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HomeMy WebLinkAboutNC0000396_J15050806F_Speciation_20150823+ DUKE Analytical Laboratory Page 1of35 ENERGY Order Number: Project Name: Customer Name(s): Customer Address: Lab Contact: Report Authorized By: (Signature) Program Comments: 13339 Hagers Ferry Road Huntersville, NC 28078-7929 McGuire Nuclear Complex - MG03A2 Phone: 980-875-5245 Fax: 980-875-4349 Order Summary Report J15050806 ASHEVILLE - AB GW ASSESSMENT SPECIATION Todd Plating, Kathy Webb, John Toepfer, Tim Hunsucker 200 CP and L Drive Arden, NC 28704 Peggy Kendall Phone: �j [� e peggy.kendall@duke- /Lyy �. 611I.arw.L�i energy.com a'i 2015.06.2308:44:17-04'0x' Date: Peggy Kendall Please contact the Program Manager (Peggy Kendall) with any questions regarding this report. Data Flags & Calculations: 6/23/2015 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 2015016687 ASHEVILLE 27 -May -15 9:45 AM Synterra ABMW-05BR 2015016688 ASHEVILLE 27 -May -15 9:41 AM Synterra ABMW-02 2015016689 ASHEVILLE 27 -May -15 Synterra ABMW-07S 2015016690 ASHEVILLE 27 -May -15 12:50 PM Synterra MW -08S 2015016691 ASHEVILLE 27 -May -15 2:12 PM Synterra MW -05D 2015016692 ASHEVILLE 27 -May -15 11:40 AM Synterra ABMW-02S 2015016693 ASHEVILLE 27 -May -15 2:44 PM Synterra GW -1 BR 7 Total Samples Page 2 of 35 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 35 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: 6/23/2015 Certificate of Laboratory Analysis Page 4 of 35 This report shall not be reproduced, except in full. Order # J15050806 Site: ABMW-05BR Collection Date: 27 -May -15 9:45 AM Analyte Result Units Qualifiers RDL DF Speciation of an Element - (Analysis Performed by Brooks Rand Labs LLC) Vendor Parameter Complete Sample #: 2015016687 Matrix: GW—WW Method Analysis Date/Time Analyst Vendor Method V_BRAND Certificate of Laboratory Analysis Page 5 of 35 This report shall not be reproduced, except in full. Order # J15050806 Site: ABMW-02 Collection Date: 27 -May -15 9:41 AM Analyte Result Units Qualifiers RDL DF Speciation of an Element - (Analysis Performed by Brooks Rand Labs LLC) Vendor Parameter Complete Sample #: 2015016688 Matrix: GW—WW Method Analysis Date/Time Analyst Vendor Method V_BRAND Certificate of Laboratory Analysis Page 6 of 35 This report shall not be reproduced, except in full. Order # J15050806 Site: ABMW-07S Collection Date: 27 -May -15 Analyte Result Units Qualifiers RDL DF Speciation of an Element - (Analysis Performed by Brooks Rand Labs LLC) Vendor Parameter Complete Sample #: 2015016689 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 # J15050806 Site: MW -08S Collection Date: 27 -May -15 12:50 PM Analyte Result Units Qualifiers RDL DF Speciation of an Element - (Analysis Performed by Brooks Rand Labs LLC) Vendor Parameter Complete Sample #: 2015016690 Matrix: GW—WW Page 7 of 35 Method Analysis Date/Time Analyst Vendor Method V_BRAND Certificate of Laboratory Analysis Page 8 of 35 This report shall not be reproduced, except in full. Order # J15050806 Site: MW -05D Collection Date: 27 -May -15 2:12 PM Analyte Result Units Qualifiers RDL DF Speciation of an Element - (Analysis Performed by Brooks Rand Labs LLC) Vendor Parameter Complete Sample #: 2015016691 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 # J15050806 Site: ABMW-02S Collection Date: 27 -May -15 11:40 AM Analyte Result Units Qualifiers RDL DF Speciation of an Element - (Analysis Performed by Brooks Rand Labs LLC) Vendor Parameter Complete Sample #: 2015016692 Matrix: GW—WW Page 9 of 35 Method Analysis Date/Time Analyst Vendor Method V_BRAND Certificate of Laboratory Analysis Page 10 of 35 This report shall not be reproduced, except in full. Order # J15050806 Site: GW -1 BR Collection Date: 27 -May -15 2:44 PM Analyte Result Units Qualifiers RDL DF Speciation of an Element - (Analysis Performed by Brooks Rand Labs LLC) Vendor Parameter Complete Sample #: 2015016693 Matrix: GW—WW Method Analysis Date/Time Analyst Vendor Method V_BRAND Page 11 of 35 BRO�©KS RAND LABS MEANINGFUL METALS DATA June 16, 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# J15050806) Mr. Perkins, Attached is the report associated with seven (7) aqueous samples submitted for hexavalent chromium, selenium speciation, arsenic speciation, iron speciation, and manganese speciation analyses on May 27, 2015. The samples were received in a sealed cooler at 0.0°C on May 28, 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# J15050806) June 16, 2015 1. Sample Reception Page 12 of 35 Seven (7) aqueous samples were submitted for hexavalent chromium, selenium speciation, arsenic speciation, iron speciation, and manganese speciation analyses on May 27, 2015. All samples were received in acceptable condition on May 28, 2015 in a sealed container at 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 filtered (0.45µm) 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 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 Page 13 of 35 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(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-O_QO-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 Page 14 of 35 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). 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 5, 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 Analysis 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 May 29, 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 June 3-4, 2015. Aliquots of each sample are injected onto an anion exchange column and eluted isocratically. The eluting arsenic species are then Page 15 of 35 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 May 28, 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(LI) 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 4, 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-QQQ-MS All samples submitted for Mn speciation quantitation were analyzed by inductively coupled plasma triple quadrupole mass spectrometry (ICP-QQQ-MS) on June 5, 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, Page 16 of 35 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. With the exceptions noted below, all quality control parameters associated with the samples were within acceptance limits. The preparation blanks associated with the iron speciation samples were not analyzed. Two client samples (ABMW-07S and MW -08S) yielded non -detect results for total iron, demonstrating the absence of significant iron contamination due to the containers, the preservative employed, and the equipment used to collect the samples. The client sample, identified as ABMW-05BR, was analyzed as the quality control sample for iron speciation. The total iron matrix spike and matrix spike duplicate (MS/MSD) recoveries were below the lower control limit of 75% (74.2% and 69.8%, respectively). Fe(III) results are calculated as the difference between total recoverable Fe and Fe(II). Accordingly, all Fe(III) results should be considered estimated (biased low). Several Mn(II) results were 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 100.1%, 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. For the Mn(II) analytical run, a client sample from another reception date (batch QC) was analyzed as the quality control sample. The matrix spike sample and matrix spike duplicate sample (MS/MSD) spike recoveries for Mn(II) were below the lower control limit of 75%, at -494.8% and -541.0%, respectively. The native Mn(II) concentration in the quality control sample was significantly greater than the spiking level. Acceptable spike recoveries are often not realized when the ambient level analyte concentration is greater than the spiking level. No qualification of data was 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. For the Mn(IV) analysis, several total and dissolved Mn results were greater than the value of the associated high calibration standard. A linear range verification standard was analyzed at 500.0 µg/L. The Mn recovery for the linear range verification standard was acceptable, at Page 17 of 35 100.4%, demonstrating that the linear range of the analytical platform extended to 500.0 µg/L for Mn. With the exception of one sample (ABMW-02S), all reported total and dissolved Mn results were less than 500 µg/L with the dilutions at the instrument factored in. These results were within the linear range demonstrated by the linear range verification standard. No corrective actions were necessary. With the dilution accounted for, the total and dissolved Mn results for the client sample, identified as ABMW-02S (632 µg/L and 619 µg/L, respectively), were greater than the associated Mn linear range verification standard (500 µg/L). The sample was re -analyzed for total and dissolved Mn at a higher dilutions. The results of the re -analyses confirmed the initial Mn determinations. Results from the original analyses were reported. 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 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 eMDL value for Fe(II) has been generated from replicate analyses of the lowest standard in the calibration curve. The eMDL value for total recoverable Fe was set at 1/3 the value of the associated reporting limit since the standard deviation associated with the replicate analyses of the lowest standard in the calibration curve was zero. 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. Page 18 of 35 If you have any questions or concerns regarding this report, please feel free to contact me. Sincerely, it L7S�-- Jeremy Maute Project Manager Brooks Rand Labs, LLC Speciation Results for Duke Energy Project Name: Duke Energy Asheville Plant Contact: Peggy Kendall LIMS# J15050806 Date: June 16, 2015 Report Generated by: Jeremy Maute Brooks Rand Labs, LLC Samale Results H Page 19 of 35 Sample ID Cr(VI) Se(IV) Se(VI) SeCN McSe(IV) SeMe Unknown Se Species (n) ABMW-05BR 0.013 0.152 ND (< 0.043) ND (< 0.048) 0.090 ND (< 0.033) 0 (0) ABMW-02 0.013 0.181 ND (< 0.043) ND (< 0.048) ND (< 0.033) ND (< 0.033) 0 (0) ABMW-07S 0.232 0.879 0.460 ND (< 0.048) 0.212 ND (< 0.033) 0.134(l) MW -08S 0.045 0.171 0.965 ND (< 0.048) ND (< 0.033) ND (< 0.033) 0 (0) MW -05D 0.021 0.097 1.42 ND (< 0.048) ND (< 0.033) ND (< 0.033) 0 (0) ABMW-02S 0.054 0.166 1.53 ND (< 0.048) ND (< 0.033) ND (< 0.033) 0 (0) GW -1 BR 0.059 ND (< 0.007) ND (< 0.043) ND (< 0.048) ND (< 0.033) ND (< 0.033) 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 Page 20 of 35 Speciation Results for Duke Energy Project Name: Duke Energy Asheville Plant Contact: Peggy Kendall LIMS# J15050806 Date: June 16, 2015 Report Generated by: Jeremy Maute Brooks Rand Labs, LLC Sample Results (2) All results reflect the applied dilution and are reported in pg/L NR = Analysis not requested 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 Unknown As Sample ID As(III) As(V) MMAs DMAs Species ABMW-05BR 0.464 0.12 ND (< 0.054) ND (< 0.038) ND (< 0.054) ABMW-02 2060 59.6 ND (< 1.1) ND (< 0.76) 15.3 ABMW-07S NR NR NR NR NR MW -08S 0.115 ND (< 0.11) ND (< 0.054) ND (< 0.038) ND (< 0.054) MW -05D 0.144 ND (< 0.11) ND (< 0.054) ND (< 0.038) ND (< 0.054) ABMW-02S 0.084 ND (< 0.11) ND (< 0.054) ND (< 0.038) ND (< 0.054) GW -1 BR 0.068 0.29 ND (< 0.054) ND (< 0.038) ND (< 0.054) All results reflect the applied dilution and are reported in pg/L NR = Analysis not requested 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 21 of 35 Speciation Results for Duke Energy Project Name: Duke Energy Asheville Plant Contact: Peggy Kendall LIMS# J15050806 Date: June 16, 2015 Report Generated by: Jeremy Maute Brooks Rand Labs, LLC Samale Results (3 Sample ID Fe(II) Fe(III)"* I Mn (II) Mn(IV)** ABMW-05BR 5600 1660 157 25.7 ABMW-02 41.4 2860 3910 ND (< 0.098) ABMW-07S 7.3 ND (< 6.7) 887 ND (< 0.098) MW -08S 4.9 ND (< 6.7) 3350 ND (< 0.098) MW -05D 4.9 84.4 533 ND (< 0.098) ABMW-02S 26.8 22.4 19200 327 GW -1 BR 9.7 124 54.9 1.50 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) $ Fe(III) results are estimated due to failing MS/MSD recoveries. Please see narrative. **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# J15050806 Date: June 16, 2015 Report Generated by: Jeremy Maute Brooks Rand Labs, LLC Quality Control Summary - Preparation Blank Summary (1 Page 22 of 35 Analyte (Pg/L) PBW1 PBW2 PBW3 PBW4 Mean StdDev eMDL* eMDL 5x RL 5x eMDL 50x RL 50x Cr(VI) 0.002 0.005 0.001 0.005 0.003 0.002 0.001 0.007 0.050 - - Se(IV) 0.000 0.000 0.000 0.000 0.000 0.000 0.000 - - 0.007 0.50 Se(VI) 0.000 0.000 0.000 0.000 0.000 0.000 0.001 - - 0.043 0.50 SeCN 0.000 0.000 0.000 0.000 0.000 0.000 0.001 - - 0.048 0.46 McSe(IV) 0.000 0.000 0.000 0.000 0.000 0.000 0.001 - - 0.033 0.49 SeMe 0.000 0.000 0.000 0.000 0.000 0.000 0.001 - - 0.033 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 eMDL 200x RL 200x As(III) 0.000 0.000 0.000 0.000 0.000 0.000 0.002 0.018 0.20 0.36 4.0 As(V) 0.00 0.00 0.00 0.00 0.00 0.00 0.011 0.11 0.20 2.1 4.0 MMAs 0.000 0.000 0.000 0.000 0.000 0.000 0.005 0.054 0.20 1.1 4.1 DMAs 0.000 0.000 0.000 0.000 0.000 0.000 0.004 0.038 0.21 0.76 4.2 eMDL = Estimated Method Detection Limit; RL = Reporting Limit *Please see narrative regarding eMDL calculations Speciation Results for Duke Energy Project Name: Duke Energy Asheville Plant Contact: Peggy Kendall LIMS# J15050806 Date: June 16, 2015 Report Generated by: Jeremy Maute Brooks Rand Labs, LLC Quality Control Summary - Preparation Blank Summary (3) Page 23 of 35 Analyte (pg/L) PBW1* PBW2* PBW3* PBW4* Mean StdDev eMDL** eMDL 1x RL 1x eMDL 50x RL 50x eMDL 100x RL 100x Fe(II) 3.6 3.6 20 - - 360 2000 Total Fe 6.7 6.7 20 330 1000 - - eMDL = Estimated Method Detection Limit; RL = Reporting Limit *Preparation blanks for Fe speciation were not analyzed. See narrative **Please see narrative regarding eMDL calculations Quality Control Summary - Preparation Blank Summary (3 Analyte (pg/L) PBW1 PBW2 PBW3 PBW4 Mean StdDev eMDL* eMDL 10x RL 10x eMDL 25x RL 25x Mn (11) 0.24 0.05 0.02 0.72 0.10 0.32 0.086 0.86 5.0 - - Total Mn 0.057 0.005 0.064 0.004 0.042 0.033 0.000 - - 0.098 1.0 Diss Mn 0.000 -0.003 0.042 0.023 0.013 0.021 0.000 - - 0.063 1.0 eMDL = Estimated Method Detection Limit; RL = Reporting Limit *Please see narrative regarding eMDL calculations Page 24 of 35 Speciation Results for Duke Energy Project Name: Duke Energy Asheville Plant Contact: Peggy Kendall LIMS# J15050806 Date: June 16, 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 1.781 89.0 Se(IV) LCS 10.00 11.41 114.1 Se(VI) LCS 10.00 10.59 105.9 SeCN LCS 8.92 9.193 103.1 McSe(IV) LCS 6.47 6.729 104.0 SeMe LCS 9.32 9.472 101.6 Quality Control Summary - Certified Reference Materials (2) Analyte (pg/L) CRM True Value Result Recovery As(III) LCS 5.00 5.824 116.5 As(V) LCS 5.00 5.244 104.9 MMAs LCS 5.07 5.657 111.5 DMAs LCS 3.63 3.700 102.1 Quality Control Summary - Certified Reference Materials (3) Analyte (pg/L) CRM True Value Result Recovery Fe(II) ICV 500.0 442.8 88.6 Total Fe LCS 500.0 460.0 92.0 Mn (II) LCS 1.00 1.053 105.3 Total Mn TMDA-70.2 312 295.2 94.6 Diss Mn TMDA-70.2 312 308.1 98.7 Page 25 of 35 Speciation Results for Duke Energy Project Name: Duke Energy Asheville Plant Contact: Peggy Kendall LIMS# J15050806 Date: June 16, 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) GW -1 BR 0.059 0.060 0.059 0.9 Se(IV) Batch QC 0.142 0.202 0.172 35.0* Se(VI) Batch QC ND (< 0.043) ND (< 0.043) NC NC SeCN Batch QC ND (< 0.048) ND (< 0.048) NC NC McSe(IV) Batch QC ND (< 0.033) ND (< 0.033) NC NC SeMe Batch QC ND (< 0.033) ND (< 0.033) NC NC ND = Not detected at the applied dilution NC = Value was not calculated due to one or more concentrations below the eMDL *Results associated with RPD outlier were less than the reporting limit Quality Control Summary - Matrix Duplicates (2) Analyte (pg/L) Sample ID Rep 1 Rep 2 Mean RPD As(III) Batch QC ND (< 0.018) ND (< 0.018) NC NC As(V) Batch QC ND (< 0.11) ND (< 0.11) NC NC MMAs Batch QC ND (< 0.054) ND (< 0.054) NC NC DMAs Batch QC ND (< 0.038) ND (< 0.038) NC NC ND = Not detected at the applied dilution NC = Value was not calculated due to one or more concentrations below the eMDL Page 26 of 35 Speciation Results for Duke Energy Project Name: Duke Energy Asheville Plant Contact: Peggy Kendall LIMS# J15050806 Date: June 16, 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) ABMW-05BR 5596 5109 5353 9.1 Total Fe ABMW-05BR 7257 6922 7089 4.7 Mn (II) Batch QC 3291 3258 3274 1.0 Total Mn Batch QC 2834 2689 2762 5.3 Diss Mn Batch QC 2622 2632 2627 0.3 ND = Not detected at the applied dilution NC = Value was not calculated due to one or more concentrations below the eMDL *Associated results were less than the RL Page 27 of 35 Speciation Results for Duke Energy Project Name: Duke Energy Asheville Plant Contact: Peggy Kendall LIMS# J15050806 Date: June 16, 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) GW -1 BR 5.000 4.824 95.3 5.000 5.180 102.4 7.1 Se(IV) Batch QC 251.0 233.0 92.7 251.0 235.4 93.7 1.1 Se(VI) Batch QC 250.0 225.0 90.0 250.0 230.6 92.2 2.5 SeCN Batch QC 228.8 205.3 89.7 228.8 214.2 93.6 4.3 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) Batch QC 20.00 21.09 105.5 20.00 21.05 105.3 0.2 As(V) Batch QC 20.00 21.07 105.4 20.00 20.99 104.9 0.4 DMAs Batch QC 20.98 22.06 105.2 20.98 22.04 105.0 0.1 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) ABMW-05BR 50000 50120 89.5 50000 58150 105.6 14.8 Total Fe ABMW-05BR 10000 14510 74.2* 10000 14070 69.8* 3.1 Mn (II) Batch QC 50.00 3027 -494.8** 50.00 3004 -541.0** 0.8 Total Mn Batch QC 1000 3633 87.1 1000 3544 78.2 2.5 Diss Mn Batch QC 1000 3549 92.2 1000 3568 94.1 0.6 *Spike recovery is less than the lower control limit of 75%. Please see narrative **Ambient analyte concentration greater than spiking level. See case narrative. P age28of3 M 0000 H w oM0 M O C O v u 53 V a 'a v 'a d d ,n 000' N `� rp ° N N N N V `1 d N N N N N N N 'p N N O O v O p+ z U N = d +- N +- N = N = i' N C D+ rw- U ® 4= p � C O O ti. t� -0 4= O d 32 1� :2 w 8 cm cz +� w= w w C w o 15 0,0 E a E O N o ani O ami U J p ami aUi CL ami OL m ( _ 0) (D F c�a R. 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T { <i %I 4.'14 - 18804 Nortly reek Parkway BotheA, W.A 98011 15050 80& Pl o.air(bg493-3300 Fax (425) 4�183-9818 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 RR7. rPnre.centative as soon as possible 425 483-3300. r0 ect Natrie; Confirmation of Sample Reception: Yes No 'raiect Number, 10 Number: 1217608 Bottle ID Date and Time Matrix Volume Preservative Initials Requested Anal tes and Methods Comments is le ID ;♦ -OS 3R. '?#�I' 'S'� S � n9� � a5 EDTA - t As Spec CV!L-- field filtered filtered . �a Ra Nµ4Cl{1NH4SO4 Fe Spec field filtered • $O De sled HCl Mn S field filtered None Mn Spec unfiitered None Se Spec field filtered x,9' None $ W-oa i339 0 $ ig D�t'�I S EDTA -1 As S ec Cr V1 field filtered field filtered 1500 NH40HlNH4SO4 Fe Spec fieli! filtered -, 5 �� assed HCl Mn Spec field filtered 30in 9v None Mn Spec unfiltered • 3$Q�� None Se Spec field filtered u None IL E2 " riot}� �. yam$ Daterrime: =�� omments: -� s7!1 Relinquished by: (sign) _rint � ' � + � DatelTime: I '�d�o�Received a G- by: (sign) (P )— - ema; �?• ! pateffime:��.. Relinquished by: (sign) (print) Temp: Reosived by: (si ) (print) DateTme: Please account for each sample bottle as a seperate line item for verification purposes. l �� Matri)r Air, Freshwater (TW), seawater (SW), groundwater (CM), wastewater (%%)), soil (SL), sediment (SD), tissue (TS), product (P), other (0) t+.ev 1-1 (April 2005) r 31SOSO�V� :'Nlatrix; Air, Freshwater (f'NV).,Scawzwr (SW), groundwata (GW)" wftstcwRtcr TM, soil (I;L),:scdimcnt (SD), tissue (FS), product (V)�, Otner (Lj) 4- OT, —1 Itev 1.1 (April 2005) 18804 Northcreek Parkway phone (425) 483-3300 Pax {425) 4133-981.8 �Bs Bothell, NVA 98011 r Wwaria�ur r+srwu+ IPPiYJ�' . Com an Name,. BRI; Project. Man a er:.. erem &Iaute Contact Person:q By submitting of samples .the client agrees to all_terms and conditions set forth ddress: U Z.D in the quotationprovided by the BRL ptnject manager.If you are not familiar with the term and conditions associated with your project, Please contact your $RL re' resentative as soon as' possible 425 '483-33W Phone Number;. {� ... q Pax Number: - {� '%1.l Le -guested Turn Around l umc: . Email Address: 'l" !1 ,.�TG1�+R. Y •t'.t�+r t Method of Sam Ic I3elivc . 1'ro ect Name: au Courier TrackingNumber: Confirmation of Sample Reception: � Yes 13 ND Project Number Q • PO Number: Sample XD 1217608 Bottle ID Date and Time Matrix Volume Preservative Initials Re treated Anal es and Methods Comments * -CJS OD -61 -+ 15 t�11 1a5 EDTA -1 As S ec field filtered _______ NH40H/NH4SO4 C I) field filtered •2y1 p D assed HCl Fe S field filtered __ None Mn Spec field filtered' None Mn Spec unfiltered: _ B �'fl7�5 fa _T None _ Se Spec _ _ field filtered _ _.. r �---- - EDTA - 1 As. S pec; _ _field field filtered • $ul�c� NHdOHfNH4SO4� Cr(V�_ _ filtered ic'�31Q5a11 Deaassed.HCi Fe Spec . field filtered None Mn Spec field filtered *$ Mn Spec unfiltered_ _ _ _None None Se Spec field fiiltered _ __ _ _ Relinquish6d by: (sig (print},�:�� Date/Time: Comments; Received. by: {sign} (print) C Clate/Time' T r. d'10a L' Temp•. lip • O Comments: Relinquished by: (sign) (print) DateJTime: Received by; sign (print) DatelTime: Temp: Please account for each sample bottle as a seperate line item for verification purposes. Matrix: Air Vreshwatcr 04%), seawater (SW), groundwater (GW), wastewater (WM, soil (S)_), sedimenr. (91)), tissue (MS,ptoduct (l'}, other (0) Rcv 1.1. (April 2005) Nacre: N — None LUZ None - __ _� Se DTA -1 188041 Northcreek Parkway Phot c {� 373300 1_HlNH4SO4_ _ ----C Bothell, WA 98011 Fax (425) 483-9818. _ Fe None. BRL Project Mana v . erem Maute X Mn By submitting of samples the client agrees to all terms and conditions set forth .�� in the quotation provided by the BW project manager. IE you are neat familiar e with the tezm and conditions assaciated.vith your project, please contact your Se (h; 425 483-3300. BRC re' resentative as soon as. ssible _ Re uested'1'urnAcaundTime:. �`.`. Method Qf Sa lIe De]ive ���� V ���,,� Courier Trackin Number: Confirmation of'Sample Reception. Yes ® No C 1217608 te Matxixr Valurne Bottle ID Daand Time . Preservative Initiais , Requested Anal tits and Methods Comments l EDTA -1 .. -As Spec field filtered NH40HlNH4504 C�i�.._.�..---� -- field filtered .--------- r5, LA�_ �_ assed H 'DegCi Fie Spec field filtered 3413 a f None–J2M4 Mn S ec RAn field filtered un#filtered None LUZ None - __ _� Se DTA -1 As 1_HlNH4SO4_ _ ----C assed HCA _ Fe None. Mn None- Mn None Se Zelinquished by: (s'"gn) t) �a �1 DatelTime: {print). a A v' DatelTin* ' S r�R a✓ �eoeived by:. (sign) — - — Relinquished by: (sign) Datel {print} Time: DatelTime: Received by: (si rij (print) Please account for each sample bottle as a seperate line item for.verification purposes. `Matrix: Air, Freshwater (M. scawatcr (SW), grroundwatcr (C3V1), wastewater {LfVW), Boil sediment (M), tissue (1'S}:,.product (1�, other. (0) field filtered —M field filtered field filtered field filtered field filtered: unfiltered field filtered o,6C' its" 14 Rcv 1.1 (April 2005)