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HomeMy WebLinkAboutNC0000396_J15070124F_20150823+ 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: J15070124 Project Name: ASHEVILLE - AB GW ASSESSMENT SPECIATION Customer Name(s): Todd Plating, Kathy Webb, John Toepfer, Tim Hunsucker Customer Address: 200 CP and L Drive Arden, NC 28704 Lab Contact: Peggy Kendall Phone: peggy.kendall@d Report Authorized By:Uke-energy.com Date: (Signature) - - - - _ 201-5$7.27 Peggy Kendall 10:00:39 -04'00' Program Comments: Please contact the Program Manager (Peggy Kendall) with any questions regarding this report. Data Flags & Calculations: 7/27/2015 Page 1 of 27 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 2015022259 ASHEVILLE 30 -Jun -15 1:19 PM Synterra MW -22D 2015022260 ASHEVILLE 30 -Jun -15 3:12 PM Synterra MW-23DL 2015022261 ASHEVILLE 30 -Jun -15 8:55 AM Synterra MW -21 D 2015022262 ASHEVILLE 30 -Jun -15 12:26 PM Synterra MW-22BR 4 Total Samples Page 2 of 27 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 F./] 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 Page 3 of 27 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: 7/27/2015 Certificate of Laboratory Analysis Page 4 of 27 This report shall not be reproduced, except in full. Order # J15070124 Site: MW -22D Collection Date: 30 -Jun -15 1:19 PM Analyte Result Units Qualifiers RDL DF Speciation of an Element - (Analysis Performed by Brooks Rand Labs LLC) Vendor Parameter Complete Sample #: 2015022259 Matrix: GW WW Method Analysis Date/Time Analyst Vendor Method V_BRAND Certificate of Laboratory Analysis Page 5 of 27 This report shall not be reproduced, except in full. Order # J15070124 Site: MW-23DL Collection Date: 30 -Jun -15 3:12 PM Analyte Result Units Qualifiers RDL DF Speciation of an Element - (Analysis Performed by Brooks Rand Labs LLC) Vendor Parameter Complete Sample #: 2015022260 Matrix: GW WW Method Analysis Date/Time Analyst Vendor Method V_BRAND Certificate of Laboratory Analysis Page 6 of 27 This report shall not be reproduced, except in full. Order # J15070124 Site: MW -21 D Collection Date: 30 -Jun -15 8:55 AM Analyte Result Units Qualifiers RDL DF Speciation of an Element - (Analysis Performed by Brooks Rand Labs LLC) Vendor Parameter Complete Sample #: 2015022261 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 # J15070124 Site: MW-22BR Collection Date: 30 -Jun -15 12:26 PM Analyte Result Units Qualifiers RDL DF Speciation of an Element - (Analysis Performed by Brooks Rand Labs LLC) Vendor Parameter Complete Sample #: 2015022262 Matrix: GW WW Page 7 of 27 Method Analysis Date/Time Analyst Vendor Method V_BRAND Page 8 of 27 BRO�©KS RAND LABS MEANINGFUL METALS DATA July 26, 2015 Peggy Kendall Duke Energy Analytical Laboratory Mail Code MGO3A2 (Building 7405) 13339 Hagers Ferry Rd. Huntersville, NC 28078 980-875-5848 Project: Duke Energy Asheville Plant (LIMS# J15070124) Ms. Kendall, Attached is the report associated with four (4) aqueous samples submitted for hexavalent chromium, selenium speciation, arsenic speciation, iron speciation, and manganese speciation analyses on June 30, 2015. The samples were received in a sealed cooler at 0.0°C on July 1, 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) analysis was 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, it L7�-- Jeremy Maute Project 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 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 Energy Asheville Plant (LIMS# J15070124) July 26, 2015 1. Sample Reception Page 9 of 27 Four (4) aqueous samples were submitted for hexavalent chromium, selenium speciation, arsenic speciation, iron speciation, and manganese speciation analyses on June 30, 2015. The samples were received in acceptable condition on July 1, 2015 in a sealed container at a temperature of 0.0°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. An aliquot of each sample submitted for hexavalent chromium analysis was decanted 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 requiring selenium speciation evaluation was decanted into a clean polypropylene tube and each filtrate was stored in a secure, monitored cryofreezer (maintained at a temperature of -80°C) until selenium speciation analysis could be performed. An aliquot of each sample submitted for arsenic speciation analysis was decanted into a clean 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 Page 10 of 27 secure polyethylene container, known to be free from trace metals contamination, until the digestion could be performed. 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. Selenium Speciation Analysis by IC -ICP -CRC -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(LI) 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 Page 11 of 27 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). 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 July 14, 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. Selenium Speciation Analvsis by IC -ICP -CRC -MS Each sample for selenium speciation analysis was analyzed by ion chromatography inductively coupled plasma collision reaction cell mass spectrometry (IC -ICP -CRC -MS) on July 14, 2015. An aliquot of each sample is injected onto an anion exchange column and mobilized by a basic (pH > 7) gradient. 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. 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 July 9, 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 Page 12 of 27 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 July 1, 2015 and July 2, 2015, 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 July 10, 2015. Aliquots of each sample are injected onto an anion exchange column and mobilized by an acidic (pH < 7) gradient. An ion 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(IV Analysis by ICP -000 -MS All samples submitted for Mn speciation quantitation were analyzed by inductively coupled plasma triple quadrupole mass spectrometry (ICP-QQQ-MS) on July 17, 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, Page 13 of 27 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 Mn(II) result for the client sample, identified as MW -21D, was greater than the value of the associated high calibration standard. A linear range verification standard was analyzed at 2000 µg/L. The Mn(II) recovery for the linear range verification standard was acceptable, at 103.8%, demonstrating that the linear range of the analytical platform extended to 2000 µg/L for Mn(II). All reported Mn(II) results were less than 2000 µg/L with the dilutions at the instrument factored in, and thus were within the linear range demonstrated by the linear range verification standard. No corrective actions were necessary. Total and dissolved Mn results for the client sample, identified as MW -21D, were greater than the value of the associated high calibration standard. A linear range verification standard was analyzed at 2000 µg/L. The manganese recovery for the linear range verification standard was acceptable, at 96.9%, demonstrating that the linear range of the analytical platform extended to 2000 µg/L for manganese. All reported total and dissolved Mn results were less than 2000 µg/L with the dilutions at the instrument factored in, and thus were within the linear range demonstrated by the linear range verification standard. No corrective actions were necessary. 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 selenite, selenate, and selenocyanate are generated from replicate analyses of the lowest standard in the calibration curve. Not all selenium species are present in preparation blanks; therefore, eMDL calculations based on preparation blanks are artificially biased low. The eMDL values for methylseleninic acid and selenomethionine are calculated from the average eMDL of selenite, selenate, and selenocyanate. The calibration does not contain methylseleninic acid or selenomethionine due to impurities in these standards which would bias the results for other selenium species. 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 Page 14 of 27 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) conversion test for sample MW -22D did not meet the acceptance criteria. No qualification of the data was applied. The eMDL values for Fe(II) and total recoverable Fe were 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. Sincerely, Jeremy Maute Project Manager Brooks Rand Labs, LLC Speciation Results for Duke Energy Project Name: Duke Energy Asheville Plant Contact: Peggy Kendall LIMS# J15070124 Date: July 27, 2015 Report Generated by: Jeremy Maute Brooks Rand Labs, LLC Sample Results (1) Page 15 of 27 All results reflect the applied dilution and are reported in pg/L ND = Not detected at the applied dilution SeCN = Selenocyanate McSe(IV) = Methylseleninic acid SeMe = Selenomethionine Unknown Se Species = Total concentration of all unknown Se species observed by IC -ICP -MS n = number of unknown Se species observed Unknown Se Sample ID Cr(VI) Se(IV) Se(VI) SeCN McSe(IV) SeMe Species (n) MW -22D 0.484 ND (<0.082) 0.930 ND (< 0.041) ND (< 0.071) ND (< 0.071) 0 (0) MW-23DL ND (<0.021) ND (<0.082) 0.315 ND (< 0.041) ND (< 0.071) ND (< 0.071) 0 (0) MW -21 D ND (<0.021) ND (<0.082) ND (<0.091) ND (< 0.041) ND (< 0.071) ND (< 0.071) 0 (0) MW-22BR ND (<0.021) ND (<0.082) 0.309 ND (< 0.041) ND (< 0.071) ND (< 0.071) 0 (0) All results reflect the applied dilution and are reported in pg/L ND = Not detected at the applied dilution SeCN = Selenocyanate McSe(IV) = Methylseleninic acid SeMe = Selenomethionine Unknown Se Species = Total concentration of all unknown Se species observed by IC -ICP -MS n = number of unknown Se species observed Speciation Results for Duke Energy Project Name: Duke Energy Asheville Plant Contact: Peggy Kendall LIMS# J15070124 Date: July 27, 2015 Report Generated by: Jeremy Maute Brooks Rand Labs, LLC Sample Results (2) Unknown As Page 16 of 27 Sample ID As(III) As(V) MMAs DMAs Species MW -22D ND (< 0.036) ND (< 0.099) ND (< 0.060) ND (< 0.045) ND (< 0.060) MW-23DL ND (< 0.036) ND (< 0.099) ND (< 0.060) ND (< 0.045) ND (< 0.060) MW -21 D ND (< 0.036) ND (< 0.099) ND (< 0.060) ND (< 0.045) ND (< 0.060) MW-22BR ND (< 0.036) ND (< 0.099) ND (< 0.060) ND (< 0.045) ND (< 0.060) All results reflect the applied dilution and are reported in pg/L ND = Not detected at the applied dilution MMAs = monomethylarsonic acid DMAs = dimethylarsinic acid Unknown As Species = Total concentration of all unknown As species observed by IC -ICP -MS Page 17 of 27 Speciation Results for Duke Energy Project Name: Duke Energy Asheville Plant Contact: Peggy Kendall LIMS# J15070124 Date: July 27, 2015 Report Generated by: Jeremy Maute Brooks Rand Labs, LLC Samale Results (3 Sample ID Fe(II) Fe(III)* Mn (II) Mn(IV)** MW -22D 16.4 ND (< 5.0) 124 3.56 MW-23DL 8450 1320 70.3 ND (<0.18) MW -21 D 6800 1340 4650 40.0 MW-22BR 12900 1800 292 56.8 All results reflect the applied dilution and are reported in pg/L ND = Not detected at the applied dilution *Fe(III) defined as the difference between total recoverable Fe and Fe(II) **Mn(IV) operationally defined as the difference between total and dissolved Mn Speciation Results for Duke Energy Project Name: Duke Energy Asheville Plant Contact: Peggy Kendall LIMS# J15070124 Date: July 27, 2015 Report Generated by: Jeremy Maute Brooks Rand Labs, LLC Quality Control Summary - Preparation Blank Summary (1) Page 18 of 27 Analvte Woo PBW1 PBW2 PBW3 PBW4 Mean StdDev eMDL* eMDL 5x RL 5x eMDL 50x RL 50x Cr(VI) 0.006 0.012 0.005 0.001 0.006 0.004 0.004 0.021 0.050 - - Se(IV) 0.000 0.000 0.000 0.000 0.000 0.000 0.002 - - 0.082 0.50 Se(VI) 0.000 0.000 0.000 0.000 0.000 0.000 0.002 - - 0.091 0.50 SeCN 0.000 0.000 0.000 0.000 0.000 0.000 0.001 - - 0.041 0.46 McSe(IV) 0.000 0.000 0.000 0.000 0.000 0.000 0.001 - - 0.071 0.49 SeMe 0.000 0.000 0.000 0.000 0.000 0.000 0.001 - - 0.071 0.49 eMDL = Estimated Method Detection Limit; RL = Reporting Limit *Please see narrative regarding eMDL calculations Quality Control Summary - Preparation Blank Summary (2) Analyte (Pg/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 0.004 0.036 0.20 As(V) 0.000 0.000 0.000 0.000 0.000 0.000 0.010 0.099 0.20 MMAs 0.000 0.000 0.000 0.000 0.000 0.000 0.006 0.060 0.20 DMAs 0.000 0.000 0.000 0.000 0.000 0.000 0.004 0.045 0.21 eMDL = Estimated Method Detection Limit; RL = Reporting Limit *Please see narrative regarding eMDL calculations Page 19 of 27 Speciation Results for Duke Energy Project Name: Duke Energy Asheville Plant Contact: Peggy Kendall LIMS# J15070124 Date: July 27, 2015 Report Generated by: Jeremy Maute Brooks Rand Labs, LLC Quality Control Summary - Preparation Blank Summary (3 Analyte (tag/L) PBW1 PBW2 PBW3 PBW4 Mean StdDev eMDL** eMDL 1x RL 1x eMDL 100x RL 100x Fe(I1) 0.0 0.0 0.0 0.0 0.0 0.0 5.0 5.0 20 500 2000 Total Fe 0.0 0.0 0.0 0.0 0.0 0.0 5.0 5.0 20 500 2000 eMDL = Estimated Method Detection Limit; RL = Reporting Limit **Please see narrative regarding eMDL calculations Quality Control Summary - Preparation Blank SummarV (3) Analyte (tag/L) PBW1 PBW2 PBW3 PBW4 Mean StdDev eMDL* eMDL 10x RL 10x eMDL 25x RL 25x Mn (11) -0.60 -0.60 -0.60 -0.60 -0.60 0.00 0.046 0.46 5.0 - - Total Mn -0.04 0.09 0.00 -0.03 0.02 0.06 0.007 - - 0.18 1.0 Diss Mn 0.044 0.052 0.102 0.046 0.066 0.028 0.003 - - 0.083 1.0 eMDL = Estimated Method Detection Limit; RL = Reporting Limit *Please see narrative regarding eMDL calculations Page 20 of 27 Speciation Results for Duke Energy Project Name: Duke Energy Asheville Plant Contact: Peggy Kendall LIMS# J15070124 Date: July 27, 2015 Report Generated by: Jeremy Maute Brooks Rand Labs, LLC Quality Control Summary - Certified Reference Materials (1 Analyte (Ng/L) CRM True Value Result Recovery Cr(VI) LCS 2.002 1.983 99.0 Se(IV) LCS 10.00 9.836 98.4 Se(VI) LCS 10.00 9.327 93.3 SeCN LCS 8.92 8.895 99.7 McSe(IV) LCS 6.47 6.190 95.7 SeMe LCS 9.32 8.327 89.4 Quality Control Summary - Certified Reference Materials (2) Analyte (pg/L) CRM True Value Result Recovery As(III) LCS 5.000 5.116 102.3 As(V) LCS 5.000 5.581 111.6 MMAs LCS 5.073 6.163 121.5 DMAs LCS 3.625 3.631 100.2 Quality Control Summary - Certified Reference Materials (3) Analyte (pg/L) CRM True Value Result Recovery Fe(II) ICV 500.0 506.8 101.4 Total Fe TMDA-70 376.0 421.0 112.0 Mn (II) LCS 10.00 10.35 103.5 Total Mn TMDA-70.2 312 302.8 97.1 Diss Mn TMDA-70.2 312 295.0 94.6 Page 21 of 27 Speciation Results for Duke Energy Project Name: Duke Energy Asheville Plant Contact: Peggy Kendall LIMS# J15070124 Date: July 27, 2015 Report Generated by: Jeremy Maute Brooks Rand Labs, LLC Quality Control Summary - Matrix Duplicates (1) Analyte (pg/L) Sample ID Rep 1 Rep 2 Mean RPD Cr(VI) MW -22D 0.484 0.462 0.473 4.8 Se(IV) MW -21 D ND (<0.082) ND (<0.082) NC NC Se(VI) MW -21D 0.930 0.889 0.910 4.6 SeCN MW -21 D ND (< 0.041) ND (< 0.041) NC NC McSe(IV) MW -21 D ND (< 0.071) ND (< 0.071) NC NC SeMe MW -21 D ND (< 0.071) ND (< 0.071) NC NC 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) MW-23DL ND (< 0.036) ND (< 0.036) NC NC As(V) MW-23DL ND (< 0.099) ND (< 0.099) NC NC MMAs MW-23DL ND (< 0.060) ND (< 0.060) NC NC DMAs MW-23DL ND (< 0.045) ND (< 0.045) 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 27 Speciation Results for Duke Energy Project Name: Duke Energy Asheville Plant Contact: Peggy Kendall LIMS# J15070124 Date: July 27, 2015 Report Generated by: Jeremy Maute Brooks Rand Labs, LLC Quality Control Summary - Matrix Duplicates (3 Analyte (pg/L) Sample ID Rep 1 Rep 2 Mean RPD Fe(II) MW-23DL 8446 7273 7859 14.9 Total Fe MW-23DL 9769 9769 9769 0.0 Mn (II) MW -22D 123.8 127.3 125.6 2.8 Total Mn MW-23DL 61.48 66.41 63.94 7.7 Diss Mn MW-23DL 63.28 61.93 62.60 2.2 Page 23 of 27 Speciation Results for Duke Energy Project Name: Duke Energy Asheville Plant Contact: Peggy Kendall LIMS# J15070124 Date: July 27, 2015 Report Generated by: Jeremy Maute Brooks Rand Labs, LLC Qualitv Control Summary - Matrix Spike/ Matrix Spike Duplicate (1 Analyte (lag/L) Sample ID Spike Conc MS Result Recovery Spike Conc MSD Result Recovery RPD Cr(VI) MW -22D 5.000 5.362 97.8 5.000 5.412 98.8 0.9 Se(IV) MW -21 D 251.0 229.5 91.4 251.0 231.3 92.1 0.8 Se(VI) MW -21 D 250.0 226.0 90.0 250.0 226.9 90.4 0.4 SeCN MW -21 D 228.8 199.1 87.0 228.8 198.3 86.7 0.4 Quality 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) MW-23DL 20.00 18.03 90.1 20.00 17.74 88.7 1.6 As(V) MW-23DL 20.00 17.96 89.8 20.00 17.88 89.4 0.5 DMAs SMW-3C 20.98 18.16 86.6 20.98 18.43 87.8 1.5 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) MW-23DL 50000 56540 97.4 50000 53260 90.8 6.0 Total Fe MW-23DL 50000 60010 100.5 50000 60240 100.9 0.4 Mn (II) MW -22D 50.00 178.2 105.2 50.00 171.7 92.3 0.8 Total Mn MW-23DL 1000 1069 100.5 1000 1073 100.9 0.4 Diss Mn MW-23DL 1000 1090 102.8 1000 1113 105.1 2.1 'In • 1 "1 0 I Page 24 of 27 J 0 cr u ° a C N = 4.) C C CI 3iAll Z �I N N u L Q= 3 w Z Z Z. ^(U i w U U N L Q;V�� I I Z 1 C C N o '� C u _ N j O x N W C C n t/ I I KJ C 0 Vi U �c 00 G C 1 :J -a -0 vI gyp_, .�..'� � C u 1.7 N1 � 3 > fl Ln Lr - IO C C � 3 i 7 y �N y c� y r O N i V C: C c ro C L � 7 M n O u v. C � yL cn O 7 r — O x O a � � r oc `, V ly 0 N (D a) N ` � N ' > O co U) (n CO < v4w" (� N C C N N O y In eC .. U a Q � L� 7 co U O O C H y 'O Z`� m a.z E Z z awi u Z �Q z E u v 'T7 u'- p m. z_ r- r- �/ I.L.. i U C U : � I- W a c 00 O a ro :d w 7 C C .�.. CCA . C t H F" m 'In • 1 "1 0 I Page 24 of 27 J 0 cr u ° a C N = 4.) C C CI 3iAll Z �I N N u L Q= 3 w Z Z Z. ^(U i w U U N L Q;V�� I I Z 1 C C N 'In • 1 "1 0 I Page 24 of 27 J 0 cr u ° a C Ezl = 4.) C C CI 3iAll Z �I C C �►31 u �l Q= 3 w Z Z Z. ^(U o O C) � w 0 Z Z L � o C u _ N N 'In • 1 "1 0 I Page 24 of 27 J 0 U � _ C 6JI = 4.) 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N c c N GI i E a E o +y 7 0 0) r U iCc C C C 0 0 70 — C zv -0 -0 '0 TS Z Z Z (D 0= N C) co Z s Z o W 0 'o v:2 V W 'o -o v v v t�� c a a N N N N a) N O N y a � 7 N N N ti O . r 3 � 3 m w u�o N 2 b c � L Q O .0 cn U) cn cn CO). U) co CL n ami a Q VU. V oo • �I Q V LL vii L • 0 0 QO Ln 00 M _ tap �9 4 O M rN" O � A 00 In .D p N n > a _ S o z .� M v .40"ihll '- ME 0G. N c c N GI i E a E o +y 7 0 0) r U iCc C C C � r Q(n C — C zv Q p Z x (I7 W Z Z Z (D 0= N C) co Z s Z o W 0 V W O c; Z Z D a) O N y a � 7 N N N ti O . r 3 � 3 m w u�o N 2 b c � L Q O V oo • • • 0 0 QO Ln 00 M _ tap �9 4 O M rN" O � A 00 In .D p N n > a _ S K .� M .40"ihll '- ME 0G. N c c N GI i E a E o +y 7 0 0) H U � 2 — E zv vZ C Page 25 of 7 If U � � N N c c E a E o +y 0 0) H U +y 'r — E C (D s o � o V a) f y � N N N ti O � 3 m w c � L Q O Q. N N LM Lm M v � n N C > a _ S K .� w `A