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HomeMy WebLinkAboutNC0038377_Revised J15070470F_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: J15070470 Project Name: MAYO STEAM - AB GW ASSESSMENT SPECIATION Customer Name(s): Tim Hunsucker, Jerry Wylie, Kathy Webb, John Toepfer Customer Address: Lab Contact: Peggy Kendall kenddll@one: peggyd Report Authorized By: Uke-energy.com Date: (Signature)'15.08.17 Peggy Kendall 12:16:02-04'00' Program Comments: Please contact the Program Manager (Peggy Kendall) with any questions regarding this report. Data Flags & Calculations: 8/17/2015 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 2015023354 MAYO STEAM 07-Jul-15 12:25 PM Synterra E131 2015023358 MAYO STEAM 07-Jul-15 10:05 AM Synterra CW-2 2015023359 MAYO STEAM 07-Jul-15 2:15 PM Synterra S-05 2015023360 MAYO STEAM 07-Jul-15 1:17 PM Synterra BG-2 2015023361 MAYO STEAM 07-Jul-15 9:47 AM Synterra CW-2D 5 Total Samples Page 2 of 27 Page 3 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❑ 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: 8/5/2015 Certificate of Laboratory Analysis Page 4 of 27 This report shall not be reproduced, except in full. Order # J15070470 Site: EB1 Collection Date: 07-Jul-15 12:25 PM Analyte Result Units Qualifiers RDL DF Speciation of an Element - (Analysis Performed by Brooks Rand Labs LLC) Vendor Parameter Complete Sample #: 2015023354 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 # J15070470 Site: CW-2 Collection Date: 07-Jul-15 10:05 AM Analyte Result Units Qualifiers RDL DF Speciation of an Element - (Analysis Performed by Brooks Rand Labs LLC) Vendor Parameter Complete Sample #: 2015023358 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 # J15070470 Site: S-05 Collection Date: 07-Jul-15 2:15 PM Analyte Result Units Qualifiers RDL DF Speciation of an Element - (Analysis Performed by Brooks Rand Labs LLC) Vendor Parameter Complete Sample #: 2015023359 Matrix: GW WW Method Analysis Date/Time Analyst Vendor Method V_BRAND Certificate of Laboratory Analysis Page 7 of 27 This report shall not be reproduced, except in full. Order # J15070470 Site: BG-2 Collection Date: 07-Jul-15 1:17 PM Analyte Result Units Qualifiers RDL DF Speciation of an Element - (Analysis Performed by Brooks Rand Labs LLC) Vendor Parameter Complete Sample #: 2015023360 Matrix: GW WW Method Analysis Date/Time Analyst Vendor Method V_BRAND Site: CW-21D Collection Date: 07-Jul-15 9:47 AM Certificate of Laboratory Analysis Page 8 of 27 This report shall not be reproduced, except in full. Order # J15070470 Sample #: 2015023361 Matrix: GW WW Analyte Result Units Qualifiers RDL DF Method Analysis Date/Time Analyst Speciation of an Element - (Analysis Performed by Brooks Rand Labs LLC) Vendor Parameter Complete Vendor Method V_BRAND -- Additional Information -- This is a revised report and supersedes the initial report dated 8/4/15. The report has been revised to correct date analyzed values and significant figures that were reported incorrectly in the initial report. Page 9 of 27 BRO�©KS RAND LABS MEANINGFUL METALS DATA August 14, 2015 Peggy Kendall Duke Energy Analytical Laboratory Mail Code MGO3A2 (Building 7405) 13339 Hagers Ferry Rd. Huntersville, NC 28078 980-875-5848 Project: Mayo (LIMS# J15070470) Ms. Kendall, Attached is the revised report associated with five (5) aqueous samples submitted for hexavalent chromium, iron speciation, and manganese speciation analyses on July 7, 2015. The samples were received in a sealed cooler at -0.1 °C on July 8, 2015. This report has been revised to correct date analyzed values and significant figures that were reported incorrectly in the initial report. Fe(III) results for the client samples CW-2, 5-05, and CW-21) were altered. These results were calculated incorrectly in the initial report. The EDD format has been corrected to conform to the EDD design requested. No other changes have been made to this report. Hexavalent chromium analysis was performed by ion chromatography inductively coupled plasma dynamic reaction cell mass spectrometry (IC-ICP-DRC-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, k:`1 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 Page 10 of 27 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: Mayo (LIMS# J15070470) August 14, 2015 1. Sample Reception Five (5) aqueous samples were submitted for hexavalent chromium, iron speciation, and manganese speciation analyses on July 7, 2015. The samples were received in acceptable condition on July 8, 2015 in a sealed container at a temperature of -0.1 °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. 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. 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. 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 Page 11 of 27 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. 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 WIV 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). 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 15, 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. Page 12 of 27 Retention times for each eluting species are compared to known standards for species identification. Iron speciation Analvsis by Spectrophotometry All samples submitted for Fe speciation quantification were analyzed on July 8, 2015 and July 9, 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 July 13, 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 July 23, 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. Page 13 of 27 4. Analytical Issues No significant analytical issues were encountered. All quality control parameters associated with the samples were within acceptance limits. The preparation blanks associated with the iron speciation samples were not analyzed. The equipment blank sample EB 1 yielded non -detect results for both Fe(II) and total iron, demonstrating the absence of significant iron contamination due to the containers, the preservative employed, and the equipment used to collect the samples. 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 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, kL7S�-- Jeremy Maute Project Manager Brooks Rand Labs, LLC Page 14 of 27 Speciation Results for Duke Energy Project Name: Mayo Contact: Peggy Kendall LIMS# J15070470 Date: August 14, 2015 Report Generated by: Jeremy Maute Brooks Rand Labs, LLC Sample Results (1) Sample ID Cr(VI) EB1 ND (< 0.021) CW-2 0.100 S-05 0.612 BG-2 ND (< 0.021) CW-2D 0.084 All results reflect the applied dilution and are reported in pg/L ND = Not detected at the applied dilution Page 15 of 27 Speciation Results for Duke Energy Project Name: Mayo Contact: Peggy Kendall LIMS# J15070470 Date: August 14, 2015 Report Generated by: Jeremy Maute Brooks Rand Labs, LLC Sample Results (2 Sample ID Fe(II) Fe(III)* Mn (II) Mn(IV)** EB1 ND(<5.0) ND(<5.0) ND(<0.46) ND(<0.39) CW-2 ND(<5.0) 7.0 347 19.3 S-05 ND(<5.0) 11.6 6.78 32.0 BG-2 331 ND(<5.0) 141 8.53 CW-2D ND(<5.0) 7.0 7.00 77.7 All results reflect the applied dilution and are reported in Ng/L ND = Not detected at the applied dilution *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 16 of 27 Speciation Results for Duke Energy Project Name: Mayo Contact: Peggy Kendall LIMS# J15070470 Date: August 14, 2015 Report Generated by: Jeremy Maute Brooks Rand Labs, LLC Quality Control Summary - Preparation Blank Summary (1) Analyte (Ng/L) PBW1 PBW2 PBW3 PBW4 Mean StdDev eMDL* eMDL 5x RL 5x Cr(VI) 0.002 0.000 0.001 0.002 0.001 0.001 0.004 0.021 0.050 eMDL = Estimated Method Detection Limit; RL = Reporting Limit *Please see narrative regarding eMDL calculations Page 17 of 27 Speciation Results for Duke Energy Project Name: Mayo Contact: Peggy Kendall LIMS# J15070470 Date: August 14, 2015 Report Generated by: Jeremy Maute Brooks Rand Labs, LLC Qualitv Control Summary - Preparation Blank Summary (2 Analyte (tag/L) PBW1* PBW2* PBW3* PBW4* Mean StdDev eMDL** eMDL 1x RL 1x Fe(II) 5.0 5.0 20 Total Fe 5.0 5.0 20 eMDL = Estimated Method Detection Limit; RL = Reporting Limit *Preparation blanks for Fe speciation were not analyzed. See narrative. **Please see narrative regarding eMDL calculations Qualitv Control Summary - Preparation Blank Summary (2 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 0.16 0.21 0.15 0.14 0.17 0.03 0.004 - - 0.10 1.0 Diss Mn 0.32 0.08 0.07 0.03 0.16 0.13 0.016 - - 0.39 1.0 eMDL = Estimated Method Detection Limit; RL = Reporting Limit *Please see narrative regarding eMDL calculations Page 18 of 27 Speciation Results for Duke Energy Project Name: Mayo Contact: Peggy Kendall LIMS# J15070470 Date: August 14, 2015 Report Generated by: Jeremy Maute Brooks Rand Labs, LLC Quality Control Summary - Certified Reference Materials (1 Analyte (lag/L) CRM True Value Result Recovery Cr(VI) LCS 2.002 1.983 99.0 Quality Control Summary - Certified Reference Materials (2) Analyte (lag/L) CRM True Value Result Recovery Fe(II) Total Fe ICV TMDA-70 500.0 369.0 468.0 394.0 93.6 106.8 Mn (II) Total Mn Diss Mn LCS TMDA-70.2 TMDA-70.2 10.00 312 312 10.35 302.6 308.2 103.5 97.0 98.8 Page 19 of 27 Speciation Results for Duke Energy Project Name: Mayo Contact: Peggy Kendall LIMS# J15070470 Date: August 14, 2015 Report Generated by: Jeremy Maute Brooks Rand Labs, LLC Quality Control Summary - Matrix Duplicates (1) Analvte (ua/L) Sample ID Rea 1 Rea 2 Mean RPD ND = Not detected at the applied dilution NC = Value was not calculated due to one or more concentrations below the eMDL Page 20 of 27 Speciation Results for Duke Energy Project Name: Mayo Contact: Peggy Kendall LIMS# J15070470 Date: August 14, 2015 Report Generated by: Jeremy Maute Brooks Rand Labs, LLC Quality Control Summary - Matrix Duplicates (2) Analyte (pg/L) Sample ID Rep 1 Rep 2 Mean RPD Fe(II) CW-2 ND (< 5.0) ND (< 5.0) NC NC Total Fe CW-2 7.0 ND (< 5.0) NC NC Mn (II) Batch QC 344.9 336.9 340.9 2.3 Total Mn Batch QC 0.32 0.42 0.37 26.3* Diss Mn Batch QC ND(<0.39) ND(<0.39) NC NC NC = Value was not calculated due to one or more concentrations below the eMDL *Results associated with RPD outlier are less than the Reporting Limit Page 21 of 27 Speciation Results for Duke Energy Project Name: Mayo Contact: Peggy Kendall LIMS# J15070470 Date: August 14, 2015 Report Generated by: Jeremy Maute Brooks Rand Labs, LLC Quality 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) Batch QC 5.000 4.857 97.1 5.000 4.917 98.3 1.2 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 Fe(I1) CW-2 500.0 519.8 104.0 500.0 558.5 111.7 7.2 Total Fe CW-2 500.0 472.8 94.6 500.0 472.8 94.6 0.0 Mn (II) Batch QC 50.0 390.8 99.8 50.0 398.1 114.4 0.8 Total Mn Batch QC 1000 1060 105.9 1000 960.4 96.0 9.8 Diss Mn Batch QC 1000 914.4 91.4 1000 927.9 92.8 1.5 0 `" o l C M 00 U ca U v, l °o G C O a v 00 b -a m a 00 R N C K�ojji L Q0 0, ox G H O ii .� L w -2 D O� y= t �;���_ (ID w� i �. �C M 3 1(U �' pia t, T > .I II O N b U U U tt o U) U) U) (1) U) ) CL U) J U CG y 61 U CIS � U Qi C U � cc G cc C C sU-I CC, U v .y rj� G G Q V -< 0 O -O p i it L. ~ E �✓ Q �° G 7 aC V O G .00 O M O C cCa C O O '�i LI o ,�, i O n w C C F� n Cr y CT al. 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