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NC0003433_J15060668F_20150902
+ DUKE Analytical Laboratory ENERGY 13339 Hagers Ferry Road Huntersville, NC 28078-7929 McGuire Nuclear Complex - MG03A2 Phone:980-875-5245 Fax:980-875-4349 Order Summary Report Order Number: J15060668 Project Name: CAPE FEAR - AB GW ASSESSMENT SPECIATION Customer Name(s): Tim Hunsucker, Chris Suttell, Kathy Webb, John Toepfer Customer Address: Lab Contact: Peggy Kendall kendal� o e: Peggy Report Authorized By: Uke-energy.com Date: (Signature) 1WPeggy Kendall 2015-.97.15 11:25:46-04'00' Program Comments: Please contact the Program Manager (Peggy Kendall) with any questions regarding this report. Data Flags & Calculations: 7/15/2015 Page 1 of 29 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. Sample ID's & Descriptions: Collection Sample ID Plant/Station Date and Time Collected By Sample Description 2015020235 Cape Fear 16-Jun-15 1:28 PM Kyle Donovan ABMW-4 2015020236 Cape Fear 16-Jun-15 2:35 PM Kyle Donovan ABMW-4S 2015020237 Cape Fear 16-Jun-15 10:40 AM Kyle Donovan ABMW-2SU 2015020238 Cape Fear 16-Jun-15 9:42 AM Kyle Donovan ABMW-2SL 2015020239 Cape Fear 16-Jun-15 2:07 PM Kyle Donovan MW-10D 5 Total Samples Page 2 of 29 Page 3 of 29 Technical Validation Review Checklist: COC and .pdf report are in agreement with sample totals Yes No and analyses (compliance programs and procedures). All Results are less than the laboratory reporting limits. ❑ Yes❑ No All laboratory QA/QC requirements are acceptable.❑ Yes ❑ No Report Sections Included: U Job Summary Report ❑ Sample Identification n Technical Validation of Data Package ❑ Analytical Laboratory Certificate of Analysis ❑ Analytical Laboratory QC Report Sub -contracted Laboratory Results ❑ Customer Specific Data Sheets, Reports, & Documentation ❑ Customer Database Entries 66 Chain of Custody [I/0] Electronic Data Deliverable (EDD) Sent Separately Reviewed By: Peggy Kendall Date: 7/15/2015 Certificate of Laboratory Analysis Page 4 of 29 This report shall not be reproduced, except in full. Order # J15060668 Site: ABMW-4 Collection Date: 16-Jun-15 1:28 PM Analyte Result Units Qualifiers RDL DF Speciation of an Element - (Analysis Performed by Brooks Rand Labs LLC) Vendor Parameter Complete Sample #: 2015020235 Matrix: GW WW Method Analysis Date/Time Analyst Vendor Method V_BRAND Certificate of Laboratory Analysis Page 5 of 29 This report shall not be reproduced, except in full. Order # J15060668 Site: ABMW-4S Collection Date: 16-Jun-15 2:35 PM Analyte Result Units Qualifiers RDL DF Speciation of an Element - (Analysis Performed by Brooks Rand Labs LLC) Vendor Parameter Complete Sample #: 2015020236 Matrix: GW WW Method Analysis Date/Time Analyst Vendor Method V_BRAND Certificate of Laboratory Analysis This report shall not be reproduced, except in full. Order # J15060668 Site: ABMW-2SU Collection Date: 16-Jun-15 10:40 AM Analyte Result Units Qualifiers RDL DF Speciation of an Element - (Analysis Performed by Brooks Rand Labs LLC) Vendor Parameter Complete Sample #: 2015020237 Matrix: GW WW Page 6 of 29 Method Analysis Date/Time Analyst Vendor Method V_BRAND Certificate of Laboratory Analysis Page 7 of 29 This report shall not be reproduced, except in full. Order # J15060668 Site: ABMW-2SL Collection Date: 16-Jun-15 9:42 AM Analyte Result Units Qualifiers RDL DF Speciation of an Element - (Analysis Performed by Brooks Rand Labs LLC) Vendor Parameter Complete Sample #: 2015020238 Matrix: GW WW Method Analysis Date/Time Analyst Vendor Method V_BRAND Certificate of Laboratory Analysis Page 8 of 29 This report shall not be reproduced, except in full. Order # J15060668 Site: MW-10D Collection Date: 16-Jun-15 2:07 PM Analyte Result Units Qualifiers RDL DF Speciation of an Element - (Analysis Performed by Brooks Rand Labs LLC) Vendor Parameter Complete Sample #: 2015020239 Matrix: GW WW Method Analysis Date/Time Analyst Vendor Method V_BRAND Page 9 of 29 BRO�©KS RAND LABS MEANINGFUL METALS DATA July 14, 2015 Peggy Kendall Duke Energy Analytical Laboratory Mail Code MGO3A2 (Building 7405) 13339 Hagers Ferry Rd. Huntersville, NC 28078 (704) 875-5245 Project: Duke Cape Fear Plant (LIMS# J15060668) Ms. Kendall, Attached is the report associated with five (5) aqueous samples submitted for hexavalent chromium, arsenic speciation, iron speciation, and manganese speciation analyses on June 16, 2015. The samples were received in a sealed cooler at 1.1 °C on June 17, 2015. Hexavalent chromium analysis was performed by ion chromatography inductively coupled plasma dynamic reaction cell mass spectrometry (IC-ICP-DRC-MS). Selenium speciation and arsenic speciation analyses were performed via ion chromatography inductively coupled plasma collision reaction cell mass spectrometry (IC-ICP-CRC-MS). All samples requesting iron speciation analysis were analyzed by spectrophotometry. Mn (II) and arsenic speciation analyses were performed via IC- ICP-CRC-MS. Mn(IV) analysis were performed via digestion and subsequent analysis by inductively coupled plasma triple quadrupole mass spectrometry (ICP-QQQ-MS). Any issues associated with the analyses are addressed in the following report. If you have any questions, please feel free to contact me at your convenience. Sincerely, Russell Gerads Business Development Manager Brooks Rand Labs, LLC 3958 6th Ave NW • Seattle, WA 98107 • T: 206-632-6206 • F: 206-632-6017 • www.brooksrand.com • brl@brooksrand.com Page 10 of 29 Brooks Rand Labs, LLC Report prepared for: Peggy Kendall Duke Energy Analytical Laboratory Mail Code MGO3A2 (Building 7405) 13339 Hagers Ferry Rd. Huntersville, NC 28078 Project: Duke Cape Fear Plant (LIMS# J15060668) July 14, 2015 1. Sample Reception Five (5) aqueous samples were submitted for hexavalent chromium, arsenic speciation, iron speciation, and manganese speciation analyses on June 16, 2015. All samples were received in acceptable condition on June 17, 2015 in a sealed container at 1.1 °C. All samples were received in a laminar flow clean hood, void of trace metals contamination and ultra -violet radiation, and were designated discrete sample identifiers. Sample fractions requesting hexavalent chromium, arsenic speciation, and iron speciation analyses were field filtered by the client. Two containers were submitted for each client sample requesting manganese speciation, one field filtered fraction and one unfiltered fraction. An aliquot of each sample submitted for hexavalent chromium analysis was filtered into a clean polypropylene tube. All hexavalent chromium sample fractions were stored in a secure refrigerator maintained at a temperature of 4°C, until the analyses could be performed. An aliquot of each sample submitted for arsenic speciation analysis was filtered (0.45µm) into a polypropylene centrifuge tube; all filtrates and original bottles were then stored in a secure, monitored refrigerator (maintained at a temperature of <6°C) until the analyses could be performed. The sample fractions requesting iron speciation analysis were stored in a secure, monitored refrigerator (maintained at a temperature of <6°C) until the analyses could be performed. An aliquot of each filtered sample submitted for manganese speciation analysis was decanted into a polypropylene centrifuge tube for Mn(II) analysis. These fractions were stored in a secure, monitored refrigerator (maintained at a temperature of <6°C) until the analyses could be performed. Subsequently, the original bottles (filtered and unfiltered fractions) intended for Mn speciation were preserved to pH < 2 with concentrated HNO3 and then stored in a secure polyethylene container, known to be free from trace metals contamination, until the digestion could be performed. Page 11 of 29 2. Sample Preparation All sample preparation is performed in laminar flow clean hoods known to be free from trace metals contamination. All applied water for dilutions and sample preservatives are monitored for contamination to account for any biases associated with the sample results. Hexavalent Chromium Analysis by IC-ICP-DRC-MS Prior to analysis, an aliquot of each sample was filtered with a syringe filter (0.45µm) and injected directly into a sealed autosampler vial. No further sample preparation was performed as any chemical alteration of a sample may shift the equilibrium of the system, resulting in changes in speciation ratios. Arsenic Speciation Analysis by IC-ICP-CRC-MS An aliquot of each sample was filtered directly into a sealed autosampler vial. No further sample preparation was performed as a buffered EDTA solution was provided by Brooks Rand Labs for field -preservation of the submitted samples. Iron Speciation Analysis by Spectrophotometry No sample preparation was required as a de - gassed HCL solution was provided by Brooks Rand Labs for field -preservation of the submitted samples. Manganese Mn(II Analysis by IC-ICP-CRC-MS An aliquot of each sample was filtered (0.45µm) directly into an autosampler vial for Mn(II) analysis. No additional sample preparation was performed as any chemical alteration of the samples may shift the equilibrium of the system resulting in changes in speciation ratios. Manganese Mn(IV Analysis by ICP-QQQ-MS Each filtered and unfiltered sample submitted for Mn speciation analysis was preserved with 1 % HNO3 (v/v) upon sample receipt. Each sample fraction was then further digested on a hotblock apparatus with aliquots of 50% HNO3 (v/v) and 50% HCl (v/v), in accordance with the digestion procedure specified in EPA Method 200.8. All resulting sample digests were analyzed for total manganese via inductively coupled plasma triple quadrupole mass spectrometry (ICP-QQQ-MS). 3. Sample Analysis All sample analysis is preceded by a minimum of a five -point calibration curve spanning the entire concentration range of interest. Calibration curves are performed at the beginning of each analytical day. All calibration curves, associated with each species of interest, are standardized by linear regression resulting in a response factor. All sample results are instrument blank corrected to account for any operational biases associated with the analytical platform. Prior to sample analysis, all calibration curves are verified using second source standards which are identified as initial calibration verification standards (ICV). Page 12 of 29 Ongoing instrument performance is identified by the analysis of continuing calibration verification standards (CCV) and continuing calibration blanks (CCB) at a minimum interval of every ten analytical runs. Hexavalent Chromium Analysis by IC-ICP-DRC-MS Each sample for hexavalent chromium analysis was analyzed by ion chromatography inductively coupled plasma dynamic reaction cell mass spectrometry (IC-ICP-DRC-MS) on June 22, 2015. An aliquot of each sample is injected onto an anion exchange column and mobilized by a basic (pH > 7) gradient. The eluting chromium species are then introduced into a radio frequency (RF) plasma where energy -transfer processes cause desolvation, atomization, and ionization. The ions are extracted from the plasma through a differentially -pumped vacuum interface and travel through a pressurized chamber (DRC) containing a reaction gas which preferentially reacts with interfering ions of the same target mass to charge ratios (m/z). A solid-state detector detects ions transmitted through the mass analyzer and the resulting current is processed by a data handling system. Retention times for each eluting species are compared to known standards for species identification. Arsenic Speciation Analysis by IC-ICP-CRC-MS Each sample was analyzed for arsenic speciation via ion chromatography inductively coupled plasma collision reaction cell mass spectrometry (IC-ICP-CRC-MS) on June 26, 2015. Aliquots of each sample are injected onto an anion exchange column and eluted isocratically. The eluting arsenic species are then introduced into a radio frequency (RF) plasma where energy -transfer processes cause desolvation, atomization, and ionization. The ions are extracted from the plasma through a differentially -pumped vacuum interface and travel through a pressurized chamber (CRC) containing a specific collision gas. Polyatomic interferences, due to their inherently larger size, collide more frequently with the collision gas and therefore may be separated from the analyte of interest via kinetic energy discrimination (KED). A solid-state detector detects ions transmitted through the mass analyzer on the basis of their mass -to -charge ratio (m/z), and the resulting current is processed by a data handling system. Retention times for each eluting species are compared to known standards for species identification. Iron Speciation Analysis by Spectrophotometry All samples submitted for Fe speciation quantification were analyzed on June 17, 2015, and in accordance with the scientifically accepted method outlined by: Stookey, L.L., (1970). "Ferrozine - A new spectrophotometric reagent for iron", Anal.Chem., 42:779-81. Manganese Mn(II Analysis by IC-ICP-CRC-MS All samples for Mn(II) analysis were analyzed by ion chromatography inductively coupled plasma collision reaction cell mass spectrometry (IC-ICP-CRC-MS) on June 29, 2015. Aliquots of each sample are injected onto an anion exchange column and mobilized by an acidic (pH < 7) gradient. An ion Page 13 of 29 pairing agent provides a dynamic ion exchange mechanism for the cationic manganese species on the chromatographic column. The differences in the affinity of manganese species towards the ion pair agent and the column results in separation. The eluting selenium species are then introduced into a radio frequency (RF) plasma where energy -transfer processes cause desolvation, atomization, and ionization. The ions are extracted from the plasma through a differentially -pumped vacuum interface and travel through a pressurized chamber (CRC) containing a reaction gas which preferentially reacts with interfering ions of the same target mass to charge ratios (m/z). A solid-state detector detects ions transmitted through the mass analyzer and the resulting current is processed by a data handling system. Retention times for each eluting species are compared to known standards for species identification. Manganese Mn(IL) Analysis by ICP-QQQ-MS All samples submitted for Mn speciation quantitation were analyzed by inductively coupled plasma triple quadrupole mass spectrometry (ICP-QQQ-MS) on June 30, 2015. Aliquots of each sample digest are introduced into a radio frequency (RF) plasma where energy -transfer processes cause desolvation, atomization, and ionization. The ions are extracted from the plasma through a differentially -pumped vacuum interface and travel through an initial quadrupole (Q1), which filters the target masses prior to their entrance into a second chamber. The second chamber contains specific reactive gasses or collision gasses that preferentially react either with interfering ions of the same target mass to charge ratios (m/z) or with the target analyte, producing an entirely different mass to charge ratio (m/z) which can then be differentiated from the initial interferences. The ions then exit the collision/reaction cell into and additional quadrupole (Q2). A solid-state detector detects ions transmitted through the mass analyzer, on the basis of their mass -to -charge ratio (m/z), and the resulting current is processed by a data handling system. 4. Analytical Issues No significant analytical issues were encountered. All quality control parameters associated with the samples were within acceptance limits. The sample identified as ABMW-4 was initially analyzed on June 26, 2015 for arsenic speciation analysis. The arsenite concentration exceeded the range of the calibration. The sample was reanalyzed on July 14, 2015 which confirmed the initial result. Since all quality control parameters were within acceptance limits and the arsenite concentrations were confirmed by a higher dilution the original result has been reported. Unknown arsenic species were present in various samples associated with the arsenic speciation analysis resulting in late elution into following sample injections. The late eluting peaks did not affect the target arsenic species; however, differentiation between late eluting peaks and other unknown arsenic species for a given sample could not be accomplished. Page 14 of 29 Mn(IV) is quantified by analyzing the water samples for total Mn and dissolved Mn. Mn(IV) is operationally defined as the difference between the filtered and unfiltered total Mn concentrations, since it is thermodynamically favored to be in the form of a precipitate. The estimated method detection limit (eMDL) for hexavalent chromium is generated from replicate analyses of the lowest standard in the calibration curve. The eMDL values for arsenite, arsenate, and dimethylarsinic acid are generated using the standard deviation of replicate analyses of the lowest standard in the calibration curve. The eMDL for monomethylarsonic acid is calculated from the average eMDL of the three arsenic species contained in the calibration (i.e., arsenite, arsenate, and dimethylarsinic acid); the calibration and CCVs do not contain monomethylarsonic acid due to impurities in this standard which would bias the results for other arsenic species. The Fe(II) result of sample ABMW-4 was slightly greater than the associated total recoverable Fe result. However, the relative percent difference was 18% and meet the criteria for duplicate precision. All iron reported should be considered to be in the Fe(II) form. The F(III) result for sample ABMW-4 was reported as non -detectable at an eMDL of 5.0 µg/L. The eMDL value for Fe(II) and total recoverable Fe was set at 5 based on the sensitivity of the instrument. The eMDL for Mn(II) has been generated from replicate analyses of the lowest standard in the calibration curve. The eMDL values for Mn(IV) been calculated using the standard deviation of the method blanks prepared and analyzed concurrently with the submitted samples. If you have any questions or concerns regarding this report, please feel free to contact me. Sincerel Russell Gerads Business Development Director Brooks Rand Labs, LLC Page 15 of 29 Speciation Results for Duke Energy Project Name: Duke Cape Fear Plant Contact: Jay Perkins LIMS# J15060668 Date: July 14, 2015 Report Generated by: Russell Gerads Brooks Rand Labs, LLC Sample Results (1) Sample ID Cr(VI) ABMW-4 ND (<0.005) ABMW-4S ABMW-25U ABMW-25L MW-10D 0.005 ND (<0.005) ND (<0.005) 0.006 All results reflect the applied dilution and are reported in Ng/L ND = Not detected at the applied dilution Page 16 of 29 Speciation Results for Duke Energy Project Name: Duke Cape Fear Plant Contact: Jay Perkins LIMS# J15060668 Date: July 14, 2015 Report Generated by: Russell Gerads Brooks Rand Labs, LLC Sample Results (2) Sample ID As(III) As(V) MMAs ABMW-4 699 15.2 ND (<0.053) ABMW-4S 1.69 0.420 ND (<0.053) ABMW-25U 0.174 0.196 ND (<0.053) ABMW-25L 0.916 0.140 ND (<0.053) MW-10D 0.318 0.603 ND (<0.053) All results reflect the applied dilution and are reported in pg/L MMAs = monomethylarsonic acid DMAs = dimethylarsinic acid Unknown As Species = Total concentration of all unknown As species observed by NA = Not available. Please see narrative. Page 17 of 29 Speciation Results for Duke Energy Project Name: Duke Cape Fear Plant Contact: Jay Perkins LIMS# J15060668 Date: July 14, 2015 Report Generated by: Russell Gerads Brooks Rand Labs, LLC Sample Results (3 Sample ID Fe(II) Fe(III)* Mn (II) Mn(IV)** ABMW-4 2860 ND (< 5.0) 378 ND (<0.38) ABMW-4S 26900 2890 1790 31.3 ABMW-25U 11400 652 1570 83.2 ABMW-25L 5000 685 630 ND (<0.38) MW-10D 43.0 9 1100 ND (<0.38) All results reflect the applied dilution and are reported in Ng/L ND = Not detected at the applied dilution NR = Analysis not requested *Fe(III) operationally defined as the difference between total recoverable Fe and Fe(II) *Mn(IV) operationally defined as the difference between total and dissolved Mn Page 18 of 29 Speciation Results for Duke Energy Project Name: Duke Cape Fear Plant Contact: Jay Perkins LIMS# J15060668 Date: July 14, 2015 Report Generated by: Russell Gerads Brooks Rand Labs, LLC Quality Control Summary - Preparation Blank Summary (1) Analyte (pg/L) PBW1 PBW2 PBW3 PBW4 Mean StdDev eMDL* eMDL 5x RL 5x Cr(VI) -0.001 0.000 0.001 0.002 0.001 0.001 0.001 0.005 0.050 eMDL = Estimated Method Detection Limit; RL = Reporting Limit *Please see narrative regarding eMDL calculations Quality Control Summary - Preparation Blank Summary (2) Analyte (Ng/L) PBW1 PBW2 PBW3 PBW4 Mean StdDev eMDL* eMDL 10x RL 10x As(III) 0.000 0.000 0.000 0.000 0.000 0.000 0.005 0.049 0.20 As(V) 0.000 0.000 0.000 0.000 0.000 0.000 0.003 0.028 0.20 MMAs 0.000 0.000 0.000 0.000 0.000 0.000 0.005 0.053 0.20 DMAs 0.000 0.000 0.000 0.000 0.000 0.000 0.008 0.083 0.21 eMDL = Estimated Method Detection Limit; RL = Reporting Limit *Please see narrative regarding eMDL calculations Page 19 of 29 Speciation Results for Duke Energy Project Name: Duke Cape Fear Plant Contact: Jay Perkins LIMS# J15060668 Date: July 14, 2015 Report Generated by: Russell Gerads Brooks Rand Labs, LLC Qualitv Control Summary - Preparation Blank Summary (3 Analyte (lag/L) PBW1 PBW2 PBW3 PBW4 Mean StdDev eMDL** eMDL 1x RL 1x Fe(II) 0.0 0.0 0.0 0.0 0.0 0.0 5.0 5.0 20 Total Fe -5.0 -5.0 -5.0 -5.0 -5.0 0.0 5.0 5.0 20 eMDL = Estimated Method Detection Limit; RL = Reporting Limit **Please see narrative regarding eMDL calculations Quality Control Summary - Preparation Blank Summary (3) Analyte (lag/L) PBW1 PBW2 PBW3 PBW4 Mean StdDev eMDL* eMDL 10x RL 10x eMDL 25x RL 25x Mn (II) -0.23 0.21 0.00 -0.27 -0.01 0.22 0.026 0.26 5.0 - - Total Mn 0.055 0.037 0.047 0.086 0.046 0.021 0.003 - - 0.06 1.0 Diss Mn 0.214 0.005 -0.067 -0.031 0.051 0.126 0.015 - - 0.38 1.0 eMDL = Estimated Method Detection Limit; RL = Reporting Limit *Please see narrative regarding eMDL calculations Page 20 of 29 Speciation Results for Duke Energy Project Name: Duke Cape Fear Plant Contact: Jay Perkins LIMS# J15060668 Date: July 14, 2015 Report Generated by: Russell Gerads Brooks Rand Labs, LLC Quality Control Summary - Certified Reference Materials (1 Analyte (lag/L) CRM True Value Result Recovery Cr(VI) LCS 2.002 1.967 98.2 Quality Control Summary - Certified Reference Materials (2) Analyte (lag/L) CRM True Value Result Recovery As(III) LCS 5.00 5.04 100.9 As(V) LCS 5.00 4.58 91.6 MMAs LCS 5.07 5.73 113.0 DMAs LCS 3.63 3.51 96.8 Quality Control Summary - Certified Reference Materials (3) Analyte (lag/L) CRM True Value Result Recovery Fe(II) ICV 500.0 519.0 103.8 Total Fe TMDA-70 369.0 400.0 108.4 Mn (II) LCS 10.00 10.26 102.6 Total Mn TMDA-70.2 312 315 101.1 Diss Mn TMDA-70.2 312 310 99.5 Page 21 of 29 Speciation Results for Duke Energy Project Name: Duke Cape Fear Plant Contact: Jay Perkins LIMS# J15060668 Date: July 14, 2015 Report Generated by: Russell Gerads Brooks Rand Labs, LLC Quality Control Summary - Matrix Duplicates (1) Analyte (pg/L) Sample ID Rep 1 Rep 2 Mean RPD Cr(VI) MW-10D 0.006 0.005 0.005 13.9 ND = Not detected at the applied dilution NC = Value was not calculated due to one or more concentrations below the eMDL Quality Control Summary - Matrix Duplicates (2) Analyte (pg/L) Sample ID Rep 1 Rep 2 Mean RPD As(III) Batch QC 0.324 0.310 0.317 4.3 As(V) Batch QC ND (<0.028) ND (<0.028) NC NC MMAs Batch QC ND (<0.053) ND (<0.053) NC NC DMAs Batch QC ND (<0.083) ND (<0.083) NC NC ND = Not detected at the applied dilution NC = Value was not calculated due to one or more concentrations below the eMDL Page 22 of 29 Speciation Results for Duke Energy Project Name: Duke Cape Fear Plant Contact: Jay Perkins LIMS# J15060668 Date: July 14, 2015 Report Generated by: Russell Gerads Brooks Rand Labs, LLC Qualitv Control Summary - Matrix Duplicates (2 Analyte (pg/L) Sample ID Rep 1 Rep 2 Mean RPD Fe(II) Batch QC 110500 111400 110950 0.8 Total Fe Batch QC 113700 113700 113700 0.0 Mn (II) ABMW-4S 1792 1843 1817 2.8 Total Mn MW-1OD 1069 1106 1088 3.4 Diss Mn MW-1OD 1073 1079 1076 0.5 Page 23 of 29 Speciation Results for Duke Energy Project Name: Duke Cape Fear Plant Contact: Jay Perkins LIMS# J15060668 Date: July 14, 2015 Report Generated by: Russell Gerads Brooks Rand Labs, LLC Qualitv Control Summary - Matrix Spike/Matrix Spike Duplicate 0 Analyte (lag/L) Sample ID Spike Conc MS Result Recovery Spike Conc MSD Result Recovery RPD Cr(VI) Batch QC 5.000 4.523 90.3 5.000 4.552 90.9 0.6 Qualitv Control Summary - Matrix Spike/Matrix Spike Duplicate (2) Analyte (lag/L) Sample ID Spike Conc MS Result Recovery Spike Conc MSD Result Recovery RPD As(III) As(V) DMAs Batch QC Batch QC Batch QC 20.00 20.00 20.98 18.71 17.94 19.03 92.0 89.7 90.7 20.00 20.00 20.98 17.93 17.78 17.66 88.1 88.9 84.2 4.3 0.9 7.4 Quality Control Summary - Matrix Spike/Matrix Spike Duplicate (3) Analyte (lag/L) Sample ID Spike Conc MS Result Recovery Spike Conc MSD Result Recovery RPD Fe(I1) Total Fe Batch QC Batch QC 100000 100000 199500 201000 88.6 87.3 100000 100000 200000 191900 89.1 78.2 0.3 4.6 Mn (II) Total Mn Diss Mn ABMW-4S MW-10D MW-10D 500.0 1000 1000 2290 2046 2051 94.7 95.8 97.5 500.0 1000 1000 2288 2069 2072 94.1 98.1 99.6 0.8 1.1 1.0 „ � a w -=I 0 c- 00 00 0 0 a o v I i C M p v O L S CO v Ti -0 -D _0 00 p Cl. 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Cn �_ G) Un Cn (n: 10 U U N C U U C �c�Nc a v C Q uL co Q LL���n' o 0 z sp � `� Oa O > w � °= z � pp' 00 O R: 7 O C ca 0o C p .0 cr N (; a. j a » � � C i v O U v O U -. cif y = Cl) T M Q z ay c c c Q Z a> c c Wo�zZz wo�zz >~ z Z76 0 0 C Q � i 7 cc •� .Q � � ,n n cl `J J 7j 00 C) ;� Q \ -fQ :7s- r oscnmcnmT l•0 U. (JoQo4 ° z �'' • c E �LLvi C ty O x .p .p O C U C) U U Q LL W C L. uO 2 w �����...�..�n 97 of 9Q (�A 1886 Northcreek Parkviay Phone (4.- q 483.3300 Bothell, WA 98011 Fax (425) 483-9818 ame• Contact Person: ;3RL Pro'eet :.iL cr:! lercrny Nfautr Address: By submitting of samples the client agrees to all terms and conditions set forth in the quotation provided by the BRL project manager. If you are not familiar With the term and conditions associated with your project, please contact your Phone Number. - BRL re resentativc as soon as ossible 425 483-3300. Fax Number: Email Address: Re uested Turn Around Time: Project Name: Method of Sample Delivery: Project PJtunoer: Courier Tracking Number: Confi, nation of Sample Reception: PO Number: 1217608 ® Yes El No Sample ID Bottle ID Date and Time Matrix Volume Preservative Inirials Re uested Anah tes and Methods Comments •tw-u �jj �� tM ' , EDTA - 1 As Spec Ifield filtered _ NH4OHiNH4SO4 Cr(VI) field filtered i f HCl I, - Fe Spec field filtered - None r Mn S ec field filtered None Mn Spec unfiltered None li Se Spec field filtered % �� EDTA - 1 As S ec field filtered field filtered NH4OH/NH4SO4 I=• Cr VI De assed HCI fZ r Fe Spec field filtered ` None -'. Mn Spec ---- field filtered None > Mn Spec unfiltered Se S ec Feld filtered Relinquished by: (sign) � (print) feA4— Date/Time: b /���5` /$05— Received by: (sign) (print)„-,-- �� / (� Datefi-ime: � Comments: �1 Temp: 1, 1 Relinquished by: (sign) (print) Comments: Date/Time: Received by: (sign) (print) Date/Time: Please account for each samnlc bc.tle aS a Temp: Matrix: Air, Freshwater 01Y7, seawater (SkX�, groundwater (GW), Wtater (WW), soil (SL), sediment (SD), tissue (TS), product (I'), ottier (0) 11ev i.I (Apni 2005) R�^I� 18804 Northcreek Park,�iay Phone (4. q 183.3" A; f3S Bothell, WA 98011 Fax (425 483-9818 BR-1 Prujeci '.Iaiu r: lercrry N4a111r !Company Name: -, n Te Contact Person: <z-. • i .. <. ; . ; By submitting of samples the client agrees to all terms and conditions set forth in the quotation provided by the BRL project manager. If you are not familiar with the term and conditions associated with your project, please contact your BRL re resentanvc. as soon as possible 425 483-3300. Address: L - L' e . je Phone Number: ' 70 " c � Fax Number: Requested Turn Around Time: Email Address: _ , ,. a�/c��L,y 'i .," _ �� Method of Sample Delivery: Project Name: ( rc_a — Courier Tracking Number: Project Number: ConL:natlon of Sample Reception: Yes NO PO Number: 1217608 Sample ID Mottle ID Date and Time Matrix C--1 -' Volume Preservative EDTA - 1 Initials Requested Analytes and Methods As Spec Comments field filtered ' ? `7" - NH40HINH4SO4 1` Cr(VI) field filtered `�" . %K Degassed HO Fe Spec _ field filtered 14L"' .3 5 pia None i" _ Mn Spec field filtered _ None t Mn Spec unfiltered t+;,- None t: K C> Se Spec field filtered tat! `"'' - -'v , w EDTA - 1 As Spec field filtered _ NH40H/NH4SO4 Cr(VI) field filtered Degassed HCt # Fe Ep ec field filtered None Mn Spec field filtered_ None Mn S� unfiltered field filtered Relinquished by: (sign) 7 -- print K ' �c�c� 1 Dateffime: / C' fVIE✓1C Received by: (sign) (print)-i� Date/Time: } ) 11 2 m Comments: Temp: 4G Relinquished by: (sign) (print) Date[Time. Received by: (sign) (print) DateiTime: Comments: Temp: Please account for each sample bc:de as a seperate line item for verification purposes. Matrix: Air, Freshwater (IBC/}, seawater (SW), groundwater (GM, wastewater (WM, soil (SL), sediment (SD), tissue (TS), product (13), other (0) irev �A (April 2005) 122nc JQ QJ 7Q ��•�� �f.^VU L/%.E3S 1880-t Northcreek i arkuay Bothell, WA 98011- _ _ _ _ Phone (4. q 483.3 100 Fax 425) 483-9818 Com an BRL 13ru'ecL -Lui r: lerc-my M mre - Contact Person: Kcr=-1, i.. LV) By submitting of samples the client agrees to all terns and conditions set forth in the quotation provided by the BRL project manager. If you are not familiar with the term and conditions associated with your project, please contact your BRL representative as soon as possible 425 483-3300. Address: 6 i ., , Si- c 1 c J c � fc �-• �<�t.. r v Phone Number: 4 - ? Fax Number: Reauested Turn Around Ti.-ne: Email Address: '' : -+ C _ Method of Sample Delivery: Project Name: ,,y Courier Tracking Number: Project Number: PO Number: 1217608 ConLi .nation of Sample Reception: No Sample IDiC:t Bottle ID Date and Time Matrix L Volume Preservative EDTA - 1 Initials Requested Analytes and Methods As Spec. Comments field filtered M Vv- ( &Y/A 7/ tr: /qo-7 p1 w - to (D _ i Nt;7 NH40HiNH4SO4 Cr VI field filtered i M w - 10D C33 77 Y(c ! 07 Degassed HCl i Fe Spec field filtered Mw - �p 3b6 C6 C, yo7 None Mn Spec field filtered /1w ,Ofl BSc(. 7y 6, /yv7 None MnSpec unfiltered 22`/1 7.),5 6%r�"" — yG7 None Se Spec field filtered EDTA - 1 As Spec field filtered NH40H/NH4SO4 Cr(VI)� field filtered De assed HCI Fe Spec field filtered None Mn Spec field filtered None Mn Spec unfiltered ..Se S Ec feel here Relinquished by: (sign) Received by: (sign) (print) (p int) KyI z— nc.1 ctn >�l Date/Time:I /6��� Date/Time: Comments: Temp: - C, Relinquished by: (sign) Received by: (sign) (print) (print) Datet7ime: Date/Time: Comments: Temp: Please account for each sample bc.de as a seperate line item for verification purposes. Matrix: Air, Freshwater 0--NV), seawater (SW), groundwater (GW), wastewater (WW), soil (SL), sediment (SD), tissue (I'S), product (P), other (0) i'ev ,A (Apo; 2005)