245.1 09/23/2015 14:31 ACPAYNE0.05 1 Mercury Dissolved (cold vapor) in Water (Filtered) Mercury (Hg)< 0.05 ug/L EPA 245.1 09/23/2015 14:54 ACPAYNE0.05 1 Mercury Dissolved (cold vapor) in Water (0.1mm FILTER) Mercury (Hg)< 0.05 ug/L EPA 245.1 09/24/2015 16:18 ACPAYNE0.05 1 DISSOLVED METALS BY ICP Aluminum (Al)0.048 mg/L EPA 200.7 09/24/2015 09:35 FCJORDA0.005 1 Barium (Ba)0.032 mg/L EPA 200.7 09/24/2015 09:35 FCJORDA0.005 1 Boron (B)< 0.05 mg/L EPA 200.7 09/24/2015 09:35 FCJORDA0.05 1 Iron (Fe)0.249 mg/L EPA 200.7 09/24/2015 09:35 FCJORDA0.01 1 Manganese (Mn)0.031 mg/L EPA 200.7 09/24/2015 09:35 FCJORDA0.005 1 Strontium (Sr)0.033 mg/L EPA 200.7 09/24/2015 09:35 FCJORDA0.005 1 Zinc (Zn)< 0.005 mg/L EPA 200.7 09/24/2015 09:35 FCJORDA0.005 1 DISSOLVED METALS BY ICP (0.1mm FILTER) Aluminum (Al)0.046 mg/L EPA 200.7 09/24/2015 10:17 FCJORDA0.005 1 Barium (Ba)0.032 mg/L EPA 200.7 09/24/2015 10:17 FCJORDA0.005 1 Boron (B)< 0.05 mg/L EPA 200.7 09/24/2015 10:17 FCJORDA0.05 1 Iron (Fe)0.223 mg/L EPA 200.7 09/24/2015 10:17 FCJORDA0.01 1 Manganese (Mn)0.030 mg/L EPA 200.7 09/24/2015 10:17 FCJORDA0.005 1 Strontium (Sr)0.033 mg/L EPA 200.7 09/24/2015 10:17 FCJORDA0.005 1 Zinc (Zn)0.006 mg/L EPA 200.7 09/24/2015 10:17 FCJORDA0.005 1 UNDIGESTED METALS BY ICP Calcium (Ca)3.10 mg/L EPA 200.7 09/24/2015 11:11 FCJORDA0.01 1 Magnesium (Mg)1.53 mg/L EPA 200.7 09/24/2015 11:11 FCJORDA0.005 1 Potassium (K)1.23 mg/L EPA 200.7 09/24/2015 11:11 FCJORDA0.1 1 Sodium (Na)5.60 mg/L EPA 200.7 09/24/2015 11:11 FCJORDA0.05 1 TOTAL RECOVERABLE METALS BY ICP Aluminum (Al)0.316 mg/L EPA 200.7 09/24/2015 10:14 MHH71310.005 1 Barium (Ba)0.033 mg/L EPA 200.7 09/24/2015 10:14 MHH71310.005 1 Boron (B)< 0.05 mg/L EPA 200.7 09/24/2015 10:14 MHH71310.05 1 Iron (Fe)0.487 mg/L EPA 200.7 09/24/2015 10:14 MHH71310.01 1 Manganese (Mn)0.030 mg/L EPA 200.7 09/24/2015 10:14 MHH71310.005 1 Strontium (Sr)0.031 mg/L EPA 200.7 09/24/2015 10:14 MHH71310.005 1 Zinc (Zn)0.007 mg/L EPA 200.7 09/24/2015 10:14 MHH71310.005 1 Page 10 of 22 Certificate of Laboratory Analysis This report shall not be reproduced, except in full. Order # J15090625 2015031377 Collection Date:22-Sep-15 4:14 PM Site:AW-8C Matrix:GW_WW Analyte Analysis Date/TimeMethodUnits Qualifiers RDLResult Sample #: AnalystDF TOTAL RECOVERABLE METALS BY ICP-MS (DISSOLVED) Antimony (Sb)< 1 ug/L EPA 200.8 09/23/2015 13:28 MHALL311 Arsenic (As)< 1 ug/L EPA 200.8 09/23/2015 13:28 MHALL311 Beryllium (Be)< 1 ug/L EPA 200.8 09/23/2015 13:28 MHALL311 Cadmium (Cd)< 1 ug/L EPA 200.8 09/23/2015 13:28 MHALL311 Chromium (Cr)< 1 ug/L EPA 200.8 09/23/2015 13:28 MHALL311 Cobalt (Co)1.16 ug/L EPA 200.8 09/23/2015 13:28 MHALL311 Copper (Cu)< 1 ug/L EPA 200.8 09/23/2015 13:28 MHALL311 Lead (Pb)< 1 ug/L EPA 200.8 09/23/2015 13:28 MHALL311 Molybdenum (Mo)< 1 ug/L EPA 200.8 09/23/2015 13:28 MHALL311 Nickel (Ni)< 1 ug/L EPA 200.8 09/23/2015 13:28 MHALL311 Selenium (Se)< 1 ug/L EPA 200.8 09/23/2015 13:28 MHALL311 Thallium (Tl) Low Level < 0.2 ug/L EPA 200.8 09/23/2015 13:28 MHALL30.2 1 Vanadium (V) Low Level < 0.3 ug/L EPA 200.8 09/23/2015 13:28 MHALL30.3 1 Total Recoverable Metals Dissolved 0.1mm Filter Antimony (Sb)< 1 ug/L EPA 200.8 09/24/2015 13:01 MHALL311 Arsenic (As)< 1 ug/L EPA 200.8 09/24/2015 13:01 MHALL311 Beryllium (Be)< 1 ug/L EPA 200.8 09/24/2015 13:01 MHALL311 Cadmium (Cd)< 1 ug/L EPA 200.8 09/24/2015 13:01 MHALL311 Chromium (Cr)< 1 ug/L EPA 200.8 09/24/2015 13:01 MHALL311 Cobalt (Co)1.21 ug/L EPA 200.8 09/24/2015 13:01 MHALL311 Copper (Cu)< 1 ug/L EPA 200.8 09/24/2015 13:01 MHALL311 Lead (Pb)< 1 ug/L EPA 200.8 09/24/2015 13:01 MHALL311 Molybdenum (Mo)< 1 ug/L EPA 200.8 09/24/2015 13:01 MHALL311 Nickel (Ni)< 1 ug/L EPA 200.8 09/24/2015 13:01 MHALL311 Selenium (Se)< 1 ug/L EPA 200.8 09/24/2015 13:01 MHALL311 Thallium (Tl) Low Level < 0.2 ug/L EPA 200.8 09/24/2015 13:01 MHALL30.2 1 Vanadium (V) Low Level < 0.3 ug/L EPA 200.8 09/24/2015 13:01 MHALL30.3 1 Page 11 of 22 Certificate of Laboratory Analysis This report shall not be reproduced, except in full. Order # J15090625 2015031377 Collection Date:22-Sep-15 4:14 PM Site:AW-8C Matrix:GW_WW Analyte Analysis Date/TimeMethodUnits Qualifiers RDLResult Sample #: AnalystDF TOTAL RECOVERABLE METALS BY ICP-MS Antimony (Sb)< 1 ug/L EPA 200.8 09/23/2015 14:40 MHALL311 Arsenic (As)< 1 ug/L EPA 200.8 09/23/2015 14:40 MHALL311 Beryllium (Be)< 1 ug/L EPA 200.8 09/23/2015 14:40 MHALL311 Cadmium (Cd)< 1 ug/L EPA 200.8 09/23/2015 14:40 MHALL311 Chromium (Cr)< 1 ug/L EPA 200.8 09/23/2015 14:40 MHALL311 Cobalt (Co)1.33 ug/L EPA 200.8 09/23/2015 14:40 MHALL311 Copper (Cu)< 1 ug/L EPA 200.8 09/23/2015 14:40 MHALL311 Lead (Pb)< 1 ug/L EPA 200.8 09/23/2015 14:40 MHALL311 Molybdenum (Mo)< 1 ug/L EPA 200.8 09/23/2015 14:40 MHALL311 Nickel (Ni)1.25 ug/L EPA 200.8 09/23/2015 14:40 MHALL311 Selenium (Se)< 1 ug/L EPA 200.8 09/23/2015 14:40 MHALL311 Thallium (Tl) Low Level < 0.2 ug/L EPA 200.8 09/23/2015 14:40 MHALL30.2 1 Vanadium (V) Low Level 0.877 ug/L EPA 200.8 09/23/2015 14:40 MHALL30.3 1 Page 12 of 22 Certificate of Laboratory Analysis This report shall not be reproduced, except in full. Order # J15090625 2015031378 Collection Date:22-Sep-15 2:42 PM Site:MW-23E Matrix:GW_WW Analyte Analysis Date/TimeMethodUnits Qualifiers RDLResult Sample #: AnalystDF MERCURY (COLD VAPOR) IN WATER Mercury (Hg)< 0.05 ug/L EPA 245.1 09/23/2015 14:33 ACPAYNE0.05 1 Mercury Dissolved (cold vapor) in Water (Filtered) Mercury (Hg)< 0.05 ug/L EPA 245.1 09/23/2015 14:57 ACPAYNE0.05 1 Mercury Dissolved (cold vapor) in Water (0.1mm FILTER) Mercury (Hg)< 0.05 ug/L EPA 245.1 09/24/2015 16:20 ACPAYNE0.05 1 DISSOLVED METALS BY ICP Aluminum (Al)0.018 mg/L EPA 200.7 09/24/2015 09:39 FCJORDA0.005 1 Barium (Ba)0.007 mg/L EPA 200.7 09/24/2015 09:39 FCJORDA0.005 1 Boron (B)2.46 mg/L EPA 200.7 09/24/2015 09:39 FCJORDA0.05 1 Iron (Fe)0.010 mg/L EPA 200.7 09/24/2015 09:39 FCJORDA0.01 1 Manganese (Mn)< 0.005 mg/L EPA 200.7 09/24/2015 09:39 FCJORDA0.005 1 Strontium (Sr)0.105 mg/L EPA 200.7 09/24/2015 09:39 FCJORDA0.005 1 Zinc (Zn)< 0.005 mg/L EPA 200.7 09/24/2015 09:39 FCJORDA0.005 1 DISSOLVED METALS BY ICP (0.1mm FILTER) Aluminum (Al)0.043 mg/L EPA 200.7 09/24/2015 10:21 FCJORDA0.005 1 Barium (Ba)0.007 mg/L EPA 200.7 09/24/2015 10:21 FCJORDA0.005 1 Boron (B)2.46 mg/L EPA 200.7 09/24/2015 10:21 FCJORDA0.05 1 Iron (Fe)< 0.01 mg/L EPA 200.7 09/24/2015 10:21 FCJORDA0.01 1 Manganese (Mn)< 0.005 mg/L EPA 200.7 09/24/2015 10:21 FCJORDA0.005 1 Strontium (Sr)0.105 mg/L EPA 200.7 09/24/2015 10:21 FCJORDA0.005 1 Zinc (Zn)< 0.005 mg/L EPA 200.7 09/24/2015 10:21 FCJORDA0.005 1 UNDIGESTED METALS BY ICP Calcium (Ca)6.72 mg/L EPA 200.7 09/24/2015 11:15 FCJORDA0.01 1 Magnesium (Mg)8.86 mg/L EPA 200.7 09/24/2015 11:15 FCJORDA0.005 1 Potassium (K)69.8 mg/L EPA 200.7 09/24/2015 11:15 FCJORDA1010 Sodium (Na)503 mg/L EPA 200.7 09/24/2015 11:15 FCJORDA510 TOTAL RECOVERABLE METALS BY ICP Aluminum (Al)0.140 mg/L EPA 200.7 09/24/2015 10:18 MHH71310.005 1 Barium (Ba)0.007 mg/L EPA 200.7 09/24/2015 10:18 MHH71310.005 1 Boron (B)2.42 mg/L EPA 200.7 09/24/2015 10:18 MHH71310.05 1 Iron (Fe)0.251 mg/L EPA 200.7 09/24/2015 10:18 MHH71310.01 1 Manganese (Mn)0.006 mg/L EPA 200.7 09/24/2015 10:18 MHH71310.005 1 Strontium (Sr)0.114 mg/L EPA 200.7 09/24/2015 10:18 MHH71310.005 1 Zinc (Zn)< 0.005 mg/L EPA 200.7 09/24/2015 10:18 MHH71310.005 1 Page 13 of 22 Certificate of Laboratory Analysis This report shall not be reproduced, except in full. Order # J15090625 2015031378 Collection Date:22-Sep-15 2:42 PM Site:MW-23E Matrix:GW_WW Analyte Analysis Date/TimeMethodUnits Qualifiers RDLResult Sample #: AnalystDF TOTAL RECOVERABLE METALS BY ICP-MS (DISSOLVED) Antimony (Sb)< 1 ug/L EPA 200.8 09/23/2015 13:33 MHALL311 Arsenic (As)1.03 ug/L EPA 200.8 09/23/2015 13:33 MHALL311 Beryllium (Be)< 1 ug/L EPA 200.8 09/23/2015 13:33 MHALL311 Cadmium (Cd)< 1 ug/L EPA 200.8 09/23/2015 13:33 MHALL311 Chromium (Cr)< 1 ug/L EPA 200.8 09/23/2015 13:33 MHALL311 Cobalt (Co)< 1 ug/L EPA 200.8 09/23/2015 13:33 MHALL311 Copper (Cu)< 1 ug/L EPA 200.8 09/23/2015 13:33 MHALL311 Lead (Pb)< 1 ug/L EPA 200.8 09/23/2015 13:33 MHALL311 Molybdenum (Mo)15.1 ug/L EPA 200.8 09/23/2015 13:33 MHALL311 Nickel (Ni)< 1 ug/L EPA 200.8 09/23/2015 13:33 MHALL311 Selenium (Se)< 1 ug/L EPA 200.8 09/23/2015 13:33 MHALL311 Thallium (Tl) Low Level < 0.2 ug/L EPA 200.8 09/23/2015 13:33 MHALL30.2 1 Vanadium (V) Low Level < 0.3 ug/L EPA 200.8 09/23/2015 13:33 MHALL30.3 1 Total Recoverable Metals Dissolved 0.1mm Filter Antimony (Sb)< 1 ug/L EPA 200.8 09/24/2015 13:26 MHALL311 Arsenic (As)1.04 ug/L EPA 200.8 09/24/2015 13:26 MHALL311 Beryllium (Be)< 1 ug/L EPA 200.8 09/24/2015 13:26 MHALL311 Cadmium (Cd)< 1 ug/L EPA 200.8 09/24/2015 13:26 MHALL311 Chromium (Cr)< 1 ug/L EPA 200.8 09/24/2015 13:26 MHALL311 Cobalt (Co)< 1 ug/L EPA 200.8 09/24/2015 13:26 MHALL311 Copper (Cu)< 1 ug/L EPA 200.8 09/24/2015 13:26 MHALL311 Lead (Pb)< 1 ug/L EPA 200.8 09/24/2015 13:26 MHALL311 Molybdenum (Mo)15.4 ug/L EPA 200.8 09/24/2015 13:26 MHALL311 Nickel (Ni)< 1 ug/L EPA 200.8 09/24/2015 13:26 MHALL311 Selenium (Se)< 1 ug/L EPA 200.8 09/24/2015 13:26 MHALL311 Thallium (Tl) Low Level < 0.2 ug/L EPA 200.8 09/24/2015 13:26 MHALL30.2 1 Vanadium (V) Low Level 0.644 ug/L EPA 200.8 09/24/2015 13:26 MHALL30.3 1 Page 14 of 22 Certificate of Laboratory Analysis This report shall not be reproduced, except in full. Order # J15090625 2015031378 Collection Date:22-Sep-15 2:42 PM Site:MW-23E Matrix:GW_WW Analyte Analysis Date/TimeMethodUnits Qualifiers RDLResult Sample #: AnalystDF TOTAL RECOVERABLE METALS BY ICP-MS Antimony (Sb)< 1 ug/L EPA 200.8 09/23/2015 14:45 MHALL311 Arsenic (As)1.02 ug/L EPA 200.8 09/23/2015 14:45 MHALL311 Beryllium (Be)< 1 ug/L EPA 200.8 09/23/2015 14:45 MHALL311 Cadmium (Cd)< 1 ug/L EPA 200.8 09/23/2015 14:45 MHALL311 Chromium (Cr)< 1 ug/L EPA 200.8 09/23/2015 14:45 MHALL311 Cobalt (Co)< 1 ug/L EPA 200.8 09/23/2015 14:45 MHALL311 Copper (Cu)< 1 ug/L EPA 200.8 09/23/2015 14:45 MHALL311 Lead (Pb)< 1 ug/L EPA 200.8 09/23/2015 14:45 MHALL311 Molybdenum (Mo)14.6 ug/L EPA 200.8 09/23/2015 14:45 MHALL311 Nickel (Ni)< 1 ug/L EPA 200.8 09/23/2015 14:45 MHALL311 Selenium (Se)< 1 ug/L EPA 200.8 09/23/2015 14:45 MHALL311 Thallium (Tl) Low Level < 0.2 ug/L EPA 200.8 09/23/2015 14:45 MHALL30.2 1 Vanadium (V) Low Level 0.864 ug/L EPA 200.8 09/23/2015 14:45 MHALL30.3 1 Page 15 of 22 Certificate of Laboratory Analysis This report shall not be reproduced, except in full. Order # J15090625 2015031379 Collection Date:22-Sep-15 12:31 PM Site:ABMW-15 Matrix:GW_WW Analyte Analysis Date/TimeMethodUnits Qualifiers RDLResult Sample #: AnalystDF MERCURY (COLD VAPOR) IN WATER Mercury (Hg)< 0.05 ug/L EPA 245.1 09/23/2015 14:35 ACPAYNE0.05 1 Mercury Dissolved (cold vapor) in Water (Filtered) Mercury (Hg)< 0.05 ug/L EPA 245.1 09/23/2015 14:59 ACPAYNE0.05 1 Mercury Dissolved (cold vapor) in Water (0.1mm FILTER) Mercury (Hg)< 0.05 ug/L EPA 245.1 09/24/2015 16:22 ACPAYNE0.05 1 DISSOLVED METALS BY ICP Aluminum (Al)0.126 mg/L EPA 200.7 09/24/2015 09:43 FCJORDA0.005 1 Barium (Ba)0.538 mg/L EPA 200.7 09/24/2015 09:43 FCJORDA0.005 1 Boron (B)3.58 mg/L EPA 200.7 09/24/2015 09:43 FCJORDA0.05 1 Iron (Fe)0.078 mg/L EPA 200.7 09/24/2015 09:43 FCJORDA0.01 1 Manganese (Mn)0.077 mg/L EPA 200.7 09/24/2015 09:43 FCJORDA0.005 1 Strontium (Sr)5.96 mg/L EPA 200.7 09/24/2015 09:43 FCJORDA0.005 1 Zinc (Zn)< 0.005 mg/L EPA 200.7 09/24/2015 09:43 FCJORDA0.005 1 DISSOLVED METALS BY ICP (0.1mm FILTER) Aluminum (Al)0.104 mg/L EPA 200.7 09/24/2015 10:25 FCJORDA0.005 1 Barium (Ba)0.539 mg/L EPA 200.7 09/24/2015 10:25 FCJORDA0.005 1 Boron (B)3.59 mg/L EPA 200.7 09/24/2015 10:25 FCJORDA0.05 1 Iron (Fe)0.073 mg/L EPA 200.7 09/24/2015 10:25 FCJORDA0.01 1 Manganese (Mn)0.077 mg/L EPA 200.7 09/24/2015 10:25 FCJORDA0.005 1 Strontium (Sr)5.99 mg/L EPA 200.7 09/24/2015 10:25 FCJORDA0.005 1 Zinc (Zn)< 0.005 mg/L EPA 200.7 09/24/2015 10:25 FCJORDA0.005 1 UNDIGESTED METALS BY ICP Calcium (Ca)116 mg/L EPA 200.7 09/24/2015 11:22 FCJORDA110 Magnesium (Mg)46.1 mg/L EPA 200.7 09/24/2015 11:22 FCJORDA0.05 10 Potassium (K)20.0 mg/L EPA 200.7 09/24/2015 11:22 FCJORDA110 Sodium (Na)68.0 mg/L EPA 200.7 09/24/2015 11:22 FCJORDA0.05 1 TOTAL RECOVERABLE METALS BY ICP Aluminum (Al)0.575 mg/L EPA 200.7 09/24/2015 10:23 MHH71310.005 1 Barium (Ba)0.532 mg/L EPA 200.7 09/24/2015 10:23 MHH71310.005 1 Boron (B)3.50 mg/L EPA 200.7 09/24/2015 10:23 MHH71310.05 1 Iron (Fe)0.317 mg/L EPA 200.7 09/24/2015 10:23 MHH71310.01 1 Manganese (Mn)0.077 mg/L EPA 200.7 09/24/2015 10:23 MHH71310.005 1 Strontium (Sr)5.75 mg/L EPA 200.7 09/24/2015 10:23 MHH71310.005 1 Zinc (Zn)0.055 mg/L EPA 200.7 09/24/2015 10:23 MHH71310.005 1 Page 16 of 22 Certificate of Laboratory Analysis This report shall not be reproduced, except in full. Order # J15090625 2015031379 Collection Date:22-Sep-15 12:31 PM Site:ABMW-15 Matrix:GW_WW Analyte Analysis Date/TimeMethodUnits Qualifiers RDLResult Sample #: AnalystDF TOTAL RECOVERABLE METALS BY ICP-MS (DISSOLVED) Antimony (Sb)< 1 ug/L EPA 200.8 09/23/2015 13:38 MHALL311 Arsenic (As)493 ug/L EPA 200.8 09/23/2015 13:38 MHALL311 Beryllium (Be)< 1 ug/L EPA 200.8 09/23/2015 13:38 MHALL311 Cadmium (Cd)< 1 ug/L EPA 200.8 09/23/2015 13:38 MHALL311 Chromium (Cr)< 1 ug/L EPA 200.8 09/23/2015 13:38 MHALL311 Cobalt (Co)< 1 ug/L EPA 200.8 09/23/2015 13:38 MHALL311 Copper (Cu)< 1 ug/L EPA 200.8 09/23/2015 13:38 MHALL311 Lead (Pb)< 1 ug/L EPA 200.8 09/23/2015 13:38 MHALL311 Molybdenum (Mo)132 ug/L EPA 200.8 09/23/2015 13:38 MHALL311 Nickel (Ni)1.04 ug/L EPA 200.8 09/23/2015 13:38 MHALL311 Selenium (Se)< 1 ug/L EPA 200.8 09/23/2015 13:38 MHALL311 Thallium (Tl) Low Level < 0.2 ug/L EPA 200.8 09/23/2015 13:38 MHALL30.2 1 Vanadium (V) Low Level 3.14 ug/L EPA 200.8 09/23/2015 13:38 MHALL30.3 1 Total Recoverable Metals Dissolved 0.1mm Filter Antimony (Sb)< 1 ug/L EPA 200.8 09/24/2015 13:31 MHALL311 Arsenic (As)500 ug/L EPA 200.8 09/24/2015 13:31 MHALL31010 Beryllium (Be)< 1 ug/L EPA 200.8 09/24/2015 13:31 MHALL311 Cadmium (Cd)< 1 ug/L EPA 200.8 09/24/2015 13:31 MHALL311 Chromium (Cr)< 1 ug/L EPA 200.8 09/24/2015 13:31 MHALL311 Cobalt (Co)< 1 ug/L EPA 200.8 09/24/2015 13:31 MHALL311 Copper (Cu)< 1 ug/L EPA 200.8 09/24/2015 13:31 MHALL311 Lead (Pb)< 1 ug/L EPA 200.8 09/24/2015 13:31 MHALL311 Molybdenum (Mo)134 ug/L EPA 200.8 09/24/2015 13:31 MHALL311 Nickel (Ni)1.00 ug/L EPA 200.8 09/24/2015 13:31 MHALL311 Selenium (Se)< 1 ug/L EPA 200.8 09/24/2015 13:31 MHALL311 Thallium (Tl) Low Level < 0.2 ug/L EPA 200.8 09/24/2015 13:31 MHALL30.2 1 Vanadium (V) Low Level 2.87 ug/L EPA 200.8 09/24/2015 13:31 MHALL30.3 1 Page 17 of 22 Certificate of Laboratory Analysis This report shall not be reproduced, except in full. Order # J15090625 2015031379 Collection Date:22-Sep-15 12:31 PM Site:ABMW-15 Matrix:GW_WW Analyte Analysis Date/TimeMethodUnits Qualifiers RDLResult Sample #: AnalystDF TOTAL RECOVERABLE METALS BY ICP-MS Antimony (Sb)< 1 ug/L EPA 200.8 09/23/2015 14:50 MHALL311 Arsenic (As)477 ug/L EPA 200.8 09/23/2015 14:50 MHALL311 Beryllium (Be)< 1 ug/L EPA 200.8 09/23/2015 14:50 MHALL311 Cadmium (Cd)< 1 ug/L EPA 200.8 09/23/2015 14:50 MHALL311 Chromium (Cr)1.22 ug/L EPA 200.8 09/23/2015 14:50 MHALL311 Cobalt (Co)< 1 ug/L EPA 200.8 09/23/2015 14:50 MHALL311 Copper (Cu)1.35 ug/L EPA 200.8 09/23/2015 14:50 MHALL311 Lead (Pb)< 1 ug/L EPA 200.8 09/23/2015 14:50 MHALL311 Molybdenum (Mo)132 ug/L EPA 200.8 09/23/2015 14:50 MHALL311 Nickel (Ni)1.65 ug/L EPA 200.8 09/23/2015 14:50 MHALL311 Selenium (Se)< 1 ug/L EPA 200.8 09/23/2015 14:50 MHALL311 Thallium (Tl) Low Level < 0.2 ug/L EPA 200.8 09/23/2015 14:50 MHALL30.2 1 Vanadium (V) Low Level 5.08 ug/L EPA 200.8 09/23/2015 14:50 MHALL30.3 1 Page 18 of 22 Certificate of Laboratory Analysis This report shall not be reproduced, except in full. Order # J15090625 2015031380 Collection Date:22-Sep-15 7:25 AM Site:Filter Blank Matrix:GW_WW Analyte Analysis Date/TimeMethodUnits Qualifiers RDLResult Sample #: AnalystDF Mercury Dissolved (cold vapor) in Water (Filtered) Mercury (Hg)< 0.05 ug/L EPA 245.1 09/23/2015 15:01 ACPAYNE0.05 1 Mercury Dissolved (cold vapor) in Water (0.1mm FILTER) Mercury (Hg)< 0.05 ug/L EPA 245.1 09/24/2015 16:25 ACPAYNE0.05 1 DISSOLVED METALS BY ICP Aluminum (Al)< 0.005 mg/L EPA 200.7 09/24/2015 09:47 FCJORDA0.005 1 Barium (Ba)< 0.005 mg/L EPA 200.7 09/24/2015 09:47 FCJORDA0.005 1 Boron (B)< 0.05 mg/L EPA 200.7 09/24/2015 09:47 FCJORDA0.05 1 Iron (Fe)< 0.01 mg/L EPA 200.7 09/24/2015 09:47 FCJORDA0.01 1 Manganese (Mn)< 0.005 mg/L EPA 200.7 09/24/2015 09:47 FCJORDA0.005 1 Strontium (Sr)< 0.005 mg/L EPA 200.7 09/24/2015 09:47 FCJORDA0.005 1 Zinc (Zn)< 0.005 mg/L EPA 200.7 09/24/2015 09:47 FCJORDA0.005 1 DISSOLVED METALS BY ICP (0.1mm FILTER) Aluminum (Al)< 0.005 mg/L EPA 200.7 09/24/2015 10:29 FCJORDA0.005 1 Barium (Ba)< 0.005 mg/L EPA 200.7 09/24/2015 10:29 FCJORDA0.005 1 Boron (B)< 0.05 mg/L EPA 200.7 09/24/2015 10:29 FCJORDA0.05 1 Iron (Fe)< 0.01 mg/L EPA 200.7 09/24/2015 10:29 FCJORDA0.01 1 Manganese (Mn)< 0.005 mg/L EPA 200.7 09/24/2015 10:29 FCJORDA0.005 1 Strontium (Sr)< 0.005 mg/L EPA 200.7 09/24/2015 10:29 FCJORDA0.005 1 Zinc (Zn)< 0.005 mg/L EPA 200.7 09/24/2015 10:29 FCJORDA0.005 1 TOTAL RECOVERABLE METALS BY ICP-MS (DISSOLVED) Antimony (Sb)< 1 ug/L EPA 200.8 09/23/2015 13:43 MHALL311 Arsenic (As)< 1 ug/L EPA 200.8 09/23/2015 13:43 MHALL311 Beryllium (Be)< 1 ug/L EPA 200.8 09/23/2015 13:43 MHALL311 Cadmium (Cd)< 1 ug/L EPA 200.8 09/23/2015 13:43 MHALL311 Chromium (Cr)< 1 ug/L EPA 200.8 09/23/2015 13:43 MHALL311 Cobalt (Co)< 1 ug/L EPA 200.8 09/23/2015 13:43 MHALL311 Copper (Cu)< 1 ug/L EPA 200.8 09/23/2015 13:43 MHALL311 Lead (Pb)< 1 ug/L EPA 200.8 09/23/2015 13:43 MHALL311 Molybdenum (Mo)< 1 ug/L EPA 200.8 09/23/2015 13:43 MHALL311 Nickel (Ni)< 1 ug/L EPA 200.8 09/23/2015 13:43 MHALL311 Selenium (Se)< 1 ug/L EPA 200.8 09/23/2015 13:43 MHALL311 Thallium (Tl) Low Level < 0.2 ug/L EPA 200.8 09/23/2015 13:43 MHALL30.2 1 Vanadium (V) Low Level < 0.3 ug/L EPA 200.8 09/23/2015 13:43 MHALL30.3 1 Page 19 of 22 Certificate of Laboratory Analysis This report shall not be reproduced, except in full. Order # J15090625 2015031380 Collection Date:22-Sep-15 7:25 AM Site:Filter Blank Matrix:GW_WW Analyte Analysis Date/TimeMethodUnits Qualifiers RDLResult Sample #: AnalystDF Total Recoverable Metals Dissolved 0.1mm Filter Antimony (Sb)< 1 ug/L EPA 200.8 09/24/2015 13:36 MHALL311 Arsenic (As)< 1 ug/L EPA 200.8 09/24/2015 13:36 MHALL311 Beryllium (Be)< 1 ug/L EPA 200.8 09/24/2015 13:36 MHALL311 Cadmium (Cd)< 1 ug/L EPA 200.8 09/24/2015 13:36 MHALL311 Chromium (Cr)< 1 ug/L EPA 200.8 09/24/2015 13:36 MHALL311 Cobalt (Co)< 1 ug/L EPA 200.8 09/24/2015 13:36 MHALL311 Copper (Cu)< 1 ug/L EPA 200.8 09/24/2015 13:36 MHALL311 Lead (Pb)< 1 ug/L EPA 200.8 09/24/2015 13:36 MHALL311 Molybdenum (Mo)< 1 ug/L EPA 200.8 09/24/2015 13:36 MHALL311 Nickel (Ni)< 1 ug/L EPA 200.8 09/24/2015 13:36 MHALL311 Selenium (Se)< 1 ug/L EPA 200.8 09/24/2015 13:36 MHALL311 Thallium (Tl) Low Level < 0.2 ug/L EPA 200.8 09/24/2015 13:36 MHALL30.2 1 Vanadium (V) Low Level < 0.3 ug/L EPA 200.8 09/24/2015 13:36 MHALL30.3 1 Page 20 of 22 Certificate of Laboratory Analysis This report shall not be reproduced, except in full. Order # J15090625 2015031381 Collection Date:22-Sep-15 7:25 AM Site:Equipment Blank Matrix:GW_WW Analyte Analysis Date/TimeMethodUnits Qualifiers RDLResult Sample #: AnalystDF MERCURY (COLD VAPOR) IN WATER Mercury (Hg)< 0.05 ug/L EPA 245.1 09/23/2015 14:38 ACPAYNE0.05 1 UNDIGESTED METALS BY ICP Calcium (Ca)< 0.01 mg/L EPA 200.7 09/24/2015 11:37 FCJORDA0.01 1 Magnesium (Mg)< 0.005 mg/L EPA 200.7 09/24/2015 11:37 FCJORDA0.005 1 Potassium (K)< 0.1 mg/L EPA 200.7 09/24/2015 11:37 FCJORDA0.1 1 Sodium (Na)< 0.05 mg/L EPA 200.7 09/24/2015 11:37 FCJORDA0.05 1 TOTAL RECOVERABLE METALS BY ICP Aluminum (Al)0.023 mg/L EPA 200.7 09/24/2015 10:31 MHH71310.005 1 Barium (Ba)< 0.005 mg/L EPA 200.7 09/24/2015 10:31 MHH71310.005 1 Boron (B)< 0.05 mg/L EPA 200.7 09/24/2015 10:31 MHH71310.05 1 Iron (Fe)< 0.01 mg/L EPA 200.7 09/24/2015 10:31 MHH71310.01 1 Manganese (Mn)< 0.005 mg/L EPA 200.7 09/24/2015 10:31 MHH71310.005 1 Strontium (Sr)< 0.005 mg/L EPA 200.7 09/24/2015 10:31 MHH71310.005 1 Zinc (Zn)< 0.005 mg/L EPA 200.7 09/24/2015 10:31 MHH71310.005 1 TOTAL RECOVERABLE METALS BY ICP-MS Antimony (Sb)< 1 ug/L EPA 200.8 09/23/2015 14:55 MHALL311 Arsenic (As)< 1 ug/L EPA 200.8 09/23/2015 14:55 MHALL311 Beryllium (Be)< 1 ug/L EPA 200.8 09/23/2015 14:55 MHALL311 Cadmium (Cd)< 1 ug/L EPA 200.8 09/23/2015 14:55 MHALL311 Chromium (Cr)< 1 ug/L EPA 200.8 09/23/2015 14:55 MHALL311 Cobalt (Co)< 1 ug/L EPA 200.8 09/23/2015 14:55 MHALL311 Copper (Cu)< 1 ug/L EPA 200.8 09/23/2015 14:55 MHALL311 Lead (Pb)< 1 ug/L EPA 200.8 09/23/2015 14:55 MHALL311 Molybdenum (Mo)< 1 ug/L EPA 200.8 09/23/2015 14:55 MHALL311 Nickel (Ni)< 1 ug/L EPA 200.8 09/23/2015 14:55 MHALL311 Selenium (Se)< 1 ug/L EPA 200.8 09/23/2015 14:55 MHALL311 Thallium (Tl) Low Level < 0.2 ug/L EPA 200.8 09/23/2015 14:55 MHALL30.2 1 Vanadium (V) Low Level < 0.3 ug/L EPA 200.8 09/23/2015 14:55 MHALL30.3 1 Qualifiers: M1 Matrix spike recovery was High: the associated Laboratory Control Spike (LCS) was acceptable. M2 Matrix spike recovery was Low: the associated Laboratory Control Spike (LCS) was acceptable. M4 The spike recovery value was unusable since the analyte concentration in the sample was disproportionate to the spike level. The associated Laboratory Control Spike recovery was acceptable. Page 21 of 22 Page 22 of 22 13339 Hagers Ferry Road Huntersville, NC 28078-7929 McGuire Nuclear Complex - MG03A2 Phone: 980-875-5245 Fax: 980-875-4349 Order Summary Report Analytical Laboratory Order Number:J15090668 Project Name:SUTTON - AB GW ASSESSMENT WATER Lab Contact:Mary Ann Ogle Date:10/1/2015 Customer Address: Customer Name(s):Perry Waldrep, Tim Hunsucker,Brandon Russo, Kathy Webb, John Toepfer Phone: 980-875-5274 Report Authorized By: (Signature) Program Comments: Please contact the Program Manager (Mary Ann Ogle) with any questions regarding this report. Data Flags & Calculations: Any analytical tests or individual analytes within a test flagged with a Qualifier indicate a deviation from the method quality system or quality control requirement. The qualifier description is found at the end of the Certificate of Analysis (sample results) under the qualifiers heading. All results are reported on a dry weight basis unless otherwise noted. Subcontracted data included on the Duke Certificate of Analysis is to be used as information only. Certified vendor results can be found in the subcontracted lab final report. Duke Energy Analytical Laboratory subcontracts analyses to other vendor laboratories that have been qualified by Duke Energy to perform these analyses except where noted. Data Package: This data package includes analytical results that are applicable only to the samples described in this narrative. An estimation of the uncertainty of measurement for the results in the report is available upon request. This report shall not be reproduced, except in full, without the written consent of the Analytical Laboratory. Please contact the Analytical laboratory with any questions. The order of individual sections within this report is as follows: Job Summary Report, Sample Identification, Technical Validation of Data Package, Analytical Laboratory Certificate of Analysis, Analytical Laboratory QC Reports, Sub-contracted Laboratory Results, Customer Specific Data Sheets, Reports & Documentation, Customer Database Entries, Test Case Narratives, Chain of Custody (COC) Certification: The Analytical Laboratory holds the following State Certifications : North Carolina (DENR) Certificate #248, South Carolina (DHEC) Laboratory ID # 99005. Contact the Analytical Laboratory for definitive information about the certification status of specific methods. Mary Ann Ogle Page 1 of 34 Sample ID's & Descriptions: Sample ID Plant/Station Collection Date and Time Collected By Sample Description 2015031561 Sutton 23-Sep-15 2:51 PM ILLEGIBLE MW-37B 2015031562 Sutton 23-Sep-15 12:35 PM ILLEGIBLE ABMW-2S 2015031563 Sutton 23-Sep-15 11:19 AM ILLEGIBLE AW-9D 2015031564 Sutton 23-Sep-15 11:24 AM ILLEGIBLE AW-9C 2015031565 Sutton 23-Sep-15 10:26 AM ILLEGIBLE SMW-1C 2015031566 Sutton 23-Sep-15 9:30 AM ILLEGIBLE MW-36C 2015031567 Sutton 23-Sep-15 9:28 AM ILLEGIBLE MW-36B 2015031568 Sutton 23-Sep-15 8:40 AM ILLEGIBLE PZ-1B 2015031569 Sutton 23-Sep-15 8:30 AM ILLEGIBLE GWPZ-1A 2015031570 Sutton 23-Sep-15 3:06 PM ILLEGIBLE Filter Blank 2015031571 Sutton 23-Sep-15 3:06 PM ILLEGIBLE Equipment Blank 11 Total Samples Page 2 of 34 COC and .pdf report are in agreement with sample totals and analyses (compliance programs and procedures). All Results are less than the laboratory reporting limits. All laboratory QA/QC requirements are acceptable. Yes No Technical Validation Review Checklist: Yes No Yes No Report Sections Included: Job Summary Report Sub-contracted Laboratory Results Sample Identification Customer Specific Data Sheets, Reports, & Documentation Technical Validation of Data Package Customer Database Entries Analytical Laboratory Certificate of Analysis Analytical Laboratory QC Report Chain of Custody Reviewed By:DBA Account Date:10/1/2015 Electronic Data Deliverable (EDD) Sent Separately Page 3 of 34 Certificate of Laboratory Analysis This report shall not be reproduced, except in full. Order # J15090668 2015031561 Collection Date:23-Sep-15 2:51 PM Site:MW-37B Matrix:GW_WW Analyte Analysis Date/TimeMethodUnits Qualifiers RDLResult Sample #: AnalystDF MERCURY (COLD VAPOR) IN WATER Mercury (Hg)< 0.05 ug/L EPA 245.1 09/24/2015 14:41 ACPAYNE0.05 1 Mercury Dissolved (cold vapor) in Water (Filtered) Mercury (Hg)< 0.05 ug/L EPA 245.1 09/24/2015 15:31 ACPAYNE0.05 1 Mercury Dissolved (cold vapor) in Water (0.1mm FILTER) Mercury (Hg)< 0.05 ug/L EPA 245.1 09/24/2015 16:27 ACPAYNE0.05 1 DISSOLVED METALS BY ICP Aluminum (Al)0.718 mg/L EPA 200.7 09/25/2015 10:13 FCJORDA0.005 1 Barium (Ba)0.008 mg/L EPA 200.7 09/25/2015 10:13 FCJORDA0.005 1 Boron (B)< 0.05 mg/L EPA 200.7 09/25/2015 10:13 FCJORDA0.05 1 Iron (Fe)0.021 mg/L EPA 200.7 09/25/2015 10:13 FCJORDA0.01 1 Manganese (Mn)< 0.005 mg/L EPA 200.7 09/25/2015 10:13 FCJORDA0.005 1 Strontium (Sr)< 0.005 mg/L EPA 200.7 09/25/2015 10:13M1 FCJORDA0.005 1 Zinc (Zn)< 0.005 mg/L EPA 200.7 09/25/2015 10:13 FCJORDA0.005 1 DISSOLVED METALS BY ICP (0.1mm FILTER) Aluminum (Al)0.727 mg/L EPA 200.7 09/25/2015 11:10 FCJORDA0.005 1 Barium (Ba)0.011 mg/L EPA 200.7 09/25/2015 11:10 FCJORDA0.005 1 Boron (B)< 0.05 mg/L EPA 200.7 09/25/2015 11:10 FCJORDA0.05 1 Iron (Fe)0.037 mg/L EPA 200.7 09/25/2015 11:10 FCJORDA0.01 1 Manganese (Mn)0.008 mg/L EPA 200.7 09/25/2015 11:10 FCJORDA0.005 1 Strontium (Sr)0.008 mg/L EPA 200.7 09/25/2015 11:10M1 FCJORDA0.005 1 Zinc (Zn)0.013 mg/L EPA 200.7 09/25/2015 11:10 FCJORDA0.005 1 UNDIGESTED METALS BY ICP Calcium (Ca)0.430 mg/L EPA 200.7 09/25/2015 12:31 FCJORDA0.01 1 Magnesium (Mg)0.112 mg/L EPA 200.7 09/25/2015 12:31 FCJORDA0.005 1 Potassium (K)0.242 mg/L EPA 200.7 09/25/2015 12:31 FCJORDA0.1 1 Sodium (Na)1.82 mg/L EPA 200.7 09/25/2015 12:31 FCJORDA0.05 1 TOTAL RECOVERABLE METALS BY ICP Aluminum (Al)0.696 mg/L EPA 200.7 09/28/2015 09:11 MHH71310.005 1 Barium (Ba)0.008 mg/L EPA 200.7 09/28/2015 09:11 MHH71310.005 1 Boron (B)< 0.05 mg/L EPA 200.7 09/28/2015 09:11 MHH71310.05 1 Iron (Fe)0.079 mg/L EPA 200.7 09/28/2015 09:11 MHH71310.01 1 Manganese (Mn)< 0.005 mg/L EPA 200.7 09/28/2015 09:11 MHH71310.005 1 Strontium (Sr)< 0.005 mg/L EPA 200.7 09/28/2015 09:11 MHH71310.005 1 Zinc (Zn)< 0.005 mg/L EPA 200.7 09/28/2015 09:11 MHH71310.005 1 Page 4 of 34 Certificate of Laboratory Analysis This report shall not be reproduced, except in full. Order # J15090668 2015031561 Collection Date:23-Sep-15 2:51 PM Site:MW-37B Matrix:GW_WW Analyte Analysis Date/TimeMethodUnits Qualifiers RDLResult Sample #: AnalystDF TOTAL RECOVERABLE METALS BY ICP-MS (DISSOLVED) Antimony (Sb)< 1 ug/L EPA 200.8 09/28/2015 14:41 MHALL311 Arsenic (As)< 1 ug/L EPA 200.8 09/28/2015 14:41 MHALL311 Beryllium (Be)< 1 ug/L EPA 200.8 09/28/2015 14:41 MHALL311 Cadmium (Cd)< 1 ug/L EPA 200.8 09/28/2015 14:41 MHALL311 Chromium (Cr)< 1 ug/L EPA 200.8 09/28/2015 14:41 MHALL311 Cobalt (Co)< 1 ug/L EPA 200.8 09/28/2015 14:41 MHALL311 Copper (Cu)< 1 ug/L EPA 200.8 09/28/2015 14:41 MHALL311 Lead (Pb)< 1 ug/L EPA 200.8 09/28/2015 14:41 MHALL311 Molybdenum (Mo)< 1 ug/L EPA 200.8 09/28/2015 14:41 MHALL311 Nickel (Ni)< 1 ug/L EPA 200.8 09/28/2015 14:41 MHALL311 Selenium (Se)< 1 ug/L EPA 200.8 09/28/2015 14:41 MHALL311 Thallium (Tl) Low Level < 0.2 ug/L EPA 200.8 09/28/2015 14:41 MHALL30.2 1 Vanadium (V) Low Level < 0.3 ug/L EPA 200.8 09/28/2015 14:41 MHALL30.3 1 Total Recoverable Metals Dissolved 0.1mm Filter Antimony (Sb)< 1 ug/L EPA 200.8 09/28/2015 13:04 MHALL311 Arsenic (As)< 1 ug/L EPA 200.8 09/28/2015 13:04 MHALL311 Beryllium (Be)< 1 ug/L EPA 200.8 09/28/2015 13:04 MHALL311 Cadmium (Cd)< 1 ug/L EPA 200.8 09/28/2015 13:04 MHALL311 Chromium (Cr)< 1 ug/L EPA 200.8 09/28/2015 13:04 MHALL311 Cobalt (Co)< 1 ug/L EPA 200.8 09/28/2015 13:04 MHALL311 Copper (Cu)< 1 ug/L EPA 200.8 09/28/2015 13:04 MHALL311 Lead (Pb)< 1 ug/L EPA 200.8 09/28/2015 13:04 MHALL311 Molybdenum (Mo)< 1 ug/L EPA 200.8 09/28/2015 13:04 MHALL311 Nickel (Ni)< 1 ug/L EPA 200.8 09/28/2015 13:04 MHALL311 Selenium (Se)< 1 ug/L EPA 200.8 09/28/2015 13:04 MHALL311 Thallium (Tl) Low Level < 0.2 ug/L EPA 200.8 09/28/2015 13:04 MHALL30.2 1 Vanadium (V) Low Level < 0.3 ug/L EPA 200.8 09/28/2015 13:04 MHALL30.3 1 Page 5 of 34 Certificate of Laboratory Analysis This report shall not be reproduced, except in full. Order # J15090668 2015031561 Collection Date:23-Sep-15 2:51 PM Site:MW-37B Matrix:GW_WW Analyte Analysis Date/TimeMethodUnits Qualifiers RDLResult Sample #: AnalystDF TOTAL RECOVERABLE METALS BY ICP-MS Antimony (Sb)< 1 ug/L EPA 200.8 09/28/2015 16:28 MHALL311 Arsenic (As)< 1 ug/L EPA 200.8 09/28/2015 16:28 MHALL311 Beryllium (Be)< 1 ug/L EPA 200.8 09/28/2015 16:28 MHALL311 Cadmium (Cd)< 1 ug/L EPA 200.8 09/28/2015 16:28 MHALL311 Chromium (Cr)< 1 ug/L EPA 200.8 09/28/2015 16:28 MHALL311 Cobalt (Co)< 1 ug/L EPA 200.8 09/28/2015 16:28 MHALL311 Copper (Cu)< 1 ug/L EPA 200.8 09/28/2015 16:28 MHALL311 Lead (Pb)< 1 ug/L EPA 200.8 09/28/2015 16:28 MHALL311 Molybdenum (Mo)< 1 ug/L EPA 200.8 09/28/2015 16:28 MHALL311 Nickel (Ni)< 1 ug/L EPA 200.8 09/28/2015 16:28 MHALL311 Selenium (Se)< 1 ug/L EPA 200.8 09/28/2015 16:28 MHALL311 Thallium (Tl) Low Level 0.350 ug/L EPA 200.8 09/28/2015 16:28 MHALL30.2 1 Vanadium (V) Low Level < 0.3 ug/L EPA 200.8 09/28/2015 16:28 MHALL30.3 1 Page 6 of 34 Certificate of Laboratory Analysis This report shall not be reproduced, except in full. Order # J15090668 2015031562 Collection Date:23-Sep-15 12:35 PM Site:ABMW-2S Matrix:GW_WW Analyte Analysis Date/TimeMethodUnits Qualifiers RDLResult Sample #: AnalystDF MERCURY (COLD VAPOR) IN WATER Mercury (Hg)< 0.05 ug/L EPA 245.1 09/24/2015 14:43 ACPAYNE0.05 1 Mercury Dissolved (cold vapor) in Water (Filtered) Mercury (Hg)< 0.05 ug/L EPA 245.1 09/24/2015 15:38 ACPAYNE0.05 1 Mercury Dissolved (cold vapor) in Water (0.1mm FILTER) Mercury (Hg)< 0.05 ug/L EPA 245.1 09/29/2015 14:25 ACPAYNE0.05 1 DISSOLVED METALS BY ICP Aluminum (Al)0.035 mg/L EPA 200.7 09/25/2015 10:24 FCJORDA0.005 1 Barium (Ba)1.70 mg/L EPA 200.7 09/25/2015 10:24 FCJORDA0.005 1 Boron (B)0.270 mg/L EPA 200.7 09/25/2015 10:24 FCJORDA0.05 1 Iron (Fe)16.0 mg/L EPA 200.7 09/25/2015 10:24 FCJORDA0.01 1 Manganese (Mn)0.542 mg/L EPA 200.7 09/25/2015 10:24 FCJORDA0.005 1 Strontium (Sr)1.71 mg/L EPA 200.7 09/25/2015 10:24 FCJORDA0.005 1 Zinc (Zn)0.018 mg/L EPA 200.7 09/25/2015 10:24 FCJORDA0.005 1 DISSOLVED METALS BY ICP (0.1mm FILTER) Aluminum (Al)0.034 mg/L EPA 200.7 09/25/2015 11:21 FCJORDA0.005 1 Barium (Ba)1.69 mg/L EPA 200.7 09/25/2015 11:21 FCJORDA0.005 1 Boron (B)0.273 mg/L EPA 200.7 09/25/2015 11:21 FCJORDA0.05 1 Iron (Fe)15.0 mg/L EPA 200.7 09/25/2015 11:21 FCJORDA0.01 1 Manganese (Mn)0.543 mg/L EPA 200.7 09/25/2015 11:21 FCJORDA0.005 1 Strontium (Sr)1.71 mg/L EPA 200.7 09/25/2015 11:21 FCJORDA0.005 1 Zinc (Zn)0.022 mg/L EPA 200.7 09/25/2015 11:21 FCJORDA0.005 1 UNDIGESTED METALS BY ICP Calcium (Ca)64.8 mg/L EPA 200.7 09/25/2015 12:42 FCJORDA0.01 1 Magnesium (Mg)7.49 mg/L EPA 200.7 09/25/2015 12:42 FCJORDA0.005 1 Potassium (K)8.12 mg/L EPA 200.7 09/25/2015 12:42 FCJORDA0.1 1 Sodium (Na)20.1 mg/L EPA 200.7 09/25/2015 12:42 FCJORDA0.05 1 TOTAL RECOVERABLE METALS BY ICP Aluminum (Al)0.034 mg/L EPA 200.7 09/28/2015 09:24 MHH71310.005 1 Barium (Ba)1.71 mg/L EPA 200.7 09/28/2015 09:24 MHH71310.005 1 Boron (B)0.258 mg/L EPA 200.7 09/28/2015 09:24 MHH71310.05 1 Iron (Fe)16.1 mg/L EPA 200.7 09/28/2015 09:24 MHH71310.01 1 Manganese (Mn)0.513 mg/L EPA 200.7 09/28/2015 09:24 MHH71310.005 1 Strontium (Sr)1.71 mg/L EPA 200.7 09/28/2015 09:24 MHH71310.005 1 Zinc (Zn)< 0.005 mg/L EPA 200.7 09/28/2015 09:24 MHH71310.005 1 Page 7 of 34 Certificate of Laboratory Analysis This report shall not be reproduced, except in full. Order # J15090668 2015031562 Collection Date:23-Sep-15 12:35 PM Site:ABMW-2S Matrix:GW_WW Analyte Analysis Date/TimeMethodUnits Qualifiers RDLResult Sample #: AnalystDF TOTAL RECOVERABLE METALS BY ICP-MS (DISSOLVED) Antimony (Sb)< 1 ug/L EPA 200.8 09/28/2015 14:56 MHALL311 Arsenic (As)35.3 ug/L EPA 200.8 09/28/2015 14:56 MHALL311 Beryllium (Be)< 1 ug/L EPA 200.8 09/28/2015 14:56 MHALL311 Cadmium (Cd)< 1 ug/L EPA 200.8 09/28/2015 14:56 MHALL311 Chromium (Cr)< 1 ug/L EPA 200.8 09/28/2015 14:56 MHALL311 Cobalt (Co)< 1 ug/L EPA 200.8 09/28/2015 14:56 MHALL311 Copper (Cu)< 1 ug/L EPA 200.8 09/28/2015 14:56 MHALL311 Lead (Pb)< 1 ug/L EPA 200.8 09/28/2015 14:56 MHALL311 Molybdenum (Mo)2.75 ug/L EPA 200.8 09/28/2015 14:56 MHALL311 Nickel (Ni)< 1 ug/L EPA 200.8 09/28/2015 14:56 MHALL311 Selenium (Se)< 1 ug/L EPA 200.8 09/28/2015 14:56 MHALL311 Thallium (Tl) Low Level < 0.2 ug/L EPA 200.8 09/28/2015 14:56 MHALL30.2 1 Vanadium (V) Low Level 0.768 ug/L EPA 200.8 09/28/2015 14:56 MHALL30.3 1 Total Recoverable Metals Dissolved 0.1mm Filter Antimony (Sb)< 1 ug/L EPA 200.8 09/28/2015 13:20 MHALL311 Arsenic (As)35.5 ug/L EPA 200.8 09/28/2015 13:20 MHALL311 Beryllium (Be)< 1 ug/L EPA 200.8 09/28/2015 13:20 MHALL311 Cadmium (Cd)< 1 ug/L EPA 200.8 09/28/2015 13:20 MHALL311 Chromium (Cr)< 1 ug/L EPA 200.8 09/28/2015 13:20 MHALL311 Cobalt (Co)< 1 ug/L EPA 200.8 09/28/2015 13:20 MHALL311 Copper (Cu)< 1 ug/L EPA 200.8 09/28/2015 13:20 MHALL311 Lead (Pb)< 1 ug/L EPA 200.8 09/28/2015 13:20 MHALL311 Molybdenum (Mo)3.16 ug/L EPA 200.8 09/28/2015 13:20 MHALL311 Nickel (Ni)< 1 ug/L EPA 200.8 09/28/2015 13:20 MHALL311 Selenium (Se)< 1 ug/L EPA 200.8 09/28/2015 13:20 MHALL311 Thallium (Tl) Low Level < 0.2 ug/L EPA 200.8 09/28/2015 13:20 MHALL30.2 1 Vanadium (V) Low Level 0.766 ug/L EPA 200.8 09/28/2015 13:20 MHALL30.3 1 Page 8 of 34 Certificate of Laboratory Analysis This report shall not be reproduced, except in full. Order # J15090668 2015031562 Collection Date:23-Sep-15 12:35 PM Site:ABMW-2S Matrix:GW_WW Analyte Analysis Date/TimeMethodUnits Qualifiers RDLResult Sample #: AnalystDF TOTAL RECOVERABLE METALS BY ICP-MS Antimony (Sb)< 1 ug/L EPA 200.8 09/28/2015 16:13 MHALL311 Arsenic (As)38.3 ug/L EPA 200.8 09/28/2015 16:13 MHALL311 Beryllium (Be)< 1 ug/L EPA 200.8 09/28/2015 16:13 MHALL311 Cadmium (Cd)< 1 ug/L EPA 200.8 09/28/2015 16:13 MHALL311 Chromium (Cr)< 1 ug/L EPA 200.8 09/28/2015 16:13 MHALL311 Cobalt (Co)< 1 ug/L EPA 200.8 09/28/2015 16:13 MHALL311 Copper (Cu)< 1 ug/L EPA 200.8 09/28/2015 16:13 MHALL311 Lead (Pb)< 1 ug/L EPA 200.8 09/28/2015 16:13 MHALL311 Molybdenum (Mo)3.11 ug/L EPA 200.8 09/28/2015 16:13 MHALL311 Nickel (Ni)< 1 ug/L EPA 200.8 09/28/2015 16:13 MHALL311 Selenium (Se)< 1 ug/L EPA 200.8 09/28/2015 16:13 MHALL311 Thallium (Tl) Low Level < 0.2 ug/L EPA 200.8 09/28/2015 16:13 MHALL30.2 1 Vanadium (V) Low Level 0.941 ug/L EPA 200.8 09/28/2015 16:13 MHALL30.3 1 Page 9 of 34 Certificate of Laboratory Analysis This report shall not be reproduced, except in full. Order # J15090668 2015031563 Collection Date:23-Sep-15 11:19 AM Site:AW-9D Matrix:GW_WW Analyte Analysis Date/TimeMethodUnits Qualifiers RDLResult Sample #: AnalystDF MERCURY (COLD VAPOR) IN WATER Mercury (Hg)< 0.05 ug/L EPA 245.1 09/24/2015 14:45 ACPAYNE0.05 1 Mercury Dissolved (cold vapor) in Water (Filtered) Mercury (Hg)< 0.05 ug/L EPA 245.1 09/24/2015 15:40 ACPAYNE0.05 1 Mercury Dissolved (cold vapor) in Water (0.1mm FILTER) Mercury (Hg)< 0.05 ug/L EPA 245.1 09/29/2015 14:27 ACPAYNE0.05 1 DISSOLVED METALS BY ICP Aluminum (Al)0.007 mg/L EPA 200.7 09/25/2015 10:28 FCJORDA0.005 1 Barium (Ba)0.022 mg/L EPA 200.7 09/25/2015 10:28 FCJORDA0.005 1 Boron (B)0.587 mg/L EPA 200.7 09/25/2015 10:28 FCJORDA0.05 1 Iron (Fe)0.175 mg/L EPA 200.7 09/25/2015 10:28 FCJORDA0.01 1 Manganese (Mn)0.054 mg/L EPA 200.7 09/25/2015 10:28 FCJORDA0.005 1 Strontium (Sr)0.134 mg/L EPA 200.7 09/25/2015 10:28 FCJORDA0.005 1 Zinc (Zn)0.009 mg/L EPA 200.7 09/25/2015 10:28 FCJORDA0.005 1 DISSOLVED METALS BY ICP (0.1mm FILTER) Aluminum (Al)0.007 mg/L EPA 200.7 09/25/2015 11:25 FCJORDA0.005 1 Barium (Ba)0.021 mg/L EPA 200.7 09/25/2015 11:25 FCJORDA0.005 1 Boron (B)0.590 mg/L EPA 200.7 09/25/2015 11:25 FCJORDA0.05 1 Iron (Fe)0.139 mg/L EPA 200.7 09/25/2015 11:25 FCJORDA0.01 1 Manganese (Mn)0.056 mg/L EPA 200.7 09/25/2015 11:25 FCJORDA0.005 1 Strontium (Sr)0.134 mg/L EPA 200.7 09/25/2015 11:25 FCJORDA0.005 1 Zinc (Zn)0.013 mg/L EPA 200.7 09/25/2015 11:25 FCJORDA0.005 1 UNDIGESTED METALS BY ICP Calcium (Ca)16.7 mg/L EPA 200.7 09/25/2015 12:46 FCJORDA0.01 1 Magnesium (Mg)9.28 mg/L EPA 200.7 09/25/2015 12:46 FCJORDA0.005 1 Potassium (K)9.61 mg/L EPA 200.7 09/25/2015 12:46 FCJORDA0.1 1 Sodium (Na)176 mg/L EPA 200.7 09/25/2015 12:46 FCJORDA0.5 10 TOTAL RECOVERABLE METALS BY ICP Aluminum (Al)0.169 mg/L EPA 200.7 09/28/2015 09:28 MHH71310.005 1 Barium (Ba)0.009 mg/L EPA 200.7 09/28/2015 09:28 MHH71310.005 1 Boron (B)0.570 mg/L EPA 200.7 09/28/2015 09:28 MHH71310.05 1 Iron (Fe)0.479 mg/L EPA 200.7 09/28/2015 09:28 MHH71310.01 1 Manganese (Mn)0.049 mg/L EPA 200.7 09/28/2015 09:28 MHH71310.005 1 Strontium (Sr)0.127 mg/L EPA 200.7 09/28/2015 09:28 MHH71310.005 1 Zinc (Zn)< 0.005 mg/L EPA 200.7 09/28/2015 09:28 MHH71310.005 1 Page 10 of 34 Certificate of Laboratory Analysis This report shall not be reproduced, except in full. Order # J15090668 2015031563 Collection Date:23-Sep-15 11:19 AM Site:AW-9D Matrix:GW_WW Analyte Analysis Date/TimeMethodUnits Qualifiers RDLResult Sample #: AnalystDF TOTAL RECOVERABLE METALS BY ICP-MS (DISSOLVED) Antimony (Sb)< 1 ug/L EPA 200.8 09/28/2015 15:01 MHALL311 Arsenic (As)< 1 ug/L EPA 200.8 09/28/2015 15:01 MHALL311 Beryllium (Be)< 1 ug/L EPA 200.8 09/28/2015 15:01 MHALL311 Cadmium (Cd)< 1 ug/L EPA 200.8 09/28/2015 15:01 MHALL311 Chromium (Cr)< 1 ug/L EPA 200.8 09/28/2015 15:01 MHALL311 Cobalt (Co)< 1 ug/L EPA 200.8 09/28/2015 15:01 MHALL311 Copper (Cu)< 1 ug/L EPA 200.8 09/28/2015 15:01 MHALL311 Lead (Pb)< 1 ug/L EPA 200.8 09/28/2015 15:01 MHALL311 Molybdenum (Mo)10.0 ug/L EPA 200.8 09/28/2015 15:01 MHALL311 Nickel (Ni)< 1 ug/L EPA 200.8 09/28/2015 15:01 MHALL311 Selenium (Se)< 1 ug/L EPA 200.8 09/28/2015 15:01 MHALL311 Thallium (Tl) Low Level < 0.2 ug/L EPA 200.8 09/28/2015 15:01 MHALL30.2 1 Vanadium (V) Low Level < 0.3 ug/L EPA 200.8 09/28/2015 15:01 MHALL30.3 1 Total Recoverable Metals Dissolved 0.1mm Filter Antimony (Sb)< 1 ug/L EPA 200.8 09/28/2015 13:25 MHALL311 Arsenic (As)< 1 ug/L EPA 200.8 09/28/2015 13:25 MHALL311 Beryllium (Be)< 1 ug/L EPA 200.8 09/28/2015 13:25 MHALL311 Cadmium (Cd)< 1 ug/L EPA 200.8 09/28/2015 13:25 MHALL311 Chromium (Cr)< 1 ug/L EPA 200.8 09/28/2015 13:25 MHALL311 Cobalt (Co)< 1 ug/L EPA 200.8 09/28/2015 13:25 MHALL311 Copper (Cu)< 1 ug/L EPA 200.8 09/28/2015 13:25 MHALL311 Lead (Pb)< 1 ug/L EPA 200.8 09/28/2015 13:25 MHALL311 Molybdenum (Mo)9.42 ug/L EPA 200.8 09/28/2015 13:25 MHALL311 Nickel (Ni)< 1 ug/L EPA 200.8 09/28/2015 13:25 MHALL311 Selenium (Se)< 1 ug/L EPA 200.8 09/28/2015 13:25 MHALL311 Thallium (Tl) Low Level < 0.2 ug/L EPA 200.8 09/28/2015 13:25 MHALL30.2 1 Vanadium (V) Low Level < 0.3 ug/L EPA 200.8 09/28/2015 13:25 MHALL30.3 1 Page 11 of 34 Certificate of Laboratory Analysis This report shall not be reproduced, except in full. Order # J15090668 2015031563 Collection Date:23-Sep-15 11:19 AM Site:AW-9D Matrix:GW_WW Analyte Analysis Date/TimeMethodUnits Qualifiers RDLResult Sample #: AnalystDF TOTAL RECOVERABLE METALS BY ICP-MS Antimony (Sb)< 1 ug/L EPA 200.8 09/28/2015 16:33 MHALL311 Arsenic (As)< 1 ug/L EPA 200.8 09/28/2015 16:33 MHALL311 Beryllium (Be)< 1 ug/L EPA 200.8 09/28/2015 16:33 MHALL311 Cadmium (Cd)< 1 ug/L EPA 200.8 09/28/2015 16:33 MHALL311 Chromium (Cr)< 1 ug/L EPA 200.8 09/28/2015 16:33 MHALL311 Cobalt (Co)< 1 ug/L EPA 200.8 09/28/2015 16:33 MHALL311 Copper (Cu)< 1 ug/L EPA 200.8 09/28/2015 16:33 MHALL311 Lead (Pb)< 1 ug/L EPA 200.8 09/28/2015 16:33 MHALL311 Molybdenum (Mo)10.3 ug/L EPA 200.8 09/28/2015 16:33 MHALL311 Nickel (Ni)< 1 ug/L EPA 200.8 09/28/2015 16:33 MHALL311 Selenium (Se)< 1 ug/L EPA 200.8 09/28/2015 16:33 MHALL311 Thallium (Tl) Low Level < 0.2 ug/L EPA 200.8 09/28/2015 16:33 MHALL30.2 1 Vanadium (V) Low Level 0.690 ug/L EPA 200.8 09/28/2015 16:33 MHALL30.3 1 Page 12 of 34 Certificate of Laboratory Analysis This report shall not be reproduced, except in full. Order # J15090668 2015031564 Collection Date:23-Sep-15 11:24 AM Site:AW-9C Matrix:GW_WW Analyte Analysis Date/TimeMethodUnits Qualifiers RDLResult Sample #: AnalystDF MERCURY (COLD VAPOR) IN WATER Mercury (Hg)< 0.05 ug/L EPA 245.1 09/24/2015 14:48 ACPAYNE0.05 1 Mercury Dissolved (cold vapor) in Water (Filtered) Mercury (Hg)< 0.05 ug/L EPA 245.1 09/24/2015 15:42 ACPAYNE0.05 1 Mercury Dissolved (cold vapor) in Water (0.1mm FILTER) Mercury (Hg)< 0.05 ug/L EPA 245.1 09/24/2015 16:29 ACPAYNE0.05 1 DISSOLVED METALS BY ICP Aluminum (Al)0.144 mg/L EPA 200.7 09/25/2015 10:32 FCJORDA0.005 1 Barium (Ba)0.075 mg/L EPA 200.7 09/25/2015 10:32 FCJORDA0.005 1 Boron (B)0.384 mg/L EPA 200.7 09/25/2015 10:32 FCJORDA0.05 1 Iron (Fe)0.029 mg/L EPA 200.7 09/25/2015 10:32 FCJORDA0.01 1 Manganese (Mn)0.167 mg/L EPA 200.7 09/25/2015 10:32 FCJORDA0.005 1 Strontium (Sr)0.129 mg/L EPA 200.7 09/25/2015 10:32 FCJORDA0.005 1 Zinc (Zn)0.006 mg/L EPA 200.7 09/25/2015 10:32 FCJORDA0.005 1 DISSOLVED METALS BY ICP (0.1mm FILTER) Aluminum (Al)0.122 mg/L EPA 200.7 09/25/2015 11:29 FCJORDA0.005 1 Barium (Ba)0.077 mg/L EPA 200.7 09/25/2015 11:29 FCJORDA0.005 1 Boron (B)0.393 mg/L EPA 200.7 09/25/2015 11:29 FCJORDA0.05 1 Iron (Fe)0.026 mg/L EPA 200.7 09/25/2015 11:29 FCJORDA0.01 1 Manganese (Mn)0.172 mg/L EPA 200.7 09/25/2015 11:29 FCJORDA0.005 1 Strontium (Sr)0.133 mg/L EPA 200.7 09/25/2015 11:29 FCJORDA0.005 1 Zinc (Zn)0.009 mg/L EPA 200.7 09/25/2015 11:29 FCJORDA0.005 1 UNDIGESTED METALS BY ICP Calcium (Ca)15.1 mg/L EPA 200.7 09/25/2015 12:54 FCJORDA0.01 1 Magnesium (Mg)3.65 mg/L EPA 200.7 09/25/2015 12:54 FCJORDA0.005 1 Potassium (K)3.43 mg/L EPA 200.7 09/25/2015 12:54 FCJORDA0.1 1 Sodium (Na)18.2 mg/L EPA 200.7 09/25/2015 12:54 FCJORDA0.05 1 TOTAL RECOVERABLE METALS BY ICP Aluminum (Al)0.151 mg/L EPA 200.7 09/28/2015 10:05 MHH71310.005 1 Barium (Ba)0.076 mg/L EPA 200.7 09/28/2015 10:05 MHH71310.005 1 Boron (B)0.367 mg/L EPA 200.7 09/28/2015 10:05 MHH71310.05 1 Iron (Fe)0.088 mg/L EPA 200.7 09/28/2015 10:05 MHH71310.01 1 Manganese (Mn)0.164 mg/L EPA 200.7 09/28/2015 10:05 MHH71310.005 1 Strontium (Sr)0.126 mg/L EPA 200.7 09/28/2015 10:05 MHH71310.005 1 Zinc (Zn)< 0.005 mg/L EPA 200.7 09/28/2015 10:05 MHH71310.005 1 Page 13 of 34 Certificate of Laboratory Analysis This report shall not be reproduced, except in full. Order # J15090668 2015031564 Collection Date:23-Sep-15 11:24 AM Site:AW-9C Matrix:GW_WW Analyte Analysis Date/TimeMethodUnits Qualifiers RDLResult Sample #: AnalystDF TOTAL RECOVERABLE METALS BY ICP-MS (DISSOLVED) Antimony (Sb)< 1 ug/L EPA 200.8 09/28/2015 15:07 MHALL311 Arsenic (As)< 1 ug/L EPA 200.8 09/28/2015 15:07 MHALL311 Beryllium (Be)< 1 ug/L EPA 200.8 09/28/2015 15:07 MHALL311 Cadmium (Cd)< 1 ug/L EPA 200.8 09/28/2015 15:07 MHALL311 Chromium (Cr)< 1 ug/L EPA 200.8 09/28/2015 15:07 MHALL311 Cobalt (Co)< 1 ug/L EPA 200.8 09/28/2015 15:07 MHALL311 Copper (Cu)< 1 ug/L EPA 200.8 09/28/2015 15:07 MHALL311 Lead (Pb)< 1 ug/L EPA 200.8 09/28/2015 15:07 MHALL311 Molybdenum (Mo)< 1 ug/L EPA 200.8 09/28/2015 15:07 MHALL311 Nickel (Ni)< 1 ug/L EPA 200.8 09/28/2015 15:07 MHALL311 Selenium (Se)< 1 ug/L EPA 200.8 09/28/2015 15:07 MHALL311 Thallium (Tl) Low Level < 0.2 ug/L EPA 200.8 09/28/2015 15:07 MHALL30.2 1 Vanadium (V) Low Level < 0.3 ug/L EPA 200.8 09/28/2015 15:07 MHALL30.3 1 Total Recoverable Metals Dissolved 0.1mm Filter Antimony (Sb)< 1 ug/L EPA 200.8 09/28/2015 13:30 MHALL311 Arsenic (As)< 1 ug/L EPA 200.8 09/28/2015 13:30 MHALL311 Beryllium (Be)< 1 ug/L EPA 200.8 09/28/2015 13:30 MHALL311 Cadmium (Cd)< 1 ug/L EPA 200.8 09/28/2015 13:30 MHALL311 Chromium (Cr)< 1 ug/L EPA 200.8 09/28/2015 13:30 MHALL311 Cobalt (Co)< 1 ug/L EPA 200.8 09/28/2015 13:30 MHALL311 Copper (Cu)< 1 ug/L EPA 200.8 09/28/2015 13:30 MHALL311 Lead (Pb)< 1 ug/L EPA 200.8 09/28/2015 13:30 MHALL311 Molybdenum (Mo)< 1 ug/L EPA 200.8 09/28/2015 13:30 MHALL311 Nickel (Ni)< 1 ug/L EPA 200.8 09/28/2015 13:30 MHALL311 Selenium (Se)< 1 ug/L EPA 200.8 09/28/2015 13:30 MHALL311 Thallium (Tl) Low Level < 0.2 ug/L EPA 200.8 09/28/2015 13:30 MHALL30.2 1 Vanadium (V) Low Level < 0.3 ug/L EPA 200.8 09/28/2015 13:30 MHALL30.3 1 Page 14 of 34 Certificate of Laboratory Analysis This report shall not be reproduced, except in full. Order # J15090668 2015031564 Collection Date:23-Sep-15 11:24 AM Site:AW-9C Matrix:GW_WW Analyte Analysis Date/TimeMethodUnits Qualifiers RDLResult Sample #: AnalystDF TOTAL RECOVERABLE METALS BY ICP-MS Antimony (Sb)< 1 ug/L EPA 200.8 09/28/2015 16:38 MHALL311 Arsenic (As)< 1 ug/L EPA 200.8 09/28/2015 16:38 MHALL311 Beryllium (Be)< 1 ug/L EPA 200.8 09/28/2015 16:38 MHALL311 Cadmium (Cd)< 1 ug/L EPA 200.8 09/28/2015 16:38 MHALL311 Chromium (Cr)< 1 ug/L EPA 200.8 09/28/2015 16:38 MHALL311 Cobalt (Co)< 1 ug/L EPA 200.8 09/28/2015 16:38 MHALL311 Copper (Cu)< 1 ug/L EPA 200.8 09/28/2015 16:38 MHALL311 Lead (Pb)< 1 ug/L EPA 200.8 09/28/2015 16:38 MHALL311 Molybdenum (Mo)< 1 ug/L EPA 200.8 09/28/2015 16:38 MHALL311 Nickel (Ni)< 1 ug/L EPA 200.8 09/28/2015 16:38 MHALL311 Selenium (Se)< 1 ug/L EPA 200.8 09/28/2015 16:38 MHALL311 Thallium (Tl) Low Level < 0.2 ug/L EPA 200.8 09/28/2015 16:38 MHALL30.2 1 Vanadium (V) Low Level 0.412 ug/L EPA 200.8 09/28/2015 16:38 MHALL30.3 1 Page 15 of 34 Certificate of Laboratory Analysis This report shall not be reproduced, except in full. Order # J15090668 2015031565 Collection Date:23-Sep-15 10:26 AM Site:SMW-1C Matrix:GW_WW Analyte Analysis Date/TimeMethodUnits Qualifiers RDLResult Sample #: AnalystDF MERCURY (COLD VAPOR) IN WATER Mercury (Hg)< 0.05 ug/L EPA 245.1 09/24/2015 14:50 ACPAYNE0.05 1 Mercury Dissolved (cold vapor) in Water (Filtered) Mercury (Hg)< 0.05 ug/L EPA 245.1 09/24/2015 15:45 ACPAYNE0.05 1 Mercury Dissolved (cold vapor) in Water (0.1mm FILTER) Mercury (Hg)< 0.05 ug/L EPA 245.1 09/24/2015 16:32 ACPAYNE0.05 1 DISSOLVED METALS BY ICP Aluminum (Al)0.175 mg/L EPA 200.7 09/25/2015 10:36 FCJORDA0.005 1 Barium (Ba)0.036 mg/L EPA 200.7 09/25/2015 10:36 FCJORDA0.005 1 Boron (B)0.758 mg/L EPA 200.7 09/25/2015 10:36 FCJORDA0.05 1 Iron (Fe)0.608 mg/L EPA 200.7 09/25/2015 10:36 FCJORDA0.01 1 Manganese (Mn)0.738 mg/L EPA 200.7 09/25/2015 10:36 FCJORDA0.005 1 Strontium (Sr)0.464 mg/L EPA 200.7 09/25/2015 10:36 FCJORDA0.005 1 Zinc (Zn)0.009 mg/L EPA 200.7 09/25/2015 10:36 FCJORDA0.005 1 DISSOLVED METALS BY ICP (0.1mm FILTER) Aluminum (Al)0.144 mg/L EPA 200.7 09/25/2015 11:38 FCJORDA0.005 1 Barium (Ba)0.034 mg/L EPA 200.7 09/25/2015 11:38 FCJORDA0.005 1 Boron (B)0.760 mg/L EPA 200.7 09/25/2015 11:38 FCJORDA0.05 1 Iron (Fe)0.589 mg/L EPA 200.7 09/25/2015 11:38 FCJORDA0.01 1 Manganese (Mn)0.737 mg/L EPA 200.7 09/25/2015 11:38 FCJORDA0.005 1 Strontium (Sr)0.462 mg/L EPA 200.7 09/25/2015 11:38 FCJORDA0.005 1 Zinc (Zn)0.012 mg/L EPA 200.7 09/25/2015 11:38 FCJORDA0.005 1 UNDIGESTED METALS BY ICP Calcium (Ca)36.4 mg/L EPA 200.7 09/25/2015 12:59 FCJORDA0.01 1 Magnesium (Mg)7.82 mg/L EPA 200.7 09/25/2015 12:59 FCJORDA0.005 1 Potassium (K)5.45 mg/L EPA 200.7 09/25/2015 12:59 FCJORDA0.1 1 Sodium (Na)41.7 mg/L EPA 200.7 09/25/2015 12:59 FCJORDA0.05 1 TOTAL RECOVERABLE METALS BY ICP Aluminum (Al)0.179 mg/L EPA 200.7 09/28/2015 09:36 MHH71310.005 1 Barium (Ba)0.032 mg/L EPA 200.7 09/28/2015 09:36 MHH71310.005 1 Boron (B)0.742 mg/L EPA 200.7 09/28/2015 09:36 MHH71310.05 1 Iron (Fe)0.592 mg/L EPA 200.7 09/28/2015 09:36 MHH71310.01 1 Manganese (Mn)0.750 mg/L EPA 200.7 09/28/2015 09:36 MHH71310.005 1 Strontium (Sr)0.449 mg/L EPA 200.7 09/28/2015 09:36 MHH71310.005 1 Zinc (Zn)0.025 mg/L EPA 200.7 09/28/2015 09:36 MHH71310.005 1 Page 16 of 34 Certificate of Laboratory Analysis This report shall not be reproduced, except in full. Order # J15090668 2015031565 Collection Date:23-Sep-15 10:26 AM Site:SMW-1C Matrix:GW_WW Analyte Analysis Date/TimeMethodUnits Qualifiers RDLResult Sample #: AnalystDF TOTAL RECOVERABLE METALS BY ICP-MS (DISSOLVED) Antimony (Sb)< 1 ug/L EPA 200.8 09/29/2015 12:07 MHALL311 Arsenic (As)< 1 ug/L EPA 200.8 09/29/2015 12:07 MHALL311 Beryllium (Be)< 1 ug/L EPA 200.8 09/29/2015 12:07 MHALL311 Cadmium (Cd)< 1 ug/L EPA 200.8 09/29/2015 12:07 MHALL311 Chromium (Cr)< 1 ug/L EPA 200.8 09/29/2015 12:07 MHALL311 Cobalt (Co)2.57 ug/L EPA 200.8 09/29/2015 12:07 MHALL311 Copper (Cu)< 1 ug/L EPA 200.8 09/29/2015 12:07 MHALL311 Lead (Pb)< 1 ug/L EPA 200.8 09/29/2015 12:07 MHALL311 Molybdenum (Mo)< 1 ug/L EPA 200.8 09/29/2015 12:07 MHALL311 Nickel (Ni)< 1 ug/L EPA 200.8 09/29/2015 12:07 MHALL311 Selenium (Se)< 1 ug/L EPA 200.8 09/29/2015 12:07 MHALL311 Thallium (Tl) Low Level < 0.2 ug/L EPA 200.8 09/29/2015 12:07 MHALL30.2 1 Vanadium (V) Low Level 1.29 ug/L EPA 200.8 09/29/2015 12:07 MHALL30.3 1 Total Recoverable Metals Dissolved 0.1mm Filter Antimony (Sb)< 1 ug/L EPA 200.8 09/28/2015 13:50 MHALL311 Arsenic (As)< 1 ug/L EPA 200.8 09/28/2015 13:50 MHALL311 Beryllium (Be)< 1 ug/L EPA 200.8 09/28/2015 13:50 MHALL311 Cadmium (Cd)< 1 ug/L EPA 200.8 09/28/2015 13:50 MHALL311 Chromium (Cr)< 1 ug/L EPA 200.8 09/28/2015 13:50 MHALL311 Cobalt (Co)2.55 ug/L EPA 200.8 09/28/2015 13:50 MHALL311 Copper (Cu)< 1 ug/L EPA 200.8 09/28/2015 13:50 MHALL311 Lead (Pb)< 1 ug/L EPA 200.8 09/28/2015 13:50 MHALL311 Molybdenum (Mo)< 1 ug/L EPA 200.8 09/28/2015 13:50 MHALL311 Nickel (Ni)< 1 ug/L EPA 200.8 09/28/2015 13:50 MHALL311 Selenium (Se)< 1 ug/L EPA 200.8 09/28/2015 13:50 MHALL311 Thallium (Tl) Low Level < 0.2 ug/L EPA 200.8 09/28/2015 13:50 MHALL30.2 1 Vanadium (V) Low Level 0.867 ug/L EPA 200.8 09/28/2015 13:50 MHALL30.3 1 Page 17 of 34 Certificate of Laboratory Analysis This report shall not be reproduced, except in full. Order # J15090668 2015031565 Collection Date:23-Sep-15 10:26 AM Site:SMW-1C Matrix:GW_WW Analyte Analysis Date/TimeMethodUnits Qualifiers RDLResult Sample #: AnalystDF TOTAL RECOVERABLE METALS BY ICP-MS Antimony (Sb)< 1 ug/L EPA 200.8 09/28/2015 16:43 MHALL311 Arsenic (As)< 1 ug/L EPA 200.8 09/28/2015 16:43 MHALL311 Beryllium (Be)< 1 ug/L EPA 200.8 09/28/2015 16:43 MHALL311 Cadmium (Cd)< 1 ug/L EPA 200.8 09/28/2015 16:43 MHALL311 Chromium (Cr)< 1 ug/L EPA 200.8 09/28/2015 16:43 MHALL311 Cobalt (Co)2.52 ug/L EPA 200.8 09/28/2015 16:43 MHALL311 Copper (Cu)< 1 ug/L EPA 200.8 09/28/2015 16:43 MHALL311 Lead (Pb)< 1 ug/L EPA 200.8 09/28/2015 16:43 MHALL311 Molybdenum (Mo)< 1 ug/L EPA 200.8 09/28/2015 16:43 MHALL311 Nickel (Ni)< 1 ug/L EPA 200.8 09/28/2015 16:43 MHALL311 Selenium (Se)< 1 ug/L EPA 200.8 09/28/2015 16:43 MHALL311 Thallium (Tl) Low Level < 0.2 ug/L EPA 200.8 09/28/2015 16:43 MHALL30.2 1 Vanadium (V) Low Level 1.23 ug/L EPA 200.8 09/28/2015 16:43 MHALL30.3 1 Page 18 of 34 Certificate of Laboratory Analysis This report shall not be reproduced, except in full. Order # J15090668 2015031566 Collection Date:23-Sep-15 9:30 AM Site:MW-36C Matrix:GW_WW Analyte Analysis Date/TimeMethodUnits Qualifiers RDLResult Sample #: AnalystDF MERCURY (COLD VAPOR) IN WATER Mercury (Hg)< 0.05 ug/L EPA 245.1 09/24/2015 14:53 ACPAYNE0.05 1 Mercury Dissolved (cold vapor) in Water (Filtered) Mercury (Hg)< 0.05 ug/L EPA 245.1 09/24/2015 15:47 ACPAYNE0.05 1 Mercury Dissolved (cold vapor) in Water (0.1mm FILTER) Mercury (Hg)< 0.05 ug/L EPA 245.1 09/24/2015 16:34 ACPAYNE0.05 1 DISSOLVED METALS BY ICP Aluminum (Al)0.116 mg/L EPA 200.7 09/25/2015 10:39 FCJORDA0.005 1 Barium (Ba)0.027 mg/L EPA 200.7 09/25/2015 10:39 FCJORDA0.005 1 Boron (B)0.542 mg/L EPA 200.7 09/25/2015 10:39 FCJORDA0.05 1 Iron (Fe)0.012 mg/L EPA 200.7 09/25/2015 10:39 FCJORDA0.01 1 Manganese (Mn)0.404 mg/L EPA 200.7 09/25/2015 10:39 FCJORDA0.005 1 Strontium (Sr)0.287 mg/L EPA 200.7 09/25/2015 10:39 FCJORDA0.005 1 Zinc (Zn)0.017 mg/L EPA 200.7 09/25/2015 10:39 FCJORDA0.005 1 DISSOLVED METALS BY ICP (0.1mm FILTER) Aluminum (Al)0.081 mg/L EPA 200.7 09/25/2015 12:00 FCJORDA0.005 1 Barium (Ba)0.027 mg/L EPA 200.7 09/25/2015 12:00 FCJORDA0.005 1 Boron (B)0.543 mg/L EPA 200.7 09/25/2015 12:00 FCJORDA0.05 1 Iron (Fe)< 0.01 mg/L EPA 200.7 09/25/2015 12:00 FCJORDA0.01 1 Manganese (Mn)0.410 mg/L EPA 200.7 09/25/2015 12:00 FCJORDA0.005 1 Strontium (Sr)0.291 mg/L EPA 200.7 09/25/2015 12:00 FCJORDA0.005 1 Zinc (Zn)0.020 mg/L EPA 200.7 09/25/2015 12:00 FCJORDA0.005 1 UNDIGESTED METALS BY ICP Calcium (Ca)23.1 mg/L EPA 200.7 09/25/2015 13:03 FCJORDA0.01 1 Magnesium (Mg)6.25 mg/L EPA 200.7 09/25/2015 13:03 FCJORDA0.005 1 Potassium (K)9.08 mg/L EPA 200.7 09/25/2015 13:03 FCJORDA0.1 1 Sodium (Na)42.8 mg/L EPA 200.7 09/25/2015 13:03 FCJORDA0.05 1 TOTAL RECOVERABLE METALS BY ICP Aluminum (Al)0.206 mg/L EPA 200.7 09/28/2015 09:40 MHH71310.005 1 Barium (Ba)0.026 mg/L EPA 200.7 09/28/2015 09:40 MHH71310.005 1 Boron (B)0.525 mg/L EPA 200.7 09/28/2015 09:40 MHH71310.05 1 Iron (Fe)0.076 mg/L EPA 200.7 09/28/2015 09:40 MHH71310.01 1 Manganese (Mn)0.379 mg/L EPA 200.7 09/28/2015 09:40 MHH71310.005 1 Strontium (Sr)0.281 mg/L EPA 200.7 09/28/2015 09:40 MHH71310.005 1 Zinc (Zn)0.017 mg/L EPA 200.7 09/28/2015 09:40 MHH71310.005 1 Page 19 of 34 Certificate of Laboratory Analysis This report shall not be reproduced, except in full. Order # J15090668 2015031566 Collection Date:23-Sep-15 9:30 AM Site:MW-36C Matrix:GW_WW Analyte Analysis Date/TimeMethodUnits Qualifiers RDLResult Sample #: AnalystDF TOTAL RECOVERABLE METALS BY ICP-MS (DISSOLVED) Antimony (Sb)< 1 ug/L EPA 200.8 09/29/2015 12:13 MHALL311 Arsenic (As)< 1 ug/L EPA 200.8 09/29/2015 12:13 MHALL311 Beryllium (Be)< 1 ug/L EPA 200.8 09/29/2015 12:13 MHALL311 Cadmium (Cd)< 1 ug/L EPA 200.8 09/29/2015 12:13 MHALL311 Chromium (Cr)< 1 ug/L EPA 200.8 09/29/2015 12:13 MHALL311 Cobalt (Co)18.3 ug/L EPA 200.8 09/29/2015 12:13 MHALL311 Copper (Cu)< 1 ug/L EPA 200.8 09/29/2015 12:13 MHALL311 Lead (Pb)< 1 ug/L EPA 200.8 09/29/2015 12:13 MHALL311 Molybdenum (Mo)< 1 ug/L EPA 200.8 09/29/2015 12:13 MHALL311 Nickel (Ni)1.28 ug/L EPA 200.8 09/29/2015 12:13 MHALL311 Selenium (Se)44.2 ug/L EPA 200.8 09/29/2015 12:13 MHALL311 Thallium (Tl) Low Level 0.230 ug/L EPA 200.8 09/29/2015 12:13 MHALL30.2 1 Vanadium (V) Low Level 0.350 ug/L EPA 200.8 09/29/2015 12:13 MHALL30.3 1 Total Recoverable Metals Dissolved 0.1mm Filter Antimony (Sb)< 1 ug/L EPA 200.8 09/28/2015 13:40 MHALL311 Arsenic (As)< 1 ug/L EPA 200.8 09/28/2015 13:40 MHALL311 Beryllium (Be)< 1 ug/L EPA 200.8 09/28/2015 13:40 MHALL311 Cadmium (Cd)< 1 ug/L EPA 200.8 09/28/2015 13:40 MHALL311 Chromium (Cr)< 1 ug/L EPA 200.8 09/28/2015 13:40 MHALL311 Cobalt (Co)17.7 ug/L EPA 200.8 09/28/2015 13:40 MHALL311 Copper (Cu)< 1 ug/L EPA 200.8 09/28/2015 13:40 MHALL311 Lead (Pb)< 1 ug/L EPA 200.8 09/28/2015 13:40 MHALL311 Molybdenum (Mo)< 1 ug/L EPA 200.8 09/28/2015 13:40 MHALL311 Nickel (Ni)1.29 ug/L EPA 200.8 09/28/2015 13:40 MHALL311 Selenium (Se)41.7 ug/L EPA 200.8 09/28/2015 13:40 MHALL311 Thallium (Tl) Low Level 0.211 ug/L EPA 200.8 09/28/2015 13:40 MHALL30.2 1 Vanadium (V) Low Level < 0.3 ug/L EPA 200.8 09/28/2015 13:40 MHALL30.3 1 Page 20 of 34 Certificate of Laboratory Analysis This report shall not be reproduced, except in full. Order # J15090668 2015031566 Collection Date:23-Sep-15 9:30 AM Site:MW-36C Matrix:GW_WW Analyte Analysis Date/TimeMethodUnits Qualifiers RDLResult Sample #: AnalystDF TOTAL RECOVERABLE METALS BY ICP-MS Antimony (Sb)< 1 ug/L EPA 200.8 09/28/2015 16:49 MHALL311 Arsenic (As)< 1 ug/L EPA 200.8 09/28/2015 16:49 MHALL311 Beryllium (Be)< 1 ug/L EPA 200.8 09/28/2015 16:49 MHALL311 Cadmium (Cd)< 1 ug/L EPA 200.8 09/28/2015 16:49 MHALL311 Chromium (Cr)< 1 ug/L EPA 200.8 09/28/2015 16:49 MHALL311 Cobalt (Co)18.0 ug/L EPA 200.8 09/28/2015 16:49 MHALL311 Copper (Cu)< 1 ug/L EPA 200.8 09/28/2015 16:49 MHALL311 Lead (Pb)< 1 ug/L EPA 200.8 09/28/2015 16:49 MHALL311 Molybdenum (Mo)< 1 ug/L EPA 200.8 09/28/2015 16:49 MHALL311 Nickel (Ni)1.38 ug/L EPA 200.8 09/28/2015 16:49 MHALL311 Selenium (Se)42.7 ug/L EPA 200.8 09/28/2015 16:49 MHALL311 Thallium (Tl) Low Level 0.226 ug/L EPA 200.8 09/28/2015 16:49 MHALL30.2 1 Vanadium (V) Low Level 0.607 ug/L EPA 200.8 09/28/2015 16:49 MHALL30.3 1 Page 21 of 34 Certificate of Laboratory Analysis This report shall not be reproduced, except in full. Order # J15090668 2015031567 Collection Date:23-Sep-15 9:28 AM Site:MW-36B Matrix:GW_WW Analyte Analysis Date/TimeMethodUnits Qualifiers RDLResult Sample #: AnalystDF MERCURY (COLD VAPOR) IN WATER Mercury (Hg)< 0.05 ug/L EPA 245.1 09/24/2015 15:07 ACPAYNE0.05 1 Mercury Dissolved (cold vapor) in Water (Filtered) Mercury (Hg)< 0.05 ug/L EPA 245.1 09/24/2015 15:49 ACPAYNE0.05 1 Mercury Dissolved (cold vapor) in Water (0.1mm FILTER) Mercury (Hg)< 0.05 ug/L EPA 245.1 09/29/2015 14:30 ACPAYNE0.05 1 DISSOLVED METALS BY ICP Aluminum (Al)< 0.005 mg/L EPA 200.7 09/25/2015 10:43 FCJORDA0.005 1 Barium (Ba)0.044 mg/L EPA 200.7 09/25/2015 10:43 FCJORDA0.005 1 Boron (B)0.236 mg/L EPA 200.7 09/25/2015 10:43 FCJORDA0.05 1 Iron (Fe)< 0.01 mg/L EPA 200.7 09/25/2015 10:43 FCJORDA0.01 1 Manganese (Mn)< 0.005 mg/L EPA 200.7 09/25/2015 10:43 FCJORDA0.005 1 Strontium (Sr)0.256 mg/L EPA 200.7 09/25/2015 10:43 FCJORDA0.005 1 Zinc (Zn)< 0.005 mg/L EPA 200.7 09/25/2015 10:43 FCJORDA0.005 1 DISSOLVED METALS BY ICP (0.1mm FILTER) Aluminum (Al)< 0.005 mg/L EPA 200.7 09/25/2015 12:04 FCJORDA0.005 1 Barium (Ba)0.042 mg/L EPA 200.7 09/25/2015 12:04 FCJORDA0.005 1 Boron (B)0.218 mg/L EPA 200.7 09/25/2015 12:04 FCJORDA0.05 1 Iron (Fe)< 0.01 mg/L EPA 200.7 09/25/2015 12:04 FCJORDA0.01 1 Manganese (Mn)< 0.005 mg/L EPA 200.7 09/25/2015 12:04 FCJORDA0.005 1 Strontium (Sr)0.249 mg/L EPA 200.7 09/25/2015 12:04 FCJORDA0.005 1 Zinc (Zn)< 0.005 mg/L EPA 200.7 09/25/2015 12:04 FCJORDA0.005 1 UNDIGESTED METALS BY ICP Calcium (Ca)20.2 mg/L EPA 200.7 09/25/2015 13:07 FCJORDA0.01 1 Magnesium (Mg)2.78 mg/L EPA 200.7 09/25/2015 13:07 FCJORDA0.005 1 Potassium (K)4.82 mg/L EPA 200.7 09/25/2015 13:07 FCJORDA0.1 1 Sodium (Na)7.11 mg/L EPA 200.7 09/25/2015 13:07 FCJORDA0.05 1 TOTAL RECOVERABLE METALS BY ICP Aluminum (Al)0.428 mg/L EPA 200.7 09/28/2015 09:44 MHH71310.005 1 Barium (Ba)0.042 mg/L EPA 200.7 09/28/2015 09:44 MHH71310.005 1 Boron (B)0.211 mg/L EPA 200.7 09/28/2015 09:44 MHH71310.05 1 Iron (Fe)0.255 mg/L EPA 200.7 09/28/2015 09:44 MHH71310.01 1 Manganese (Mn)< 0.005 mg/L EPA 200.7 09/28/2015 09:44 MHH71310.005 1 Strontium (Sr)0.250 mg/L EPA 200.7 09/28/2015 09:44 MHH71310.005 1 Zinc (Zn)< 0.005 mg/L EPA 200.7 09/28/2015 09:44 MHH71310.005 1 Page 22 of 34 Certificate of Laboratory Analysis This report shall not be reproduced, except in full. Order # J15090668 2015031567 Collection Date:23-Sep-15 9:28 AM Site:MW-36B Matrix:GW_WW Analyte Analysis Date/TimeMethodUnits Qualifiers RDLResult Sample #: AnalystDF TOTAL RECOVERABLE METALS BY ICP-MS (DISSOLVED) Antimony (Sb)6.31 ug/L EPA 200.8 09/29/2015 12:18 MHALL311 Arsenic (As)< 1 ug/L EPA 200.8 09/29/2015 12:18 MHALL311 Beryllium (Be)< 1 ug/L EPA 200.8 09/29/2015 12:18 MHALL311 Cadmium (Cd)< 1 ug/L EPA 200.8 09/29/2015 12:18 MHALL311 Chromium (Cr)< 1 ug/L EPA 200.8 09/29/2015 12:18 MHALL311 Cobalt (Co)< 1 ug/L EPA 200.8 09/29/2015 12:18 MHALL311 Copper (Cu)< 1 ug/L EPA 200.8 09/29/2015 12:18 MHALL311 Lead (Pb)< 1 ug/L EPA 200.8 09/29/2015 12:18 MHALL311 Molybdenum (Mo)115 ug/L EPA 200.8 09/29/2015 12:18 MHALL311 Nickel (Ni)< 1 ug/L EPA 200.8 09/29/2015 12:18 MHALL311 Selenium (Se)13.9 ug/L EPA 200.8 09/29/2015 12:18 MHALL311 Thallium (Tl) Low Level 0.450 ug/L EPA 200.8 09/29/2015 12:18 MHALL30.2 1 Vanadium (V) Low Level 1.14 ug/L EPA 200.8 09/29/2015 12:18 MHALL30.3 1 Total Recoverable Metals Dissolved 0.1mm Filter Antimony (Sb)5.53 ug/L EPA 200.8 09/28/2015 13:45 MHALL311 Arsenic (As)< 1 ug/L EPA 200.8 09/28/2015 13:45 MHALL311 Beryllium (Be)< 1 ug/L EPA 200.8 09/28/2015 13:45 MHALL311 Cadmium (Cd)< 1 ug/L EPA 200.8 09/28/2015 13:45 MHALL311 Chromium (Cr)< 1 ug/L EPA 200.8 09/28/2015 13:45 MHALL311 Cobalt (Co)< 1 ug/L EPA 200.8 09/28/2015 13:45 MHALL311 Copper (Cu)< 1 ug/L EPA 200.8 09/28/2015 13:45 MHALL311 Lead (Pb)< 1 ug/L EPA 200.8 09/28/2015 13:45 MHALL311 Molybdenum (Mo)109 ug/L EPA 200.8 09/28/2015 13:45 MHALL311 Nickel (Ni)< 1 ug/L EPA 200.8 09/28/2015 13:45 MHALL311 Selenium (Se)13.3 ug/L EPA 200.8 09/28/2015 13:45 MHALL311 Thallium (Tl) Low Level 0.442 ug/L EPA 200.8 09/28/2015 13:45 MHALL30.2 1 Vanadium (V) Low Level 0.972 ug/L EPA 200.8 09/28/2015 13:45 MHALL30.3 1 Page 23 of 34 Certificate of Laboratory Analysis This report shall not be reproduced, except in full. Order # J15090668 2015031567 Collection Date:23-Sep-15 9:28 AM Site:MW-36B Matrix:GW_WW Analyte Analysis Date/TimeMethodUnits Qualifiers RDLResult Sample #: AnalystDF TOTAL RECOVERABLE METALS BY ICP-MS Antimony (Sb)5.25 ug/L EPA 200.8 09/28/2015 16:54 MHALL311 Arsenic (As)< 1 ug/L EPA 200.8 09/28/2015 16:54 MHALL311 Beryllium (Be)< 1 ug/L EPA 200.8 09/28/2015 16:54 MHALL311 Cadmium (Cd)< 1 ug/L EPA 200.8 09/28/2015 16:54 MHALL311 Chromium (Cr)< 1 ug/L EPA 200.8 09/28/2015 16:54 MHALL311 Cobalt (Co)< 1 ug/L EPA 200.8 09/28/2015 16:54 MHALL311 Copper (Cu)< 1 ug/L EPA 200.8 09/28/2015 16:54 MHALL311 Lead (Pb)< 1 ug/L EPA 200.8 09/28/2015 16:54 MHALL311 Molybdenum (Mo)109 ug/L EPA 200.8 09/28/2015 16:54 MHALL311 Nickel (Ni)< 1 ug/L EPA 200.8 09/28/2015 16:54 MHALL311 Selenium (Se)13.5 ug/L EPA 200.8 09/28/2015 16:54 MHALL311 Thallium (Tl) Low Level 0.462 ug/L EPA 200.8 09/28/2015 16:54 MHALL30.2 1 Vanadium (V) Low Level 2.03 ug/L EPA 200.8 09/28/2015 16:54 MHALL30.3 1 Page 24 of 34 Certificate of Laboratory Analysis This report shall not be reproduced, except in full. Order # J15090668 2015031568 Collection Date:23-Sep-15 8:40 AM Site:PZ-1B Matrix:GW_WW Analyte Analysis Date/TimeMethodUnits Qualifiers RDLResult Sample #: AnalystDF MERCURY (COLD VAPOR) IN WATER Mercury (Hg)< 0.05 ug/L EPA 245.1 09/24/2015 14:55 ACPAYNE0.05 1 Mercury Dissolved (cold vapor) in Water (Filtered) Mercury (Hg)< 0.05 ug/L EPA 245.1 09/24/2015 15:52 ACPAYNE0.05 1 Mercury Dissolved (cold vapor) in Water (0.1mm FILTER) Mercury (Hg)< 0.05 ug/L EPA 245.1 09/24/2015 16:46 ACPAYNE0.05 1 DISSOLVED METALS BY ICP Aluminum (Al)0.005 mg/L EPA 200.7 09/25/2015 10:47 FCJORDA0.005 1 Barium (Ba)0.050 mg/L EPA 200.7 09/25/2015 10:47 FCJORDA0.005 1 Boron (B)0.239 mg/L EPA 200.7 09/25/2015 10:47 FCJORDA0.05 1 Iron (Fe)< 0.01 mg/L EPA 200.7 09/25/2015 10:47 FCJORDA0.01 1 Manganese (Mn)< 0.005 mg/L EPA 200.7 09/25/2015 10:47 FCJORDA0.005 1 Strontium (Sr)0.245 mg/L EPA 200.7 09/25/2015 10:47 FCJORDA0.005 1 Zinc (Zn)< 0.005 mg/L EPA 200.7 09/25/2015 10:47 FCJORDA0.005 1 DISSOLVED METALS BY ICP (0.1mm FILTER) Aluminum (Al)< 0.005 mg/L EPA 200.7 09/25/2015 12:08 FCJORDA0.005 1 Barium (Ba)0.047 mg/L EPA 200.7 09/25/2015 12:08 FCJORDA0.005 1 Boron (B)0.229 mg/L EPA 200.7 09/25/2015 12:08 FCJORDA0.05 1 Iron (Fe)< 0.01 mg/L EPA 200.7 09/25/2015 12:08 FCJORDA0.01 1 Manganese (Mn)< 0.005 mg/L EPA 200.7 09/25/2015 12:08 FCJORDA0.005 1 Strontium (Sr)0.241 mg/L EPA 200.7 09/25/2015 12:08 FCJORDA0.005 1 Zinc (Zn)< 0.005 mg/L EPA 200.7 09/25/2015 12:08 FCJORDA0.005 1 UNDIGESTED METALS BY ICP Calcium (Ca)19.1 mg/L EPA 200.7 09/25/2015 13:11 FCJORDA0.01 1 Magnesium (Mg)2.71 mg/L EPA 200.7 09/25/2015 13:11 FCJORDA0.005 1 Potassium (K)5.11 mg/L EPA 200.7 09/25/2015 13:11 FCJORDA0.1 1 Sodium (Na)10.3 mg/L EPA 200.7 09/25/2015 13:11 FCJORDA0.05 1 TOTAL RECOVERABLE METALS BY ICP Aluminum (Al)0.085 mg/L EPA 200.7 09/28/2015 09:48 MHH71310.005 1 Barium (Ba)0.047 mg/L EPA 200.7 09/28/2015 09:48 MHH71310.005 1 Boron (B)0.222 mg/L EPA 200.7 09/28/2015 09:48 MHH71310.05 1 Iron (Fe)0.038 mg/L EPA 200.7 09/28/2015 09:48 MHH71310.01 1 Manganese (Mn)< 0.005 mg/L EPA 200.7 09/28/2015 09:48 MHH71310.005 1 Strontium (Sr)0.244 mg/L EPA 200.7 09/28/2015 09:48 MHH71310.005 1 Zinc (Zn)< 0.005 mg/L EPA 200.7 09/28/2015 09:48 MHH71310.005 1 Page 25 of 34 Certificate of Laboratory Analysis This report shall not be reproduced, except in full. Order # J15090668 2015031568 Collection Date:23-Sep-15 8:40 AM Site:PZ-1B Matrix:GW_WW Analyte Analysis Date/TimeMethodUnits Qualifiers RDLResult Sample #: AnalystDF TOTAL RECOVERABLE METALS BY ICP-MS (DISSOLVED) Antimony (Sb)6.42 ug/L EPA 200.8 09/28/2015 15:27 MHALL311 Arsenic (As)< 1 ug/L EPA 200.8 09/28/2015 15:27 MHALL311 Beryllium (Be)< 1 ug/L EPA 200.8 09/28/2015 15:27 MHALL311 Cadmium (Cd)< 1 ug/L EPA 200.8 09/28/2015 15:27 MHALL311 Chromium (Cr)< 1 ug/L EPA 200.8 09/28/2015 15:27 MHALL311 Cobalt (Co)< 1 ug/L EPA 200.8 09/28/2015 15:27 MHALL311 Copper (Cu)< 1 ug/L EPA 200.8 09/28/2015 15:27 MHALL311 Lead (Pb)< 1 ug/L EPA 200.8 09/28/2015 15:27 MHALL311 Molybdenum (Mo)66.4 ug/L EPA 200.8 09/28/2015 15:27 MHALL311 Nickel (Ni)< 1 ug/L EPA 200.8 09/28/2015 15:27 MHALL311 Selenium (Se)15.8 ug/L EPA 200.8 09/28/2015 15:27 MHALL311 Thallium (Tl) Low Level 0.628 ug/L EPA 200.8 09/28/2015 15:27 MHALL30.2 1 Vanadium (V) Low Level 7.87 ug/L EPA 200.8 09/28/2015 15:27 MHALL30.3 1 Total Recoverable Metals Dissolved 0.1mm Filter Antimony (Sb)6.03 ug/L EPA 200.8 09/28/2015 13:55 MHALL311 Arsenic (As)< 1 ug/L EPA 200.8 09/28/2015 13:55 MHALL311 Beryllium (Be)< 1 ug/L EPA 200.8 09/28/2015 13:55 MHALL311 Cadmium (Cd)< 1 ug/L EPA 200.8 09/28/2015 13:55 MHALL311 Chromium (Cr)< 1 ug/L EPA 200.8 09/28/2015 13:55 MHALL311 Cobalt (Co)< 1 ug/L EPA 200.8 09/28/2015 13:55 MHALL311 Copper (Cu)< 1 ug/L EPA 200.8 09/28/2015 13:55 MHALL311 Lead (Pb)< 1 ug/L EPA 200.8 09/28/2015 13:55 MHALL311 Molybdenum (Mo)66.5 ug/L EPA 200.8 09/28/2015 13:55 MHALL311 Nickel (Ni)< 1 ug/L EPA 200.8 09/28/2015 13:55 MHALL311 Selenium (Se)16.3 ug/L EPA 200.8 09/28/2015 13:55 MHALL311 Thallium (Tl) Low Level 0.634 ug/L EPA 200.8 09/28/2015 13:55 MHALL30.2 1 Vanadium (V) Low Level 7.80 ug/L EPA 200.8 09/28/2015 13:55 MHALL30.3 1 Page 26 of 34 Certificate of Laboratory Analysis This report shall not be reproduced, except in full. Order # J15090668 2015031568 Collection Date:23-Sep-15 8:40 AM Site:PZ-1B Matrix:GW_WW Analyte Analysis Date/TimeMethodUnits Qualifiers RDLResult Sample #: AnalystDF TOTAL RECOVERABLE METALS BY ICP-MS Antimony (Sb)6.19 ug/L EPA 200.8 09/28/2015 16:59 MHALL311 Arsenic (As)< 1 ug/L EPA 200.8 09/28/2015 16:59 MHALL311 Beryllium (Be)< 1 ug/L EPA 200.8 09/28/2015 16:59 MHALL311 Cadmium (Cd)< 1 ug/L EPA 200.8 09/28/2015 16:59 MHALL311 Chromium (Cr)< 1 ug/L EPA 200.8 09/28/2015 16:59 MHALL311 Cobalt (Co)< 1 ug/L EPA 200.8 09/28/2015 16:59 MHALL311 Copper (Cu)< 1 ug/L EPA 200.8 09/28/2015 16:59 MHALL311 Lead (Pb)< 1 ug/L EPA 200.8 09/28/2015 16:59 MHALL311 Molybdenum (Mo)65.7 ug/L EPA 200.8 09/28/2015 16:59 MHALL311 Nickel (Ni)< 1 ug/L EPA 200.8 09/28/2015 16:59 MHALL311 Selenium (Se)16.2 ug/L EPA 200.8 09/28/2015 16:59 MHALL311 Thallium (Tl) Low Level 0.695 ug/L EPA 200.8 09/28/2015 16:59 MHALL30.2 1 Vanadium (V) Low Level 8.32 ug/L EPA 200.8 09/28/2015 16:59 MHALL30.3 1 Page 27 of 34 Certificate of Laboratory Analysis This report shall not be reproduced, except in full. Order # J15090668 2015031569 Collection Date:23-Sep-15 8:30 AM Site:GWPZ-1A Matrix:GW_WW Analyte Analysis Date/TimeMethodUnits Qualifiers RDLResult Sample #: AnalystDF MERCURY (COLD VAPOR) IN WATER Mercury (Hg)< 0.05 ug/L EPA 245.1 09/24/2015 14:57 ACPAYNE0.05 1 Mercury Dissolved (cold vapor) in Water (Filtered) Mercury (Hg)< 0.05 ug/L EPA 245.1 09/24/2015 15:54 ACPAYNE0.05 1 Mercury Dissolved (cold vapor) in Water (0.1mm FILTER) Mercury (Hg)< 0.05 ug/L EPA 245.1 09/24/2015 16:53 ACPAYNE0.05 1 DISSOLVED METALS BY ICP Aluminum (Al)0.038 mg/L EPA 200.7 09/25/2015 10:51 FCJORDA0.005 1 Barium (Ba)0.009 mg/L EPA 200.7 09/25/2015 10:51 FCJORDA0.005 1 Boron (B)0.063 mg/L EPA 200.7 09/25/2015 10:51 FCJORDA0.05 1 Iron (Fe)< 0.01 mg/L EPA 200.7 09/25/2015 10:51 FCJORDA0.01 1 Manganese (Mn)< 0.005 mg/L EPA 200.7 09/25/2015 10:51 FCJORDA0.005 1 Strontium (Sr)0.056 mg/L EPA 200.7 09/25/2015 10:51 FCJORDA0.005 1 Zinc (Zn)< 0.005 mg/L EPA 200.7 09/25/2015 10:51 FCJORDA0.005 1 DISSOLVED METALS BY ICP (0.1mm FILTER) Aluminum (Al)0.015 mg/L EPA 200.7 09/25/2015 12:12 FCJORDA0.005 1 Barium (Ba)0.008 mg/L EPA 200.7 09/25/2015 12:12 FCJORDA0.005 1 Boron (B)0.060 mg/L EPA 200.7 09/25/2015 12:12 FCJORDA0.05 1 Iron (Fe)< 0.01 mg/L EPA 200.7 09/25/2015 12:12 FCJORDA0.01 1 Manganese (Mn)< 0.005 mg/L EPA 200.7 09/25/2015 12:12 FCJORDA0.005 1 Strontium (Sr)0.055 mg/L EPA 200.7 09/25/2015 12:12 FCJORDA0.005 1 Zinc (Zn)< 0.005 mg/L EPA 200.7 09/25/2015 12:12 FCJORDA0.005 1 UNDIGESTED METALS BY ICP Calcium (Ca)7.86 mg/L EPA 200.7 09/25/2015 13:15 FCJORDA0.01 1 Magnesium (Mg)0.688 mg/L EPA 200.7 09/25/2015 13:15 FCJORDA0.005 1 Potassium (K)1.56 mg/L EPA 200.7 09/25/2015 13:15 FCJORDA0.1 1 Sodium (Na)1.23 mg/L EPA 200.7 09/25/2015 13:15 FCJORDA0.05 1 TOTAL RECOVERABLE METALS BY ICP Aluminum (Al)0.422 mg/L EPA 200.7 09/28/2015 09:52 MHH71310.005 1 Barium (Ba)0.008 mg/L EPA 200.7 09/28/2015 09:52 MHH71310.005 1 Boron (B)0.057 mg/L EPA 200.7 09/28/2015 09:52 MHH71310.05 1 Iron (Fe)0.193 mg/L EPA 200.7 09/28/2015 09:52 MHH71310.01 1 Manganese (Mn)< 0.005 mg/L EPA 200.7 09/28/2015 09:52 MHH71310.005 1 Strontium (Sr)0.052 mg/L EPA 200.7 09/28/2015 09:52 MHH71310.005 1 Zinc (Zn)< 0.005 mg/L EPA 200.7 09/28/2015 09:52 MHH71310.005 1 Page 28 of 34 Certificate of Laboratory Analysis This report shall not be reproduced, except in full. Order # J15090668 2015031569 Collection Date:23-Sep-15 8:30 AM Site:GWPZ-1A Matrix:GW_WW Analyte Analysis Date/TimeMethodUnits Qualifiers RDLResult Sample #: AnalystDF TOTAL RECOVERABLE METALS BY ICP-MS (DISSOLVED) Antimony (Sb)3.17 ug/L EPA 200.8 09/28/2015 15:32 MHALL311 Arsenic (As)< 1 ug/L EPA 200.8 09/28/2015 15:32 MHALL311 Beryllium (Be)< 1 ug/L EPA 200.8 09/28/2015 15:32 MHALL311 Cadmium (Cd)< 1 ug/L EPA 200.8 09/28/2015 15:32 MHALL311 Chromium (Cr)< 1 ug/L EPA 200.8 09/28/2015 15:32 MHALL311 Cobalt (Co)< 1 ug/L EPA 200.8 09/28/2015 15:32 MHALL311 Copper (Cu)< 1 ug/L EPA 200.8 09/28/2015 15:32 MHALL311 Lead (Pb)< 1 ug/L EPA 200.8 09/28/2015 15:32 MHALL311 Molybdenum (Mo)59.9 ug/L EPA 200.8 09/28/2015 15:32 MHALL311 Nickel (Ni)< 1 ug/L EPA 200.8 09/28/2015 15:32 MHALL311 Selenium (Se)2.86 ug/L EPA 200.8 09/28/2015 15:32 MHALL311 Thallium (Tl) Low Level < 0.2 ug/L EPA 200.8 09/28/2015 15:32 MHALL30.2 1 Vanadium (V) Low Level 1.26 ug/L EPA 200.8 09/28/2015 15:32 MHALL30.3 1 Total Recoverable Metals Dissolved 0.1mm Filter Antimony (Sb)3.12 ug/L EPA 200.8 09/28/2015 14:01 MHALL311 Arsenic (As)< 1 ug/L EPA 200.8 09/28/2015 14:01 MHALL311 Beryllium (Be)< 1 ug/L EPA 200.8 09/28/2015 14:01 MHALL311 Cadmium (Cd)< 1 ug/L EPA 200.8 09/28/2015 14:01 MHALL311 Chromium (Cr)< 1 ug/L EPA 200.8 09/28/2015 14:01 MHALL311 Cobalt (Co)< 1 ug/L EPA 200.8 09/28/2015 14:01 MHALL311 Copper (Cu)< 1 ug/L EPA 200.8 09/28/2015 14:01 MHALL311 Lead (Pb)< 1 ug/L EPA 200.8 09/28/2015 14:01 MHALL311 Molybdenum (Mo)62.4 ug/L EPA 200.8 09/28/2015 14:01 MHALL311 Nickel (Ni)< 1 ug/L EPA 200.8 09/28/2015 14:01 MHALL311 Selenium (Se)2.74 ug/L EPA 200.8 09/28/2015 14:01 MHALL311 Thallium (Tl) Low Level < 0.2 ug/L EPA 200.8 09/28/2015 14:01 MHALL30.2 1 Vanadium (V) Low Level 0.991 ug/L EPA 200.8 09/28/2015 14:01 MHALL30.3 1 Page 29 of 34 Certificate of Laboratory Analysis This report shall not be reproduced, except in full. Order # J15090668 2015031569 Collection Date:23-Sep-15 8:30 AM Site:GWPZ-1A Matrix:GW_WW Analyte Analysis Date/TimeMethodUnits Qualifiers RDLResult Sample #: AnalystDF TOTAL RECOVERABLE METALS BY ICP-MS Antimony (Sb)2.93 ug/L EPA 200.8 09/28/2015 17:04 MHALL311 Arsenic (As)< 1 ug/L EPA 200.8 09/28/2015 17:04 MHALL311 Beryllium (Be)< 1 ug/L EPA 200.8 09/28/2015 17:04 MHALL311 Cadmium (Cd)< 1 ug/L EPA 200.8 09/28/2015 17:04 MHALL311 Chromium (Cr)< 1 ug/L EPA 200.8 09/28/2015 17:04 MHALL311 Cobalt (Co)< 1 ug/L EPA 200.8 09/28/2015 17:04 MHALL311 Copper (Cu)< 1 ug/L EPA 200.8 09/28/2015 17:04 MHALL311 Lead (Pb)< 1 ug/L EPA 200.8 09/28/2015 17:04 MHALL311 Molybdenum (Mo)59.2 ug/L EPA 200.8 09/28/2015 17:04 MHALL311 Nickel (Ni)< 1 ug/L EPA 200.8 09/28/2015 17:04 MHALL311 Selenium (Se)2.54 ug/L EPA 200.8 09/28/2015 17:04 MHALL311 Thallium (Tl) Low Level < 0.2 ug/L EPA 200.8 09/28/2015 17:04 MHALL30.2 1 Vanadium (V) Low Level 1.52 ug/L EPA 200.8 09/28/2015 17:04 MHALL30.3 1 Page 30 of 34 Certificate of Laboratory Analysis This report shall not be reproduced, except in full. Order # J15090668 2015031570 Collection Date:23-Sep-15 3:06 PM Site:Filter Blank Matrix:GW_WW Analyte Analysis Date/TimeMethodUnits Qualifiers RDLResult Sample #: AnalystDF Mercury Dissolved (cold vapor) in Water (Filtered) Mercury (Hg)< 0.05 ug/L EPA 245.1 09/24/2015 15:56 ACPAYNE0.05 1 Mercury Dissolved (cold vapor) in Water (0.1mm FILTER) Mercury (Hg)< 0.05 ug/L EPA 245.1 09/24/2015 16:56 ACPAYNE0.05 1 DISSOLVED METALS BY ICP Aluminum (Al)0.028 mg/L EPA 200.7 09/25/2015 10:55 FCJORDA0.005 1 Barium (Ba)< 0.005 mg/L EPA 200.7 09/25/2015 10:55 FCJORDA0.005 1 Boron (B)< 0.05 mg/L EPA 200.7 09/25/2015 10:55 FCJORDA0.05 1 Iron (Fe)< 0.01 mg/L EPA 200.7 09/25/2015 10:55 FCJORDA0.01 1 Manganese (Mn)< 0.005 mg/L EPA 200.7 09/25/2015 10:55 FCJORDA0.005 1 Strontium (Sr)< 0.005 mg/L EPA 200.7 09/25/2015 10:55 FCJORDA0.005 1 Zinc (Zn)< 0.005 mg/L EPA 200.7 09/25/2015 10:55 FCJORDA0.005 1 DISSOLVED METALS BY ICP (0.1mm FILTER) Aluminum (Al)< 0.005 mg/L EPA 200.7 09/25/2015 12:16 FCJORDA0.005 1 Barium (Ba)< 0.005 mg/L EPA 200.7 09/25/2015 12:16 FCJORDA0.005 1 Boron (B)< 0.05 mg/L EPA 200.7 09/25/2015 12:16 FCJORDA0.05 1 Iron (Fe)< 0.01 mg/L EPA 200.7 09/25/2015 12:16 FCJORDA0.01 1 Manganese (Mn)< 0.005 mg/L EPA 200.7 09/25/2015 12:16 FCJORDA0.005 1 Strontium (Sr)< 0.005 mg/L EPA 200.7 09/25/2015 12:16 FCJORDA0.005 1 Zinc (Zn)< 0.005 mg/L EPA 200.7 09/25/2015 12:16 FCJORDA0.005 1 TOTAL RECOVERABLE METALS BY ICP-MS (DISSOLVED) Antimony (Sb)< 1 ug/L EPA 200.8 09/28/2015 15:37 MHALL311 Arsenic (As)< 1 ug/L EPA 200.8 09/28/2015 15:37 MHALL311 Beryllium (Be)< 1 ug/L EPA 200.8 09/28/2015 15:37 MHALL311 Cadmium (Cd)< 1 ug/L EPA 200.8 09/28/2015 15:37 MHALL311 Chromium (Cr)< 1 ug/L EPA 200.8 09/28/2015 15:37 MHALL311 Cobalt (Co)< 1 ug/L EPA 200.8 09/28/2015 15:37 MHALL311 Copper (Cu)< 1 ug/L EPA 200.8 09/28/2015 15:37 MHALL311 Lead (Pb)< 1 ug/L EPA 200.8 09/28/2015 15:37 MHALL311 Molybdenum (Mo)< 1 ug/L EPA 200.8 09/28/2015 15:37 MHALL311 Nickel (Ni)< 1 ug/L EPA 200.8 09/28/2015 15:37 MHALL311 Selenium (Se)< 1 ug/L EPA 200.8 09/28/2015 15:37 MHALL311 Thallium (Tl) Low Level < 0.2 ug/L EPA 200.8 09/28/2015 15:37 MHALL30.2 1 Vanadium (V) Low Level 0.445 ug/L EPA 200.8 09/28/2015 15:37 MHALL30.3 1 Page 31 of 34 Certificate of Laboratory Analysis This report shall not be reproduced, except in full. Order # J15090668 2015031570 Collection Date:23-Sep-15 3:06 PM Site:Filter Blank Matrix:GW_WW Analyte Analysis Date/TimeMethodUnits Qualifiers RDLResult Sample #: AnalystDF Total Recoverable Metals Dissolved 0.1mm Filter Antimony (Sb)< 1 ug/L EPA 200.8 09/28/2015 14:06 MHALL311 Arsenic (As)< 1 ug/L EPA 200.8 09/28/2015 14:06 MHALL311 Beryllium (Be)< 1 ug/L EPA 200.8 09/28/2015 14:06 MHALL311 Cadmium (Cd)< 1 ug/L EPA 200.8 09/28/2015 14:06 MHALL311 Chromium (Cr)< 1 ug/L EPA 200.8 09/28/2015 14:06 MHALL311 Cobalt (Co)< 1 ug/L EPA 200.8 09/28/2015 14:06 MHALL311 Copper (Cu)< 1 ug/L EPA 200.8 09/28/2015 14:06 MHALL311 Lead (Pb)< 1 ug/L EPA 200.8 09/28/2015 14:06 MHALL311 Molybdenum (Mo)< 1 ug/L EPA 200.8 09/28/2015 14:06 MHALL311 Nickel (Ni)< 1 ug/L EPA 200.8 09/28/2015 14:06 MHALL311 Selenium (Se)< 1 ug/L EPA 200.8 09/28/2015 14:06 MHALL311 Thallium (Tl) Low Level < 0.2 ug/L EPA 200.8 09/28/2015 14:06 MHALL30.2 1 Vanadium (V) Low Level < 0.3 ug/L EPA 200.8 09/28/2015 14:06 MHALL30.3 1 Page 32 of 34 Certificate of Laboratory Analysis This report shall not be reproduced, except in full. Order # J15090668 2015031571 Collection Date:23-Sep-15 3:06 PM Site:Equipment Blank Matrix:GW_WW Analyte Analysis Date/TimeMethodUnits Qualifiers RDLResult Sample #: AnalystDF MERCURY (COLD VAPOR) IN WATER Mercury (Hg)< 0.05 ug/L EPA 245.1 09/24/2015 15:00 ACPAYNE0.05 1 UNDIGESTED METALS BY ICP Calcium (Ca)0.011 mg/L EPA 200.7 09/25/2015 13:19 FCJORDA0.01 1 Magnesium (Mg)< 0.005 mg/L EPA 200.7 09/25/2015 13:19 FCJORDA0.005 1 Potassium (K)< 0.1 mg/L EPA 200.7 09/25/2015 13:19 FCJORDA0.1 1 Sodium (Na)< 0.05 mg/L EPA 200.7 09/25/2015 13:19 FCJORDA0.05 1 TOTAL RECOVERABLE METALS BY ICP Aluminum (Al)0.029 mg/L EPA 200.7 09/28/2015 09:57 MHH71310.005 1 Barium (Ba)< 0.005 mg/L EPA 200.7 09/28/2015 09:57 MHH71310.005 1 Boron (B)< 0.05 mg/L EPA 200.7 09/28/2015 09:57 MHH71310.05 1 Iron (Fe)< 0.01 mg/L EPA 200.7 09/28/2015 09:57 MHH71310.01 1 Manganese (Mn)< 0.005 mg/L EPA 200.7 09/28/2015 09:57 MHH71310.005 1 Strontium (Sr)< 0.005 mg/L EPA 200.7 09/28/2015 09:57 MHH71310.005 1 Zinc (Zn)< 0.005 mg/L EPA 200.7 09/28/2015 09:57 MHH71310.005 1 TOTAL RECOVERABLE METALS BY ICP-MS Antimony (Sb)< 1 ug/L EPA 200.8 09/28/2015 17:09 MHALL311 Arsenic (As)< 1 ug/L EPA 200.8 09/28/2015 17:09 MHALL311 Beryllium (Be)< 1 ug/L EPA 200.8 09/28/2015 17:09 MHALL311 Cadmium (Cd)< 1 ug/L EPA 200.8 09/28/2015 17:09 MHALL311 Chromium (Cr)< 1 ug/L EPA 200.8 09/28/2015 17:09 MHALL311 Cobalt (Co)< 1 ug/L EPA 200.8 09/28/2015 17:09 MHALL311 Copper (Cu)< 1 ug/L EPA 200.8 09/28/2015 17:09 MHALL311 Lead (Pb)< 1 ug/L EPA 200.8 09/28/2015 17:09 MHALL311 Molybdenum (Mo)< 1 ug/L EPA 200.8 09/28/2015 17:09 MHALL311 Nickel (Ni)< 1 ug/L EPA 200.8 09/28/2015 17:09 MHALL311 Selenium (Se)< 1 ug/L EPA 200.8 09/28/2015 17:09 MHALL311 Thallium (Tl) Low Level < 0.2 ug/L EPA 200.8 09/28/2015 17:09 MHALL30.2 1 Vanadium (V) Low Level < 0.3 ug/L EPA 200.8 09/28/2015 17:09 MHALL30.3 1 Qualifiers: M1 Matrix spike recovery was High: the associated Laboratory Control Spike (LCS) was acceptable. Page 33 of 34 Page 34 of 34 Corrective Action Plan Part 1 November 2015 L.V. Sutton Energy Complex SynTerra P:\Duke Energy Progress.1026\108. Sutton Ash Basin GW Assessment Plan\16.Corrective Action Plan\FINAL CAP REPORT\Final LV Sutton CAP Report 11-02-2015.docx APPENDIX C SOIL SORPTION REPORT Soil Sorption Evaluation L.V. Sutton Energy Complex Prepared for SynTerra 148 River Street # 220, Greenville, SC 29601 Investigators William G. Langley, Ph.D., P.E. Shubhashini Oza, Ph.D. UNC Charlotte Civil and Environmental Engineering EPIC Building, 3252, 9201 University City Blvd, Charlotte, NC 28223 October 31, 2015 Soil Sorption Evaluation Sutton Steam Station UNC Charlotte ii | P a g e Table of Contents List of Tables ------------------------------------------------------------------------------------------------- iii List of Figures ------------------------------------------------------------------------------------------------ iv 1. Introduction ----------------------------------------------------------------------------------------------- 1 2. Background ----------------------------------------------------------------------------------------------- 1 3. Experiment: Kd Determination------------------------------------------------------------------------- 2 3.1 Sample Storage and Preparation ----------------------------------------------------------------- 2 3.2 Metal Oxy-hydroxide Phases --------------------------------------------------------------------- 3 3.3 Test Solution ---------------------------------------------------------------------------------------- 3 3.4 Equipment Setup ----------------------------------------------------------------------------------- 3 4. Model Equations for Kd Determination -------------------------------------------------------------- 4 5. Leaching for Ash Samples------------------------------------------------------------------------------ 5 6. Results ----------------------------------------------------------------------------------------------------- 5 7. References ------------------------------------------------------------------------------------------------ 8 Appendix – A -------------------------------------------------------------------------------------------------- 9 Appendix – B ------------------------------------------------------------------------------------------------- 18 Soil Sorption Evaluation Sutton Steam Station UNC Charlotte iii | P a g e List of Tables Table 1: Site specific soil samples analyzed for Kd ........................................................................ 9 Table 2: Synthetic ground water constituents and trace metals concentrations.............................. 9 Table 3: Oxidation-reduction potential values for selected soil samples (ASTM G200-09) ....... 10 Table 4: Summary of batch and column Kd (mL/g) for SW – 3C (10 – 12 ft.) ............................ 11 Table 5: Summary of batch and column Kd (mL/g) for SW – 3C (41 – 43 ft.) ............................ 11 Table 6: Summary of batch and column Kd (mL/g) for SW – 3C (48 – 53 ft.) ............................ 11 Table 7: Summary of batch and column Kd (mL/g) for ABMW – 1D (38 – 48 ft.) ..................... 12 Table 8: Summary of batch and column Kd (mL/g) for ABMW – 1D (83 - 88 ft.) ...................... 12 Table 9: Summary of batch and column Kd (mL/g) for ABMW – 2D (0 - 8 ft.) .......................... 12 Table 10: Summary of batch and column Kd (mL/g) for ABMW – 2D (10 – 12 ft.) ................... 13 Table 11: Summary of batch and column Kd (mL/g) for ABMW – 2D (53 – 60 ft.) ................... 13 Table 12: Summary of batch and column Kd (mL/g) for MW – 23E (145 – 147 ft.) ................... 13 Table 13: Kd Qualifiers for batch and column plots ..................................................................... 14 Table 14: Ogata-Banks parameters used in developing column Kd ............................................. 15 Table 15: HFO, HMO and HAO................................................................................................... 16 Table 16: Method 1313 leaching - pH, ORP and conductivity (at natural pH) ............................ 17 Table 17: Method 1313 leaching (at natural pH) data for ash samples collected at the site ........ 17 Soil Sorption Evaluation Sutton Steam Station UNC Charlotte iv | P a g e List of Figures Figure 1: Tumbler for 1313, 1316 and batch Kd ........................................................................... 18 Figure 2: Batch filtration set-up .................................................................................................... 18 Figure 3: Column set-up ............................................................................................................... 19 Figure 4: Syringe filtration for extraction of HFO/HMO/HAO ................................................... 20 Figure 5: Arsenic batch Kd - ABMW – 2D (0 – 8 ft.) .................................................................. 21 Figure 6: Arsenic column Kd - ABMW – 2D (0 – 8 ft.) ............................................................... 21 Figure 7: Barium column Kd - ABMW - 2D (0 - 8 ft.) ................................................................. 22 Figure 8: Boron column Kd - ABMW - 2D (0 - 8 ft.) ................................................................... 23 Figure 9: Cobalt batch Kd - ABMW – 2D (0 – 8 ft.) .................................................................... 24 Figure 10: Cobalt column Kd - ABMW – 2D (0 – 8 ft.) ............................................................... 24 Figure 11: Manganese batch Kd - ABMW – 2D (0 – 8 ft.) ........................................................... 25 Figure 12: Selenium batch Kd - ABMW – 2D (0 – 8 ft.) .............................................................. 26 Figure 13: Selenium column Kd - ABMW – 2D (0 – 8 ft.) .......................................................... 26 Figure 14: Vanadium batch Kd - ABMW – 2D (0 – 8 ft.) ............................................................ 27 Figure 15: Vanadium column Kd - ABMW – 2D (0 – 8 ft.) ......................................................... 27 Figure 16: Arsenic batch Kd - ABMW – 2D (10 – 12 ft.) ............................................................ 28 Figure 17: Arsenic column Kd - ABMW – 2D (10 – 12 ft.) ......................................................... 28 Figure 18: Barium batch Kd - ABMW – 2D (10 – 12 ft.) ............................................................. 29 Figure 19: Barium column Kd - ABMW – 2D (10 – 12 ft.).......................................................... 29 Figure 20: Boron column Kd - ABMW - 2D (10 - 12 ft.) ............................................................. 30 Figure 21: Cobalt batch Kd - ABMW – 2D (10 – 12 ft.) .............................................................. 31 Figure 22: Cobalt column Kd - ABMW – 2D (10 – 12 ft.) ........................................................... 31 Figure 23: Iron batch Kd - ABMW – 2D (10 – 12 ft.) .................................................................. 32 Figure 24: Manganese batch Kd - ABMW – 2D (10 – 12 ft.) ....................................................... 33 Figure 25: Selenium column Kd - ABMW – 2D (10 – 12 ft.) ...................................................... 34 Figure 26: Vanadium batch Kd - ABMW – 2D (10 – 12 ft.) ........................................................ 35 Figure 27: Vanadium column Kd - ABMW – 2D (10 – 12 ft.) ..................................................... 35 Figure 28: Arsenic batch Kd - ABMW – 2D (53 – 60 ft.) ............................................................ 36 Figure 29: Arsenic column Kd - ABMW – 2D (53 – 60 ft.) ......................................................... 36 Figure 30: Barium column Kd - ABMW - 2D (53 - 60 ft.) ........................................................... 37 Soil Sorption Evaluation Sutton Steam Station UNC Charlotte v | P a g e Figure 31: Boron column Kd - ABMW - 2D (53 - 60 ft.) ............................................................. 38 Figure 32: Cobalt batch Kd - ABMW – 2D (53 – 60 ft.) .............................................................. 39 Figure 33: Manganese batch Kd - ABMW – 2D (53 – 60 ft.) ....................................................... 40 Figure 34: Selenium batch Kd - ABMW – 2D (53 – 60 ft.) .......................................................... 41 Figure 35: Selenium column Kd - ABMW – 2D (53 – 60 ft.) ...................................................... 41 Figure 36: Vanadium batch Kd - ABMW – 2D (53 – 60 ft.) ........................................................ 42 Figure 37: Vanadium column Kd - ABMW – 2D (53 – 60 ft.) ..................................................... 42 Figure 38: Arsenic batch Kd – SW – 3C (10 – 12 ft.) ................................................................... 43 Figure 39: Arsenic column Kd – SW – 3C (10 – 12 ft.) ................................................................ 43 Figure 40: Barium batch Kd - SW – 3C (10 – 12 ft.) .................................................................... 44 Figure 41: Barium column Kd - SW – 3C (10 – 12 ft.) ................................................................. 44 Figure 42: Boron column Kd - SC - 3C (10 - 12 ft.) ..................................................................... 45 Figure 43: Cobalt batch Kd - SW – 3C (10 – 12 ft.) ..................................................................... 46 Figure 44: Cobalt column Kd - SW – 3C (10 – 12 ft.) .................................................................. 46 Figure 45: Manganese batch Kd - SW – 3C (10 – 12 ft.) .............................................................. 47 Figure 46: Selenium batch Kd - SW – 3C (10 – 12 ft.) ................................................................. 48 Figure 47: Selenium column Kd - SW – 3C (10 – 12 ft.).............................................................. 48 Figure 48: Vanadium batch Kd - SW – 3C (10 – 12 ft.) ............................................................... 49 Figure 49: Vanadium column Kd - SW – 3C (10 – 12 ft.) ............................................................ 49 Figure 50: Arsenic batch Kd - SW – 3C (41 – 43 ft.) Figure 51: Arsenic column Kd - SW – 3C (41 – 43 ft.)Trial A ................................................................ 50 Figure 52: Arsenic column Kd - SW – 3C (41 – 43 ft.)Trial B Figure 53: Arsenic column Kd - SW – 3C (41 – 43 ft.)Trial C ................................................. 50 Figure 54: Barium batch Kd - SW – 3C (41 – 43 ft.) Figure 55: Barium column Kd - SW – 3C (41 – 43 ft.)Trial A ................................................................ 51 Figure 56: Barium column Kd - SW – 3C (41 – 43 ft.)Trial B Figure 57: Barium column Kd - SW – 3C (41 – 43 ft.)Trial C .................................................. 51 Figure 58: Boron column Kd - SW – 3C (41 – 43 ft.)Trial A ....................................................... 52 Figure 59: Boron column Kd - SW – 3C (41 – 43 ft.)Trial B Figure 60: Boron column Kd - SW – 3C (41 – 43 ft.)Trial C .................................................... 52 Figure 61: Cobalt column Kd - SW – 3C (41 – 43 ft.) Trial A ..................................................... 53 Soil Sorption Evaluation Sutton Steam Station UNC Charlotte vi | P a g e Figure 62: Cobalt column Kd - SW – 3C (41 – 43 ft.) Trial B Figure 63: Cobalt column Kd - SW – 3C (41 – 43 ft.) Trial C .................................................. 53 Figure 64: Manganese batch Kd - SW – 3C (41 – 43 ft.) .............................................................. 54 Figure 65: Selenium batch Kd - SW – 3C (41 – 43 ft.) Figure 66: Selenium column Kd - SW – 3C (41 – 43 ft.) Trial A ............................................................ 55 Figure 67: Selenium column Kd - SW – 3C (41 – 43 ft.) Trial B Figure 68: Selenium column Kd - SW – 3C (41 – 43 ft.) Trial C .............................................. 55 Figure 69: Vanadium batch Kd - SW – 3C (41 – 43 ft.) Figure 70: Vanadium column Kd - SW – 3C (41 – 43 ft.) Trial A ............................................................ 56 Figure 71: Vanadium column Kd - SW – 3C (41 – 43 ft.) Trial B Figure 72: Vanadium column Kd - SW – 3C (41 – 43 ft.) Trial C ............................................ 56 Figure 73: Arsenic batch Kd - SW – 3C (48 – 53 ft.) .................................................................... 57 Figure 74: Arsenic column Kd - SW – 3C (48 – 53 ft.) ................................................................ 57 Figure 75: Barium batch Kd - SW – 3C (48 – 53 ft.) .................................................................... 58 Figure 76: Barium column Kd - SW – 3C (48 – 53 ft.) ................................................................. 58 Figure 77: Boron column Kd - SC - 3C (48 - 53 ft.) ..................................................................... 59 Figure 78: Cobalt column Kd - SC - 3C (48 - 53 ft.) .................................................................... 60 Figure 79: Iron batch Kd - SW – 3C (48 – 53 ft.) ......................................................................... 61 Figure 80: Manganese batch Kd - SW – 3C (48 – 53 ft.) .............................................................. 62 Figure 81: Selenium batch Kd - SW – 3C (48 – 53 ft.) ................................................................. 63 Figure 82: Selenium column Kd - SW – 3C (48 – 53 ft.).............................................................. 63 Figure 83: Vanadium batch Kd - SW – 3C (48 – 53 ft.) ............................................................... 64 Figure 84: Vanadium column Kd - SW – 3C (48 – 53 ft.) ............................................................ 64 Figure 85: Arsenic batch Kd – MW – 23E (145 – 147 ft.) ............................................................ 65 Figure 86: Arsenic column Kd – MW – 23E (145 – 147 ft.) ........................................................ 65 Figure 87: Barium column Kd – MW – 23E (145 – 147 ft.) ......................................................... 66 Figure 88: Boron column Kd – MW – 23E (145 – 147 ft.) ........................................................... 67 Figure 89: Cobalt column Kd – MW – 23E (145 – 147 ft.) .......................................................... 68 Figure 90: Manganese batch Kd – MW – 23E (145 – 147 ft.) ...................................................... 69 Figure 91: Selenium batch Kd - MW – 23E (145 – 147 ft.) .......................................................... 70 Figure 92: Selenium column Kd - MW – 23E (145 – 147 ft.) ...................................................... 70 Soil Sorption Evaluation Sutton Steam Station UNC Charlotte vii | P a g e Figure 93: Vanadium batch Kd - MW – 23E (145 – 147 ft.) ........................................................ 71 Figure 94: Vanadium column Kd - MW – 23E (145 – 147 ft.) ..................................................... 71 Figure 95: Barium batch Kd - ABMW - 1D (38 - 48 ft.) .............................................................. 72 Figure 96: Boron batch Kd - ABMW – 1D (38 – 48 ft.) ............................................................... 72 Figure 97: Cobalt batch Kd - ABMW – 1D (38 – 48 ft.) .............................................................. 73 Figure 98: Selenium batch Kd - ABMW – 1D (38 – 48 ft.) .......................................................... 73 Figure 99: Arsenic batch Kd - ABMW – 1D (83 – 88 ft.) ............................................................ 74 Figure 100: Arsenic column Kd - ABMW – 1D (83 – 88 ft.) ....................................................... 74 Figure 101: Barium column Kd – ABMW - 1D (83 - 88 ft.) ........................................................ 75 Figure 102: Boron column Kd – ABMW- 1D (83 - 88 ft.) ........................................................... 76 Figure 103: Cobalt batch Kd - ABMW – 1D (83 – 88 ft.) ............................................................ 77 Figure 104: Cobalt column Kd - ABMW – 1D (83 - 88 ft.).......................................................... 77 Figure 105: Manganese batch Kd - ABMW – 1D (83 – 88 ft.) ..................................................... 78 Figure 106: Selenium batch Kd - ABMW – 1D (83 – 88 ft.) ........................................................ 79 Figure 107: Selenium column Kd - ABMW – 1D (83 – 88 ft.) .................................................... 79 Figure 108: Vanadium batch Kd - ABMW – 1D (83 – 88 ft.) ...................................................... 80 Figure 109: Vanadium column Kd - ABMW – 1D (83 – 88 ft.) ................................................... 80 Figure 110: pH vs L/S for ABMW – 01 D (38-48 ft.) .................................................................. 81 Figure 111: ORP vs L/S for ABMW – 01 D (38-48 ft.) ............................................................... 81 Figure 112: Conductivity vs L/S for ABMW – 01 D (38-48 ft.) .................................................. 82 Figure 113: pH vs L/S for ABMW – 01 D (83-88 ft.) .................................................................. 82 Figure 114: ORP vs L/S for ABMW – 01 D (83-88 ft.) ............................................................... 83 Figure 115: Conductivity vs L/S for ABMW – 01 D (83-88 ft.) .................................................. 83 Figure 116: pH vs L/S for ABMW – 02 D (0-8 ft.) ...................................................................... 84 Figure 117: ORP vs L/S for ABMW – 02 D (0-8 ft.) ................................................................... 84 Figure 118: Conductivity vs L/S for ABMW – 02 D (0-8 ft.) ...................................................... 85 Figure 119: pH vs L/S for ABMW – 02 D (10-12 ft.) .................................................................. 85 Figure 120: ORP vs L/S for ABMW – 02 D (10-12 ft.) ............................................................... 86 Figure 121: Conductivity vs L/S for ABMW – 02 D (10-12 ft.) .................................................. 86 Figure 122: pH vs L/S for ABMW – 02 D (53-60 ft.) .................................................................. 87 Figure 123: ORP vs L/S for ABMW – 02 D (53-60 ft.) ............................................................... 87 Soil Sorption Evaluation Sutton Steam Station UNC Charlotte viii | P a g e Figure 124: Conductivity vs L/S for ABMW – 02 D (53-60 ft.) .................................................. 88 Figure 125: pH vs L/S for SW – 3 C (10-12 ft.) ........................................................................... 88 Figure 126: ORP vs L/S for SW – 3 C (10-12 ft.) ........................................................................ 89 Figure 127: Conductivity vs L/S for SW – 3 C (10-12 ft.) ........................................................... 89 Figure 128: pH vs L/S for SW – 3 C (41-43 ft.) ........................................................................... 90 Figure 129: ORP vs L/S for SW – 3 C (41-43 ft.) ........................................................................ 90 Figure 130: Conductivity vs L/S for SW – 3 C (41-43 ft.) ........................................................... 91 Figure 131: pH vs L/S for SW – 3 C (48-53 ft.) ........................................................................... 91 Figure 132: ORP vs L/S for SW – 3 C (48-53 ft.) ........................................................................ 92 Figure 133: Conductivity vs L/S for SW – 3 C (48-53 ft.) ........................................................... 92 Figure 134: pH vs L/S for MW – 23 E ......................................................................................... 93 Figure 135: ORP vs L/S for MW – 23 E ...................................................................................... 93 Figure 136: Conductivity vs L/S for MW – 23 E ......................................................................... 94 Figure 137: Molybdenum 1316 AB – 1 (38 – 48FT).................................................................... 94 Figure 138: Selenium 1316 AB – 1 (38 – 48FT) .......................................................................... 95 Figure 139: Boron 1316 AB – 2 (0 – 8FT) ................................................................................... 95 Figure 140: Manganese 1316 AB – 2 (0 – 8FT) ........................................................................... 96 Figure 141: Molybdenum 1316 AB – 2 (0 – 8FT)........................................................................ 96 Figure 142: pH at varying L/S ratio for 1316 testing of AB – 1 (38 – 48FT) .............................. 97 Figure 143: ORP at varying L/S ratio for 1316 testing of AB – 1 (38 – 48FT) ........................... 97 Figure 144: Conductivity at varying L/S ratio for 1316 testing of AB – 1 (38 – 48FT) .............. 98 Figure 145: pH at varying L/S ratio for 1316 testing of AB – 2 (0 – 8FT) .................................. 98 Figure 146: ORP at varying L/S ratio for 1316 testing of AB – 2 (0 – 8FT) ............................... 99 Figure 147: Conductivity at varying L/S ratio for 1316 testing of AB – 2 (0 – 8FT) .................. 99 Soil Sorption Evaluation Sutton Steam Station UNC Charlotte 1 | P a g e 1. Introduction Duke Energy Progress, LLC. (Duke Energy), owns and operates the L.V. Sutton Energy Complex located in Lumberton, North Carolina. The plant retired in 2013. The coal ash residue from the coal combustion process for power generation was placed in the plant’s ash basin, which is permitted by the North Carolina Department of Environmental and Natural Resources (NCDENR) Division of Water Resources (DWR) under the National Pollution Discharge Elimination System. In a Notice of Regulatory Requirements (NORR) letter dated August 13, 2014, the Division of Water Resources (DWR) requested that Duke Energy prepare a Groundwater Assessment Plan to identify the source and cause of possible contamination, any potential hazards to public health and safety, and actions taken to mitigate them, and all receptors and complete exposure pathways. In addition, the plan should determine the horizontal and vertical extent of possible soil and groundwater contamination and all significant factors affecting contaminant transport and the geological and hydrogeological features influencing the movement, chemical, and physical character of the contaminants. The work plan was also prepared to fulfill the requirements stipulated in Coal Ash Management Act 2014 – North Carolina Senate Bill 729: The Groundwater Assessment Plan includes the collection of groundwater and surface water information to prepare a Comprehensive Site Assessment Report and support the development of a groundwater computer model to evaluate the long term fate and transport of constituents of concern (COCs) in groundwater associated with the ash basin. Critical input parameters for the model are site specific soil sorption coefficients Kd for each COC. This report presents the initial results of sorption testing on selected soils from the Sutton Steam Station to quantify the Kd terms. Testing was performed at the Civil and Environmental Engineering laboratories in the EPIC building at UNC Charlotte. Soil samples were collected during the geotechnical and environmental exploration program at the facility between March and June 2015, thirty five of which were delivered to UNC Charlotte between March 24th and June 26th of 2015. 2. Background In groundwater, sorption is quantified by the equilibrium relationship between chemicals in the dissolved and adsorbed phases. Experiments to quantify sorption can be conducted using batch or column procedures. A batch sorption procedure consists of combining soil samples and solutions across a range of soil-to-solution ratios, followed by shaking until chemical equilibrium is achieved. Initial and final concentrations of chemicals in the solution determine the adsorbed amount of chemical and provide data for developing plots of adsorbed versus dissolved chemical. If the plot, or isotherm, is linear, then the single-valued coefficient Kd, with units of volume per unit mass, represents the slope of the isotherm. Depending on the chemical, its dissolved phase concentration, and the soil characteristics, nonlinear isotherms, characterized by two or more coefficients, may result. The column sorption procedure consists of passing a solution of known chemical concentration through a cylindrical column packed with the soil sample. A plot of the chemical constituent Soil Sorption Evaluation Sutton Steam Station UNC Charlotte 2 | P a g e measured in the column effluent is plotted versus time or its equivalent, pore volumes passed. This so-called breakthrough curve is plotted together with the analytical solution of the advection-dispersion-adsorption equation from which the linear sorption coefficient Kd is estimated by visual curve fitting [1]. When comparing the merits of the two procedures for quantifying sorption, the batch procedure provides a more effective contact between the solution and soil, while the column procedure may more representative of in-situ groundwater flow conditions where solution soil contact is non-uniform and less than fully effective. Both batch and column procedures were employed for the sorption experiments on soils from the facility. Depending on practical considerations, the batch procedure may be designed to capture a wide range of Kd values. Metal oxy-hydroxide phases of iron, manganese, and aluminum in soils are considered to be the most important surface reactive phases for cationic and anionic constituents in many subsurface environments [2]. Quantities of these phases in a given soil can thus be considered as a proxy for COC sorption capacity for a given soil. In this study, oxy-hydroxide phases of iron, manganese, and aluminum (hereafter referred to as HFO, HMO, and HAO) were measured concurrently with sorption coefficients for selected COCs and soil samples. 3. Experiment: Kd Determination 3.1 Sample Storage and Preparation Nine soil samples were selected for determination of sorption coefficients (Table 1). The basis for selection was to provide adequate coverage of the saturated zone beneath and down gradient of the ash basin. Preserved soils arrived at the EPIC lab in air-tight plastic bags on ice in coolers. Samples were stored in their original containers in a cold room at less than 4° C until tested. For batch and column procedures, soil samples were disaggregated, homogenized, and air-dried at room temperature in aluminum pans (21” x 13” x 4”), for a minimum of 72 hours, with turning every 12 hours. The dry samples were then sieved to a particle diameter of less than 2 mm (#10 U.S. Standard mesh). Sample splits for column testing were sieved a second time to remove particles less than 0.30 mm (#50 U.S. Standard mesh) in order to have sufficient permeability of the sample such that water passed through the column without operational problems, such as leaking or reduced flow. Bedrock samples were fragmented using a Sotec Systems Universal Testing Machine (UTM). Fragmentation was continued until the approximate grain size was 2.0 to 0.30 mm by visual inspection. Like the soil samples, bedrock samples intended for column testing were sieved a second time to remove particles less than 0.30 mm in diameter (#50 U.S. Standard mesh) to minimize operational problems associated with the small particle size. Soil samples for batch sorption testing were weighed and placed in 250 mL wide-mouth HDPE bottles with polypropylene screw tops (in accordance with U.S. Environmental Protection Agency (EPA) Technical Resource Document EPA/530/SW-87/006-F). For each test on a single sample, soil masses of 10, 25, 50, 75, and 100 grams were placed in separate bottles. The columns were 8 inch long (20.3cm) polyethylene tubes with dimensions 0.675 in. (16 mm) I.D. by 0.75 in. (19 mm) O.D. Each column setup included two polypropylene end caps with barbed Soil Sorption Evaluation Sutton Steam Station UNC Charlotte 3 | P a g e fittings which accept 0.25 to 0.375 in. (6.4 to 9.5 mm) I.D. tubing. Two discs of porous polyethylene and polymer mesh screen were placed between the end cap and tube to retain the soil in the column. A modified slurry packing method was used to provide homogenous sample packing without preferential flow in the columns [3]. With one end cap in place, acid-washed Ottawa sand was added through the open end to a depth of about 2 cm to ensure the effective dispersal of flow across the column cross section. With the lower end cap and sand in place, 3 mL of 18 MΩ water (high purity de-ionized water) was added to the column. Then sample material was added in 5 cm lifts. The column assembly was weighed after each addition of water and soil. In order to eliminate trapped air, the column was placed on a vibrating table for 15 seconds. This process also ensured proper compaction while promoting a uniform density throughout the column. The sequence of adding water and sample material followed by vibrating was continued until roughly 2 cm of column head space remained. A 2 cm thick sand layer was added at the top of the compacted sample and the upper end cap was attached. The length of material in the column was measured in order to estimate the dry bulk density and porosity of the packed sample. Experimental set-up is presented in Figure 4. 3.2 Metal Oxy-hydroxide Phases The analytical method for determining hydrous ferric oxide (HFO) and hydrous aluminum oxide (HAO) was adapted from Chou and Zhou [4] and that for hydrous manganese oxide (HMO) from T.T.Chao [5]. The HFO and HAO method calls for extracting the soil sample using a 0.25M NH2OH·HCl-0.25M HCl combined solution as the extractant at 50° C for 30 minutes (soil/liquid = 0.1 g/25 mL). The HMO methods calls for extracting the soil samples using a 0.1 M NH2OH·HCl-0.25M HCl combined solution as the extractant at 25° C for 2 hours (soil/liquid = 0.025 g/50 mL) (Figure 4). 3.3 Test Solution A synthetic groundwater with chemical composition provided shown in Table 2 was prepared using reagent grade solid chemicals and 18 MΩ water. Target COC concentrations were attained by diluting concentrated reference standards to the synthetic groundwater solution. After adding the reference standards, the COC-amended feed solution was back-titrated as needed to an approximate pH range of 6.5 to 7.5 using 0.1 N sodium hydroxide solution. Iron and manganese were omitted from the list of target COCs given that they were considered to likely leach when exposed to the synthetic groundwater. 3.4 Equipment Setup The COC-amended solutions were prepared in 10 liter and 20 liter LDPE carboys for the batch and column experiments, respectively. For each batch experiment, 200 mL of solution was added to each 250 mL bottle to obtain soil mass to solution ratios of 50, 125, 250, 375, and 500 mg/L. The soil-solution mixtures were equilibrated in a rotary mixer operating at 60 rpm for 24 hours. The experimental set-up and filtration details are presented in Figure 1 and 2. Following equilibration, water samples were drawn, filtered, and preserved for analysis of eight COCs Soil Sorption Evaluation Sutton Steam Station UNC Charlotte 4 | P a g e (arsenic, boron, barium, cobalt, iron, manganese, selenium, and vanadium). Sample blanks were included in selected experiments to confirm stability of the solution. For the column experiments, Masterflex peristaltic pump drives with 12-channel, 8-roller cartridge pump heads and cartridges were connected between the carboys and the columns using Tygon tubing, valves, and fittings. The columns were operated in the up-flow mode. The flow rate was set to pass approximately twelve pore volumes, or approximately 200 m L, per day through each column. Before pumping began with the COC-amended solutions, the columns were fully saturated by slowly pumping reagent water in the up-flow mode. The COC-amended solutions were stirred continuously using magnetic stirrers. The arrangement of the carboys, pump, and columns is shown in Figure 4. Real-time, grab sample volumes of approximately 50 mL were drawn for each sampling event. The sample time and total volume pumped since the previous sampling event were recorded for calculating flow rates and pore volume passed. Concurrent samples of the feed solutions were also taken for each sampling event. Each sample was proportioned, filtered, and preserved for the analyses of six COC’s (arsenic, boron, barium, cobalt, selenium, and vanadium). Iron and manganese Kd values were determined from the combination of batch and HFO-HMO values and not by the column method. 4. Model Equations for Kd Determination After equilibration of a batch soil-solution mixture, the COC concentration in solution will be reduced due to sorption. This may be expressed as 𝑥 𝑚= [(𝐶𝑚−𝐶)/𝑚]∗𝑉 where, x/m is the soil concentration (μg/g), Co is the initial solution concentration (μg/L), C is the final solution concentration, m is the soil sample mass, and V is the volume of solution. For sorption characterized by a linear isotherm, a plot of measured solution concentration versus calculated soil concentration for each soil sample (five data points: one for each soil to solution ratio) will yield the linear Kd term as the slope of x/m versus C. For the steady-state flow regime considered in the column tests, van Genuchten and Alves [6] presented the following form of the Ogata-Banks (O-B)[1] equation for one-dimensional, advection-dispersion equation with sorption as a close approximation to that for a finite length, lab-scale column [6]: 𝐶(𝑥,𝑡)=𝐶0 2 [𝑒𝑟𝑒𝑐(𝑅𝑥−𝑣𝑡 2√𝐶𝑅𝑡)+𝑒𝑥𝑚(𝑣𝑥/𝐶)𝑒𝑟𝑒𝑐(𝑅𝑥+𝑣𝑡 2√𝐶𝑅𝑡)] where, C(x,t) is the solute concentration (M/L3), x is the column length (L), t is the elapsed time (T), C0 is the feed concentration (M/L3), R is the dimensionless retardation coefficient, v is the seepage velocity (L/T), and D is the soil dispersion coefficient (L2/T). For sorption characterized by a linear isotherm, the Kd term (L3/M) is incorporated in R: Soil Sorption Evaluation Sutton Steam Station UNC Charlotte 5 | P a g e 𝑅=1 +𝜌𝑏𝐾𝑑 𝑚 Where, ρb is the dry bulk density of the soil (M/L3) and n is the porosity. For the given test conditions where dispersion was dominant over diffusion, the soil dispersion coefficient D is equal to the product of the longitudinal dispersivity, aL (L) and the seepage velocity. Supporting data used to estimate Kd based on O-B equation are provided in Table 14. For plotting the analytical results together with the O-B equation, cumulative pore volumes corresponding to the elapsed time of each sampling event were calculated using measured water volumes pumped and the column pore volume. For each COC and soil column, Kd was estimated by visually fitting the plotted O-B equation to the measured solution concentrations. 5. Leaching for Ash Samples The site specific ash samples were subjected to two leaching protocols, Method 1313 and Method 1316. Method 1313: Liquid-Solid Partitioning as a Function of Extract pH using a Parallel Batch Extraction Procedure [7]. The procedure calls for reaching nine specific pH targets after mixing. If the natural pH of the material, without acid or based addition, is not one of the target pH positions, the natural pH is a tenth position in the procedure. For the purpose of this study, site specific ash samples were analyzed at the natural pH of the material only. The ash samples were extracted for 24 hours with 18 MΩ water. The leachate from the extraction step was filtered using 0.45µ filter paper and analyzed for pH, ORP, conductivity and concentration of anions and cations. Method 1316: Liquid-Solid Partitioning as a Function of Liquid-Solid Ratio using a Parallel Batch Extraction Procedure [8]. This method consists of five parallel extractions over a range of liquid/solid (L/S) values from 0.5 to 10 mL eluent/g dry material. In addition to the five test extractions, a method blank without solid sample was carried out to verify that analyte interferences were not introduced as a consequence of reagent impurities or equipment contamination. The 250 mL test bottles equilibrated for 24 hours with 18 MΩ (high-purity de- ionized water) water (and as per method specification). At the end of the contact interval, the leachate from the extraction step was filtered (0.45µ filter paper) and analyzed for pH, ORP, conductivity and concentration of anions and cations. 6. Results The oxidation and reduction potential (ORP) values of soil samples measured as per ASTM G 200 – 09 are listed in Table 3[9]. The sorption test results are grouped by soil sample. Batch and column results are tabulated in Tables 4 to 12. The Kd result for COCs are assigned qualifiers as presented in Table 13. The parameters used in Ogata-Banks equation for developing the Kd column plots are presented in Table 14. Batch and column test results for the COCs are shown in Figure 5 through 109 for each soil sample. Soil Sorption Evaluation Sutton Steam Station UNC Charlotte 6 | P a g e At the conclusion of the breakthrough experiment six pore volumes of 18 MΩ water was passed through the column (data not shown in column Kd plots). No significant COC desorption was observed based on the column effluent monitoring. General comments for Kd experiments: The sorption coefficients extracted from the experimental results in this study may be affected to some extent by factors related to the experimental design. They include the following:  The goal of the batch and column sorption studies was to expose each soil sample to COCs in the aqueous phase and allow COC adsorption to occur until equilibrium is achieved. A solution intended to represent a generic groundwater was used as the background solution to which COCs were added. This solution differs from the in-situ solution in groundwater from which the soil sample was sampled. As a result, the soil sample is exposed to a geochemical environment in which a number of chemical reactions may take place in addition to sorption.  The number of COCs for which sorption estimates are required for each sample necessitates combining a number of COCs in a single solution for simultaneous measurement. These COCs may interact chemically, thus altering their respective sorption characteristics for individual soil samples.  Sorption characteristics for selected COCs are sensitive to redox conditions. Experiments in the lab were conducted in atmospheric conditions unless otherwise noted. The resulting sorption coefficients may not be representative of other redox settings.  Sample splits for column testing were sieved to remove particle sizes less than 0.30 mm in order to have sufficient permeability of the sample to pass water through the column without operational problems such as leaking and reduced flow. This could also affect the observed Kd value. Specific comments for batch and column Kd experiments are summarized as follows  Batch Kd for As ranged from 8.7 to 501.1 mL/g and column Kd ranged from 27 to 120 mL/g.  Batch Kd for B was negligible for all samples and very low sorption of 1.7 mL/g was observed in the case of ABMW – 1D (38 – 48 ft.). In columns, Kd ranged between 10 to 40 mL/g.  Batch Kd for Ba ranged from 8.0 to 42.1 mL/g, while ABMW – 1D (0 – 8 ft.) and ABMW – 1D (83 – 88 ft.) indicated negligible sorption. In columns, Kd ranged between 15 to 580 mL/g .  Batch Kd for Co ranged from 10.7 to 740.0 mL/g, while SW – 3C (48 – 53 ft.) indicated negligible sorption. In columns, Kd ranged between 60 to 800 mL/g. Soil Sorption Evaluation Sutton Steam Station UNC Charlotte 7 | P a g e  Fe and Mn were not included in the test solution, so its occurrence in the batch test solution is indicative of leaching. HFO and HMO values were used as the initial concentration to predict the Kd values for Fe and Mn, respectively. If the concentration of Fe and Mn increased with mass of soil per unit volume of test solution during batch experiments, it is an indication of a linear leaching model, as opposed to a linear sorption model.  Batch Kd for Se ranged from 2.0 to 107.3 mL/g and in column Kd ranged from 24 to 150 mL/g.  Batch Kd for V ranged from 1.9 to 538.4 mL/g, while ABMW – 1D (38 – 48 ft.) indicated negligible sorption. In column, Kd ranged between 50 to 675 mL/g. pH, ORP, and conductivity at different liquid to solid (L/S) ratios for batch experiments are depicted through Figures 110 to 136. HFO, HMO and HAO results are presented in Table 15. The leaching test for 1313 are tabulated in Table 16 and 17. From Table 17 it can be observed that beryllium, cadmium, chromium, cobalt, copper, nickel, lead, thallium and zinc leaching are negligible and close to minimum detection limit (< 1 ppb). Arsenic, boron, iron, molybdenum, selenium and vanadium indicated significant leaching. The leaching trend for 1316 is depicted through Figure 137 to 147. Soil Sorption Evaluation Sutton Steam Station UNC Charlotte 8 | P a g e 7. References 1. Akio Ogata, R.B.B., A Solution of the Differential Equation of Longitudinal Dispersion in Porous Media. Geological Survey Professional Paper 411 - A, 1961: p. 1-13. 2. Robert G. Ford, R.T.W., Robert W. Puls, Monitored Natural Attenuation of Inorganic Contaminants in Ground Water. 2007, National Risk Management Research Laboratory, U.S. EPA: Cincinnati, Ohio. 3. Oliviera, I.B., A.H. Demond, and A. Salehzadeh, Packing of Sands for the Production of Homogeneous Porous Media. Soil Science Society of America Journal, 1996. 60(1): p. 49-53. 4. Chao, T.T. and L. Zhou, Extraction Techniques for Selective Dissolution of Amorphous Iron Oxides from Soils and Sediments. Soil Sci. Soc. Am. J., 1983. 47(2): p. 225-232. 5. Chao, T.T., Selective Dissolution of Manganese Oxides from Soils and Sediments with Acidified Hydroxylamine Hydrochloride. Soil Science Society of America Journal, 1972. 36(5): p. 764-768. 6. W.J.Alves, M.T.v.G.a., Analytical Solutions of the One-Dimensional Convetive- Dispersive Solute Transport Equation. 1982. 7. USEPA, Method 1313: Liquid-Solid Partitioning as a Function of pH for Constituents in Solid Materials Using a Parallel Batch Extraction Procedure. 2012, USEPA: Alexandria, VA. 8. USEPA, Method 1316: Liquid-Solid Partitioning as a Function of Liquid-to-Solid Ration in Solid Materials Using a Parallel Batch Procedure. 2012, USEPA: Alexandria, VA. p. 1-20. 9. ASTM, ASTM G 200 - 09 "Standard Test Method for Measurement of Oxidation- Reduction Potential (ORP of Soil)". 2014, ASTM International: West Conshohocken, PA. Soil Sorption Evaluation Sutton Steam Station UNC Charlotte 9 | P a g e Appendix – A Table 1: Site specific soil samples analyzed for Kd Sample Name Depth (ft) SW – 3C 10 – 12 SW – 3C 41 – 43 SW – 3C 48 – 53 ABMW – 1D 38 – 48 ABMW – 1D 83 – 88 ABMW – 2D 0 – 8 ABMW – 2D 10 – 12 ABMW – 2D 53 – 60 MW – 23E 145 – 147 Table 2: Synthetic ground water constituents and trace metals concentrations Chemical Concentration Units CaSO4. 2H2O 20.0 ppm MgSO4 5.0 ppm Na(HCO3) 10.0 ppm Arsenic 500 ppb Barium 500 ppb Boron 500 ppb Cobalt 500 ppb Selenium 500 ppb Vanadium 500 ppb Soil Sorption Evaluation Sutton Steam Station UNC Charlotte 10 | P a g e Table 3: Oxidation-reduction potential values for selected soil samples (ASTM G200-09) Sl. No. Sample Name Depth ORP (mv) ft. Trial A Trial B Trial C Average 1 AB-1 38-48 165.7 157.3 152.7 158.6 2 AB-1 85-88 282.5 244.7 253.0 260.1 3 AB-2 53-60 -290.8 -187.1 -134.1 -160.6 4 AB-2 0-8 -146.3 -- -216.7 -181.5 5 AB-2 10-12' 326.2 336.7 341.7 334.9 6 AW-2C 45-47 409.0 470.9 477.9 452.6 7 AW-2D 62-64 212.0 206.0 221.7 213.2 8 AW-5E 148-150 239.6 193.5 174.6 202.6 9 AW-5E 108-110 193.5 233.1 239.9 222.2 10 AW-5E 55-57 438.3 432.5 434.9 435.2 11 AW-5E 45-47 304.7 370.5 395 356.7 12 AW-6E 148-150 170.3 148.0 181.1 166.5 13 AW-9D 47-50 423.2 440.3 441.9 435.1 14 AW-9D 10-12' 371.7 360.9 352.3 361.6 15 AW-9D 55-57 210.1 223.4 224.4 219.3 16 MW-23E 8-10 371.1 368.9 358.7 366.2 17 MW-23E 43-45 344.3 338.3 340.5 339.7 18 MW-23E 60-62 315.3 303.8 276.7 298.6 19 SMW-1C 12-15 422.0 426.2 441.7 430.0 20 SMW-1C 45-48 318.4 317.8 321.2 319.1 21 SMW-1C 40-44 349.4 346.6 360.3 352.1 22 SMW-6D 103 259.3 242.9 244.1 248.7 23 SMW-6D 44-48 315.1 317.2 323.7 318.7 24 SMW-6D 40-43 -142.9 -179.0 -162.3 -161.4 25 SW-3 10-12' 375.9 377.6 374.6 376.0 26 SW-3 48-53 227.4 243.6 252 241.0 27 SW-3C 41-43 372.0 382.2 386.3 380.2 28 MW-23E 145-147 TOO DRY Soil Sorption Evaluation Sutton Steam Station UNC Charlotte 11 | P a g e Table 4: Summary of batch and column Kd (mL/g) for SW – 3C (10 – 12 ft.) Batch Column Trial – A R2 Trial – B R2 Arsenic 78.8 0.78 76.2 0.84 27.0 Boron Non-linear isotherm 20.0 Barium 20.0 0.99 16.1 0.95 75.0 Cobalt 28.3 0.89 24.4 0.69 130.0 Manganese 0.03 0.67 0.03 0.68 NA Selenium 7.2 0.71 6.9 0.55 30.0 Vanadium 14.7 0.76 14.1 0.70 50.0 Table 5: Summary of batch and column Kd (mL/g) for SW – 3C (41 – 43 ft.) Table 6: Summary of batch and column Kd (mL/g) for SW – 3C (48 – 53 ft.) Batch Column Metals Trial – A R2 Trial – B R2 Arsenic 394 0.88 501.1 0.87 120.0 Boron Non-linear isotherm 20.0 Barium 8.4 0.63 8.2 0.72 85.0 Cobalt Non-linear isotherm 60.0 Iron 0.012 0.99 0.012 0.99 NA Manganese 0.004 0.99 0.004 0.99 NA Selenium 58.2 0.79 81.8 0.82 150.0 Vanadium 302.2 0.68 538.4 0.78 675.0 Batch Column Trial – A R2 Trial – B R2 Trial A Trial B Trial C Arsenic 117.9 0.92 236.2 0.92 50.0 40.0 50.0 Boron Non-linear isotherm - 30.0 40.0 Barium - - 3.9 0.43 110.0 65.0 100.0 Cobalt Non-linear isotherm 125.0 90.0 150.0 Manganese 0.001 0.97 0.001 0.97 NA Selenium 107.3 0.95 90.0 75.0 125.0 Vanadium 66.4 0.78 - - 100.0 75.0 150.0 Soil Sorption Evaluation Sutton Steam Station UNC Charlotte 12 | P a g e Table 7: Summary of batch and column Kd (mL/g) for ABMW – 1D (38 – 48 ft.) Batch Metals Trial – A R2 Trial – B R2 Arsenic Non-linear isotherm Boron 1.7 0.74 - - Barium - - 42.1 0.54 Cobalt 512.7 0.99 543.7 0.99 Selenium 2.3 0.57 2.0 0.62 Vanadium Non-linear isotherm Table 8: Summary of batch and column Kd (mL/g) for ABMW – 1D (83 - 88 ft.) Batch Column Metals Trial – A R2 Trial – B R2 Arsenic 63.8 0.80 59.2 0.68 50.0 Boron Non-linear isotherm 10.0 Barium Non-linear isotherm 450.0 Cobalt 736.6 0.68 740.0 0.44 550.0 Manganese 0.006 0.96 0.005 0.99 NA Selenium 10.8 0.56 - - 30.0 Vanadium 58.8 0.55 66.7 0.78 150.0 Table 9: Summary of batch and column Kd (mL/g) for ABMW – 2D (0 - 8 ft.) Batch Column Metals Trial – A R2 Trial – B R2 Arsenic 30.5 0.86 31.1 0.89 35.0 Boron Non-linear isotherm 20.0 Barium Non-linear isotherm 15.0 Cobalt 263.9 0.84 313.7 0.98 250.0 Manganese 0.01 0.71 0.01 0.65 NA Selenium 7.6 0.99 7.6 0.98 24.0 Vanadium 17.4 0.95 17.3 0.97 50.0 Soil Sorption Evaluation Sutton Steam Station UNC Charlotte 13 | P a g e Table 10: Summary of batch and column Kd (mL/g) for ABMW – 2D (10 – 12 ft.) Batch Column Metals Trial – A R2 Trial – B R2 Arsenic 8.7 0.87 - - 70.0 Boron Non-linear isotherm NA Barium - - 8.0 0.84 160.0 Cobalt 11.0 0.75 10.7 0.50 225.0 Iron 0.06 0.80 0.06 0.95 NA Manganese 0.03 0.90 0.03 0.90 NA Selenium Non-linear isotherm 75.0 Vanadium 1.9 0.51 2.2 0.53 120.0 Table 11: Summary of batch and column Kd (mL/g) for ABMW – 2D (53 – 60 ft.) Batch Column Metals Trial – A R2 Trial – B R2 Arsenic 35.3 0.63 31.5 0.53 35.0 Boron Non-linear isotherm 30.0 Barium Non-linear isotherm 580.0 Cobalt 406.0 0.72 436.0 0.61 800.0 Manganese 0.01 0.90 0.01 0.95 NA Selenium 8.9 0.81 7.8 0.54 45.0 Vanadium 45.9 0.77 40.1 0.68 130.0 Table 12: Summary of batch and column Kd (mL/g) for MW – 23E (145 – 147 ft.) Batch Column Metals Trial – A R2 Trial – B R2 Arsenic 32.4 0.69 31.9 0.66 50.0 Boron Non-linear isotherm NA Barium Non-linear isotherm 500.0 Cobalt Non-linear isotherm 690.0 Manganese 0.16 0.95 0.16 0.94 NA Selenium 13.3 0.72 13.1 0.73 70.0 Vanadium 49.5 0.81 49.0 0.80 150.0 Soil Sorption Evaluation Sutton Steam Station UNC Charlotte 14 | P a g e Table 13: Kd Qualifiers for batch and column plots Batch Kd Qualifiers Sl. No. Description Qualifier Identification Number 1 The concentration distribution is sufficient for the selected L/S ratio and given COC under consideration. Q – B – 1 2 The range of final COC concentration is narrow, such that normal variation due to the analytical method resulted in a non-linear isotherm. Q – B – 2 3 The range of final COC concentration is narrow and low, such that normal variation due to the analytical method resulted in a non-linear isotherm. Q – B – 3 4 Leachable COC is present in the soil sample prior to testing. This resulted in higher concentration of COC in the final COC concentration at the end of batch experiment. The mass balance approach for estimating sorption can only be done if leachable COC is known. Q – B – 4 5 Anomalous variability in the experimental results resulted in a non-linear isotherm. Q – B – 5 6 Initial COC concentration in the synthetic ground water is not sufficient to produce a well-defined linear isotherm. Q – B – 6 Column Kd Qualifiers Sl. No. Description Qualifier Identification Number 1 The breakthrough curve is sufficient for applying the Ogata- Banks model equation. Q – C – 1 2 The COC reached breakthrough although the concentration was less than the feedstock. Other chemical interactions between soil and synthetic ground water occurring after the initial breakthrough caused a transient decrease in effluent concentration with increased pore volumes (very commonly observed with arsenic in most soil samples from various sites). Q – C – 2 3 Effluent and influent concentrations are essentially the same over the period of data collection, indicating minimal COC sorption onto the soil (observed frequently with boron and molybdenum). Q – C – 3 4 Breakthrough was not observed. A conservation estimate of sorption was made by assuming breakthrough occurred at the end of the data collection period. Q – C – 4 5 The model equation is fit to the initial segment of the breakthrough curve to yield a conservative estimate of sorption. Q – C – 5 Table 14: Ogata-Banks parameters used in developing column Kd Parameter Units SW – 3C ABMW – 1D ABMW – 2D MW – 23E 10 – 12 ft. 41 – 43 ft. 48 – 53 ft. 38 – 48 ft. 83 – 88 ft. 0 – 8 ft. 10 – 12 ft. 53 – 60 ft. 145 – 147 ft. Trial A Trial B Trial C Effective porosity (n) 0.71 0.81 0.80 0.81 0.78 0.61 0.80 0.76 0.79 0.79 0.59 Bulk density (ρb) g/cm3 1.34 Column diameter cm 1.50 Column area cm2 1.77 Column length cm 17.0 Diffusivity (Do) cm2/s 9.00E-06 b 0.05 a 0.66 w = a*(n – b) 0.43 0.50 0.50 0.50 0.48 0.37 0.50 0.50 0.49 0.49 0.35 Effective molecular diffusion coefficient (D*) cm2/s 3.91E-06 4.51E-06 4.47E-06 4.52E-06 4.36E-06 3.31E-06 4.46E-06 4.23E-06 4.37E-06 4.39E-06 3.19E-06 Dispersivity factor 0.02 – 0.2 Dispersivity cm 0.03 – 3.40 Average flow rate (Q) cm3/day 102.00 173.00 136.50 181.00 190.62 204.00 120.00 96.00 195.00 104.00 98.00 Bulk volume cm3 30.04 Pore volume cm3 21.30 24.29 24.09 24.36 23.53 18.23 24.04 22.88 23.59 23.69 17.63 Hydraulic detention Day 0.29 0.17 0.22 0.17 0.27 0.15 0.25 0.31 0.15 0.29 0.31 Linear velocity cm/day 81.45 120.81 96.31 126.62 79.21 190.24 84.98 71.50 140.43 74.60 94.68 Table 15: HFO, HMO and HAO Samples tested for Kd Sample Name Depth HFO HAO HMO ft. mg/Kg mg/Kg mg/Kg SW – 3C 10 – 12 352.8 971.75 < 2.0 SW – 3C 41 – 43 724.0 693.3 < 2.0 SW – 3C 48 – 53 1338.9 748.8 7.8 ABMW – 1D 38 – 48 2281.9 4760.0 6.4 ABMW – 1D 83 – 88 3375.4 426.1 46.4 ABMW – 2D 0 – 8 1818.5 2368.2 9.0 ABMW – 2D 10 – 12 1091.5 4209.9 < 2.0 ABMW – 2D 53 – 60 2070.5 425.5 10.0 MW – 23E 145 – 147 1550.4 528.7 52.0 Samples not tested for Kd Sample Name Depth HFO HAO HMO ft. mg/Kg mg/Kg mg/Kg AW – 5E 45 - 47 2324.7 478.4 3.2 AW – 5E 148 - 150 1357.9 478.5 39.8 AW – 5E 55 – 57 1878.3 536.2 11.0 AW – 6E 148 - 150 1322.6 411.1 430.0 AW – 2D 45 – 47 223.8 4850.3 < 2.0 AW – 2D 62 – 64 422.4 32.6 25.7 AW – 9D 55 – 57 1685.7 1550.4 25.6 AW – 9D 47 - 50 2062.6 831.5 < 2.0 AW – 9D 10 - 12 41.8 554.4 < 2.0 SMW – 1C 45 – 48 999.5 296.0 26.2 SW – 2C 43 – 45 841.8 381.5 176.2 SMW – 6D 44 – 48 915.1 240.1 22.4 SMW – 1C 12 – 15 93.6 1198.1 11.6 SMW – 6D 102 - 103 487.0 275.1 23.8 SMW – 1C 40 – 44 2248.1 542.1 24.0 SMW – 6D 40 - 43 2035.0 467.0 29.8 MW – 23E 60 - 62 407.3 37.3 47.0 MW – 23E 8 – 10 117.0 2.1 3.0 MW – 23E 43 – 45 1630.0 < 1 23.7 Table 16: Method 1313 leaching - pH, ORP and conductivity (at natural pH) Sample Name Depth Collected Trial ORP Conductivity pH ft. mv µS/cm AB - 1 38 - 48 A 239.50 65.40 8.07 B 239.60 68.50 8.12 Table 17: Method 1313 leaching (at natural pH) data for ash samples collected at the site Sample Name Depth Collected Trial As B Be Cd Cr Co Cu Fe Mn Mo Ni Pb Se Tl V Zn ft. ppb ppb ppb ppb ppb ppb ppb ppb ppb ppb ppb ppb ppb ppb ppb ppb AB - 1 38 - 48 A 253.5 190.2 < 1 < 1 4.1 < 1 1.3 111.0 5.4 24.6 1.7 < 1 25.5 < 1 376.5 2.0 B 256.1 195.7 < 1 < 1 4.2 < 1 1.7 65.4 5.2 25.0 1.5 < 1 25.9 < 1 376.8 2.3 Appendix – B Figure 1: Tumbler for 1313, 1316 and batch Kd Figure 2: Batch filtration set-up Soil Sorption Evaluation Sutton Steam Station UNC Charlotte 19 | P a g e Figure 3: Column set-up Soil Sorption Evaluation Sutton Steam Station UNC Charlotte 20 | P a g e Figure 4: Syringe filtration for extraction of HFO/HMO/HAO Soil Sorption Evaluation Sutton Steam Station UNC Charlotte 21 | P a g e Kd plots Figure 5: Arsenic batch Kd - ABMW – 2D (0 – 8 ft.) Figure 6: Arsenic column Kd - ABMW – 2D (0 – 8 ft.) Q-B-1 Q-C-1 Soil Sorption Evaluation Sutton Steam Station UNC Charlotte 22 | P a g e Figure 7: Barium column Kd - ABMW - 2D (0 - 8 ft.) Q-C-1 Soil Sorption Evaluation Sutton Steam Station UNC Charlotte 23 | P a g e Figure 8: Boron column Kd - ABMW - 2D (0 - 8 ft.) Q-C-1 Soil Sorption Evaluation Sutton Steam Station UNC Charlotte 24 | P a g e Figure 9: Cobalt batch Kd - ABMW – 2D (0 – 8 ft.) Figure 10: Cobalt column Kd - ABMW – 2D (0 – 8 ft.) Q-B-2 Q-C-1 Soil Sorption Evaluation Sutton Steam Station UNC Charlotte 25 | P a g e Figure 11: Manganese batch Kd - ABMW – 2D (0 – 8 ft.) Q-B-2 Soil Sorption Evaluation Sutton Steam Station UNC Charlotte 26 | P a g e Figure 12: Selenium batch Kd - ABMW – 2D (0 – 8 ft.) Figure 13: Selenium column Kd - ABMW – 2D (0 – 8 ft.) Q-B-1 Q-C-1 Soil Sorption Evaluation Sutton Steam Station UNC Charlotte 27 | P a g e Figure 14: Vanadium batch Kd - ABMW – 2D (0 – 8 ft.) Figure 15: Vanadium column Kd - ABMW – 2D (0 – 8 ft.) Q-B-1 Q-C-1 Soil Sorption Evaluation Sutton Steam Station UNC Charlotte 28 | P a g e Figure 16: Arsenic batch Kd - ABMW – 2D (10 – 12 ft.) Figure 17: Arsenic column Kd - ABMW – 2D (10 – 12 ft.) Q-B-1 Q-C-1 Soil Sorption Evaluation Sutton Steam Station UNC Charlotte 29 | P a g e Figure 18: Barium batch Kd - ABMW – 2D (10 – 12 ft.) Figure 19: Barium column Kd - ABMW – 2D (10 – 12 ft.) Q-B-1 Q-C-1 Soil Sorption Evaluation Sutton Steam Station UNC Charlotte 30 | P a g e Figure 20: Boron column Kd - ABMW - 2D (10 - 12 ft.) Q-C-3 Soil Sorption Evaluation Sutton Steam Station UNC Charlotte 31 | P a g e Figure 21: Cobalt batch Kd - ABMW – 2D (10 – 12 ft.) Figure 22: Cobalt column Kd - ABMW – 2D (10 – 12 ft.) Q-B-1 Q-C-1 Soil Sorption Evaluation Sutton Steam Station UNC Charlotte 32 | P a g e Figure 23: Iron batch Kd - ABMW – 2D (10 – 12 ft.) Q-B-1 Soil Sorption Evaluation Sutton Steam Station UNC Charlotte 33 | P a g e Figure 24: Manganese batch Kd - ABMW – 2D (10 – 12 ft.) Q-B-2 Soil Sorption Evaluation Sutton Steam Station UNC Charlotte 34 | P a g e Figure 25: Selenium column Kd - ABMW – 2D (10 – 12 ft.) Q-C-1 Soil Sorption Evaluation Sutton Steam Station UNC Charlotte 35 | P a g e Figure 26: Vanadium batch Kd - ABMW – 2D (10 – 12 ft.) Figure 27: Vanadium column Kd - ABMW – 2D (10 – 12 ft.) Q-B-1 Q-C-1 Soil Sorption Evaluation Sutton Steam Station UNC Charlotte 36 | P a g e Figure 28: Arsenic batch Kd - ABMW – 2D (53 – 60 ft.) Figure 29: Arsenic column Kd - ABMW – 2D (53 – 60 ft.) Q-B-1 Q-C-1 Soil Sorption Evaluation Sutton Steam Station UNC Charlotte 37 | P a g e Figure 30: Barium column Kd - ABMW - 2D (53 - 60 ft.) Q-C-4 Soil Sorption Evaluation Sutton Steam Station UNC Charlotte 38 | P a g e Figure 31: Boron column Kd - ABMW - 2D (53 - 60 ft.) Q-C-4 Soil Sorption Evaluation Sutton Steam Station UNC Charlotte 39 | P a g e Figure 32: Cobalt batch Kd - ABMW – 2D (53 – 60 ft.) Q-B-3 Soil Sorption Evaluation Sutton Steam Station UNC Charlotte 40 | P a g e Figure 33: Manganese batch Kd - ABMW – 2D (53 – 60 ft.) Q-B-1 Soil Sorption Evaluation Sutton Steam Station UNC Charlotte 41 | P a g e Figure 34: Selenium batch Kd - ABMW – 2D (53 – 60 ft.) Figure 35: Selenium column Kd - ABMW – 2D (53 – 60 ft.) Q-B-1 Q-C-1 Soil Sorption Evaluation Sutton Steam Station UNC Charlotte 42 | P a g e Figure 36: Vanadium batch Kd - ABMW – 2D (53 – 60 ft.) Figure 37: Vanadium column Kd - ABMW – 2D (53 – 60 ft.) Q-B-1 Q-C-1 Soil Sorption Evaluation Sutton Steam Station UNC Charlotte 43 | P a g e Figure 38: Arsenic batch Kd – SW – 3C (10 – 12 ft.) Figure 39: Arsenic column Kd – SW – 3C (10 – 12 ft.) Q-B-2 Q-C-2 Soil Sorption Evaluation Sutton Steam Station UNC Charlotte 44 | P a g e Figure 40: Barium batch Kd - SW – 3C (10 – 12 ft.) Figure 41: Barium column Kd - SW – 3C (10 – 12 ft.) Q-B-1 Q-C-1 Soil Sorption Evaluation Sutton Steam Station UNC Charlotte 45 | P a g e Figure 42: Boron column Kd - SC - 3C (10 - 12 ft.) Q-C-1 Soil Sorption Evaluation Sutton Steam Station UNC Charlotte 46 | P a g e Figure 43: Cobalt batch Kd - SW – 3C (10 – 12 ft.) Figure 44: Cobalt column Kd - SW – 3C (10 – 12 ft.) Q-B-1 Q-C-1 Soil Sorption Evaluation Sutton Steam Station UNC Charlotte 47 | P a g e Figure 45: Manganese batch Kd - SW – 3C (10 – 12 ft.) Q-B-2 Soil Sorption Evaluation Sutton Steam Station UNC Charlotte 48 | P a g e Figure 46: Selenium batch Kd - SW – 3C (10 – 12 ft.) Figure 47: Selenium column Kd - SW – 3C (10 – 12 ft.) Q-B-1 Q-C-1 Soil Sorption Evaluation Sutton Steam Station UNC Charlotte 49 | P a g e Figure 48: Vanadium batch Kd - SW – 3C (10 – 12 ft.) Figure 49: Vanadium column Kd - SW – 3C (10 – 12 ft.) Q-B-1 Q-C-1 Soil Sorption Evaluation Sutton Steam Station UNC Charlotte 50 | P a g e Figure 50: Arsenic batch Kd - SW – 3C (41 – 43 ft.) Figure 51: Arsenic column Kd - SW – 3C (41 – 43 ft.)Trial A Figure 52: Arsenic column Kd - SW – 3C (41 – 43 ft.)Trial B Figure 53: Arsenic column Kd - SW – 3C (41 – 43 ft.)Trial C Q-B-3 Trial A Q-C-1 Trial B Q-C-1 Trial C Q-C-1 Soil Sorption Evaluation Sutton Steam Station UNC Charlotte 51 | P a g e Figure 54: Barium batch Kd - SW – 3C (41 – 43 ft.) Figure 55: Barium column Kd - SW – 3C (41 – 43 ft.)Trial A Figure 56: Barium column Kd - SW – 3C (41 – 43 ft.)Trial B Figure 57: Barium column Kd - SW – 3C (41 – 43 ft.)Trial C Q-B-2 Trial A Q-C-1 Trial B Q-C-1 Trial C Q-C-1 Soil Sorption Evaluation Sutton Steam Station UNC Charlotte 52 | P a g e Figure 58: Boron column Kd - SW – 3C (41 – 43 ft.)Trial A Figure 59: Boron column Kd - SW – 3C (41 – 43 ft.)Trial B Figure 60: Boron column Kd - SW – 3C (41 – 43 ft.)Trial C Trial A Q-C-3 Trial B Q-C-1 Trial C Q-C-1 Soil Sorption Evaluation Sutton Steam Station UNC Charlotte 53 | P a g e Figure 61: Cobalt column Kd - SW – 3C (41 – 43 ft.) Trial A Figure 62: Cobalt column Kd - SW – 3C (41 – 43 ft.) Trial B Figure 63: Cobalt column Kd - SW – 3C (41 – 43 ft.) Trial C Trial A Q-C-1 Trial B Q-C-1 Trial C Q-C-1 Soil Sorption Evaluation Sutton Steam Station UNC Charlotte 54 | P a g e Figure 64: Manganese batch Kd - SW – 3C (41 – 43 ft.) Q-B-1 Soil Sorption Evaluation Sutton Steam Station UNC Charlotte 55 | P a g e Figure 65: Selenium batch Kd - SW – 3C (41 – 43 ft.) Figure 66: Selenium column Kd - SW – 3C (41 – 43 ft.) Trial A Figure 67: Selenium column Kd - SW – 3C (41 – 43 ft.) Trial B Figure 68: Selenium column Kd - SW – 3C (41 – 43 ft.) Trial C Q-B-3 Trial A Q-C-1 Trial B Q-C-1 Trial C Q-C-1 Soil Sorption Evaluation Sutton Steam Station UNC Charlotte 56 | P a g e Figure 69: Vanadium batch Kd - SW – 3C (41 – 43 ft.) Figure 70: Vanadium column Kd - SW – 3C (41 – 43 ft.) Trial A Figure 71: Vanadium column Kd - SW – 3C (41 – 43 ft.) Trial B Figure 72: Vanadium column Kd - SW – 3C (41 – 43 ft.) Trial C Q-B-3 Trial A Q-C-1 Trial B Q-C-1 Trial C Q-C-1 Soil Sorption Evaluation Sutton Steam Station UNC Charlotte 57 | P a g e Figure 73: Arsenic batch Kd - SW – 3C (48 – 53 ft.) Figure 74: Arsenic column Kd - SW – 3C (48 – 53 ft.) Q-B-3 Q-C-5 Soil Sorption Evaluation Sutton Steam Station UNC Charlotte 58 | P a g e Figure 75: Barium batch Kd - SW – 3C (48 – 53 ft.) Figure 76: Barium column Kd - SW – 3C (48 – 53 ft.) Q-B-2 Q-C-1 Soil Sorption Evaluation Sutton Steam Station UNC Charlotte 59 | P a g e Figure 77: Boron column Kd - SC - 3C (48 - 53 ft.) Q-C-1 Soil Sorption Evaluation Sutton Steam Station UNC Charlotte 60 | P a g e Figure 78: Cobalt column Kd - SC - 3C (48 - 53 ft.) Q-C-1 Soil Sorption Evaluation Sutton Steam Station UNC Charlotte 61 | P a g e Figure 79: Iron batch Kd - SW – 3C (48 – 53 ft.) Q-B-1 Soil Sorption Evaluation Sutton Steam Station UNC Charlotte 62 | P a g e Figure 80: Manganese batch Kd - SW – 3C (48 – 53 ft.) Q-B-1 Soil Sorption Evaluation Sutton Steam Station UNC Charlotte 63 | P a g e Figure 81: Selenium batch Kd - SW – 3C (48 – 53 ft.) Figure 82: Selenium column Kd - SW – 3C (48 – 53 ft.) Q-B-2 Q-C-1 Soil Sorption Evaluation Sutton Steam Station UNC Charlotte 64 | P a g e Figure 83: Vanadium batch Kd - SW – 3C (48 – 53 ft.) Figure 84: Vanadium column Kd - SW – 3C (48 – 53 ft.) Q-B-3 Q-C-4 Soil Sorption Evaluation Sutton Steam Station UNC Charlotte 65 | P a g e Figure 85: Arsenic batch Kd – MW – 23E (145 – 147 ft.) Figure 86: Arsenic column Kd – MW – 23E (145 – 147 ft.) Q-B-1 Q-C-5 Soil Sorption Evaluation Sutton Steam Station UNC Charlotte 66 | P a g e Figure 87: Barium column Kd – MW – 23E (145 – 147 ft.) Q-C-4 Soil Sorption Evaluation Sutton Steam Station UNC Charlotte 67 | P a g e Figure 88: Boron column Kd – MW – 23E (145 – 147 ft.) Q-C-3 Soil Sorption Evaluation Sutton Steam Station UNC Charlotte 68 | P a g e Figure 89: Cobalt column Kd – MW – 23E (145 – 147 ft.) Q-C-4 Soil Sorption Evaluation Sutton Steam Station UNC Charlotte 69 | P a g e Figure 90: Manganese batch Kd – MW – 23E (145 – 147 ft.) Q-B-2 Soil Sorption Evaluation Sutton Steam Station UNC Charlotte 70 | P a g e Figure 91: Selenium batch Kd - MW – 23E (145 – 147 ft.) Figure 92: Selenium column Kd - MW – 23E (145 – 147 ft.) Q-B-1 Q-C-1 Soil Sorption Evaluation Sutton Steam Station UNC Charlotte 71 | P a g e Figure 93: Vanadium batch Kd - MW – 23E (145 – 147 ft.) Figure 94: Vanadium column Kd - MW – 23E (145 – 147 ft.) Q-B-1 Q-C-5 Soil Sorption Evaluation Sutton Steam Station UNC Charlotte 72 | P a g e Figure 95: Barium batch Kd - ABMW - 1D (38 - 48 ft.) Q-B-2 Figure 96: Boron batch Kd - ABMW – 1D (38 – 48 ft.) Q-B-2 Soil Sorption Evaluation Sutton Steam Station UNC Charlotte 73 | P a g e Figure 97: Cobalt batch Kd - ABMW – 1D (38 – 48 ft.) Q-B-3 Figure 98: Selenium batch Kd - ABMW – 1D (38 – 48 ft.) Q-B-2 Soil Sorption Evaluation Sutton Steam Station UNC Charlotte 74 | P a g e Figure 99: Arsenic batch Kd - ABMW – 1D (83 – 88 ft.) Figure 100: Arsenic column Kd - ABMW – 1D (83 – 88 ft.) Q-B-2 Q-C-5 Soil Sorption Evaluation Sutton Steam Station UNC Charlotte 75 | P a g e Figure 101: Barium column Kd – ABMW - 1D (83 - 88 ft.) Q-C-1 Soil Sorption Evaluation Sutton Steam Station UNC Charlotte 76 | P a g e Figure 102: Boron column Kd – ABMW- 1D (83 - 88 ft.) Q-C-1 Soil Sorption Evaluation Sutton Steam Station UNC Charlotte 77 | P a g e Figure 103: Cobalt batch Kd - ABMW – 1D (83 – 88 ft.) Figure 104: Cobalt column Kd - ABMW – 1D (83 - 88 ft.) Q-B-3 Q-C-5 Soil Sorption Evaluation Sutton Steam Station UNC Charlotte 78 | P a g e Figure 105: Manganese batch Kd - ABMW – 1D (83 – 88 ft.) Q-B-1 Soil Sorption Evaluation Sutton Steam Station UNC Charlotte 79 | P a g e Figure 106: Selenium batch Kd - ABMW – 1D (83 – 88 ft.) Figure 107: Selenium column Kd - ABMW – 1D (83 – 88 ft.) Q-B-1 Q-C-1 Soil Sorption Evaluation Sutton Steam Station UNC Charlotte 80 | P a g e Figure 108: Vanadium batch Kd - ABMW – 1D (83 – 88 ft.) Figure 109: Vanadium column Kd - ABMW – 1D (83 – 88 ft.) Q-B-2 Q-C-1 Soil Sorption Evaluation Sutton Steam Station UNC Charlotte 81 | P a g e Figure 110: pH vs L/S for ABMW – 01 D (38-48 ft.) Figure 111: ORP vs L/S for ABMW – 01 D (38-48 ft.) 8.30 8.35 8.40 8.45 8.50 8.55 8.60 0 20 40 60 80 100 120 pH L/S (mL/g) pH vs L/S Trial A Trial B 160 170 180 190 200 210 220 230 240 250 260 0 20 40 60 80 100 120 OR P ( m V ) L/S (mL/g) ORP vs L/S Trial A Trial B Soil Sorption Evaluation Sutton Steam Station UNC Charlotte 82 | P a g e Figure 112: Conductivity vs L/S for ABMW – 01 D (38-48 ft.) Figure 113: pH vs L/S for ABMW – 01 D (83-88 ft.) 150 170 190 210 230 250 270 290 0 20 40 60 80 100 120 Co n d u c t i v i t y ( µ S / c m ) L/S (mL/g) Conductivity vs L/S Trial A Trial B 7.80 7.90 8.00 8.10 8.20 8.30 8.40 8.50 8.60 8.70 8.80 8.90 0 20 40 60 80 100 120 pH L/S (mL/g) pH vs L/S Trial A Trial B Soil Sorption Evaluation Sutton Steam Station UNC Charlotte 83 | P a g e Figure 114: ORP vs L/S for ABMW – 01 D (83-88 ft.) Figure 115: Conductivity vs L/S for ABMW – 01 D (83-88 ft.) 210 215 220 225 230 235 240 245 0 20 40 60 80 100 120 OR P ( m V ) L/S (mL/g) ORP vs L/S Trial A Trial B 0 100 200 300 400 500 600 700 0 20 40 60 80 100 120 Co n d u c t i v i t y ( µ S / c m ) L/S (mL/g) Conductivity vs L/S Trial A Trial B Soil Sorption Evaluation Sutton Steam Station UNC Charlotte 84 | P a g e Figure 116: pH vs L/S for ABMW – 02 D (0-8 ft.) Figure 117: ORP vs L/S for ABMW – 02 D (0-8 ft.) 7.25 7.30 7.35 7.40 7.45 7.50 7.55 7.60 0 20 40 60 80 100 120 pH L/S (mL/g) pH vs L/S Trial A Trial B 265 270 275 280 285 290 295 300 305 310 315 0 20 40 60 80 100 120 OR P ( m V ) L/S (mL/g) ORP vs L/S Trial A Trial B Soil Sorption Evaluation Sutton Steam Station UNC Charlotte 85 | P a g e Figure 118: Conductivity vs L/S for ABMW – 02 D (0-8 ft.) Figure 119: pH vs L/S for ABMW – 02 D (10-12 ft.) 150 160 170 180 190 200 210 220 230 240 250 0 20 40 60 80 100 120 Co n d u c t i v i t y ( µ S / c m ) L/S (mL/g) Conductivity vs L/S Trial A Trial B 6.95 7.00 7.05 7.10 7.15 7.20 7.25 7.30 0 20 40 60 80 100 120 pH L/S (mL/g) pH vs L/S Trial A Trial B Soil Sorption Evaluation Sutton Steam Station UNC Charlotte 86 | P a g e Figure 120: ORP vs L/S for ABMW – 02 D (10-12 ft.) Figure 121: Conductivity vs L/S for ABMW – 02 D (10-12 ft.) 295 300 305 310 315 320 325 330 335 340 0 20 40 60 80 100 120 OR P ( m V ) L/S (mL/g) ORP vs L/S Trial A Trial B 136 138 140 142 144 146 148 150 152 154 156 0 20 40 60 80 100 120 Co n d u c t i v i t y ( µ S / c m ) L/S (mL/g) Conductivity vs L/S Trial A Trial B Soil Sorption Evaluation Sutton Steam Station UNC Charlotte 87 | P a g e Figure 122: pH vs L/S for ABMW – 02 D (53-60 ft.) Figure 123: ORP vs L/S for ABMW – 02 D (53-60 ft.) 7.90 8.00 8.10 8.20 8.30 8.40 8.50 8.60 8.70 0 20 40 60 80 100 120 pH L/S (mL/g) pH vs L/S Trial A Trial B 215 220 225 230 235 240 245 250 0 20 40 60 80 100 120 OR P ( m V ) L/S (mL/g) ORP vs L/S Trial A Trial B Soil Sorption Evaluation Sutton Steam Station UNC Charlotte 88 | P a g e Figure 124: Conductivity vs L/S for ABMW – 02 D (53-60 ft.) Figure 125: pH vs L/S for SW – 3 C (10-12 ft.) 0 100 200 300 400 500 600 700 800 0 20 40 60 80 100 120 Co n d u c t i v i t y ( µ S / c m ) L/S (mL/g) Conductivity vs L/S Trial A Trial B 6.50 6.55 6.60 6.65 6.70 6.75 6.80 0 20 40 60 80 100 120 pH L/S (mL/g) pH vs L/S Trial A Trial B Soil Sorption Evaluation Sutton Steam Station UNC Charlotte 89 | P a g e Figure 126: ORP vs L/S for SW – 3 C (10-12 ft.) Figure 127: Conductivity vs L/S for SW – 3 C (10-12 ft.) 308 310 312 314 316 318 320 322 324 326 0 20 40 60 80 100 120 OR P ( m V ) L/S (mL/g) ORP vs L/S Trial A Trial B 136 138 140 142 144 146 148 150 152 154 156 158 0 20 40 60 80 100 120 Co n d u c t i v i t y ( µ S / c m ) L/S (mL/g) Conductivity vs L/S Trial A Trial B Soil Sorption Evaluation Sutton Steam Station UNC Charlotte 90 | P a g e Figure 128: pH vs L/S for SW – 3 C (41-43 ft.) Figure 129: ORP vs L/S for SW – 3 C (41-43 ft.) 4.00 4.50 5.00 5.50 6.00 6.50 7.00 0 20 40 60 80 100 120 pH L/S (mL/g) pH vs L/S Trial A Trial B 360 370 380 390 400 410 420 430 0 20 40 60 80 100 120 OR P ( m V ) L/S (mL/g) ORP vs L/S Trial A Trial B Soil Sorption Evaluation Sutton Steam Station UNC Charlotte 91 | P a g e Figure 130: Conductivity vs L/S for SW – 3 C (41-43 ft.) Figure 131: pH vs L/S for SW – 3 C (48-53 ft.) 0 50 100 150 200 250 0 20 40 60 80 100 120 Co n d u c t i v i t y ( µ S / c m ) L/S (mL/g) Conductivity vs L/S Trial A Trial B 4.00 4.10 4.20 4.30 4.40 4.50 4.60 4.70 4.80 4.90 0 20 40 60 80 100 120 pH L/S (mL/g) pH vs L/S Trial A Trial B Soil Sorption Evaluation Sutton Steam Station UNC Charlotte 92 | P a g e Figure 132: ORP vs L/S for SW – 3 C (48-53 ft.) Figure 133: Conductivity vs L/S for SW – 3 C (48-53 ft.) 335 340 345 350 355 360 365 0 20 40 60 80 100 120 OR P ( m V ) L/S (mL/g) ORP vs L/S Trial A Trial B 0 100 200 300 400 500 600 0 20 40 60 80 100 120 Co n d u c t i v i t y ( µ S / c m ) L/S (mL/g) Conductivity vs L/S Trial A Trial B Soil Sorption Evaluation Sutton Steam Station UNC Charlotte 93 | P a g e Figure 134: pH vs L/S for MW – 23 E Figure 135: ORP vs L/S for MW – 23 E 7.90 8.00 8.10 8.20 8.30 8.40 8.50 8.60 8.70 8.80 8.90 0 20 40 60 80 100 120 pH L/S (mL/g) pH vs L/S Trial A Trial B 200 202 204 206 208 210 212 214 216 0 20 40 60 80 100 120 OR P ( m V ) L/S (mL/g) ORP vs L/S Trial A Trial B Soil Sorption Evaluation Sutton Steam Station UNC Charlotte 94 | P a g e Figure 136: Conductivity vs L/S for MW – 23 E Figure 137: Molybdenum 1316 AB – 1 (38 – 48FT) 0 200 400 600 800 1000 1200 1400 1600 1800 2000 0 20 40 60 80 100 120 Co n d u c t i v i t y ( µ S / c m ) L/S (mL/g) Conductivity vs L/S Trial A Trial B Soil Sorption Evaluation Sutton Steam Station UNC Charlotte 95 | P a g e Figure 138: Selenium 1316 AB – 1 (38 – 48FT) Figure 139: Boron 1316 AB – 2 (0 – 8FT) Soil Sorption Evaluation Sutton Steam Station UNC Charlotte 96 | P a g e Figure 140: Manganese 1316 AB – 2 (0 – 8FT) Figure 141: Molybdenum 1316 AB – 2 (0 – 8FT) Soil Sorption Evaluation Sutton Steam Station UNC Charlotte 97 | P a g e Figure 142: pH at varying L/S ratio for 1316 testing of AB – 1 (38 – 48FT) Figure 143: ORP at varying L/S ratio for 1316 testing of AB – 1 (38 – 48FT) Soil Sorption Evaluation Sutton Steam Station UNC Charlotte 98 | P a g e Figure 144: Conductivity at varying L/S ratio for 1316 testing of AB – 1 (38 – 48FT) Figure 145: pH at varying L/S ratio for 1316 testing of AB – 2 (0 – 8FT) Soil Sorption Evaluation Sutton Steam Station UNC Charlotte 99 | P a g e Figure 146: ORP at varying L/S ratio for 1316 testing of AB – 2 (0 – 8FT) Figure 147: Conductivity at varying L/S ratio for 1316 testing of AB – 2 (0 – 8FT) Corrective Action Plan Part 1 November 2015 L.V. Sutton Energy Complex SynTerra P:\Duke Energy Progress.1026\108. Sutton Ash Basin GW Assessment Plan\16.Corrective Action Plan\FINAL CAP REPORT\Final LV Sutton CAP Report 11-02-2015.docx APPENDIX D GEOCHEMICAL MODELING REPORT Analysis of geochemical phenomena controlling mobility of ions from coal ash basins at the Duke Energy L. V. Sutton Energy Complex Brian A. Powell, Ph.D. 112 Cherry Street Pendleton, SC 29670 (864) 760-7685 bpowell@clemson.edu Executive Summary The goal of this geochemical modeling effort is to describe the partitioning of several constituents of interest between the aqueous and solid phases (i.e. pore waters and surrounding aquifer solids) in the subsurface by considering sorption of the constituent to the aquifer solids and precipitation/coprecipitation in mineral phases. The two geochemical conditions which have the most influence on the extent of partitioning are the pH and oxidation/reduction potential (EH) of the pore water. Therefore, a major effort was undertaken to describe the chemical speciation expected under the variable conditions at the Sutton Site (particularly with respect to changes in pH and oxidation/reduction potential (EH) and relate the expected speciation to observed behavior of each constituent. The partitioning and solubility of constituents is highly depended on the pH of the pore water. This is because the majority of constituents of interest exists as anionic or cationic species. Sorption of charged species to mineral surfaces changes with pH because the surface charge of all mineral surfaces transitions from a positively charged surface at low pH to a negatively charged surface at high pH. Therefore, sorption of anionic species will be stronger at low pH where the anions are attracted to the positively charged surfaces (vice versa regarding the cationic species). Similarly, the solubility of a mineral phase will also be pH dependent because lower pH values tend to favor formation of more soluble cationic species of most alkali elements, alkali earth elements, and transition metals. Conversely, low pH values will facilitate protonation of most oxoanions (such as the conjugate bases AsO4-3, SeO3-2) which can form neutrally charged H3AsO4 and H2SeO3 species at low pH. At higher pH values, these oxoanions deprotonate and persist as anionic species which are generally very soluble and will only weakly sorb to mineral surfaces. Therefore, generally low pH conditions will favor higher aqueous concentrations of cationic constituents (e.g. Ba+2, Cr+3, Co2+, Fe-2/Fe+3) whereas higher aqueous concentrations of anionic species (e.g. AsO4-3, SeO3 -2, H2VO4 -2, H2BO3 -) will be expected in higher pH pore waters. Since the partitioning of these constituents is highly dependent on the pH and the chemical speciation of the constituent, consideration of potential changes in the constituent chemical species due to changes in oxidation state is imperative. For example, Cr(III) generally exists as the cat ion Cr+3 which is relatively insoluble and sorbs strongly to mineral surfaces. However, upon oxidation to Cr(VI), the oxoanion chromate CrO4 -2 becomes the dominant species which is highly soluble and mobile under neutral to high pH conditions. The geochemical model considers changes in oxidation state for all redox active constituents of interest (Se, As, Fe, V, Mn, Cr, Co, S). The geochemical model developed in this work considered changes in chemical speciation (i.e. ionic aqueous species and oxidation states), precipitation of discrete mineral phases, and sorption to mineral surfaces using the United States Geological Service program PHREEQC. To provide a self- consistent set of thermodynamic constants for sorption reactions, all sorption was modeled assuming hyrous ferric oxide was the dominant sorbing surface based on the database developed by Dzomback and Morel [1]. The concentration of iron sorption sites was estimated based on the extractable iron content of the aquifer solids from the Sutton Site. The behavior of several constituents of interest from the model output was compared with observations of dissolved concentrations of each ion in pore waters from the Sutton Site as well as laboratory batch sorption experiments conducted by collaborators at the University of North Carolina Charlotte. The model output verified the geochemical behavior of the constituents of interest described above. Species found to be relatively mobile with low distribution coefficients were borate, barium, and zinc. Low distribution coefficients were predicted for some additional species such as arsenic, iron, manganese, selenium, and vanadium. However, these low values were generally predicted for the “worst case” scenario of pH and EH conditions for each ion. Given more realistic pH and EH conditions from laboratory conditions, the predicted and experimental distribution coefficients were in general agreement. A notable disagreement was a 1000x difference between the modeled and experimental distribution coefficients for boron partitioning. Boron sorption was under predicted by the model. This could be due to the need for updated thermodynamic constants for borate sorption in the model, consideration of boron sorption to alternate phases, or consideration of boron substitution into mineral phases. However, reactive transport models used to predict boron transport at the site assume that boron is highly mobile consistent with the low distribution coefficients developed from the geochemical model. The capacity of the aquifer solids to sequester the constituents of interest was estimated by assuming the aquifer solids contained 0.05 moles of sorption sites per mole of extractable iron. The number of moles of several constituents of interest in the pore fluid was estimated assuming all constituents were present at the NC2L standard levels. Assuming 100% sorption of the summation of the total moles of all constituents, less than 1% of the total available sorption sites was occupied. Therefore it appears the aquifer solids have sufficient sorption capacity for high concentrations of all constituents though the actual sorbed concentrations will vary based on the sorption affinity (i. e. distribution coefficient) of individual constituents. 1. Introduction A geochemical modeling effort was undertaken to describe the chemical speciation expected under the variable conditions at the Sutton Site (particularly with respect to changes in pH and oxidation/reduction potential (EH) and relate the expected speciation to observed behavior of each constituent. The modeling effort consists of 1) analysis of the dominant aqueous species under the EH/pH conditions of the site, 2) discussion of the trends observed in measurements of various analytes in groundwater samples from the site, 3) quantitative surface complexation modeling to predict observed distribution coefficient (Kd) values and relate the sorption behavior to changes in aqueous chemical speciation, and 4) estimation of the sorption capacity of solid phases based on assumed site densities of iron and aluminum hydroxide minerals (represented by hydrous ferric oxide and gibbsite). The modeled Kd values are compared with experimentally derived Kd values measured by collaborators at the University of North Carolina- Charlotte (UNCC). For both the Kd modeling and sorption capacity estimation, extractable Fe and Al concentrations were used to estimate the available sorption sites. The extractable Fe and Al measurements were provided by collaborators at UNCC. Hydrous ferric oxide (HFO) and gibbsite (HAO) minerals were used as the basis for sorption and capacity determination because of the available thermochemical databases for surface complexation modeling of many constituents of interest [1, 2]. 2. Pourbaix Diagrams To gain an understanding of the aqueous chemical species of each constituent of interest, Pourbaix diagrams were generated using Geochemist Workbench v10. To perform these simulations, the WATEQ4F database was utilized because this is the same database used in PHREEQC modeling of the sorption behavior described below. However, for Se and V, were not available in the Geochemist Workbench database. Instead, the LLNL.v8.r6+ database was used to generate the Pourbaix diagrams for Se and V described below. Constants for Se and V were added to the PHREEQC database for the sorption modeling below. However, based on the similarity of the revised WATEQ4F database used in PHREEQC modeling and the LLNL.v8.r6+ database, the speciation exhibited in the Pourbaix diagrams below is representative of the species. In these Pourbaix diagrams, the EH and pH measurements from the Sutton site are shown as individual datapoints. A generic groundwater chemistry containing 500 ppb of each constituent of concern was used in the simulations (Table 2.1). These concentrations are generally higher than the concentrations observed in Sutton groundwater samples. Therefore, if precipitation is not observed in these diagrams for the EH-pH regions of interest, it will not be occurring for lower concentrations which would be less saturated. The dominant aqueous species is shown in the blue regions and dominant precipitated solid phases are shown in yellow regions. Table 2.1: Concentrations of reagents used to generate Pourbaix diagrams Species Concentration (ppm) Concentration (mol/L) CaSO4. 2H2O 20.0 1.47 x 10-4 MgSO4 5.0 4.17 x 10-5 Na(HCO3) 10.0 1.19 x 10-4 Arsenic 0.5 6.67 x 10-6 Barium 0.5 3.64 x 10-6 Boron 0.5 4.62 x 10-5 Cobalt 0.5 8.49 x 10-6 Selenium 0.5 6.33 x 10-6 Vanadium 0.5 9.82 x 10-6 Chromium 0.5 9.66 x 10-6 Nitrate 1.5 2.43 x 10-5 It is important to note in these diagrams that only the most abundant aqueous species is shown in these plots. There are numerous aqueous and mineral species contributing to the reactivity of these systems. These diagrams only serve to show major trends in the speciation. More detailed calculations using PHREEQC below consider all aqueous species involved and changes with respect to EH and pH as done in these Pourbaix diagrams. However, in those models sorption is considered and distribution coefficients are calculated which consider all of the chemical species present under a given set of conditions. Thus, while these Pourbaix diagrams are useful tools to identify the major species, it is important to note several limitations:  The dividing lines between boxes are where species may be equal but there is no information in the diagram regarding the uncertainty of the simulation or the change in speciation as pH and Eh moves away from the boundary lines. So there may be significant concentrations of other species present which cannot be seen on the diagrams.  The speciation is also considered only for the conditions given (listed in Table 2.1). Altering the concentrations of aqueous constituents may influence the data.  The Pourbaix diagrams report the activity of species, not molar concentrations. So corrections must be made to get molar units or mass units that are typical measures of concentration.  These Pourbaix diagrams show only the aqueous species and precipitates with no consideration of sorption. Therefore, when comparing these with pore water measurements at the site, some consideration must be made regarding the potential for a species to be present in the subsurface but sorbed to the solid phase and not present in the pore water. A notable example of the significance of this is discussed below with regard to As speciation. The Pourbaix diagrams predict that As(V) will be the dominant oxidation state in many waters. However pore water speciation measurements indicate that As(III) is the dominant aqueous oxidation state. Since As(V) sorbs strongly to mineral surfaces under the pH of the pore waters, the As(V) may indeed be present in the system but sorbed to the mineral surface and not measured in pore water samples. Arsenic Under mildly oxidizing to strongly oxidizing conditions, arsenic can exist as the arsenate (AsO4 -3) and arsenite (AsO3 -3) oxoanions (Figure 2.1). Both are weak acids and persist in solution as HxAsOy x-2y species [3]. At the Sutton site, the arsenate As(V) ion is the likely dominant species. The relatively low pH of the surficial upper and surficial lower zones maintain monovalent H2AsO4 - while the higher pH Pee Dee upper and lower zones will facilitate formation of HAsO4-. The relatively lower EH of the ash pore water could stabilize the arsenite anion (As(III)) which would be expected to persist as the neutrally charged H3AsO4 or anionic H2AsO3-. Such changes in redox speciation or protonation state can have profound impacts on the mobility of arsenic. Changes in ionic charge will alter the strength of interactions with mineral surfaces. Generally as the pH decreases and mineral surfaces develop increasingly positive net surface charges, sorption of As(III) and As(V) oxoanions will increase [4, 5]. Reduction of As(V) to As(III) will cause greater overall mobility of As because of the lower sorption affinity of As(III) relative to As(V) [6]. Borate As shown in Figure 2.2, boron exhibits relatively simple chemistry existing as either neutrally charged boric acid, noted in the literature as either B(OH)3 or H3BO3, or as a borate anion H2BO3 - which persists above pH 9. Borate exhibits no redox reactions and solely exists as B(III). The relatively simple aqueous speciation of borate is due to lack of affinity to form complexes with other ions. This lack of chemical reactivity also limits borate sorption to mineral surfaces. Thus boron is essentially inert and behaves as a highly mobile ion in the subsurface. Selenium Selenium exists as oxyanionic species under oxidizing conditions as selenite (SeO3 -2) or selenate (SeO4 -2). The dominant form is SeO4 -2, though below pH 2 protonation to form HSeO4 - occurs. Selenite is a weaker acid than selenate and persists as H2SeO3, HSeO3 -, and SeO3 -2 in the pH ranges 0-3, 3-8.5, and >8.5, respectively (Figure 2.3). Similar to arsenic’s behavior, both selenite and selenate sorb to mineral surfaces (primarily iron oxides) [5-7]. However, both are subject to competition from other oxoanions such as phosphate and sulfate. Selenium is readily reduced to zero valent Se0 which is relatively stable under mildly reducing conditions. Under strongly reducing conditions reduction to Se(-II) may occur. Formation of reduced Se species can lead significant sequestration of Se via precipitation of iron selenides (FeSe, FeSe2) or coprecipitation in iron sulfide FeS. Based on the EH-pH measurements shown in Figure 2.3, the dominant selenium species within these systems is expected to be Se(IV) which will primarily exist as HSeO3- and SeO3-2. However, it is noteworthy that these Pourbaix diagrams show only the dominant species. Thus significant fractions of Se(VI) may coexist. Additionally, zero valent Se 0 may also persist in the low EH groundwaters from the Sutton site (Figure 2.3). Figure 2.1: Pourbaix diagram of arsenic species with (top) and without (bottom) precipitation allowed in the simulation. Figure 2.2: Pourbaix diagram of boron species with (top) and without (bottom) precipitation allowed in the simulation. Note there was no precipitation occurring in the simulation so the plots are identical. Figure 2.3: Pourbaix diagram of selenium species with (top) and without (bottom) precipitation allowed in the simulation. Vanadium Vanadium exhibits very complex chemical speciation in aqueous systems because of it’s possibility to exist in multiple oxidation states: V(III), V(IV), and V(V) (Figure 2.4). Under the EH-pH conditions of the Sutton site, pentavalent H2VO4 - and VO3OH-2 appear to be the dominant species in the upper and lower surficial and upper and lower Pee Dee zones, respectively. Reduction of V(V) to V(IV) and precipitation of V2O4 may also be a means of controlling the mobility of vanadium. Similar to selenium and arsenic, sorption of H2VO4- is relatively strong and increases with decreasing pH. However, the lower pH also generally stabilizes lower vanadium oxidation states. Thus, vanadium could become mobile as V(III) and V(IV) at low pH values if oxidizing conditions are not maintained. Cobalt Despite having an accessible Co(III) oxidation state, the dominant oxidation state of cobalt under all conditions is Co(II). The dominant ions at neutral are Co2+ and HCoO2- (Figure 2.5). As a cationic species, Co2+ sorption will increase with increasing pH. This is a manifestation of the attraction of Co2+ to mineral surfaces as the surface transitions from a net positive charge to a net negative charge with increasing pH. Formation of CoS2 (Cattierite), CoSe (Freboldite), and Safflorite (CoAs2) precipitates are favored in Figure 2.5 under reducing conditions. However, it is noteworthy that these simulations were run with significantly higher Co, As, and Se concentrations than what has been measured in groundwaters at the Sutton site. Therefore, sufficiently high concentrations of cobalt, arsenide, and selenide may not persist to form discrete precipitates. Chromium Chromium is dominated by the trivalent and hexavalent oxidation states (Cr(III) and Cr(VI)) (Figure 2.6). The trivalent state exists as a triply charged ion at low pH and undergoes hydrolysis to form neutrally charged Cr(OH)3(aq) and anionic Cr(OH)4- species with increasing pH. These hydrolysis reactions are also potentially coupled with sorption of the cationic species to mineral surfaces with increasing pH and/or formation of discrete precipitates (i.e. Cr2O3) provided the concentration of Cr is sufficiently high. The hexavalent phase exists as the anions HCrO4- and CrO4-2 at environmentally relevant pH values. These are generally soluble states but exhibit moderately strong sorption affinity to metal oxide minerals such as iron oxides [1, 6]. Figure 2.4: Pourbaix diagram of vanadium species with (top) and without (bottom) precipitation allowed in the simulation. Figure 2.5: Pourbaix diagram of cobalt species with (top) and without (bottom) precipitation allowed in the simulation. Figure 2.6: Pourbaix diagram of chromium species with (top) and without (bottom) precipitation allowed in the simulation. 3. Observations from groundwater measurements There are several notable features of the groundwater measurements at the Sutton site which help to edify the mobility of major constituents. These features are discussed below along with the relevant implications. Correlation between dissolved oxygen (DO) concentrations in the water with pH clearly shows that high dissolved oxygen conditions are only maintained for samples below pH 7 (Figure 3.1). This is supported by EH measurements in the same waters. Fitting a trendline to all the available EH vs. pH datapoints in Figure 3.2 gives a slope of 69 mV per unit change in pH. This is close to the Nernstian slope of 59 mV for oxidation or reduction of water. Therefore, it is assumed from these data that oxygen is the dominant redox buffer in these systems. The absence of strongly oxidizing conditions at high pH indicate that when describing the transport of constituents in this system, potentially highly mobile or highly immobile species which persist under high pH/high EH conditions do not necessarily need to be considered. For example, it is unlikely the systems will reach sufficiently high pH and EH conditions to facilitate significant Se(IV) oxidation to Se(VI). As discussed below, stabilization of Se(VI) primarily occurs at higher pH values. Therefore, it is unlikely that the sustained higher EH/low pH conditions would facilitate formation of the higher mobile Se(VI). This can have an impact on Se mobility since Se(VI) is generally more mobile that Se(IV). Additional discussion of such changes in redox speciation and the subsequent influence on sorption is provided below in the context of PHREEQC speciation modeling. Figure 3.1: Correlation between pH and dissolved oxygen (DO) groundwater measurements at the Sutton site. 0 1 2 3 4 5 6 7 8 3 4 5 6 7 8 9 10 11 Di s s o l v e d O x y g e n ( m g / L ) pH Figure 3.2: Correlation between pH and EH groundwater measurements at the Sutton site. The general behavior of many species can be delineated via comparisons of the dissolved concentration in groundwater samples versus pH. Such plots for the Sutton Energy Complex site are shown below for several major ions and constituents of interest (Figures 3.3-3.6). While there is significant scatter in the data which is an inherent function of the heterogeneous nature of the site, general trends in ion behavior become apparent. These trends are speculative based on known behavior of the ions but require further experimental effort to prove. Some noteworthy observations from these data are:  Aluminum and iron concentrations decrease with increasing pH. This is consistent with the pH dependent dissolution of iron and aluminum oxides and aluminosilicate minerals.  Arsenic concentrations appear to remain relatively constant. Sorption of As(III) and As(V) will decrease with increasing pH. Therefore the relatively constant concertation could be indicative of a solubility control. This may be a manifestation of sorption of the anionic species at low pH and precipitation/coprecipitation with metal oxide minerals at high pH (consistent with the decreasing concentrations of aluminum and iron as discussed above.  Boron aqueous concentrations remain relatively constant around 1000 ppb above pH 5. Below pH 5, sorption of the neutrally charged H3BO3 or anionic H2BO3 - complexes likely reduces the aqueous concentration.  Chloride concentrations are highly variable but generally increase with pH. This is consistent with a small degree of chloride sorption to metal oxide surfaces which will have net positive surface charges at lower pH values. -200 -100 0 100 200 300 400 500 600 3 4 5 6 7 8 9 10 11 EH ( m V ) pH Ash Pore Water Surficial Upper Surficial Lower Pee Dee Upper Pee Dee Lower  Few samples contained concentrations of thallium above detection limits. Samples which were above detection limits were generally at low pH indicating sorption of cobalt and thallium may be a dominant control of the aqueous concentrations. Dissolved concentrations of Zn are also very low and close to detection limits.  Concentrations of divalent ions (Ca2+, Sr2+, Zn2+, Ni2+) are highly variable. Generally these ions exhibit a decrease in concentration with decreasing pH. This could indicate sorption to phyllosilicate minerals via ion exchange which should increase as the pH decreases to mildly acidic conditions. Figure 3.3: Correlation between dissolved concentrations of aluminum, arsenic, boron, and chloride in Sutton site groundwaters with changes in pH. Concentration vs pH plots are separated into four plots for clarity in Figures 3.3-3.6. 1.0E+00 1.0E+01 1.0E+02 1.0E+03 1.0E+04 3 4 5 6 7 8 9 10 11 Di s s o l v e d C o n c e n t r a t i o n Al , A s , a n d B u n i t s i n m g/ L Cl u n i t s i n m g / L pH Aluminum Arsenic Boron Chloride Figure 3.4: Correlation between dissolved concentrations of calcium, cobalt, iron, and molybdenum in Sutton site groundwaters with changes in pH. Concentration vs pH plots are separated into four plots for clarity in Figures 3.3-3.6. Figure 3.5: Correlation between dissolved concentrations of nickel, potassium, and selenium in Sutton site groundwaters with changes in pH. Concentration vs pH plots are separated into four plots for clarity in Figures 3.3-3.6. 1.0E-01 1.0E+00 1.0E+01 1.0E+02 1.0E+03 1.0E+04 3 4 5 6 7 8 9 10 11 Di s s o l v e d c o n c e n t r a t i o n Co , M o , a n d F e u n i t s i n m g/ L Ca u n i t s i n m g / L pH Calcium Cobalt Iron Molybdenum 1.0E-01 1.0E+00 1.0E+01 1.0E+02 3 4 5 6 7 8 9 10 11 Di s s o l v e d c o n c e n t r a t i o n Ni a n d S e u n i t s i n m g/ L K u n i t s i n m g / L pH Nickel Potassium Selenium Figure 3.6: Correlation between dissolved concentrations of strontium, thallium, vanadium, and zinc in Sutton site groundwaters with changes in pH. The majority of waters contained Zn concentrations below the detection limit of 0.005 mg/L. Concentration vs pH plots are separated into four plots for clarity in Figures 3.3-3.6. Select samples were passed through 450 nm and 100 nm filters in order to monitor formation of precipitates or association with suspended particles. The fraction of each analyte passing through a 100 nm filter is shown in Figure 3.7. The number of samples with measureable analyte concentrations in the filtrate is listed above each datapoint (n = x where x is the number of samples). The error bars represent the standard deviation of all measureable samples. Consistent with the data in Figures 3.3 and 3.4 demonstrating that dissolved concentrations of Al and Fe are likely controlled by solubility, a large fraction of Al and Fe is removed from solution by filtration at 100 nm. Thus, a significant fraction of Fe and Al could be present as a particulate phase. A large number of other ions are completely soluble as indicated by having 100% pass through a 100 nm filter for multiple samples. These soluble ions include: antimony, arsenic, barium, boron, manganese, molybdenum, selenium, strontium, and thallium. Cobalt, thallium, vanadium, and zinc all showed some removal by filtration but not on the same extent observed for Fe and Al. This behavior is consistent with the moderate sorption expected of these ions based on the groundwater measurements discussed above and the sorption modeling discussed below. 1.0E-03 1.0E-02 1.0E-01 1.0E+00 1.0E+01 1.0E+02 3 4 5 6 7 8 9 10 11 Di s s o l v e d c o n c e n t r a t i o n Tl a n d V u n i t s i n m g/ L Sr a n d Z n u n i t s i n m g / L pH Strontium Thalium Vanadium Zinc Figure 3.7: Soluble fraction of several constituents of interest defined as the fraction passing through a 100nm filter. 4. Sorption Model Development To examine the sorption behavior of multiple ions of interest in these systems, a combined aqueous speciation and surface complexation model was developed using the United States Geological Survey (USGS) geochemical modeling program PHREEQC. Equilibrium constants for aqueous speciation reactions were taken from the USGS WATEQ4F database. This database contained the reactions for most elements of interest except for Co, Sb, V, and Cr. Constants for aqueous reactions and mineral formation for these elements were taken from the MINTEQ v4 database which is also issued with PHREEQC. The constants were all checked to provide a self-consistent incorporation into the revised database. The source of the MINTEQ v4 database is primarily the well-known NIST 46 database [8]. Sorption reactions were modeled using a double layer surface complexation model. To ensure self-consistency in the modeling effort, a single database of constants was used as opposed to searching out individual constants from the literature. The diffuse double layer model describing ion sorption to hydrous ferric oxide by Dzomback and Morel [1] was selected for this effort. Many surface complexation reactions for ions of interest have already been added to the PHREEQC database. Constants for Co, V, Cr, and Sb were added to the modified database. Using surface complexation models, the sorption of an element is written as a standard chemical reaction such as those shown in Table 4.1. In these equations, ≡FeOH represents a site on the HFO mineral surface where sorption can occur. Speciation models utilize this reaction convention to describe a “concentration” of surface sites to be used in a thermochemical approach to sorption modeling [1, 9-11]. The primary difficulty in this approach is quantifying the concentration of reactive surface sites. Many approaches have been used, the most common being potentiometric titrations of the solid phase to quantify surface site concentrations using proton sorption/desorption behavior and surface area analysis. These studies are typically done on pure, synthetic mineral phases and still exhibit large variations in the surface site density determined from the data. Therefore, determination of surface site densities for complex mineral assemblages cannot be accurately performed using currently available techniques. However, when the site density is either known or assumed, sites per nm2 of mineral surface area, a molar concentration of surface sites can be determined using the equation: [≡𝐹𝑑𝐿𝐻]= [𝑆𝑆]∗𝑆𝐴∗1018 𝑘𝑘2 𝑘𝑘2 ∗𝑆𝐶 6.022 𝑥 1023 (𝑎𝑠𝑘𝑘𝑠 𝑘𝑘𝑘) where [≡FeOH] is the concentration of iron sorption sites in mol/L, [SS] is the suspension of solids in g/L, SA is the surface area of the solid in m2/g, and SD is the site density of the solid (sites/nm2). Table 4.1: Example reactions used in surface complexation modeling Reaction Type Reaction Expression Stability constant Surface protonation (i.e. develops positive surface charge at low pH) SOH + H+  SOH2+ Surface deprotonation (i.e. develops negative surface charge at high pH) SOH  SO- + H+ Cation sorption SOH + Mn+  SOMn-1 + H+ Anion Sorption SOH + H+ + A-  SOH2+A- or SOH + A-  SA + OH- 𝐊𝐀= [𝐒𝐎𝐇𝟐+𝐀−] [𝐒𝐎𝐇][𝐇+][𝐀−]𝐞𝐱𝐩 (−𝑭𝚿 𝑹𝑻) The model proposed by Dzomback and Morel [1] assumes that all surfaces have a combination of strong sorption sites and weak sorption sites. As discussed above, quantifying the reactive surface site density for complex mineral assemblages such as those used in this work, is difficult if not impossible. Therefore, attempting to delineate between mineral surfaces, let alone strong and weak sites on such surfaces, would add unnecessary uncertainty and fitting parameters to the models. Therefore, sorption to only one site is considered. There are two primary approaches to modeling complex mineral assemblages such as those considered in this work. The component additivity approach considers sorption reactions to all mineral phases present in a sample [9]. Such an approach requires separate reactions for each analyte sorbing to each mineral phase present in a sample. These can be very complicated but robust models provided a means for determining the surface site density of each mineral phase is available. A simpler alternative is the generalized composite approach wherein data are modeled assuming a generic surface site (i.e. ≡SOH) which represents an average reactivity of all minerals in the solid assemblage [9]. This modeling approach still combines the flexibility of an aqueous speciation model with a sorption model under a thermochemical framework. This work assumes that sorption occurs only to iron oxide minerals. Other + 2 ++ [SOH ]FψK = exp[SOH]{H } RT  -+ - [SO ]{H } FψK = exp -[SOH] RT  + n-1 + M [SOM ]{H } FψK = exp ( 1)[SOH]{M } RT n n  mineral surfaces can be considered and modeled. However, in the absence of data with sufficient resolution to determine the presence of these mineral phases and accurate methods to determine the surface site density for the minerals being considered, fitting additional surface reactions becomes a curve fitting exercise with a high probability of a non-unique solution. By modeling only ion sorption to HFO in this work, the model is essentially the generalized composite model. Since surface site densities for the mineral phases used in this work are not know and cannot be accurately estimated, the average concentration of extractable iron was used as a proxy for surface site densities. This approach has been previously used to describe vanadium and neptunium sorption to soils. In the case of Np(V) sorption to a sandy loam soil, the model was calibrated using two soils with varying iron content and found that assuming 4% of the total extractable iron was present as surface sorption sites would accurately predict the data [12]. In this work, the extractable iron content for several solid samples has been measured and batch Kd measurements have been performed on those solids. The extractable iron content data are shown in Table 4.2. These data indicate an average extractable Fe content of 1623 mgFe/kgsolid. This was converted to moles of Fe per g of solid using the molecular weight of Fe. Then assuming 5% of the total the molar concentration of iron sorption sites was calculated as: [≡𝐹𝑑𝐿𝐻]=[𝑆𝑘𝑘𝑖𝑑]∗[𝐻𝐹𝐿]∗1𝑔 1000𝑘𝑔∗𝑘𝑘𝑘𝐻𝐹𝑁 55.845𝑔∗0.05 𝑘𝑘𝑘 ≡𝐹𝑑𝐿𝐻 𝑘𝑘𝑘 𝐻𝐹𝐿 where [≡FeOH] is the concentration of iron sorption sites in mol/L for model input, [Solid] is the concentration of solid in g/L, [HFO] is the amount of extractable Fe in mg per kg of solid, molHFO is the moles of extractable iron, and 0.05 is the assumed fraction of extractable Fe which is available for sorption sites. This assumed value is similar to value of 0.11 molsites/molHFO (0.2 molsites/molFe) used by Dzomback and Morel in a global model of ion sorption to HFO (discussed in section 6 below). Table 4.2: Extractable iron content for several solid samples from the Sutton site Sample Name Depth (ft.) HFO mgFe/kgsolid HFO molFe/gsolid SW – 3C 10 – 12 352.8 6.3E-06 SW – 3C 41 – 43 724 1.3E-05 SW – 3C 48 – 53 1338.9 2.4E-05 ABMW – 1D 38 – 48 2281.9 4.1E-05 ABMW – 1D 83 – 88 3375.4 6.0E-05 ABMW – 2D 0 – 8 1818.5 3.3E-05 ABMW – 2D 10 – 12 1091.5 2.0E-05 ABMW – 2D 53 – 60 2070.5 3.7E-05 MW – 23E 145 – 147 1550.4 2.8E-05 AVERAGE 1623 2.9E-05 The model was executed by varying the amount of [≡FeOH], pH, and redox potential using the fixed ion concentrations listed in Table 2.1. The iron sorption site densities were varied to simulate batch sorption experiments for these same samples. These values corresponded to soil suspension concentrations of 50, 125, 250, 375, and 500 g/L which converts to iron sorption site concentrations ranging from1 x 10-6 mol/L to 2.0 x 10-4. The redox potential was varied between an electron potential (pe) of -5 to 15, corresponding to a redox potential measurements of -85 to 255 mV. The pH was run at fixed values of 4, 6, and 8 for all ≡FeOH) and redox potential values listed above. The range of pH and EH values was selected from low, average, and high measured values of real samples collected from the Sutton site so that the breadth of water chemistries could be evaluated. After all [≡FeOH] concentrations, pH values, and redox potentials were run, the chemical speciation was evaluated, particularly with respect to changes in Redox speciation. 5. Description of Sorption Model Results The model output was compiled by calculating an average Kd value for model runs at single, fixed EH and pH values. Kd is a distribution coefficient used to describe sorption using the ratio of the solid phase concentration and aqueous phase concentration of an ion. This is an equilibrium coefficient thus there is an inherent assumption that there are no kinetic limitations and the sorption reaction is completely reversible. The variable surface site concentrations with constant pH and EH conditions for each experimental run allowed for the evaluation of changes in the predicted Kd value due to competition between ions for sorption sites which may be depleted in models using a low suspended solids concentration. The averaged Kd values for all pH and EH conditions examined were compiled to represent the range expected given the pH and EH values from field measurements. The Kd values calculated for the minimum and maximum pH and/or EH field measurements are shown in Table 5.1 and in graphical form in Figure 5.1. Generally the experimental data are captured by the minimum and maximum model predicted Kd values with borate as a notable exception. However, it is noteworthy that agreement is somewhat artificial because the predicted Kd value can be linearly scaled with the assumed fraction of surface reactive iron (assumed to be 5% of the total extractable iron in this model as discussed above). For comparison, experimental data from batch sorption experiments are provided where available. While the modeled and experimental Kd values are not exactly the same, the trends describing the sorption strength of ions relative to each other are well demonstrated in these predicted Kd values and the observed trends discussed with regard to the site measurements in sections 1 and 2 above are supported. An example of the model output for several constituents of interest is shown below. The aqueous changes for redox active species are shown with the Kd data as appropriate. Table 5.1: Comparison of PHREEQC model predicted Kd values and experimentally determined Kd values. Species Minimum Model Predicted Kd Maximum Model Predicted Kd Geometric Mean of Experimental Data Total Fe 3.4 x 10-9 8.7 NA Total As 3.3 2.6 x 103 48 Borate 6.8 x 10-5 3.2 x 10-3 1.7 Barium 2.2 x 10-10 4.2 x 10-3 NA Total Co 3.4 x 10-6 66 140 Lead 5.8 x 10-3 5.0 x 104 NA Manganese 1.1 x 10-6 22 NA Total Se 1.3 x 10-3 9.4 10 Total V 1.2 x 10-8 560 37 Total S 5.0 x 10-4 1.7 NA Zn 3.6 x 10-8 0.59 NA NA = Data not available Figure 5.1: Comparison of PHREEQC model predicted Kd values and experimentally determined Kd values (Data from Table 5.1 shown in graphical form). 1.0E-10 1.0E-09 1.0E-08 1.0E-07 1.0E-06 1.0E-05 1.0E-04 1.0E-03 1.0E-02 1.0E-01 1.0E+00 1.0E+01 1.0E+02 1.0E+03 1.0E+04 1.0E+05 Mo d e l p r e d i c t e d o r e x p e r i m e n t a l K d va l u e ( L / k g ) Minimum Model Predicted Kd Maximum Model Predicted Kd Geometric Mean of Expeirmental Data Based on the model predicted Kd values and the aqueous speciation underlying the models as well as the observational data from field measurements discussed in sections 1 and 2, a list of potential attenuation mechanisms for several constituents was compiled (Table 5.2). The list includes physical attenuation in the form of flow through a system which will cause dilution and which is expected for all elements. Sorption and precipitation are also considered. Sorption is defined broadly and is proposed to account any process removing aqueous ions vial chemical interactions with a surface. Thus sorption reactions can include ion exchange, surface complexation, sorption to metal oxides, sorption to metal sulfides, and sorption to organic matter. Precipitation broadly includes both homogenous mineral precipitation as well as co-precipitation. Table 5.2: Listing of primary attenuation mechanisms and general geochemical considerations for several constituents of concern Constituent Physical attenuation Precipit ation Sorption Notes Antimony √ √ Arsenic √ √ √ Sorption and solubility is highly dependent on redox speciation Barium √ √ √ Generally exists as a divalent metal ion, sorption to metal oxide surfaces is dominant Boron √ √ Exists as highly soluble, weakly sorbing oxoanion Chloride √ Exists as highly soluble, weakly sorbing anion Chromium √ √ √ Sorption and solubility is highly dependent on redox speciation Cobalt √ √ Generally exists as a divalent metal ion, sorption to metal oxide surfaces is dominant Copper √ √ Generally exists as a divalent metal ion, sorption to metal oxide surfaces is dominant Lead √ √ √ Sorption and solubility is highly dependent on redox speciation Manganese √ √ √ Sorption and solubility is highly dependent on redox speciation Molybdenum √ √ Exists as oxoanion, weak sorption to metal oxide surfaces is dominant Nickel √ √ √ Generally exists as a divalent metal ion, sorption to metal oxide surfaces is dominant Selenium √ √ √ Sorption and solubility is highly dependent on redox speciation Sulfate √ √ √ Sorption and solubility is highly dependent on redox speciation Vanadium √ √ √ Sorption and solubility is highly dependent on redox speciation Zinc √ √ √ Generally exists as a divalent metal ion, sorption to metal oxide surfaces is dominant Iron speciation was monitored both as the active sorption site and as an aqueous ion. The model results in Figure 5.1 demonstrate predominance of Fe(II) at low pH and redox environments. Sorption of Fe(III) to HFO oxide surfaces was not included in the model. The higher Kd values at low redox potentials are due to the occurrence of Fe(II) in solution. The decrease in Kd with increasing redox potential is artificial because the model does not contain reactions of Fe(III) species sorbing to Fe(III)- oxide minerals. Figure 5.2: Iron redox speciation within PHREEQC model (top) and model predicted Kd values as a function of pH and EH. 0.00 0.10 0.20 0.30 0.40 0.50 0.60 0.70 0.80 0.90 1.00 -85 -34 17 85 136 169 203 254 Fe ( I I ) / F e ( T o t a l ) R a t i o EH (mV) pH 4 pH 6 pH 8 1.00E-10 1.00E-08 1.00E-06 1.00E-04 1.00E-02 1.00E+00 1.00E+02 -85 -34 17 85 136 169 203 254 Pr e d i c t e d K d (L / k g ) EH (mV) Arsenic aqueous species are dominated by arsenite (As(III)) and arsenate (As(V)) anionic species. Arsenite is dominant in systems with lower redox potentials and generally lower pH values (Figure 5.3). Due to the stronger sorption of arsenate, the Kd values for total As increase slightly with increasing EH due to the transition from As(III) to As(V) Figure (5.4). Figure 5.3: Fraction of As(III) (top) and As(V) (bottom) in PHREEQC model predictions as a function of pH and EH. 0.00 0.10 0.20 0.30 0.40 0.50 0.60 0.70 0.80 0.90 1.00 -85 -34 17 85 136 169 203 254 As ( I I I ) / A s ( t o t a l ) R a t i o EH (mV) pH 4 pH 6 pH 8 0.00 0.10 0.20 0.30 0.40 0.50 0.60 0.70 0.80 0.90 1.00 -85 -34 17 85 136 169 203 254 As ( V ) / A s ( t o t a l ) R a t i o EH (mV) pH 4 pH 6 pH 8 Figure 5.4: PHREEQC model predicted total As Kd values as a function of pH and EH. Selenium exhibits variable and complicated redox chemistry and can exist as strongly reduced Se(-II) up to a fully oxidized Se(VI) species. The model predicted changes in Se speciation are shown in Figure 5.5. The increase in Kd with increasing EH is a manifestation of Se(-II) oxidation to Se(IV) and Se(VI) (Figure 5.6). The dominance of Se(IV) at low pH under oxidizing conditions increases the Kd values further. However, stabilization of Se(VI) at high pH, high redox conditions leads to a decrease in the predicted total Se Kd at pH 8 under oxidizing conditions. pH 4 pH 6 pH 8 1.00E+00 1.00E+01 1.00E+02 1.00E+03 1.00E+04 -85 -34 17 85 136 169 203 254 Pr e d i c t e d A s K d ( L / k g ) EH (mv) Figure 5.5: Fraction of Se(-II), Se(IV), and Se(VI) on top, middle, and bottom, respectively, as a function of EH and pH. 0.00 0.10 0.20 0.30 0.40 0.50 0.60 0.70 0.80 0.90 1.00 -85 -34 17 85 136 169 203 254 Se ( -II ) / S e ( t o t a l ) R a t i o EH (mV) pH 4 pH 6 pH 8 0.00 0.10 0.20 0.30 0.40 0.50 0.60 0.70 0.80 0.90 1.00 -85 -34 17 85 136 169 203 254 Se ( I V ) / S e ( t o t a l ) R a t i o EH (mV) pH 4 pH 6 pH 8 0.00 0.20 0.40 0.60 0.80 1.00 -85 -34 17 85 136 169 203 254 Se ( V I ) / S e ( t o t a l ) R a t i o EH( mV) pH 4 pH 6 pH 8 Figure 5.6: PHREEQC model predicted total Se Kd values as a function of pH and EH. PHREEQC model predicted Kd values for Pb2+ are shown in Figure 5.7. There is no change in redox speciation so an aqueous redox profile is not provided. The decrease in Kd values at low redox potentials is due to reduction of sulfate to sulfur and formation of Pb-sulfide. Zinc exhibits almost identical behavior to Pb2+, even including potential formation of Zn-sulfide complexes (Figure 5.8). Similar to Pb2+ and Zn2+, barium also predominantly exists as a divalent cation and sorption exhibits a strong dependence on pH (Figure 5.9). Borate exists only as B(III), predominantly H3BO3, and does not undergo any redox reactions under the given conditions. Sorption is very weak and the majority of borate remains within the aqueous phase. There is a slight decrease in sorption for oxidizing, low pH conditions that is proposed to be due to sulfate and other strongly sorbing oxoanions which can compete with borate for sorption sites (Figure 5.10). There is a large discrepancy between the experimental and predicted Kd values for borate. The reason for this is currently unclear. The sorption model here only assumes sorption to HFO based on the constants provided by Dzomback and Morel [1] . These constants could require revision or boron could be sequestered by a secondary mechanism such as isomorphic substitution into mica[13] or sorption to aluminol surface sites [2]. It is noteworthy that borate sorption to gibbsite has a surface complexation constant approximately one order of magnitude higher than that for HFO (log K of 1.57 versus 0.62 for gibbsite and HFO, respectively). Vanadium exhibits a wide range of redox states in aqueous systems and each oxidation state has a different sorption affinity (Figure 5.11 and 5.12). Generally V(III) sorbs very weakly. As the pH and redox conditions increase, V(III) oxidizes to V(IV) and V(V). These two latter oxidation states have 1.00E-10 1.00E-08 1.00E-06 1.00E-04 1.00E-02 1.00E+00 1.00E+02 -85-341785136169203254 Pr e d i c t e d K d (L / k g ) EH (mV) higher sorption affinities. Thus, the Kd increases with increasing pH and redox potential. V(IV) and V(V) have similar sorption affinities and thus the increase in Kd is a contribution from both sorption affinities. Figure 5.7: PHREEQC model predicted Pb(II) Kd values as a function of pH and EH. Figure 5.8: PHREEQC model predicted Zn(II) Kd values as a function of pH and EH. 1.00E-04 1.00E-02 1.00E+00 1.00E+02 1.00E+04 -85 -34 17 85 136 169 203 254 Pr e d i c t e d P b K d (L / k g ) EH (mV) 1.00E-09 1.00E-07 1.00E-05 1.00E-03 1.00E-01 -85 -34 17 85 136 169 203 254 Pr e d i c t e d Z n K d ( L / k g ) EH (mV) Figure 5.9: PHREEQC model predicted Ba(II) Kd values as a function of pH and EH. Figure 5.10: PHREEQC model predicted boron Kd values as a function of pH and EH. pH 4 pH 6 pH 8 1.00E-12 1.00E-10 1.00E-08 1.00E-06 1.00E-04 1.00E-02 -85 -34 17 85 136 169 203 254 Pr e d i c t e d B a K d (L / k g ) EH( mV) pH 4 pH 6 pH 8 1.00E-05 1.00E-04 1.00E-03 1.00E-02 -85 -34 17 85 136 169 203 254 Pr e d i c t e d B K d (L / k g ) EH( mV) Figure 5.11: Fraction of V(III), V(IV), and V(V) on top, middle, and bottom, respectively, as a function of EH and pH. 0.00 0.10 0.20 0.30 0.40 0.50 0.60 0.70 0.80 0.90 1.00 -85 -34 17 85 136 169 203 254 V( I I I ) / V ( t o t a l ) R a t i o EH (mV) pH 4 pH 6 pH 8 0.00 0.10 0.20 0.30 0.40 0.50 0.60 0.70 0.80 0.90 1.00 -85 -34 17 85 136 169 203 254 V( I V ) / V ( t o t a l ) R a t i o EH (mV) pH 4 pH 6 pH 8 0.00 0.10 0.20 0.30 0.40 0.50 0.60 0.70 0.80 0.90 -85 -34 17 85 136 169 203 254 V( V ) / V ( t o t a l R a t i o EH (mV) pH 4 pH 6 pH 8 Figure 5.12: PHREEQC model predicted vanadium Kd values as a function of pH and EH. pH 4 pH 6 pH 8 1.00E-10 1.00E-08 1.00E-06 1.00E-04 1.00E-02 1.00E+00 1.00E+02 -85 -34 17 85 136 169 203 254 Pr e d i c t e d V K d (L / k g ) EH (mV) 6. Analysis of redox speciation: As example To demonstrate the impact of redox speciation, a additional model was run to compare the observed As redox speciation values in groundwater samples with those from the model predictions. In the model, the same ion concentrations listed in table 2.1 (and used in the modeling effort in section 5 for direct comparison of the results) were fixed and the pH and EH were varied to match the values measured in each sample listed in the Table 6.1 below. The measured fration of As(III) and As(V) are shown in Figure 6.1 and it is clear that the fraction of As(III) increases with increasing redox potential. The two anomalous datapoints at EH values of 39 and 77 mV have the lowest measured pH values (5.9 and 5.5, respectively). The oxidation of As(III) is dependent on pH and lower pH values tend to favor the reduced state. Therefore, As(III) persists in those samples given the low pH. However, as discussed below with respect to sorption, these two samples provide a unique opportunity to demonstrate the utility of the redox coupled sorption model presented in Section 5. Table 6.1: Measured arsenic speciation in Sutton water samples and comparison of model predicted values. Note that the model includes sorption while the sample are only measuring aqueous phase concentrations. Sample ID pH EH As(III), ug/L As(V), ug/L Measured Fraction As(III) Measured Fraction As(V) Modeled Fraction As(III) Modeled Fraction As(V) Modeled Fraction As(III) Sorbed Modeled Fraction As(V) sorbed ABMW- 02D 7.9 -169.7 119 7.71 0.939 0.061 1.000 0.000 0.000 0.000 AW-05B 8.5 -90.2 0.171 0.163 0.512 0.488 0.998 0.000 0.002 0.000 AW-05D 8.4 -88.9 0.293 0.204 0.590 0.410 0.998 0.000 0.002 0.000 AW-05E 8.7 -82.1 0.333 0.312 0.516 0.484 0.998 0.000 0.002 0.000 AW-06E 8.1 1 0.381 0.135 0.738 0.262 0.000 0.083 0.000 0.917 MW-16 5.9 38.9 0.676 0.375 0.643 0.357 0.011 0.064 0.068 0.857 MW-23E 10 -172.7 0.371 0.102 0.784 0.216 0.957 0.000 0.043 0.000 MW-24C 5.5 77.1 1.74 0.3 0.853 0.147 0.000 0.095 0.000 0.904 A visual comparison of the data presented in table 6.1 is provided in Figure 6.2. To use a consistent x- axis, the data are plotted as a function of pH + pe (where pe = EH x 59mv). Generally the model predicts the predominance of As(III) at low EH/pH conditions and As(V) at high pH/EH conditions. The model does not capture the small amount of As(V) present in the samples with pe + pH values around 3. However, there is clear agreement with the predominance of the arsenite ion (As(III), HxAsO3 x-3) and a small amount of sorption of arsenite is predicted. At the low pH values (5.5 and 5.9) significant sorption of both arsenite and arsenate are predicted. The arsenate ion exhibits generally stronger sorption. Therefore, the waters under high EH conditions in which As(III) was measured as the dominant oxidation state may be a manifestation of a redox disequilibrium induced by sorption of As(V) and removal from the pore water. Thus an artificially high As(III) concentration would be measured in the pore waters. While the model does not predict the exact arsenic redox distributions measured in field samples, the general trends with regard to sorption and speciation are predicted well. Differences between the measured and predicted values could be due to local disequilibrium in samples, uncertainty in the equilibrium constants within the PHREEQC database, and/or unknown reactions taking place in the samples which are not accounted for in the model. Figure 6.1: Measured fractions of As(III) and As(V) in Sutton water samples as a function of water EH. 0.00 0.10 0.20 0.30 0.40 0.50 0.60 0.70 0.80 0.90 1.00 -200 -150 -100 -50 0 50 100 Fr a c t i o n o f S p e c i e s Eh(mV) Measured Fraction As(III) Measured Fraction As(V) Figure 6.2: Predicted and measured arsenic redox speciation in Sutton water samples. 7. Estimation of sorption capacity An overarching concern regarding the mobility of the various constituents considered in this work is the capacity of the aquifer solids to sequester each constituent. As noted above, each constituent has a different sorption affinity and there is even considerable variation between the different oxidation states of a redox active constituent. Therefore, rather than predicting capacity for each constituent, a total sorption site estimation for a generic solid can be considered and then related as needed to each constituent. Linear distribution coefficients cannot be used to predict sorption capacity because an inherent assumption is that sorption will continue to increase linearly with no consideration that the surface could become saturated. The surface complexation modeling approach used in this work can be used to estimate the site density but this is based upon a primary assumption of the concentration of reactive sorption sites on a solid phase. To estimate this value, the extractable iron and aluminum values which have been experimentally determined for several solids obtained from the Sutton site will be used. Dzomback and Morel [1] and Karmalidis and Dzomback [2] have compiled values for the surface site densities of HFO and gibbsite based on the measured sorption capacities for a wide range of cations and anions. The total concentration of surface sites (NT) within a solid suspension can be estimated using these site densities as: 𝐿𝑆=𝐿𝑆 ∗ 𝐴∗ 𝐶𝑆𝑆 ∗ 1 𝐴𝑉𝐿∗ 1018 𝑘𝑘2 𝑘2 1.00E-03 1.00E-02 1.00E-01 1.00E+00 Fr a t i o n o f S p e c i e s pH + pe Measured As(III) aq Modeled As(III) Aq Measured As(V) aq Modeled As(V) aq Modeled As(III) Sorbed Modeled As(V) sorbed where NS is the surface site density (sites/nm2), A is the surface area of the solid (m2/g), CSS is the solid suspension concentration (g/L), and AVO is Avogadro’s number (6.022 x 1023 sites/mol). Based on numerous sorption capacity studies Dzomback and Morel report the site density of HFO as 0.2 molsites/molFe for the more abundant type 2 sites (which are total reactive sites for sorption of protons, anions, and cations [1]. Similarly, a value of 8 sites/nm2 is reported for gibbsite [2]. The reported value in sites/nm2 can be converted to molsites/molAl as: 𝐿𝑆,𝑙𝑜𝑙=𝐴∗ 𝐿𝑉∗ 𝐿𝑆 1018 𝑘𝑘2 𝑘2 ∗ 1 𝑘𝑘𝑘𝑑 𝑠𝑖𝑠𝑑𝑠 6.022 𝑥 1023 where NS,mol is the site density in moles of sites per mole of mineral and MW is the molecular weight of the mineral (g/mol). Using the best-estimate surface areas of 32 m2/g for gibbsite [2] the surface site density can be reported as 0.41 molsites/molAl. The value of NT can be utilized in surface complexation modeling efforts to define a finite number of sorption sites. Thus surface saturation and competition of various ions for sorption sites can be modeled. As an example of this, sorption of B and As to HFO were modeled using a constant concentration of surface sites (3.6 x 10-4 molesites/L) and variable B and As concentrations (Figures 7.1 and 7.2). The impact of competing Na+, Ca2+, and SO4 -2 sorption was also included. The models show that due to the relatively weak sorption affinity of B, the capacity of the surface is never exceeded. There is a slight decrease in B sorption in the presence of sulfate but no competition with Na+ or Ca2+. Arsenic sorbs strongly in this simulation primarily due to the dominance of As(V) based on the fixed pH and pe values of 4 and 6.7, respectively, in the model. Sorption increases as the total As concentration increases until the concentration of sorbed As is approximately equal to the concentration of available surface sites (~3 x 10-4 mol/L) indicating the surface has become saturated under these conditions. There is completion with sulfate at low As concentrations. There is a constant concentration of sulfate in the model. Therefore, at low As concentrations, the ratio of sulfate to As is high and sulfate can outcompete As for sorption sites based on mass action. However, as the concentration of As increases and becomes comparable to that of sulfate, both anions exhibit similar sorption behavior. These simulations demonstrate how an estimation of a surface site density (i.e. concentration) can be used to approximate the sorption capacity of a solid. This can be done using a “best-estimate” surface area and the extractable Fe and Al content of a solid as described above. Using the values for site densities of 0.2 and 0.41 for Fe and Al hydroxides, respectively, the capacity of various aquifer solids were estimated based on the extractable Fe and Al content (Table 7.1). Figure 7.1: PHREEQC model of boron sorption to HFO with variable total boron concentrations using the baseline ion concentrations reported in Table 2.1. Additional simulations with 100x increases in SO4 -2, Na+, and Ca2+ are included to examine competitive sorption. Figure 7.2: PHREEQC model of arsenic sorption to HFO with variable total arsenic concentrations using the baseline ion concentrations reported in Table 2.1. Additional simulations with 100x increases in SO4 -2, Na+, and Ca2+ are included to examine competitive sorption. 1.00E-11 1.00E-10 1.00E-09 1.00E-08 1.00E-07 1.00E-06 1.00E-05 1.00E-04 1.0E-06 1.0E-05 1.0E-04 1.0E-03 1.0E-02 1.0E-01 1.0E+00 So l i d P h a s e B o r o n C o n c e n t r a t i o n (m o l / k g ) Aqueous Phase Boron (mol/L) Baseline Baseline + 100x Sulfate Baseline + 100x Ca and Na 1.00E-05 1.00E-04 1.00E-03 1.0E-06 1.0E-05 1.0E-04 1.0E-03 1.0E-02 1.0E-01 1.0E+00 As S o l i d P h a s e C o n c e n r t a t i o ( m o l / g ) As Aqueous Phase Concentration (mol/L) As Baseline As Baseline + 100x sulfate Table 7.1: Approximation of the site capacity on aquifer solids by assuming extractable Fe and Al as a proxy for reactive surface sites. Sample Name Depth Hydrous Ferric Oxide (HFO) Hydrous Aluminum Oxide (Gibbsite) Units ft. mgFe/ kgsolid molFe/ gsolid molsites/ gsolid mgAl/ kgsolid molAl/ gsolid molsites/ gsolid SW – 3C 10 – 12 352.8 6.3 x 10-6 1.3 x 10-6 971.8 3.6 x 10-5 1.5 x 10-5 SW – 3C 41 – 43 724.0 1.3 x 10-5 2.6 x 10-6 693.3 2.6 x 10-5 1.1 x 10-5 SW – 3C 48 – 53 1338.9 2.4 x 10-5 4.8 x 10-6 748.8 2.8 x 10-5 1.1 x 10-5 ABMW – 1D 38 – 48 2281.9 4.1 x 10-5 8.2 x 10-6 4760.0 1.8 x 10-4 7.2 x 10-5 ABMW – 1D 83 – 88 3375.4 6.0 x 10-5 1.2 x 10-5 426.1 1.6 x 10-5 6.5 x 10-6 ABMW – 2D 0 – 8 1818.5 3.3 x 10-5 6.5 x 10-6 2368.2 8.8 x 10-5 3.6 x 10-5 ABMW – 2D 10 – 12 1091.5 2.0 x 10-5 3.9 x 10-6 4209.9 1.6 x 10-4 6.4 x 10-5 ABMW – 2D 53 – 60 2070.5 3.7 x 10-5 7.4 x 10-6 425.5 1.6 x 10-5 6.5 x 10-6 MW – 23E 145 – 147 1550.4 2.8 x 10-5 5.6 x 10-6 528.7 2.0 x 10-5 8.0 x 10-6 AVERAGE 1622.7 2.9 x 10-5 5.8 x 10-6 1681.4 6.2 x 10-5 2.6 x 10-5 STDEV 903.7 1.6 x 10-5 3.2 x 10-6 1702.0 6.3 x 10-5 2.6 x 10-5 Using the estimated sorption site concentrations of 5.8 x 10-3 molsites/kgsolid and 2.6 x 10-2 molsites/kgsolid for HFO and gibbsite, respectively, the potential capacity of the aquifer solids to sequester the constituents of interest can be estimated. To perform this calculation in a conservative manner, it was assumed that the pore space within a 1000cm3 volume of the aquifer was saturated and the water contained each of the constituents of interest listed in Table 6.2 at a concentration corresponding to the NC2L standard level. Assuming a bulk density of 1.6 g/cm3 and effective porosity of 0.2 (which were the values used throughout the site in reactive transport modeling efforts), the pore volume would be 200 mL and the 1000cm3 area would contain 1.6 kg of solid. Assuming 100% sorption of the constituents within the pore volume, the solid phase concentration of each constituent can be calculated as: 𝐶𝑠𝑜𝑙𝑖𝑑= 𝐶𝑁𝐶2𝐿∗1𝑔 106 𝜇𝑔∗0.2𝐿 𝐿𝑉∗1.6𝑘𝑔 where Csolid is the solid phase concentration of the constituent (mol/kgsolid), CNC2L is the NC2L standard concentration of the constituent in mg/L, and MW is the molecular weight of the constituent in g/mol. Once the solid phase concentration of the constituent is estimated assuming 100% sorption, the fraction of potentially occupied sites on the solid can be calculated by taking the ratio of the sorption sites occupied by the constituent to the total available sorption sites (in units of moles per kg to maintain stoichiometry). These ratios are shown in Table 6.2 for each constituent of interest on HFO and gibbsite. The total occupied sites would be 0.23% and 0.05% for HFO and gibbsite, respectively. Therefore, either site could sorb all of the available constituents of interest considering the above assumptions and would not reach capacity until ~400x the NC2L standard levels. However, it is important to note that these calculations assume 100% sorption which will not be the case for constituents such as boron which are a significant contributor to the occupied sorption sites (Table 6.2). Therefore, although this calculation shows that it is unlikely the capacity of the aquifer solids would be exceeded, the actual aqueous phases of each constituent would be based on the Kd value for that constituent under the geochemical conditions of the pore water. Table 7.2: Estimated sorption site occupancy assuming 100% sorption of a pore volume of each constituent at the NC2L standard concentration levels. Constituent NC2L Standard (ug/L) Molecular weight of species (g/mol) Moles of constituent in 1000cm3 volume at NC2L Standard Level (mol) Solid phase concentration of constituent at 100% sorption of NC2L Standard Level (mol/kg) Fraction of HFO sorption site capacity occupied at NC2L standard level assuming 100% sorption* Fraction of gibbsite sorption site capacity occupied at NC2L standard level assuming 100% sorption** Aluminum NE 26.98 Antimony 1 121.76 1.64 x 10-9 1.0 x 10-9 1.8 x 10-7 4.0 x 10-8 Arsenic 10 74.92 2.67 x 10-8 1.7 x 10-8 2.9 x 10-6 6.5 x 10-7 Barium NE 137.33 Beryllium 4 9.0122 8.88 x 10-8 5.6 x 10-8 9.6 x 10-6 2.2 x 10-6 Boron 700 10.811 1.29 x 10-5 8.1 x 10-6 1.4 x 10-3 3.2 x 10-4 Cadmium 2 112.41 3.56 x 10-9 2.2 x 10-9 3.8 x 10-7 8.7 x 10-8 Chromium 10 51.996 3.85 x 10-8 2.4 x 10-8 4.1 x 10-6 9.4 x 10-7 Cobalt 1 58.933 3.39 x 10-9 2.1 x 10-9 3.7 x 10-7 8.3 x 10-8 Copper 1000 63.546 3.15 x 10-6 2.0 x 10-6 3.4 x 10-4 7.7 x 10-5 Iron 300 55.845 1.07 x 10-6 6.7 x 10-7 1.2 x 10-4 2.6 x 10-5 Lead 15 207.2 1.45 x 10-8 9.1 x 10-9 1.6 x 10-6 3.5 x 10-7 Manganese 50 54.938 1.82 x 10-7 1.1 x 10-7 2.0 x 10-5 4.5 x 10-6 Mercury 1 200.59 9.97 x 10-10 6.2 x 10-10 1.1 x 10-7 2.4 x 10-8 Molybdenum NE 95.94 Nickel 100 58.693 3.41 x 10-7 2.1 x 10-7 3.7 x 10-5 8.3 x 10-6 Selenium 20 78.96 5.07 x 10-8 3.2 x 10-8 5.5 x 10-6 1.2 x 10-6 Strontium NE 87.62 Thallium 0.2 204.38 1.96 x 10-10 1.2 x 10-10 2.1 x 10-8 4.8 x 10-9 Vanadium 0.3 50.942 1.18 x 10-9 7.4 x 10-10 1.3 x 10-7 2.9 x 10-8 Zinc 1000 65.39 3.06 x 10-9 1.9 x 10-9 3.3 x 10-4 7.5 x 10-5 TOTAL 2.3 x 10-3 5.1 x 10-4 *Assumes average sorption site concentration of 5.8 x 10-3 molesites/kgsolid for HFO (Table 6.1) **Assumes average sorption site concentration of 2.6 x 10-2 molesites/kgsolid for gibbsite HAO (Table 6.1) 8. Summary The modeling effort described above provides both qualitative and quantitative estimations of the chemical speciation and sorption behavior of several key constituents of interest. Relevant observations from this modeling effort are as follows.  Zn, Co, and Pb are predominantly present as divalent cations whose sorption is profoundly influenced by pH. In all cases sorption increases with increasing pH. This behavior is consistent with increasing attraction of cationic species to mineral surface as the net negative charge on the mineral surface increases with increasing pH.  The assumption that 5% of the extractable iron content is available for sorption appears to predict Kd values on the within an order of magnitude for many constituents. One anomalous finding is the prediction of borate sorption. The modeled range of 6.8 x 10-5 to 3.2 x 10-3 L/kg is significantly lower than the experimentally derived value of 1.7 L/kg. Therefore, it appears there is a mechanism which is limiting aqueous concentrations of boron which is not captured by the sorption model. This could be an isomorphic substitution for Si within micas [13], co- precipitation reaction with other mineral phases containing oxoanions such as gypsum (CaSO4), or demonstrate a need to revise the surface complexation constants reported by Dzomback and Morel [1] or consider sorption to alternate phases such as gibbsite [2]. It is important to note that the reaction rates for substitution or mineralization are not know. Thus, the rate and extent of such reactions and their potential impact on the systems is unknown and would require further examination to determine. However, based on the groundwater measurements of boron and the relatively low Kd values both predicted and measured, sorption and/or precipitation is expected to be minimal.  Speciation modeling predicts that both As(III) and As(V) to be present, with As(III) dominating the aqueous phase at the low pH and low EH conditions of the site. The reduction of As(V) to As(III) is significant as As(V) sorption is stronger and will impact the aqueous phase concentrations. Thus the observations of As(III) in groundwater samples despite the predicted stability of As(V) in the Pourbaix diagrams may be an indication of As(V) sorption leaving only As(III) in the aqueous phase. Therefore the behavior of arsenic is likely a manifestation of sorption of the anionic arsenate species at low pH and precipitation/coprecipitation with metal oxide minerals at high pH. This is consistent with the speciation model in section 5 and the groundwaters observations discussed in section 3.  The redox active constituents Se and V exhibit widely varying behavior primarily related to changes in the sorption affinity of each oxidation state. The dominant oxidation states were modeled to be Se(IV) and Se(0) as well as V(IV) and V(V). The relatively constant concentrations of Se and V in site groundwaters is consistent with a solubility control as increased sorption would be expected upon oxidation of Se(IV) to Se(VI).  Concentrations of alkali earth ions (Ba2+, Ca2+, Mg2+, Sr2+) were highly variable in groundwater measurements. Specific sorption of these ions was not considered in the model though several relevant mineral phases were included. There were no discrete solid phases predicted under the given model conditions. Thus, the behavior of ions in these systems is likely controlled by ion exchange or solubility. 9. Recommendations for additional studies A key driver in the sorption modeling described in this work is the density of surface sites. The surface complexation model in this work utilizes constants describing ion sorption to HFO. However, in the prediction of Kd values described above, specific reactions with aluminum oxide surfaces are not considered. This may have a major impact on some ions such as borate where the surface complexation constant for borate interaction with aluminum oxide surfaces is approximately 10x higher than that for iron oxide surfaces. Therefore, explicitly including the aluminum oxide surfaces and sorption reactions in a future model will likely improve the overall predictability of the model. As noted above, the maximum predicted Kds are within an approximate range of the expected/measured values. However, given the uncertainty in surface site densities, exact values cannot be calculated. However, inclusion of the aluminum oxide mineral surface reactions will provide a more complete and robust model and will certainly improve the estimation of the borate Kd values. While is it understood that the mineralogy of the site may not contain significant quantities of these discrete minerals, the aluminosilicate minerals which dominate the site will contains surficial Fe and Al groups which are likely sorption sites. However, the site density can be highly variable for different solids and is a function of the surface area of the solid and the chemical environment of the Fe and Al within the solids. Therefore, additional studies to determine the sorption site density of solid phases relevant to this site are needed to verify the assumptions of site densities used in the Kd and sorption capacity estimations. Additionally, data verifying that the predicted oxidation states of As, Se, V, and other redox active elements is sparse. Further analysis of the observed chemical speciation at the site will help to verify the modeling approach described above. This effort could be coupled with the predictive model described above which could be constrained by fixing the EH and pH of the model based on the measured values in the pore waters. The measured redox aqueous speciation could be compared with the predicted to verify these species are being accurately modeled. Also, the predictive model includes sorption reactions. Therefore, the impacts of sorption can be inferred. For example, oxidation of As(III) to As(V) will lead to increased sorption due to the higher sorption affinity of As(V) as the arsenate ion (HxAsO4 x-3). Therefore, observations of As(III) in waters with high EH values where As(V) would indeed be expected could be an indicator of As(V) sorption and removal of As from the pore water. Characterization of borate speciation within the solid phases may help to explain the discrepancy between experimental and predicted Kd values. There are multiple mechanisms through which borate could be retained within a solid and differentiating between these will provide a more robust chemical speciation model. However, such an experimental effort could be significantly hindered by the relatively low concentrations of borate in the solids which would limit the experimental approaches that could be utilized. The pore water measurements indicate that dissolved organic carbon (DOC) concentrations range from 0.2 to 40 mgC/L with a median value of 4 mgC/L. Most water samples have low to moderate concentrations. The geochemical model discussed above does not consider the impact of DOC on adsorption of the ions. The influence of DOC can be complicated and can influence cation and anion sorption in different ways. A significant fraction of DOC will be present as an anionic organic ligands at pH values over ~4.5. This is due to deprotonation of carboxylate functional groups that are ubiquitous in DOC with acid dissociation constants (pKa) which generally range from 2.5 to 4.5. These anionic ligands can then cause three potential reactions which will influence the constituents of concern. 1. The DOC can compete with other anions such as borate, arsenate, selenate, and chromate for mineral surface sorption sites. 2. The DOC can form aqueous metal-ligand complexes which would increase the solubility of the cations or cause desorption of sorbed cations. Thus the aqueous phase concentrations would increase 3. Alternatively to #2, the DOC can sorb and produce a coating of DOC on the mineral surface. This will generally occur at low pH values where the anionic DOC is attracted to the positively charged surface. Following sorption of the DOC, the surface charge could be reversed and cations could bind to the DOC coating on the mineral surface. This is referred to as a ternary surface complex where the DOC facilitates sorption by serving as a “bridge” between the cation and the mineral surface. The overall effect of this would be a decreased aqueous concentration of the cations relative to a system with no DOC. The influence of DOC as discussed above will be dependent on the nature of the DOC and the affinity of the DOC for mineral surfaces. This is dependent on the chemical properties of the DOC such as the distribution of acid functional groups and the amount of hydrophilic versus hydrophobic character of the DOC. A complete study to determine the extent of each reaction listed above would require detailed characterization of the DOC and a quantitative estimate of the sorption affinity of the DOC. However, a simpler first step in the analysis of the impact of DOC would be to perform a statistical analysis of the correlation between dissolved ion and DOC concentrations in pore waters from the site. 10. References 1. Dzombak, D.A. and F.M.M. Morel, Surface complexation modeling : hydrous ferric oxide. 1990, New York: Wiley. xvii, 393. 2. Karamalidis, A.K. and D.A. Dzombak, Surface Complexation Modeling: Gibbsite. 2010, Hoboken, NJ: John Wiley and Sons, Inc. . 3. Hem, J.D., Reactions of metal ions at surfaces of hydrous iron oxide. Geochem. Cosmochim. Acta., 1977. 41: p. 527-538. 4. Stachowicz, M., T. Hiemstra, and W.H. van Riemsdijk, Surface speciation of As(III) and As(V) in relation to charge distribution. Journal of Colloid and Interface Science, 2006. 302(1): p. 62-75. 5. Strawn, D., et al., Microscale investigation into the geochemistry of arsenic, selenium, and iron in soil developed in pyritic shale materials. Geoderma, 2002. 108(3-4): p. 237-257. 6. USEPA, Monitored Natural Attenuation of Inorganic Contaminants in Ground Water. Volume 2. Assessment for Non-Radionuclides Including Arsenic, Cadmium, Chromium, Copper, Lead, Nickel, Nitrate, Perchlorate, and Selenium.2007. 2007. 7. Zawislanski, P.T. and M. Zavarin, Nature and rates of selenium transformations: A laboratory study of Kesterson Reservoir soils. Soil Science Society of America Journal, 1996. 60(3): p. 791- 800. 8. Martell, A.E. and R.K. Smith, Critical Stability Constants, Standard Reference Database 46, Version 6.30. 2001, National Institute of Standards, Gaithersburg, MD. 9. Davis, J.A., et al., Application of the surface complexation concept to complex mineral assemblages. Environmental Science and Technology, 1998. 32: p. 2820-2828. 10. Davis, J.A., R.O. James, and J.O. Leckie, Surface ionization and complexation at the oxide-water interface.1. Computation of electrical double layer properties in simple electrolytes. Journal of Colloid and Interface Science, 1978. 63(3): p. 480-499. 11. Goldberg, S., Use of Surface Complexation Models in Soil Chemical Systems, in Advances in Agronomy, D.L. Sparks, Editor. 1990, Academic Press, Inc. p. 233-329 12. Miller, T., Conceptual model testing and development for neptunium and radium sorption to SRS sediments, in Environmental Engineering and Earth Sciences. 2010, Clemson University: Clemson 13. Sposito, G., The chemistry of soils. 1989, Oxford: Oxford University Press. Corrective Action Plan Part 1 November 2015 L.V. Sutton Energy Complex SynTerra P:\Duke Energy Progress.1026\108. Sutton Ash Basin GW Assessment Plan\16.Corrective Action Plan\FINAL CAP REPORT\Final LV Sutton CAP Report 11-02-2015.docx APPENDIX E GROUNDWATER MODELING REPORT GROUNDWATER FLOW AND TRANSPORT MODELING REPORT FOR L.V. SUTTON ENERGY COMPLEX, WILMINGTON, NC October 28, 2015 Prepared for SynTerra 148 River Street Greenville, SC 29601 Investigators Ronald W. Falta, Ph.D. Scott E. Brame, M.S. Regina Graziano, M.S. Lawrence C. Murdoch, Ph.D. TABLE OF CONTENTS 1.0 Introduction 1 1.1 General Setting and Background 1 1.2 Study Objectives 1 2.0 Conceptual Model 2 2.1 Aquifer System Framework 2 2.2 Groundwater Flow System 3 2.3 Hydrologic Boundaries 5 2.4 Hydraulic Boundaries 6 2.5 Sources and Sinks 6 2.6 Water Budget 6 2.7 Modeled Constituents of Interest 6 2.8 Constituent Transport 7 3.0 Computer Model 9 3.1 Model Selection 9 3.2 Model Description 9 4.0 Groundwater and Transport Model Construction 10 4.1 Model Domain and Grid 10 4.2 Hydraulic Parameters 11 4.3 Flow Model Boundary Conditions 12 4.4 Flow Model Sources and Sinks 12 4.5 Flow Model Calibration Targets 14 4.6 Transport Model Parameters 15 4.7 Transport Model Boundary Conditions 16 4.8 Transport Model Sources and Sinks 17 4.9 Transport Model Calibration Targets 17 5.0 Model Calibration to Current Conditions 18 5.1 Flow Model Residual Analysis 18 5.2 Flow Model Sensitivity Analysis 19 5.3 Transport Model Calibration and Sensitivity 20 6.0 Predictive Simulations of Corrective Action Scenarios 22 6.1 Corrective Action Plan #1 22 6.2 Corrective Action Plan #2 23 6.3 Corrective Action Plan #3 Error! Bookmark not defined. 7.0 References 26 LIST OF TABLES Table 1. Comparison of observed and computed heads for the calibrated flow model. Table 2. Calibrated hydraulic parameters. Table 3. Flow parameter sensitivity analysis. Results are expressed as model normalized root mean square error (NRMSE) of the simulated and observed heads. Table 4. Ash basin infiltration rates used in historical transport model. Table 5. Major supply well pumping rates used in historical transport model, gpm. Table 6. Ash basin COI source concentrations (ug/L) used in historical transport model. Table 7. Comparison of observed and simulated boron concentrations (ug/L) in monitoring wells. The green highlighted cells are deep Pee Dee wells. Table 8. Comparison of observed and simulated arsenic concentrations (ug/L) in monitoring wells. Table 9. Comparison of observed and simulated vanadium concentrations (ug/L) in monitoring wells. LIST OF FIGURES Figure 1. Site location map, Sutton Energy Complex, Wilmington, NC. Figure 2. Numerical model domain. Figure 3. Fence diagram of the 3D hydrostratigraphic model used to construct the model grid. The view is from the south, with 10x vertical exaggeration. Figure 4. Numerical grid used for flow and transport modeling. Vertical exaggeration is 10x. Figure 5. Distribution of recharge zones in the model. Figure 6. Surface water features included in the model. The light blue areas are treated as either constant head areas (lakes ponds, and rivers) or drain areas (swamps). Figure 7. Location of water supply wells in the model area. Figure 8. Zones used to define horizontal hydraulic conductivity and horizontal to vertical anisotropy in model layer 6. Figure 9. Comparison of observed and computed heads from the calibrated steady state flow model. Figure 10. Simulated heads in the top surficial aquifer model layer (model layer 3). Figure 11. Simulated heads in the bottom surficial aquifer model layer (model layer 7). Figure 12. Simulated heads in the upper part of the Pee Dee aquifer model layer (model layer 9). Figure 13. Ash basin COI source zones for model. Figure 14. Simulated June, 2015 boron concentrations (ug/L) in the second model layer of the surficial aquifer (layer 4). Figure 15. Simulated June, 2015 boron concentrations (ug/L) in the lowest model layer of the surficial aquifer (layer 7). Figure 16. Simulated June, 2015 boron concentrations (ug/L) in the upper part of the Pee Dee aquifer (layer 9). Figure 17. Simulated June, 2015 arsenic concentrations (ug/L) in the second model layer of the surficial aquifer (layer 4). Figure 18. Simulated June, 2015 arsenic concentrations (ug/L) in the lowest model layer of the surficial aquifer (layer 7). Figure 19. Simulated June, 2015 arsenic concentrations (ug/L) in the upper part of the Pee Dee aquifer (layer 9). Figure 20. Simulated June, 2015 vanadium concentrations (ug/L) in the second model layer of the surficial aquifer (layer 4). Figure 21. Simulated June, 2015 vanadium concentrations (ug/L) in the lowest model layer of the surficial aquifer (layer 7). Figure 22. Simulated June, 2015 vanadium concentrations (ug/L) in the upper part of the Pee Dee aquifer (layer 9). Figure 23. Map showing proposed ash basin closure for the CAP2 scenario which only considers the ash basin closure. Figure 24. Simulated 2020 boron concentration (ug/L) in the second model layer of the surficial aquifer (layer 4) for CAP1. Figure 25. Simulated 2020 boron concentration (ug/L) in the lowest model layer of the surficial aquifer (layer 7) for CAP1. Figure 26. Simulated 2020 arsenic concentration (ug/L) in the second model layer of the surficial aquifer (layer 4) for CAP1. Figure 27. Simulated 2020 arsenic concentration (ug/L) in the lowest model layer of the surficial aquifer (layer 7) for CAP1. Figure 28. Simulated 2020 vanadium concentration (ug/L) in the second model layer of the surficial aquifer (layer 4) for CAP1. Figure 29. Simulated 2020 vanadium concentration (ug/L) in the lowest model layer of the surficial aquifer (layer 7) for CAP1. Figure 30. Simulated 2030 boron concentration (ug/L) in the second model layer of the surficial aquifer (layer 4) for CAP1. Figure 31. Simulated 2030 boron concentration (ug/L) in the lowest model layer of the surficial aquifer (layer 7) for CAP1. Figure 32. Simulated 2030 arsenic concentration (ug/L) in the second model layer of the surficial aquifer (layer 4) for CAP1. Figure 33. Simulated 2030 arsenic concentration (ug/L) in the lowest model layer of the surficial aquifer (layer 7) for CAP1. Figure 34. Simulated 2030 vanadium concentration (ug/L) in the second model layer of the surficial aquifer (layer 4) for CAP1. Figure 35. Simulated 2030 vanadium concentration (ug/L) in the lowest model layer of the surficial aquifer (layer 7) for CAP1. Figure 36. Simulated 2045 boron concentration (ug/L) in the second model layer of the surficial aquifer (layer 4) for CAP1. Figure 37. Simulated 2045 boron concentration (ug/L) in the lowest model layer of the surficial aquifer (layer 7) for CAP1. Figure 38. Simulated 2045 arsenic concentration (ug/L) in the second model layer of the surficial aquifer (layer 4) for CAP1. Figure 39. Simulated 2045 arsenic concentration (ug/L) in the lowest model layer of the surficial aquifer (layer 7) for CAP1. Figure 40. Simulated 2045 vanadium concentration (ug/L) in the second model layer of the surficial aquifer (layer 4) for CAP1. Figure 41. Simulated 2045 vanadium concentration (ug/L) in the lowest model layer of the surficial aquifer (layer 7) for CAP1. Figure 42. Simulated steady-state hydraulic heads for CAP2. Figure 43. Simulated 2020 boron concentration (ug/L) in the second model layer of the surficial aquifer (layer 4) for CAP2. Figure 44. Simulated 2020 boron concentration (ug/L) in the lowest model layer of the surficial aquifer (layer 7) for CAP2. Figure 45. Simulated 2020 arsenic concentration (ug/L) in the second model layer of the surficial aquifer (layer 4) for CAP2. Figure 46. Simulated 2020 arsenic concentration (ug/L) in the lowest model layer of the surficial aquifer (layer 7) for CAP2. Figure 47. Simulated 2020 vanadium concentration (ug/L) in the second model layer of the surficial aquifer (layer 4) for CAP2. Figure 48. Simulated 2020 vanadium concentration (ug/L) in the lowest model layer of the surficial aquifer (layer 7) for CAP2. Figure 49. Simulated 2030 boron concentration (ug/L) in the second model layer of the surficial aquifer (layer 4) for CAP2. Figure 50. Simulated 2030 boron concentration (ug/L) in the lowest model layer of the surficial aquifer (layer 7) for CAP2. Figure 51. Simulated 2030 arsenic concentration (ug/L) in the second model layer of the surficial aquifer (layer 4) for CAP2. Figure 52. Simulated 2030 arsenic concentration (ug/L) in the lowest model layer of the surficial aquifer (layer 7) for CAP2. Figure 53. Simulated 2030 vanadium concentration (ug/L) in the second model layer of the surficial aquifer (layer 4) for CAP2. Figure 54. Simulated 2030 vanadium concentration (ug/L) in the lowest model layer of the surficial aquifer (layer 7) for CAP2. Figure 55. Simulated 2045 boron concentration (ug/L) in the second model layer of the surficial aquifer (layer 4) for CAP2. Figure 56. Simulated 2045 boron concentration (ug/L) in the lowest model layer of the surficial aquifer (layer 7) for CAP2. Figure 57. Simulated 2045 arsenic concentration (ug/L) in the second model layer of the surficial aquifer (layer 4) for CAP2. Figure 58. Simulated 2045 arsenic concentration (ug/L) in the lowest model layer of the surficial aquifer (layer 7) for CAP2. Figure 59. Simulated 2045 vanadium concentration (ug/L) in the second model layer of the surficial aquifer (layer 4) for CAP2. Figure 60. Simulated 2045 vanadium concentration (ug/L) in the lowest model layer of the surficial aquifer (layer 7) for CAP2. Figure 61. Simulated 2020 boron concentration (ug/L) in the second model layer of the surficial aquifer (layer 4) for CAP3. Figure 62. Simulated 2020 boron concentration (ug/L) in the lowest model layer of the surficial aquifer (layer 7) for CAP3. Figure 63. Simulated 2030 boron concentration (ug/L) in the second model layer of the surficial aquifer (layer 4) for CAP3. Figure 64. Simulated 2030 boron concentration (ug/L) in the lowest model layer of the surficial aquifer (layer 7) for CAP3. Figure 65. Simulated 2045 boron concentration (ug/L) in the second model layer of the surficial aquifer (layer 4) for CAP3. Figure 66. Simulated 2045 boron concentration (ug/L) in the lowest model layer of the surficial aquifer (layer 7) for CAP3. 1 1.0 INTRODUCTION Duke Energy Progress, LLC (Duke Energy) owns and operates the L.V. Sutton Energy Complex (Site) in New Hanover County, near Wilmington, North Carolina (Figure 1). The site is located on 3300 acres along the east bank of the Cape Fear River northwest of Wilmington. 1.1 General Setting and Background The Sutton Site became operational in 1954 with three coal-fired boilers. Coal ash was originally stored on-site in the “former ash disposal area” (FADA) located just north of the plant coal pile. Cooling water for the plant originally came directly from the Cape Fear River. In 1971, an 1100 acre cooling pond known as Lake Sutton was built along with an unlined ash basin known as the 1971 ash basin (also called the “old ash basin”). Another ash basin was built in 1984, and it is referred to as the 1984 ash basin (also known as the “new ash basin”). The 1984 ash basin was constructed with a one foot thick clay liner beneath it. The Sutton Plant stopped burning coal in November, 2013, and switched to natural gas for electricity generation. The site is located in a low flat area, with elevations that range from sea level (the Cape Fear River) to about 25 feet above mean sea level (MSL) on the top of some sand dunes. The water table is relatively flat, and is generally located near the ground surface, with standing water found in some low areas. The site is located in the Atlantic Coastal Plain, and is characterized by a shallow water table aquifer that is underlain by a series of confined aquifers. The groundwater salinity increases with depth, and only the top aquifers are used for drinking water. The surficial aquifer locally discharges to tidal marshes swamps, the Cape Fear River, Lake Sutton, and the Northeast Cape Fear River. There is also substantial local groundwater pumping from the surficial aquifer for water supply. 1.2 Study Objectives The purpose of this study is to predict the groundwater flow and constituent transport that will occur as a result of different possible corrective actions at the site. The study consists of three main activities: development of a calibrated steady-state flow model of current conditions, development of a historical transient model of constituent transport that is calibrated to current conditions, and predictive simulations of the different corrective action options. 2 2.0 CONCEPTUAL MODEL The site conceptual model for the Sutton Plant is primarily based on the Comprehensive Site Assessment Report (CSA Report) for the Sutton Site (SynTerra, 2015). The CSA report contains extensive detail and data related to most aspects of the site conceptual model that are used here. 2.1 Aquifer System Framework The aquifer system at the site includes both unconfined and confined aquifers. The uppermost aquifer is an unconfined surficial aquifer that consists of very high permeability sands. This unit ranges in thickness from about 40 to 60 feet. The upper part of this unit consists of well-sorted loose sand. Sixteen slug tests were performed in the upper Surficial Aquifer. Hydraulic conductivities from these tests ranged from about 25 ft/d to 176 ft/d, with a geometric mean of 47 ft/d (SynTerra, 2015). The lower 30 feet of the Surficial Aquifer consists of poorly-sorted sands with discontinuous layers of coarse sand and fine gravel. Sixteen slug tests were performed in wells screened in this unit. Hydraulic conductivities in the lower Surficial Aquifer ranged from about 23 ft/d to 172 ft/d, with a geometric mean of 86 ft/d, and a median value of about 106 ft/d. Regionally, the Surficial Aquifer is underlain by the Pee Dee confining unit. The Pee Dee confining unit is present throughout most of New Hanover County (Bukowski McSwain, et al., 2014), where if confines the underlying Pee Dee aquifer. The Sutton site is located near the limit of the Pee Dee confining unit, and the confining unit was previously believed to exist beneath the site (Bukowski McSwain, et al., 2014). However, extensive deep (up to 150 ft) drilling performed during the CSA study failed to encounter the clay confining unit at the Sutton Site. The Surficial Aquifer sands lie unconformably over the Pee Dee Formation, and the contact between the formations is sharp and distinct. The upper part of the Pee Dee Formation at the Sutton Site consists of fine sands and silts with clay lenses and laminae. The Pee Dee Formation becomes finer with depth at the Site, and often is a very dense, low -plasticity clayey silt (SynTerra, 2015). The Pee Dee Formation extends to a depth of about 350 ft at the Site, where it overlies the Black Creek confining unit (Bukowski McSwain, et al., 2014; Harden et al., 2003). On a regional basis, the upper part of the confined Pee Dee Aquifer can be a productive water producing formation (Bukowski McSwain, et al., 2014). The aquifer tends to become finer 3 grained with depth, and exhibits high salinity near the Black Creek confining unit (Harden et al., 2003). The Pee Dee Formation at the Sutton Site is not confined, and it consists of low permeability fine sands, silts, and clays. Six slug tests were performed in wells screened in the upper part of the Pee Dee (elevations ranging from -70 to -109 ft MSL). Hydraulic conductivities in the upper Pee Dee ranged from 0.007 to 0.32 ft/d, with a geometric mean value of 0.037 ft/d, and a median value of 0.039 ft/d (SynTerra, 2015). Three slug tests were performed in wells screened in the lower part of the Pee Dee (elevations from -126 to -133 ft MSL). These hydraulic conductivities ranged from 0.0003 to 0.002 ft/d. Although the Pee Dee confining unit was not encountered at the Sutton Site, the low hydraulic conductivity of the Pee Dee formation at the Site serves to isolate the shallow Surficial Aquifer from deeper units. The hydraulic conductivity of the Pee Dee formation at the Sutton Site appears to be 3 to 4 orders of magnitude lower than the hydraulic conductivity of the Surficial Aquifer. 2.2 Groundwater Flow System The shallow groundwater system is recharged from infiltrating rainwater, and from water that infiltrates through the ash basins. The average value of recharge in the vicinity of the Sutton Site was estimated from the recent USGS hydrogeology reports on New Hanover County (Bukowski McSwain, et al., 2014), Brunswick County (Harden et al., 2003), and from the map of recharge in North Carolina by Haven (2003). The USGS report on New Hanover County reports an average infiltration rate range of 12 to 16 inches per year, and the report on adjacent Brunswick County reports an average infiltration rate of 11 inches per year. The North Carolina map of recharge by Haven (2003) gives a range of 6 to 10 inches per year for the upland areas. A recharge value of 12 inches per year was used in the model for the upland areas, with lower values in the vicinity of the Sutton Plant, and the nearby Invista chemical plant. A recharge value of zero was used in the tidal marshes, rivers, and ponds that serve as discharge areas for the groundwater system. The Sutton Site ash basins are currently inactive. The ash management area consists of three locations; the FADA, the 1971 ash basin and the 1984 ash basin. The FADA operated until 1971, appears to have been a low-lying area that was filled with ash. The thickness of the ash 4 encountered there extended from the ground surface to a depth of approximately 8 feet. Groundwater was measured at approximately 3 feet below land surface in a monitoring well installed there. The 1971 ash basin area operated between 1971 and 1984, and briefly in 2013. It appears to have been excavated below grade to a depth of approximately 40 feet. Samples collected from from a deep boring indicate that the surficial sand was removed except for approximately two feet at the bottom prior to placement of the ash. The ash is approximately 79 feet deep, as measured from the top of the ash, and the top of the ash basin is approximately 40 feet above Site grade. There is a small area of standing water in the northwest portion of the 1971 ash basin which appears to be perched above the local water table based on water level measurements made in an observation well installed in the basin. The excavated sand may have been used locally in the construction of the basin or canal berms. Both the FADA and the 1971 ash basins are unlined. The 1984 basin operated from 1984 until November, 2013. It appears to have been constructed above grade and is lined with a 12-inch clay layer. The northern portion of this basin contains standing water that appears to be perched well above the local water table. No observation wells have been installed through the 1984 ash basin liner, but nearby wells outside of the basin have water level elevations that are about 15 feet below the elevation of the standing water in the northern part of the basin. Water level measurements from a pair of wells screened in and just below the ash in the 1971 basin show some of mounding of the water table above the surrounding areas. This mounding is due to the enhanced recharge in the ash basin. The ash basin in its current configuration is a closed basin with little outflow or runoff, and it is unlined. In addition to rainfall, the basin receives storm water from the Sutton Plant. Vegetation on the ash basin is sparse to nonexistent, and the ash has a moderate conductivity (on the order of 1 ft/d). This combination of factors likely leads to enhanced infiltration in the ash basin compared to the surrounding area. This recharge rate was estimated to be about 30 inches per year, based on the above factors, and the average annual rainfall rate of 55 inches per year. This recharge rate is uncertain, and the actual value could be higher or lower. Recharge to the groundwater system from the 1984 ash basin was estimated by taking the hydraulic head difference inside and outside the ash basin and using Darcy’s law to estimate the 5 rate of leakage through the 12 inch clay liner. The basin recharge value used in the steady state current model was 30 inches per year, which is equivalent to the leakage that would result from a head difference of 15 feet across the clay liner with an average hydraulic conductivity of 1.6x10-7 cm/sec (0.00045 ft/d). This recharge rate is also uncertain, but it should be less than the average rainfall rate of 55 inches per year. There is currently no surface water outflow from the 1984 basin In the past during active ash sluicing operations, large amounts of water entered the ash basins. The sluicing was performed by pumping an ash-water slurry though large (approximately 10-12 inch) pipes at flow rates of roughly 1000 to 3000 gallons per minute. The sluice pipes typically discharged into diked subareas of the ash basins, where the solids were allowed to settle. The excess water accumulated at the lower end of th e ash basins where it was discharged from an engineered control structure. The sluicing activities would have resulted in an increased rate of infiltration in the ash basins, but the actual rate of infiltration during active sluicing operations is not known. The shallow groundwater system discharges to Lake Sutton, the plant cooling water intake and discharge canals, nearby tidal marshes and swamps, and the Cape Fear and Northeast Cape Fear rivers. There are a number of public and private water supply wells located in the model area (Synterra, 2015). Two active Cape Fear Public Utility Authority public supply wells are located in the model area along with as many as 43 private supply wells. Most of these private supply wells provide water for small businesses, and are believed to have relatively low pumping rates. The nearby Invista chemical plant reportedly pumps a large volume of water from a series of supply wells in the area. While the location of some of the Invista wells are known, details of their well field and pumping rates were not available. Duke Energy has nine water supply wells on the Site property. Three of these are currently active, but they now pump at reduced rates compared to past pumping. The public and private water supply wells are discussed further in Section 4.4. 2.3 Hydrologic Boundaries The major discharging locations for the shallow water system (the cooling pond, the marshes and swamps, and the Cape Fear and Northeast Cape Fear rivers) serve as hydrologic boundaries to 6 the shallow groundwater system. There are no hydrologic boundaries in the deeper confined aquifers within the study area. 2.4 Hydraulic Boundaries The shallow groundwater system does not appear to contain impermeable barriers or boundaries in the study area. The low permeability silts and clays in the Pee Dee Formation beneath the surficial aquifer restrict flow into the deeper confined aquifers. The Pee Dee Formation is bounded below by the low permeability Black Creek confining unit, and for practical purposes, this can be considered a no-flow hydraulic barrier. 2.5 Sources and Sinks The ash basin recharge, and recharge in general is the major source of water to the shallow groundwater system. Most of this water discharges to the hydrologic boundaries described above, with a relatively small amount recharging the underlying Pee Dee aq uifer. There about 47 known private and public water supply wells within the model area (Synterra, 2015). Screen elevations and pumping rates from most of these wells are not known, but they almost certainly are screened in the surficial aquifer. 2.6 Water Budget Over the long term, the rate of water inflow to the study area is equal to the rate of water ouflow from the study area. Water enters the groundwater system through recharge, and underflow in the deeper confined aquifers. Water leaves the system through discharge to the rivers, marshes and swamps, pumping wells and through underflow in the deeper confined aquifers. 2.7 Modeled Constituents of Interest Arsenic, boron, barium, cobalt, iron, manganese, total dissolved solids (TDS), pH, and vanadium have been identified as site specific constituents of interest (COIs) based on concentrations in ash pore water that exceed the 2L or IMAC standards. Of these constituents, boron is the most prevalent in groundwater. Boron is present at relatively high concentrations in the 1971 ash basin, and a boron plume extends to wells east of the ash basins. Boron migration appears to occur mainly in the lower part of the Surficial Aquifer. Boron was detected above the 2L standard in most of the upper Pee Dee wells (elevations of about -70 to -90 ft MSL) and in all of the lower Pee Dee wells (elevations of about -120 to -130 7 ft MSL). The boron concentration in the Pee Dee Formation increases with depth, and the highest boron concentrations were found in the deepest wells. The deep wells also exhibit higher chloride concentrations. The pattern of increasing boron concentration with depth, coupled with the increased salinity and the very low hydraulic conductivity of the Pee Dee Formation suggest that the boron found in the Pee Dee Formation may be naturally occurring. Boron is present in seawater at an average concentration of 4600 ug/L, and it is known to accumulate in marine clays. Boron has been found above the NC 2L standard in the Pee Dee Formation at North Myrtle Beach, SC at a depth of 100 ft, and it is commonly encountered in deeper wells (Lee, 1984). Arsenic was detected at relatively high levels in the ash pore water in the 1971 basin, and in shallow groundwater beneath the FADA. Arsenic is not generally found in groundwater outside of the ash basin areas above the 2L standard except for one well (MW-21C) located about 500 feet outside of the 1971 ash basin, and another well (MW-15) located just south of the FADA Vanadium is present in the 1971 as basin at a concentration that exceeds the 2L standard by about a factor of ten, but there is no clear evidence of a vanadium plume in the groundwater. One shallow well (MW-20), located between the FADA and the coal pile had a high vanadium concentration (ten times the value measured in the 1971 ash basin). The vanadium concentration in that well may be due to some process other than transport from the ash basins. Vanadium is found sporadically above the 2L standard throughout the model area, at all depths, including the deep (~150 ft) lower Pee Dee wells. It appears that there is a significant background level of vanadium above the IMAC standard at the Sutton Site. The COIs selected for modeling at the Sutton Site were boron, arsenic, and vanadium. The remaining constituents (barium, cobalt, iron, manganese, TDS, and pH) were not used in the modeling exercise for one or more of the following reasons: 1) concentrations in the ash pore water do not greatly exceed likely background levels; and 2) there is no discernable plume of the constituent extending downgradient from the ash basin. 2.8 Constituent Transport The COIs that are present in the coal ash dissolve into the ash pore water. As water infiltrates through the basins, water containing COIs can enter the groundwater system through the bottom of the ash basins. Once in the groundwater system, the COIs are transported by advection and 8 dispersion, subject to retardation due to adsorption to solids. If the COIs reach a hydrologic boundary or water sink, they are removed from the groundwater system, and they enter the surface water system, where in general, they are greatly diluted. At this site, boron is the primary constituent that is migrating from the ash basins. 9 3.0 COMPUTER MODEL 3.1 Model Selection The numerical groundwater flow model was developed using MODFLOW (McDonald and Harbaugh, 1988), a three-dimensional (3D) finite difference groundwater model created by the United States Geological Survey (USGS). The chemical transport model is the Modular 3-D Transport Multi-Species (MT3DMS) model (Zheng and Wang, 1999). MODFLOW and MT3DMS are widely used in industry and government, and are considered to be industry standards. The models were assembled using the Aquaveo GMS 10.0 graphical user interface (http://www.aquaveo.com/). 3.2 Model Description MODFLOW uses Darcy’s law and the conservation of mass are used to derive water balance equations for each finite difference cell. MODFLOW considers 3D transient groundwater flow in confined and unconfined heterogeneous systems, and it can include dynamic interaction with pumping wells, recharge, evapotranspiration, rivers, streams, springs, lakes, and swamps. Several versions of MODFLOW have been developed over the years. This study uses the MODFLOW-NWT version (Niswonger, et al., 2011). The NWT version of MODFLOW provides improved numerical stability and accuracy for modeling problems with variable water tables. That improved capability is helpful in the present work where the position of the water table in the ash basin can fluctuate depending on the conditions under which the basin is operated and on the corrective action activities. MT3DMS uses the groundwater flow field from MODFLOW to simulate 3D advection and dispersion of the dissolved COIs including the effects of retardation due to COI adsorption to the soil matrix. 10 4.0 GROUNDWATER FLOW AND TRANSPORT MODEL CONSTRUCTION The flow and transport model for this site was built through a series of steps. The first step was to build a 3D model of the site hydrostratigraphy based on field data. The next step was determination of the model domain and construction of the numerical grid. The numerical grid was then populated with flow parameters which were adjusted during the steady-state flow model calibration process. Once the flow model was calibrated, the flow parameters were used to develop a transient model of the historical flow patterns at the site. The historical flow model was then used to provide the time-dependent flow field for the constituent transport simulations. Calibration of the transport model required some adjustments to the hydraulic parameters in order to reproduce the observed boron plume. This resulted in a second iteration of flow model calibration, so that the calibrated flow model matches the observed heads, and the transient flow and transport model reproduces the observed boron plume. 4.1 Model Domain and Grid The first steps in the model grid generation process were the determination of the model domain, and the construction of a 3D hydrostratigraphic model. The model has dimensions 4.5 miles by 5.1 miles, and it is aligned approximately with the peninsula that is formed by the confluence of the Cape Fear and Northeast Cape Fear rivers. (Figure 2). This alignment was chosen so that most of the outer boundaries to the shallow groundwater system would be the rivers and tidal swamps and marshes. Only a very small part of the north and south end of the model are not covered by surface water features. The model extent was made large relative to the area of interest in order to minimize the influence of outer model boundary conditions. The ground surface of the model was interpolated from NCDOT LIDAR data from 2007 (https://connect.ncdot.gov/resources/gis/pages/cont-elev_v2.aspx). The elevations for the top of the ash basin were modified using more recent surveying data. The hydrostratigraphic model (called a solids model in GMS) consists of six units: the 1971 and 1984 ash basins, the upper part of the Surficial Aquifer, the Pee Dee confining clay unit (only present to the east and south of the Sutton Site), the lower part of the Surficial Aquifer (or the uppermost part of the Pee Dee aquifer where the Pee Dee confining unit is present), the upper ¼ of the Pee Dee Formation, and the deeper part of the Pee Dee Formation. The elevation of contacts between these units were determined from boring logs from previous studies and from the recent CSA report. The contact 11 elevations were estimated for locations where well logs were not available by extrapolation of the borehole data, and by using knowledge of the regional strike and dip of the aquifers from Bukowski McSwain, et al. (2014) and Harden et al. (2003). Figure 3 shows a fence diagram of the 3D hydrostratigraphic unit viewed from the south, with a vertical exaggeration of 10x. The grey material corresponds to the ash basin, the yellow material is the upper part of the Surficial Aquifer, the green material is the Pee Dee confining clay, the thin orange layer is the lower part of the Surficial Aquifer (or the uppermost part of the Pee Dee beneath the confining unit), the darker orange layer represents the first ~ 60 ft of the Pee Dee formation, and the bottom zone represents the remaining part of the Pee Dee. The top of the Black Creek confining unit elevations from Bukowski McSwain, et al. (2014) form the base of the model. The numerical model grid is shown in Figure 4. The grid is discretized in the vertical direction using the solids model (Figure 3) to define the numerical model layers. The top 2 model layers represent the ash basin, including the berms around the edges of the ash. The model layers 3 -5 represent the upper part of the Surficial Aquifer. Model layer 6 represents the Pee Dee confining unit where it is present; otherwise it is part of the lower Surficial Aquifer, along with layer 7. Model layers 8-10 represent the upper part of the Pee Dee formation which is composed of fine sands and silts. Layers 11 and 12 represent deeper parts of the Pee Dee that contain mainly silts and clays. The bottom layer (13) is a high permeability confined aquifer that rests on top of the Black Creek confining unit. The bottom layer is located at an elevation of about -250 to -350 ft MSL. The discretization in the horizontal direction is variable, with the finest spacing (40 ft by 40 ft) located in and east of the ash basins. The grid spacing increases with distance from the ash basins to a maximum of about 400 ft by 400 ft at the outside edges of the model. The grid contains a total of 283,974 active cells. 4.2 Hydraulic Parameters The horizontal hydraulic conductivity and the horizontal to vertical hydraulic conductivity anisotropy ratio (anisotropy) are the main hydraulic parameters in the model. The distribution of these parameters is based on primarily on the model hydrostratigraphy, with some additional vertical variation. Most of the hydraulic parameter distributions in the model were uniform 12 throughout a model layer. Initial estimates of parameters were based on literature values, results of slug and core tests, and simulations performed using a preliminary flow model. The hydraulic parameter values were adjusted during the flow model calibration process described in Section 5.0 to provide a best fit to observed water levels in observation wells. 4.3 Flow Model Boundary Conditions The flow model outer boundary conditions are different for the different aquifer units. The outer lateral boundary conditions for the upper part of the surficial aquifer is almost entirely either constant head (in the rivers) or drains (in the swamps), with small areas of no-flow at the north and south ends of the model. The outer boundary of the model was purposely selected to minimize the no-flow boundaries. The nearest model boundary is more than a mile from the ash basins. The deep (layer 13) Pee Dee confined aquifer was assigned a constant head on the north and south ends of the model in order approximate the regional gradient. The north edge of the model was assigned a head of 19 ft MSL, the south edge of the model was assigned a head of 10 ft MSL All other lateral boundaries are no-flow. The base of the Black Creek aquifer in the model was considered a no flow boundary. 4.4 Flow Model Sources and Sinks The flow model sources and sinks on the interior of the model consist of recharge, lakes, marshes and swamps, the Cape Fear and Northeast Cape Fear rivers, and groundwater pumping. Recharge is a key hydrologic parameter in the model. As described in Section 2.2, the recharge rate for upland areas of the Sutton Site was assumed to be about 12 inches/year. The recharge rate was set to zero in the low swampy areas that serve as groundwater discharge zones. The recharge rates in the Sutton Plant, and the Invista chemical plant were set to 1 inch per year due to the large areas of roof and pavement. The recharge at a lined landfill to the north was set to zero. Recharge in the FADA was set to a low value during the calibration process to avoid flooding the top model cells. The current recharge rate in the 1971 and 1984 ash basins was estimated to be 30 inches/year as discussed in Section 2.2. Figure 5 shows the distribution of recharge zones in the model. The main area of recharge is the north-south peninsula between the two rivers. 13 Recharge was not adjusted much during the model calibration process, but it is included in the sensitivity analysis. The reason for not including recharge as a calibration parameter is that for steady-state unconfined flow, the hydraulic heads are determined primarily by the ratio of recharge to hydraulic conductivity, so the two parameters are not independent. In situations where the groundwater discharges to a flow measuring point (for example a gauged stream in a watershed), the flow measurement can be used to calibrate the recharge value allowing both the recharge rate and the hydraulic conductivity to be simultaneously calibrated. However, at the Sutton Site, groundwater discharge is diffuse, and occurs to many different locations in swamps, marshes, the cooling pond, and the rivers. Lake Sutton, ponds and a sump in the former coal pile area were treated as constant head zones in the model (Figure 6). The Lake Sutton has a constant pool elevation of 9.6 ft MSL. The swamps and marshes were treated as drains using the MODFLOW DRAIN package where the drain elevation in the swamps was set equal to the ground surface elevation from the LIDAR data. All constant head areas in the flow model used the MODFLOW CHD specified head package. The Cape Fear and Northeast Cape Fear rivers were broken into segments to approximate the average river gradients across the model domain. Both rivers are tidal, but only the average river stage (about 0 MSL) was used. The Cape Fear is a major river that is about 30 feet deep in the model area. The constant head cells associated with this river were applied to both layers 3 and 4 to reflect this depth. The Northeast Cape Fear River is dredged at the southern end so constant head cells were applied to layers 3 and 4 in this area. The remainder of the Northeast Cape Fear River is shallow, so constant head conditions were only applied to layer 3 in these areas. During model calibration, it was found necessary to add a small but important constant head feature between the former coal pile and the FADA in order to match the observed cone of groundwater depression in this area. At the time of groundwater measurements in June, 2015, the coal pile along with surface soils had recently been removed, lowering the ground elevation in this area below the water level in the adjacent plant intake and discharge canals. There is a low area (sump) at the northwest corner of this excavated area that collects and removes seepage and rainwater. The water elevation in this sump was estimated to be about 1 ft. MSL during the model calibration process. Because this feature is temporary, it was only used for the current conditions flow model calibration, but not for the transient transport modeling. 14 Relatively little information was available about the public and private wells in the model area. Figure 7 shows the location of water supply wells in the model area (from Synterra, 2015). Given the site hydrogeology, it is almost certain that these wells are screened in the Surficial Aquifer. In the model, well screen lengths were assumed to be 40 ft, with screens extending from the approximate base of the Surficial Aquifer upward. Some information was available about recent pumping rates in the Cape Fear Public Utility Authority wells, the Duke Energy wells, and to a lesser extent, some of the Invista wells. Synterra (2014) reported average pumping rates of 27 gpm for the two Cape Fear Public Utility Authority wells (wells NHC-SW3 and NHC-SW4). Those wells are scheduled to go offline in the fall of 2015, and the pumping rates at the time of water level measurements in June, 2015 were not available. Flow rates for the Duke Energy wells were estimated from data reported to the State through the Water Withdrawal & Transfer Registration Annual Water Use Reports (http://www.ncwater.org/Permits_and_Registration/Water_Withdrawal_and_Transfer_Registrati on/report). Those wells were apparently used much more in the past, and the most recent pumping rates were only a few gpm per well. According to the Water Withdrawal reports, the Invista plant pumps an average of about 1 million gallons per day (~700 gpm) from wells. Several possible Invista wells were located, and are reported in the CSA report (Synterra, 2015). However, the names of these wells for the most part do not match the names given in the Water Withdrawal reports. The two wells that do match the reports, wells Invista G and Invista H2 had reported average pumping rates of 56 and 93 gpm, respectively during 2014. There is a high degree of uncertainty about the actual current and historical pumping rates of these and other Invista wells in the area. No pumping rate or historical information was available for the other 39 water supply wells identified in the model area. These wells were assumed to have constant pumping rates of 1000 gallons per day. 4.5 Flow Model Calibration Targets The steady state flow model calibration targets were the 87 water level measurements made in observations wells in June, 2015. The flow model calibration target wells are listed in Table 1. 15 In general, wells with a B designation at the end of the name are screened in the upper Surficial Aquifer, those with a C designation are screened in the lower Surficial Aquifer, those with a D designation are screened in the upper Pee Dee formation, and those with an E designation are screened deeper in the Pee Dee Formation. 4.6 Transport Model Parameters The transport model uses a transient MODFLOW simulation to provide the time-dependent groundwater velocity field. The transient MODFLOW simulation was started January, 1971, and it continued through June, 2015. The Sutton Plant began operations in 1954, and it used cooling water directly from the Cape Fear River. Coal ash from this time period up through 1971 was sent to the FADA. In about 1971 major changes were made to the Sutton Site. The 1100 acre Lake Sutton cooling pond was built, with intake and discharge canals that run adjacent to the FADA, and the 1971 ash basin was built. Since these 1971 features have dominated the groundwater flow and transport at the site for more than 40 years, it was decided to start the transient model in 1971. The actual history and development of the 1971 and 1984 ash basins is complex as they evolved over the course of more than 40 years but their basic footprints appear to have been established during initial construction. The transient flow model simulates the basins as having a constant footprint over time. As was discussed earlier, the basin infiltration rate during sluicing is not known, but it was estimated by taking the results of the calibrated steady state flow model (discussed in Section 5.1) and adjusting the infiltration rate upward to better match the boron transport. The final basin recharge rates used during sluicing in the transient flow model range from 40 to 90 inches per year. These rates are much smaller than the rate of water inflow to the basins with the sluiced ash. The transient flow field was modeled as three successive steady state flow fields; one corresponding to the high infiltration rate in the 1971 basin during ash sluicing from 1971 to 1984, one corresponding to the higher infiltration rate in the 1984 basin during ash sluicing from 1984 to 2013, and one corresponding to the current basin infiltration rates from 2013 to 2015. The key transport model parameters (besides the flow field) are the constituent source concentration in the ash basin, and the constituent soil-water distribution coefficients (Kd). Secondary parameters are the longitudinal, transverse, and vertical dispersivity, and the effective 16 porosity. The constituent source concentration in the FADA and 1971 ash basin were estimated from recently measured ash pore water concentrations in monitoring wells (SynTerra, 2015). The COI source concentrations in the 1984 ash basin were assumed to be similar to those in the 1971 basin, but the 1984 basin was split into two zones during the transport model calibration. Linear adsorption Kd values for Sutton Plant COIs were measured in the laboratory using core materials from the coal ash, the Surficial Aquifer sediments, and the Pee Dee Formation (Langley, et al., 2015). In general, the measured Kd values for the constituents were highly variable, and the variability within a given material type (for example the Surficial Aquifer sediments) was larger than the variability between different materials. The measured Kd value for arsenic outside of the ash ranged from 8.7 to 500 mL/g. The measured Kd value for boron ranged from ~0 to 1100 mL/g. The measured value for Vanadium outside of the ash ranged from 1.9 mL/g to 1300 mL/g. In light of the variability of the measured Kd values, it was decided that a conservative approach would be used for the Kd value in the model. A uniform Kd value is used throughout the model for each COI. The initial value used in calibration was the minimum measured value from Langley et al. (2015). It was found during the transport model calibration that using the minimum value of Kd still resulted in very little migration of either arsenic or vanadium, so the Kd values were left at the minimum measured values. The longitudinal dispersivity was assigned a value of 20 ft, the transverse dispersivity was set to 2 ft, and the vertical dispersivity was set to .2 ft. The radial flow from the ash basins and the high rate of infiltration result in a large degree of mixing in the boron plume; the additional effects of mechanical dispersion were small. The effective porosity was assumed to be uniform, but the value was adjusted during the transport model calibration process to a final value of 0.2 in order to better match the observed boron distribution. The soil dry bulk density was set to 1.6 g/mL. 4.7 Transport Model Boundary Conditions The transport model boundary conditions are no flow on the exterior edges of the model except where constant head boundaries exist, where they are specified a concentration of zero. All of the constant head water bodies (lakes and swamps) have a fixed concentration of zero. As water 17 containing dissolved constituents enters these zones, the dissolved mass is removed from the model. The infiltrating rainwater is assumed to be clean, and enters from the top of the model. The initial condition for the current conditions transport model (back in 1971) is one of zero concentration of COIs everywhere in the model. No background concentrations are considered. 4.8 Transport Model Sources and Sinks The FADA and ash basins are the source of COIs in the model. These sources are simulated by holding the COI concentration constant in cells located inside the ash basins. This allows infiltrating water to carry dissolved constituents from the ash into the groundwater system. With the MODFLOW/MT3DMS modeling approach, it is critical that this source zone is placed in cells that contain water (not “dry cells”). Since many of the ash basin cells were dry, the specified concentration condition was placed in model layer 3 directly beneath the basin. The concentration was also specified in model layers 4-7 in a zone beneath the 1971 ash basin (Figure 8) to represent the deep ash below that basin, and in layer 3 in the FADA. The transport model sinks are the constant head lakes, marshes, swamps, and rivers. As groundwater enters these features, it is removed along with any dissolved constituent mass. Similarly, if water containing a constituent were to encounter an extraction well, the constituent would be removed with the water. 4.9 Transport Model Calibration Targets The transport model calibration targets are COI concentrations measured in 71 monitoring wells in June, 2015 (SynTerra, 2015). 18 5.0 MODEL CALIBRATION TO CURRENT CONDITIONS 5.1 Flow Model Residual Analysis The flow model was calibrated in stages starting with a model that assumed homogeneous conditions in most formations. All calibration efforts were done by trial and error. As the effort continued, some formations were given different properties in different layers. For the most part, the model layer properties were homogeneous, except for the discontinuous Pee Dee confining layer, and the deep coal ash beneath the 1971 ash basin (Figure 8). The flow calibration was done iteratively with transient transport simulations. This was necessary in order to match both the heads and the boron concentration distributions. The final calibrated flow model has a mean head residual of -0.03 ft., a root mean squared head residual of 0.56 ft., and a normalized root mean square error of 6.89%. A comparison of the observed and simulated water levels is listed in Table 1, and the observed and simulated levels are cross-plotted in Figure 9. Table 2 lists the best-fit hydraulic parameters from the calibration effort. The model showed a very low sensitivity to the conductivity of the ash and berm in the ash basin. The calibrated conductivity of the Surficial Aquifer is laterally homogeneous and weakly anisotropic. The calibrated values used in the upper and lower parts of the Surficial Aquifer of 50 ft/d and 125 ft/d are consistent with the many slug test results reported in the CSA report (Synterra, 2015). The Pee Dee formation has a low conductivity in the model (0.1 to 0.01 ft/d) that decreases with depth until the bottom layer. These calibrated values are also consistent with the slug tests reported in the CSA report. The bottom model layer was given a high conductivity in order to approximately match regional heads in the Pee Dee aquifer. The computed heads in the top Surficial Aquifer model layer (layer 3) are shown in Figure 10. The calibration wells are also shown in this figure (many of the nested wells plot on top of each other). The green, yellow, and red bars indicate the magnitude of model error at each well. The green color indicates that the difference is less than .8 ft., the yellow color indicates a difference of .8 to 1.6 ft., and the red indicates a difference of more than 1.6 ft. The shallow head contours 19 show the slight mounding in the ash basin and the temporary cone of depression in the FADA area caused by dewatering of the former coal pile area. Figure 11 shows the computed heads in the bottom of the surficial aquifer (layer 7). These heads are similar to the shallow heads. The hydraulic effect of the deep ash below the 1971 basin (the red line in Figure 11) can be seen in both the shallow and deeper heads. This zone of ash has a conductivity that is nearly 100 times lower than the deeper part of the Surficial Aquifer, and it results in locally steeper hydraulic gradients in the model. The computed head in the upper part of the Pee Dee Formation is shown in Figure 12. 5.2 Flow Model Sensitivity Analysis A parameter sensitivity analysis was performed on the calibrated model by systematically increasing and decreasing the main parameters by 50% of their calibrated value. Table 3 shows the results of the analysis, expressed in terms of the normalized root means square error (NRMSE) for each simulation, compared to the calibrated NRMSE of 6.89%. The flow model showed the highest degree of sensitivity to the upland recharge and to the Surficial Aquifer horizontal hydraulic conductivity. The model was particularly sensitive to decreasing the Surficial Aquifer hydraulic conductivity. The model was only weakly sensitive to the current ash basin recharge rates. The model was also only weakly sensitive to the pumping rates in the primary supply wells. This insensitivity is due to the high conductivity and recharge in the area and the unconfined nature of the aquifer. These factors limit the cones of depression associated with groundwater pumping. It should be pointed out, however, that the pumping wells do influence the COI transport significantly, and the values were adjusted during the transient simulation to better match the observed boron concentration distribution. The model was insensitive to the Surficial Aquifer anisotropy ratio and to the hydraulic conductivity of the coal ash. The flow model calibration was also insensitive to the conductivity of the Pee Dee Formation silts and silty sands within the parameter range of +/- 50%. Subsequent simulations run with Kh values 10 times and 100 times larger showed that the order of magnitude of the Pee Dee Formation conductivity is important, and that it needs to be at least 100 times lower than the surficial aquifer conductivity to match the observed heads at the Site. 20 5.3 Transport Model Calibration and Sensitivity The transient flow model used for transport consisted of a series of 3 steady-state flow fields: one that represents the period when the 1971 ash basin was in operation; one that r epresent the period when the 1984 ash basin was in operation; and one after the end of ash sluicing in 2013. As the transport model was calibrated, it was found necessary to adjust some of the flow sources and sinks in the model in order to reproduce the observed boron distribution. The ash basin recharge rates for the transient model are shown in Table 4. The 1984 ash basin was broken into 3 zones from south to north. Historical aerial photos show that the ash was mainly sluiced from the south end of the basin, so hydraulic heads and therefore leakage through the clay liner would have likely been higher at the southern end of the basin. This adjustment to the recharge was made to improve the match of the computed boron distribution with the observed distribution. The major pumping well flow rates in the model were also varied with time (Table 5). The final rates match the calibrated flow model, but earlier rates during the 1984-2013 period were increased somewhat to reflect higher pumping rates during this period. The transport simulations used four spatial zones of specified COI source concentration (Figure 13 and Table 6). The 1984 ash basin was split into two sections, with lower COI concentrations in the northern section. This adjustment was needed in order to match the lower boron concentrations observed in monitoring wells north of the ash basin. The COI source concentrations used in the FADA and 1971 basin reflect measured values there. The source concentrations in the southern part of the 1984 basin are similar to the 1971 basin values, and the source concentrations in the northern part of the basin are about an order of magnitude lower. The transport simulations used the lowest measured Kd values from the UNCC study (Langley, 2015). The Kd for boron was set to zero, the Kd for arsenic was set to 9 mL/g, and the Kd for vanadium was set to 2 mL/g. Table 7 shows a comparison of measured and simulated boron concentrations. The simulated boron concentrations near top of the Surficial Aquifer (model layer 4), the bottom of the Surficial Aquifer (model layer 7), and the upper part of the Pee Dee Formation (model layer 9) are shown in Figures 14, 15, and 16, respectively. The simulated boron concentrations in the Surficial Aquifer reasonably match the observed concentrations in most areas. The model shows limited boron transport in the upper Surficial Aquifer (Figure 14), with more extensive offsite transport 21 in the lower Surficial Aquifer. The model simulated boundary where the 2L standard is exceeded is close to the observed location, except in the southern part of the plume, where the model overpredicts the extent of the plume slightly. The model does not predict any significant boron transport from the coal ash basins into the Pee Dee formation. This is a consequence of the low hydraulic conductivity of the Pee Dee, which diverts groundwater flow laterally through the Surficial Aquifer. The observed concentrations of boron in the upper and lower Pee Dee wells are believed to be naturally occ urring, and cannot be explained by this model. A comparison of the measured and simulated arsenic concentrations is given in Table 8. The simulated arsenic concentrations in the upper Surficial Aquifer (model layer 4), the bottom of the Surficial Aquifer (model layer 7), and the upper Pee Dee formation (model layer 9) are shown in Figures 16, 17, and 18, respectively. The model predicts very little arsenic transport outside of the ash basin and FADA footprints. The simulated vertical extent of arsenic concentrations in excess of the 2L standard is limited to the Surficial Aquifer. These results are consistent with the field data that show only a single 2L exceedance outside of the FADA and ash basin areas. That well, MW-21C, had an arsenic concentration of 53.8 ug/L during the June, 2015 sampling. The model predicts an arsenic concentration of zero at this location. An additional arsenic transport simulation using an artificially low Kd value of 2 mL/g still failed to predict a 2L exceedance at this well. A comparison of the measured and simulated vanadium concentrations is given in Table 9. The simulated vanadium concentrations in the upper Surficial Aquifer (model layer 4), the bottom of the Surficial Aquifer (model layer 7), and the upper Pee Dee formation (model layer 9) are shown in Figures 20, 21, and 22, respectively. The model predicts relatively little vanadium transport outside of the ash basin and FADA footprints. The vertical extent of vanadium concentrations in excess of the IMAC standard is limited to the Surficial Aquifer. Vanadium is found at concentrations that exceed the IMAC standard in many wells outside the ash basins. There is no apparent pattern to these concentrations, which in some cases exceed the standard by a factor of 5. These appear to be naturally occurring background levels of vanadium at the Site. A high concentration of vanadium was observed in one shallow well (MW -20) located between the former coal pile and the FADA. The concentration of vanadium in that well 22 of 39.6 ug/L is much higher than was observed in the 1971 ash basin pore water, and it is not predicted by the model. It is likely that a source other than the coal ash is responsible for this higher concentration. 6.0 PREDICTIVE SIMULATIONS OF CORRECTIVE ACTION SCENARIOS The simulated June, 2015 concentration distributions were used as initial conditions in three predictive simulations of future flow and COI transport at the Sutton Site. Three possible scenarios were simulated: 1) Corrective Action Plan #1 (CAP1) which consists of no further action with respect to the ash basins and groundwater system; 2) Corrective Action Plan #2 (CAP2) which involves complete ash removal from the FADA, 1971, and 1984 ash basins with construction of a new lined and capped ash landfill immediately to the east; 3) Corrective Action Plan #3 (CAP3) which consists of capping the FADA and the 1971 and 1984 ash basins with an impermeable cover that prevents infiltration. The site map for CAP2 activities is shown in Figure 23. The simulations run for 30 years, with results presented at 5 years (2020), 15 years (2030), and 30 years (2045). It should be noted that these simulations do not consider the high boron concentrations that were found deep in the PeeDee formation. The simulations only include constituent concentrations that emanated from the coal ash sources on the site. 6.1 Corrective Action Plan #1 (CAP1): No Further Action This simulation assumes that site conditions remain as they were in June, 2015 for the next 30 years. Figures 24 through 41 show the simulated boron, arsenic, and vanadium concentrations in model layers 4 and 7 at five, fifteen, and thirty years. The results show that both the arsenic and the vanadium have little migration from their current distributions over the 30 year time period. The boron plume appears to be stable to slowly shrinking during this time period (compare Figures 25, 31, and 37). Although water is still infiltrating the basins at a relatively high rate in this simulation, the rate is greatly reduced from the historical active ash sluicing period. The combination of reduced boron loading to the groundwater, combined with radial flow and dilution of the outer edges of the plume by infiltrating rainwater serve to gradually stabilize and shrink the plume, although it still extends beyond the property line in 2045. 23 6.2 Corrective Action Plan #2 (CAP2): Complete Ash Removal and Construction of a Lined and Capped Landfill This simulation uses the Geosyntec design for ash removal from the FADA and ash basins, with construction of a lined and capped ash landfill east of the current basins (Figure 23). The ash removal plan is based on a figure provided by Geosyntec (2015a) that sho ws the “Wet Option”. With this plan, all ash is removed from the FADA, and Lake Sutton is allowed to fill that excavation. Ash is removed from the 1984 basin, and that area is graded so that it gently slopes towards Lake Sutton. Ash is removed from the 1971 basin, and the excavation extends nearly to the PeeDee formation in the zone where deep ash is located. The majority of the 1971 basin excavation is then connected to Lake Sutton by breaching the dike on the southwest side of the basin. The plan for the new lined and capped landfill calls for it to be constructed east of the current ash basins, close to the eastern property line (Figure 23). The landfill will occupy approximately 100 acres, and the plan calls for two stormwater retention ponds, one at the north end of the landfill, and one at the south end of the landfill. The northern pond will have an area of about 12 acres, while the southern pond will have an area of about 10.5 acres (Geosyntec, 2015b). These stormwater basins will have a large effect on the groundwater flow in the area. The ponds are unlined, and are designed to capture all runoff from the 100 acre landfill cap. The ponds have been sized to hold large storm event without overflowing. Considering the very high hydraulic conductivity of the surficial aquifer, it is expected that most of the water entering the stormwater basins will recharge the groundwater. The recharge rate in these basins was estimated by assuming that about half of the annual rainfall (30 inches per year) runs off the landfill cap, and is captured by the stormwater basins. This would be a total of 250 acre-feet of water per year. Assuming an infiltration area of about 20 acres for the two ponds, this corresponds to a recharge rate of 150 inches per year. This value was used in the CAP2 simulation. The CAP2 model assumes that site geometry changes rapidly so that the new design is largely in effect by June, 2017, when the simulation begins. The Lake Sutton constant head zone is enlarged to include the FADA and most of the 1971 ash basin. The concentrations in this the constant head zone are maintained at zero. The deep excavation in the 1971 basin is given a very 24 high conductivity, and is also maintained at zero concentrations. The remaining 1971 and 1984 ash basin areas are given the background recharge rate of 12 inches per year. The new landfill area is given a recharge rate of zero. All water supply pumping rates are assumed to remain constant at the rates used in last step of the transport flow model. The specified concentration zones that were used to represent the COI sources in the ash basins and FADA (Figure 13) are removed, but COI concentrations in all layers outside of the ash are initialized to their simulated June, 2015 values. The simulated steady-state flow field that is predicted to result from these changes is shown in Figure 42. The removal of the ash basins and construction of the landfill with stormwater retention ponds is predicted to shift the groundwater divide to the east of its current location. The simulated boron, arsenic, and vanadium concentrations in layers 4 and 7 are shown in Figures 43 to 60. In 2020, the simulation shows relatively small changes to the concentration profiles, except for the zone where the deep ash was removed from the 1971 basin. The deeper boron in the surficial aquifer (Figure 44) shows some movement away from the two stormwater basins. The simulated boron concentrations in the deeper part of the surficial a quifer appear to recede back towards the property line by 2030 (Figure 50). This is due to the combined effect of the source removal, reduced infiltration in the former ash basin areas, zero infiltration below the new landfill, and the high infiltration rates in the two stormwater basins. Relatively little effect is seen on the simulated arsenic or vanadium plumes except for the area that was excavated. By 2045, the simulation shows a much smaller boron plume (Figures 55 and 56), while the simulated arsenic and vanadium plumes show little additional movement. 6.3 Corrective Action Plan #3 (CAP3): Cap in Place This simulation assumes that the FADA and 1971 and 1984 ash basins are covered with an impermeable cap that prevents water from infiltrating into the groundwater system. This model is identical to the CAP1 simulation, except that the recharge rate in the FADA and ash basins has been set to zero. Figures 61 through 66 show the simulated boron, concentrations in model layers 4 and 7 at five, fifteen, and thirty years (arsenic and vanadium are not shown because the simulation shows little migration over the 30 year period). The simulated boron plume in 2020 25 (Figures 61 and 62) is similar to the CAP1 no further action case, but by 2030, the CAP 3 simulation shows that the boron plume is shrinking (Figures 63 and 64). By the end of the simulation in 2045, the boron plume has receded to the approximate basin and FADA boundaries (Figures 65 and 66). The reduction of the boron plume over time in this case is due in part to the reduced discharge of boron to the groundwater system, and in part to the change in the groundwater flow field. The ash basin capping would eliminate the introduction of boron from infiltrating rainwater, although some boron would enter the system from the coal ash located below the water table in the 1971 basin. The water table mound shifts eastward due to the reduction of infiltration in the basins, causing groundwater in and around the basins to flow westward, towards the cooling pond. 26 7.0 REFERENCES Bukowski McSwain, K., L.N. Gurley, and D.J. Antolino, 2014, Hydrogeology, Hydraulic Characteristics, and Water-Quality Conditions in the Surficial, Castle Hayne, and Peedee Aquifers of the Greater New Hanover County Area, North Carolina, 2012-2013, U.S. Geological Survey, Scientific Investigations Report 2014-5169, 52 p. Harden, S.L., J.M. Fine, and T.B. Spruill, 2003, Hydrogeology and Ground-Water Quality of Brunswick County, North Carolina, U.S. Geological Survey, Water-Resources Investigations Report 03-4051, 95 p. Haven, W. T. 2003. Introduction to the North Carolina Groundwater Recharge Map. Groundwater Circular Number 19. North Carolina Department of Environment and Natural Resources. Division of Water Quality, 8 p. Geosyntec, 2015a, Option 8 – Wet Option IV, L.V. Sutton Steam Station Closure Grading Options. Geosyntec, 2015b, Site Development Plan, Construction Permit Application Drawings, Onsite CCR Disposal Facility, L.V. Sutton Energy Complex, Wilmington, NC. Langley, W.G., J. Daniels, and S. Oza, 2015, Sorption Evaluation Sutton Power Plant, UNC Charlotte Department of Civil and Environmental Engineering, report prepared for SynTerra, Lee, R.W., 1984, Ground-Water Quality Data From the Southeastern Coastal Plain, Mississippi, Alabama, Georgia, South Carolina, and North Carolina, U.S. Geological Survey, Open - File Report 84-237, 20 p. McDonald, M.G. and A.W. Harbaugh, 1988, A Modular Three-Dimensional Finite-Difference Ground-Water Flow Model, U.S. Geological Survey Techniques of Water Resources Investigations, book 6, 586 p. Niswonger, R.G.,S. Panday, and I. Motomu, 2011, MODFLOW-NWT, A Newton formulation for MODFLOW-2005, U.S. Geological Survey Techniques and Methods 6-A37, 44-. SynTerra, 2014, L.V. Sutton Energy Complex, Wilmington, NC, Water Supply Well Survey Report of Findings, April 9, 2014. SynTerra, 2015, Comprehensive Site Assessment Report, L.V. Sutton Energy Complex, Wilmington, NC, August 5, 2015. US EPA, 2015, http://www.epa.gov/watersense/pubs/indoor.html accessed 8/26/15. Watermark Numerical Computing, 2004, PEST Model-Independent Parameter Estimation User Manual: 5th Edition. Zheng, C. and P.P. Wang, 1999, MT3DMS: A Modular Three-Dimensional Multi-Species Model for Simulation of Advection, Dispersion and Chemical Reactions of Contaminants in Groundwater Systems: Documentation and User’s Guide, SERDP-99-1, U.S. Army Engineer Research and Development Center, Vicksburg, MS. 27 TABLES 28 Table 1. Comparison of observed and computed heads for the calibrated flow model. Well Observed Head Computed Head Residual Head ABMW -01D 10.55 11.45 -0.90 ABMW-01S 11.16 11.63 -0.47 ABMW-02D 7.39 8.85 -1.46 ABMW-02S 7.42 8.85 -1.43 AW-01B 10.67 10.65 0.02 AW-01C 10.7 10.65 0.05 AW-02B 10.85 10.53 0.32 AW-02C 10.87 10.53 0.34 AW-02D 10.85 10.63 0.22 AW-03B 11.02 10.90 0.12 AW-03C 10.97 10.90 0.07 AW-04B 10.75 10.44 0.31 AW-04C 10.67 10.44 0.23 AW-05B 10.18 9.89 0.29 AW-05C 10.17 9.89 0.28 AW-05D 10.2 9.94 0.26 AW-05E 10.09 10.50 -0.41 AW-06B 11.06 10.83 0.23 AW-06D 10.99 10.87 0.12 AW-06E 10.82 11.33 -0.51 AW-07D 11.02 11.12 -0.10 AW-08B 9.7 10.29 -0.59 AW-08C 9.77 10.29 -0.52 AW-09B 8.61 9.21 -0.60 AW-09C 8.63 9.21 -0.58 AW-09D 8.55 9.25 -0.70 MW-08 9.87 10.01 -0.14 MW-09 10.74 10.32 0.42 MW-10 9.95 10.56 -0.61 MW-11 11.86 10.68 1.18 MW-12 10.96 10.83 0.13 MW-14 9.2 9.22 -0.02 MW-15 7.27 7.74 -0.47 MW-15D 7.21 7.80 -0.59 MW-16 9.71 9.47 0.24 MW-16D 8.39 9.46 -1.07 MW-19 9.78 10.19 -0.41 MW-20 3.73 3.30 0.43 MW-20D 4.11 4.11 0.00 MW-21C 9.79 10.13 -0.34 MW-22B 10.43 10.61 -0.18 29 MW-22C 10.39 10.61 -0.22 MW-23B 10.88 11.02 -0.14 MW-23C 10.89 11.02 -0.13 MW-23E 10.41 11.44 -1.03 MW-24B 11.03 11.36 -0.33 MW-24C 11.02 11.36 -0.34 MW-27B 9.99 10.55 -0.56 MW-27C 9.97 10.55 -0.58 MW-28B 9.66 9.88 -0.22 MW-28C 9.66 9.87 -0.21 MW-28T 9.66 9.88 -0.22 MW-31B 11.03 11.08 -0.05 MW-31C 11.03 11.07 -0.04 MW-32C 10.32 9.90 0.42 MW-33C 10.02 9.62 0.40 MW-37B 8.03 7.14 0.89 AMW-37C 8.62 7.14 1.48 MW-04B 8.31 7.51 0.80 MW-05A 9.36 9.89 -0.53 MW-05B 9.36 9.89 -0.53 MW-05C 9.32 9.89 -0.57 MW-07A 9.08 9.54 -0.46 MW-07B 9.13 9.54 -0.41 MW-07C 9.04 9.53 -0.49 PZ-10D 10.55 10.67 -0.12 PZ-10S 10.72 10.63 0.09 PZ-06D 10.62 10.04 0.58 PZ-06S 10.3 9.93 0.37 SMW-01B 10.02 9.68 0.34 SMW-01C 10.1 9.68 0.42 SMW-02B 10.03 9.29 0.74 SMW-02C 10.01 9.29 0.72 SMW-03B 9.61 8.55 1.06 SMW-03C 9.63 8.55 1.08 SMW-04B 10.7 10.33 0.37 SMW-04C 10.69 10.32 0.37 SMW-05B 10.28 9.77 0.51 SMW-05C 10.48 9.76 0.72 SMW-06B 9.96 9.24 0.72 SMW-06C 9.92 9.23 0.69 SMW-06D 10.17 10.14 0.03 GWPZ-01A 10.29 10.75 -0.46 GWPZ-01B 10.2 10.75 -0.55 LA-PZ-05 10.27 10.26 0.01 30 Table 2. Calibrated hydraulic parameters. Hydrostratigraphic Unit Model Layers Spatial Zones Horizontal Hydraulic Conductivity, ft/d Anisotropy ratio, Kh:Kv 1971 and 1984 Ash Basins 1-2 coal ash 1.5 2 1-2 ash basin berms 1.5 2 Surficial Aquifer 3-4 uniform except for deep 1971 ash 50 3 3 FADA 1.5 3 3-7 deep 1971 ash 1.5 3 5 uniform except for deep 1971 ash 125 3 6 uniform except for deep 1971 ash, Pee Dee confining layer 125 10 6 Pee Dee confining layer 0.01 5 7 uniform except for deep 1971 ash 125 10 Pee Dee Aquifer silty sand 8-10 uniform 0.1 10 Pee Dee Aquifer silt 11-12 uniform 0.01 10 Pee Dee Aquifer deep sand 13 uniform 30 10 Table 3. Flow parameter sensitivity analysis. Results are expressed as model normalized root mean square error (NRMSE) of the simulated and observed heads. Flow Parameter decrease by 50% calibrated value increase by 50% Recharge in upland areas 18.45% 6.89% 16.24% Ash basin recharge 7.14% 6.89% 7.75% Surficial aquifer Kh 29.52% 6.89% 13.04% Surficial aquifer anisotropy 6.89% 6.89% 7.01% Pee Dee Kh 7.01% 6.89% 6.89% Supply well pumping rates 7.14% 6.89% 7.88% Ash basin and berm Kh 7.01% 6.89% 6.89% 31 Table 4. Ash basin infiltration rates (inches per year) used in historical transport model. Date 1971 Basin S. 1984 Basin M. 1984 Basin N. 1984 Basin 1971-1984 90 12 12 12 1984-2013 30 60 50 40 2013-2015 30 30 30 30 Table 5. Major supply well pumping rates used in historical transport model, gpm Date PE- SW5 PE- SW6A PE- SW6B NHC- SW3 NHC- SW4 Invista 3 (H2) Invista 5 (G) Invista 6 1971- 1984 0 0 0 0 0 26 0 0 1984- 2013 10.4 10.4 10.4 27.1 27.1 52 18.2 36.5 2013- 2015 4.9 2 2.8 18.2 18.2 52 36.5 0 Table 6. Ash basin COI source concentrations (ug/L) used in historical transport model. Date 1971 basin main 1984 basin N. 1984 basin FADA 1971-1984 boron, arsenic, vanadium 4000 650 3.5 0 0 0 0 0 0 200 55 1.5 1984-2013 boron, arsenic, vanadium 4000 650 3.5 4000 650 3.5 500 50 0.35 200 55 1.5 2013-2015 boron, arsenic, vanadium 4000 650 3.5 4000 650 3.5 500 50 0.35 200 55 1.5 32 Table 7. Comparison of observed and simulated boron concentrations (ug/L) in monitoring wells. The green highlighted cells are deep Pee Dee wells. Well elevatio n boron measured model ABMW -01D -59.79 176 1094 ABMW-01S -27.75 3950 4000 ABMW-02D -33.4 604 2185 ABMW-02S 4.48 237 200 AW-01B -5.89 <50 2 AW-01C -25.95 111 27 AW-02B 4.58 <50 70 AW-02C -17.7 <50 418 AW-02D -67.88 666 0 AW-03B -4.27 <50 195 AW-03C -24.3 1430 930 AW-04B -4.28 <50 196 AW-04C -24.07 1450 973 AW-05B 1.2 <50 92 AW-05C -18.81 69 541 AW-05D -71.22 306 0 AW-05E -121.5 1950 0 AW-06B -5.16 <50 284 AW-06D -89.02 980 0 AW-06E -127.57 2740 0 AW-07D -80.7 815 0 AW-08B -9.03 <50 6 AW-08C -29.1 <50 13 AW-09B -6.37 <50 1 AW-09C -28.24 566 18 AW-09D -79.91 590 0 MW-11 -22.81 <50 115 MW-12 -30.4 1490 1409 MW-15 2.53 64 200 MW-15D -33.89 560 124 MW-16 7.11 98 22 MW-16D -33.77 733 457 MW-19 -18.77 2080 1779 MW-20 1.78 65 66 MW-20D -34.77 313 495 MW-21C -14.86 2120 1668 MW-22B -8.91 <50 1483 33 MW-22C -25.26 2560 2520 MW-23B -9.8 145 1807 MW-23C -28.33 2050 2579 MW-23E -131.21 2500 0 MW-24B -12.88 1080 1205 MW-24C -30.03 1040 2350 MW-27B -13 198 144 MW-28B 1.13 <50 98 MW-28C -14.33 <50 387 MW-31B -9.48 54 761 MW-31C -30.04 1190 1493 MW-32C -14.02 115 294 MW-33C -25.22 <50 334 MW-37B -1.62 <50 0 AMW-37C -19.56 <50 0 MW-04B -26.59 <50 0 MW-05C -29.5 <50 0 MW-07A 1.29 <50 13 MW-07B -8.87 <50 13 MW-07C -26.76 571 111 PZ-10D -66.1 363 0 SMW-01B -7.49 100 342 SMW-01C -29.51 791 529 SMW-02B -4.52 <50 80 SMW-02C -25 337 331 SMW-03B -6.97 52 34 SMW-03C -28.67 418 144 SMW-04B -3.88 <50 0 SMW-04C -29.81 85 1 SMW-05B -8.67 <50 203 SMW-05C -27.81 365 306 SMW-06B -8.03 60 268 SMW-06C -28.47 199 377 SMW-06D -92.7 990 0 34 Table 8. Comparison of observed and simulated arsenic concentrations (ug/L) in monitoring wells. Well elevation arsenic measured model ABMW -01D -59.79 1.03 0.1 ABMW-01S -27.75 654 650.0 ABMW-02D -33.4 170 0.0 ABMW-02S 4.48 54.6 55.0 AW-01B -5.89 <1 0.0 AW-01C -25.95 <1 0.0 AW-02B 4.58 <1 0.0 AW-02C -17.7 <1 0.0 AW-02D -67.88 <1 0.0 AW-03B -4.27 <1 0.0 AW-03C -24.3 1.54 0.0 AW-04B -4.28 <1 0.0 AW-04C -24.07 <1 0.0 AW-05B 1.2 <1 0.0 AW-05C -18.81 <1 0.0 AW-05D -71.22 1.36 0.0 AW-05E -121.5 <1 0.0 AW-06B -5.16 <1 0.0 AW-06D -89.02 2.14 0.0 AW-06E -127.57 <1 0.0 AW-07D -80.7 <1 0.0 AW-08B -9.03 <1 0.0 AW-08C -29.1 <1 0.0 AW-09B -6.37 <1 0.0 AW-09C -28.24 <1 0.0 AW-09D -79.91 <1 0.0 MW-11 -22.81 <1 0.0 MW-12 -30.4 <1 0.0 MW-15 2.53 23.6 55.0 MW-15D -33.89 <1 0.0 MW-16 7.11 1.59 0.1 MW-16D -33.77 <1 0.0 MW-19 -18.77 2.62 0.0 MW-20 1.78 1.12 0.0 MW-20D -34.77 2.25 0.0 MW-21C -14.86 53.8 0.0 35 MW-22B -8.91 <1 0.0 MW-22C -25.26 <1 0.0 MW-23B -9.8 <1 0.0 MW-23C -28.33 <1 0.0 MW-23E -131.21 <1 0.0 MW-24B -12.88 2.91 0.0 MW-24C -30.03 3.42 0.0 MW-27B -13 <1 0.0 MW-28B 1.13 <1 0.0 MW-28C -14.33 <1 0.0 MW-31B -9.48 <1 0.0 MW-31C -30.04 <1 0.0 MW-32C -14.02 <1 0.0 MW-33C -25.22 <1 0.0 MW-37B -1.62 <1 0.0 AMW-37C -19.56 2.56 0.0 MW-04B -26.59 <1 0.0 MW-05C -29.5 <1 0.0 MW-07A 1.29 <1 0.0 MW-07B -8.87 <1 0.0 MW-07C -26.76 <1 0.0 PZ-10D -66.1 <1 0.0 SMW-01B -7.49 <1 0.0 SMW-01C -29.51 <1 0.0 SMW-02B -4.52 1.04 0.0 SMW-02C -25 <1 0.0 SMW-03B -6.97 <1 0.0 SMW-03C -28.67 <1 0.0 SMW-04B -3.88 <1 0.0 SMW-04C -29.81 2.56 0.0 SMW-05B -8.67 1.47 0.0 SMW-05C -27.81 <1 0.0 SMW-06B -8.03 <1 0.0 SMW-06C -28.47 2.79 0.0 SMW-06D -92.7 3.82 0.0 36 Table 9. Comparison of observed and simulated vanadium concentrations (ug/L) in monitoring wells. Well elevation vanadium measured model ABMW -01D -59.79 0.642 0.0 ABMW-01S -27.75 3.45 3.5 ABMW-02D -33.4 0.504 0.0 ABMW-02S 4.48 1.46 1.5 AW-01B -5.89 <0.3 0.0 AW-01C -25.95 <0.3 0.0 AW-02B 4.58 <0.3 0.0 AW-02C -17.7 <0.3 0.0 AW-02D -67.88 <0.3 0.0 AW-03B -4.27 0.427 0.0 AW-03C -24.3 0.75 0.0 AW-04B -4.28 <0.3 0.0 AW-04C -24.07 0.518 0.0 AW-05B 1.2 <0.3 0.0 AW-05C -18.81 <0.3 0.0 AW-05D -71.22 <0.3 0.0 AW-05E -121.5 <0.3 0.0 AW-06B -5.16 <0.3 0.0 AW-06D -89.02 0.38 0.0 AW-06E -127.57 1.77 0.0 AW-07D -80.7 0.992 0.0 AW-08B -9.03 0.346 0.0 AW-08C -29.1 <0.3 0.0 AW-09B -6.37 <0.3 0.0 AW-09C -28.24 <0.3 0.0 AW-09D -79.91 <0.3 0.0 MW-11 -22.81 na 0.0 MW-12 -30.4 <0.3 0.0 MW-15 2.53 3.88 1.5 MW-15D -33.89 <0.3 0.0 MW-16 7.11 0.316 0.0 MW-16D -33.77 2.09 0.0 MW-19 -18.77 na 0.0 MW-20 1.78 39.6 0.0 MW-20D -34.77 <0.3 0.0 MW-21C -14.86 na 0.0 MW-22B -8.91 na 0.0 37 MW-22C -25.26 na 0.0 MW-23B -9.8 <0.3 0.0 MW-23C -28.33 0.323 0.0 MW-23E -131.21 1.16 0.0 MW-24B -12.88 0.555 0.0 MW-24C -30.03 0.543 0.0 MW-27B -13 <0.3 0.0 MW-28B 1.13 na 0.0 MW-28C -14.33 na 0.0 MW-31B -9.48 0.378 0.0 MW-31C -30.04 0.316 0.0 MW-32C -14.02 na 0.0 MW-33C -25.22 na 0.0 MW-37B -1.62 <0.3 0.0 AMW-37C -19.56 1.22 0.0 MW-04B -26.59 na 0.0 MW-05C -29.5 na 0.0 MW-07A 1.29 <0.3 0.0 MW-07B -8.87 <0.3 0.0 MW-07C -26.76 0.573 0.0 PZ-10D -66.1 0.397 0.0 SMW-01B -7.49 <0.3 0.0 SMW-01C -29.51 0.402 0.0 SMW-02B -4.52 1.61 0.0 SMW-02C -25 <0.3 0.0 SMW-03B -6.97 <0.3 0.0 SMW-03C -28.67 <0.3 0.0 SMW-04B -3.88 <0.3 0.0 SMW-04C -29.81 0.803 0.0 SMW-05B -8.67 0.81 0.0 SMW-05C -27.81 <0.3 0.0 SMW-06B -8.03 <0.3 0.0 SMW-06C -28.47 <0.3 0.0 SMW-06D -92.7 1.61 0.0 38 FIGURES 39 Figure 1. Site location map, Sutton Energy Complex, Wilmington, NC. 40 Figure 2. Numerical model domain. 41 Figure 3. Fence diagram of the 3D hydrostratigraphic model used to construct the model grid. The view is from the south, with 10x vertical exaggeration. 42 Figure 4. Numerical grid used for flow and transport modeling. Vertical exaggeration is 10x. 43 Figure 5. Distribution of recharge zones in the model. 44 Figure 6. Surface water features included in the model. The light blue areas are treated as either constant head areas (lakes ponds, and rivers) or drain areas (swamps). 45 Figure 7. Location of water supply wells in the model area. 46 Figure 8. Zones used to define horizontal hydraulic conductivity and horizontal to vertical anisotropy in model layer 6. 47 Figure 9. Comparison of observed and computed heads from the calibrated steady state flow model. 3 4 5 6 7 8 9 10 11 12 3 4 5 6 7 8 9 10 11 12 Computed vs. Observed Values Head Co m p u t e d Observed 48 Figure 10. Simulated heads in the top surficial aquifer model layer (model layer 3). 49 Figure 11. Simulated heads in the bottom surficial aquifer model layer (model layer 7). 50 Figure 12. Simulated heads in the upper part of the Pee Dee aquifer model layer (model layer 9). 51 Figure 13. Ash basin COI source zones for model. 52 Figure 14. Simulated June, 2015 boron concentrations (ug/L) in the second model layer of the surficial aquifer (layer 4). 53 Figure 15. Simulated June, 2015 boron concentrations (ug/L) in the lowest model layer of the surficial aquifer (layer 7). 54 Figure 16. Simulated June, 2015 boron concentrations (ug/L) in the upper part of the Pee Dee aquifer (layer 9). 55 Figure 17. Simulated June, 2015 arsenic concentrations (ug/L) in the second model layer of the surficial aquifer (layer 4). 56 Figure 18. Simulated June, 2015 arsenic concentrations (ug/L) in the lowest model layer of the surficial aquifer (layer 7). 57 Figure 19. Simulated June, 2015 arsenic concentrations (ug/L) in the upper part of the Pee Dee aquifer (layer 9). 58 Figure 20. Simulated June, 2015 vanadium concentrations (ug/L) in the second model layer of the surficial aquifer (layer 4). 59 Figure 21. Simulated June, 2015 vanadium concentrations (ug/L) in the lowest model layer of the surficial aquifer (layer 7). 60 Figure 22. Simulated June, 2015 vanadium concentrations (ug/L) in the upper part of the Pee Dee aquifer (layer 9). 61 Figure 23. Map showing proposed ash basin closure for the CAP2 scenario which only considers the ash basin closure. New onsite lined landfill North storm water pond South storm water pond All ash is removed. Lake Sutton fills the excavation in 1971 basin and FADA 62 Figure 24. Simulated 2020 boron concentration (ug/L) in the second model layer of the surficial aquifer (layer 4) for CAP1. 63 Figure 25. Simulated 2020 boron concentration (ug/L) in the lowest model layer of the surficial aquifer (layer 7) for CAP1. 64 Figure 26. Simulated 2020 arsenic concentration (ug/L) in the second model layer of the surficial aquifer (layer 4) for CAP1. 65 Figure 27. Simulated 2020 arsenic concentration (ug/L) in the lowest model layer of the surficial aquifer (layer 7) for CAP1. 66 Figure 28. Simulated 2020 vanadium concentration (ug/L) in the second model layer of the surficial aquifer (layer 4) for CAP1. 67 Figure 29. Simulated 2020 vanadium concentration (ug/L) in the lowest model layer of the surficial aquifer (layer 7) for CAP1. 68 Figure 30. Simulated 2030 boron concentration (ug/L) in the second model layer of the surficial aquifer (layer 4) for CAP1. 69 Figure 31. Simulated 2030 boron concentration (ug/L) in the lowest model layer of the surficial aquifer (layer 7) for CAP1. 70 Figure 32. Simulated 2030 arsenic concentration (ug/L) in the second model layer of the surficial aquifer (layer 4) for CAP1. 71 Figure 33. Simulated 2030 arsenic concentration (ug/L) in the lowest model layer of the surficial aquifer (layer 7) for CAP1. 72 Figure 34. Simulated 2030 vanadium concentration (ug/L) in the second model layer of the surficial aquifer (layer 4) for CAP1. 73 Figure 35. Simulated 2030 vanadium concentration (ug/L) in the lowest model layer of the surficial aquifer (layer 7) for CAP1. 74 Figure 36. Simulated 2045 boron concentration (ug/L) in the second model layer of the surficial aquifer (layer 4) for CAP1. 75 Figure 37. Simulated 2045 boron concentration (ug/L) in the lowest model layer of the surficial aquifer (layer 7) for CAP1. 76 Figure 38. Simulated 2045 arsenic concentration (ug/L) in the second model layer of the surficial aquifer (layer 4) for CAP1. 77 Figure 39. Simulated 2045 arsenic concentration (ug/L) in the lowest model layer of the surficial aquifer (layer 7) for CAP1. 78 Figure 40. Simulated 2045 vanadium concentration (ug/L) in the second model layer of the surficial aquifer (layer 4) for CAP1. 79 Figure 41. Simulated 2045 vanadium concentration (ug/L) in the lowest model layer of the surficial aquifer (layer 7) for CAP1. 80 Figure 42. Simulated steady-state hydraulic heads in model layer 7 for CAP2. 81 Figure 43. Simulated 2020 boron concentration (ug/L) in the second model layer of the surficial aquifer (layer 4) for CAP2. 82 Figure 44. Simulated 2020 boron concentration (ug/L) in the lowest model layer of the surficial aquifer (layer 7) for CAP2. 83 Figure 45. Simulated 2020 arsenic concentration (ug/L) in the second model layer of the surficial aquifer (layer 4) for CAP2. 84 Figure 46. Simulated 2020 arsenic concentration (ug/L) in the lowest model layer of the surficial aquifer (layer 7) for CAP2. 85 Figure 47. Simulated 2020 vanadium concentration (ug/L) in the second model layer of the surficial aquifer (layer 4) for CAP2. 86 Figure 48. Simulated 2020 vanadium concentration (ug/L) in the lowest model layer of the surficial aquifer (layer 7) for CAP2. 87 Figure 49. Simulated 2030 boron concentration (ug/L) in the second model layer of the surficial aquifer (layer 4) for CAP2. 88 Figure 50. Simulated 2030 boron concentration (ug/L) in the lowest model layer of the surficial aquifer (layer 7) for CAP2. 89 Figure 51. Simulated 2030 arsenic concentration (ug/L) in the second model layer of the surficial aquifer (layer 4) for CAP2. 90 Figure 52. Simulated 2030 arsenic concentration (ug/L) in the lowest model layer of the surficial aquifer (layer 7) for CAP2. 91 Figure 53. Simulated 2030 vanadium concentration (ug/L) in the second model layer of the surficial aquifer (layer 4) for CAP2. 92 Figure 54. Simulated 2030 vanadium concentration (ug/L) in the lowest model layer of the surficial aquifer (layer 7) for CAP2. 93 Figure 55. Simulated 2045 boron concentration (ug/L) in the second model layer of the surficial aquifer (layer 4) for CAP2. 94 Figure 56. Simulated 2045 boron concentration (ug/L) in the lowest model layer of the surficial aquifer (layer 7) for CAP2. 95 Figure 57. Simulated 2045 arsenic concentration (ug/L) in the second model layer of the surficial aquifer (layer 4) for CAP2. 96 Figure 58. Simulated 2045 arsenic concentration (ug/L) in the lowest model layer of the surficial aquifer (layer 7) for CAP2. 97 Figure 59. Simulated 2045 vanadium concentration (ug/L) in the second model layer of the surficial aquifer (layer 4) for CAP2. 98 Figure 60. Simulated 2045 vanadium concentration (ug/L) in the lowest model layer of the surficial aquifer (layer 7) for CAP2. 99 Figure 61. Simulated 2020 boron concentration (ug/L) in the second model layer of the surficial aquifer (layer 4) for CAP3. 100 Figure 62. Simulated 2020 boron concentration (ug/L) in the lowest model layer of the surficial aquifer (layer 7) for CAP3. 101 Figure 63. Simulated 2030 boron concentration (ug/L) in the second model layer of the surficial aquifer (layer 4) for CAP3. 102 Figure 64. Simulated 2030 boron concentration (ug/L) in the lowest model layer of the surficial aquifer (layer 7) for CAP3. 103 Figure 65. Simulated 2045 boron concentration (ug/L) in the second model layer of the surficial aquifer (layer 4) for CAP3. 104 Figure 66. Simulated 2045 boron concentration (ug/L) in the lowest model layer of the surficial aquifer (layer 7) for CAP3.