### 13339 Hagers Ferry Road Huntersville, NC 28078-7929 McGuire Nuclear Complex - MG03A2 Phone: 980-875-5245 Fax: 980-875-4349 

# Order Summary Report 

# Analytical Laboratory

Order Number: J12110239 Project Name: WWTS - Biweekly (2)

L ab Contact: Jason C Perkins 

## Date: 12/4/2012 Customer Address: 253 Plant Allen Road Customer Name(s): BillK-RonL--RobnJ-DonS-RayL

Belmont, NC 28012

Phone: 980-875-5348 Report Authorized By: (Signature)


### Program Comments: Please contact the Program Manager (Jason C Perkins) with any questions regarding this report. Data Flags & Calculations: Any analytical tests or individual analytes within a test flagged with a Qualifier indicate a deviation from the method quality system or quality control requirement. The qualifier description is found at the end of the Certificate of Analysis (sample results) under the qualifiers heading. All results are reported on a dry weight basis unless otherwise noted. Subcontracted data included on the Duke Certificate of Analysis is to be used as information only. Certified vendor results can be found in the subcontracted lab final report. Duke Energy Analytical Laboratory subcontracts analyses to other vendor laboratories that have been qualified by Duke Energy to perform these analyses except where noted. Data Package: This data package includes analytical results that are applicable only to the samples described in this narrative. An estimation of the uncertainty of measurement for the results in the report is available upon request. This report shall not be reproduced, except in full, without the written consent of the Analytical Laboratory. Please contact the Analytical laboratory with any questions. The order of individual sections within this report is as follows: Job Summary Report, Sample Identification, Technical Validation of Data Package, Analytical Laboratory Certificate of Analysis, Analytical Laboratory QC Reports, Sub-contracted Laboratory Results, Customer Specific Data Sheets, Reports & Documentation, Customer Database Entries, Test Case Narratives, Chain of Custody (COC) Certification: The Analytical Laboratory holds the following State Certifications : North Carolina (DENR) Certificate #248, South Carolina (DHEC) Laboratory ID # 99005. Contact the Analytical Laboratory for definitive information about the certification status of specific methods.

# Sample ID's & Descriptions:

Sample ID Plant/Station Collection Date and Time Collected By Sample Description 2012024485 ALLEN 13-Nov-12 11:47 AM Chris Williams FGD Purge Eff 2012024486 ALLEN 13-Nov-12 11:55 AM Chris Williams EQ Tank Eff 2012024487 ALLEN 13-Nov-12 11:58 AM Chris Williams BioReactor 1 Inf 2012024488 ALLEN 13-Nov-12 12:02 PM Chris Williams BioReactor 2 Inf 2012024489 ALLEN 13-Nov-12 12:07 PM Chris Williams BioReactor 2 Eff 2012024490 ALLEN 13-Nov-12 12:40 PM Chris Williams Filter Blk 2012024491 ALLEN 18-Oct-12 8:30 AM J. TALLENT TRIP BLANK 7 Total Samples

### COC and .pdf report are in agreement with sample totals

and analyses (compliance programs and procedures). All Results are less than the laboratory reporting limits. All laboratory QA/QC requirements are acceptable. Yes No



# Technical Validation Review Checklist:

Yes No

Yes No



# Report Sections Included:

Job Summary Report Sub-contracted Laboratory Results Sample Identification Customer Specific Data Sheets, Reports, & Documentation Technical Validation of Data Package Customer Database Entries Analytical Laboratory Certificate of Analysis Analytical Laboratory QC Report Chain of Custody

Reviewed By: 

### DBA Account Date: 

### 12/4/2012 Electronic Data Deliverable (EDD) Sent Separately

# Certificate of Laboratory Analysis This report shall not be reproduced, except in full.



## Order # J12110239

2012024485 Collection Date: 13-Nov-12 11:47 AM 

## Site: FGD Purge Eff Matrix: OTHER

Analyte Analysis Date/Time Method Units Qualifiers RDL Result 

## Sample #:

Analyst DF INORGANIC IONS BY IC Bromide 1000 mg/L EPA 300.0 11/20/2012 09:23 JAHERMA 20 200 MERCURY (COLD VAPOR) IN WATER Mercury (Hg) 30.3 ug/L EPA 245.1 11/15/2012 14:44 AGIBBS 2.5 50
TOTAL RECOVERABLE METALS BY ICP Boron (B) 24.3 mg/L EPA 200.7 11/27/2012 09:11 MHH7131 0.5 10
DISSOLVED METALS BY ICP-MS Selenium (Se) 752 ug/L EPA 200.8 11/29/2012 12:09 DJSULL1 10 10
TOTAL RECOVERABLE METALS BY ICP-MS Arsenic (As) 289 ug/L EPA 200.8 11/28/2012 11:19 KRICHAR 10 10 Chromium (Cr) 238 ug/L EPA 200.8 11/28/2012 11:19 KRICHAR 10 10 Copper (Cu) 348 ug/L EPA 200.8 11/28/2012 11:19 KRICHAR 10 10 Nickel (Ni) 322 ug/L EPA 200.8 11/28/2012 11:19 KRICHAR 10 10 Selenium (Se) 7260 ug/L EPA 200.8 11/28/2012 11:19 KRICHAR 20 20 Silver (Ag) < 10 ug/L EPA 200.8 11/28/2012 11:19 KRICHAR 10 10 Zinc (Zn) 411 ug/L EPA 200.8 11/28/2012 11:19 KRICHAR 10 10 SELENIUM SPECIATION - (Analysis Performed by Applied Speciation and Consulting, LLC) Vendor Parameter Complete Vendor Method V_AS&C
TOTAL DISSOLVED SOLIDS TDS 9900 mg/L SM2540C 11/20/2012 15:27 SWILLI3 200 1



## 2012024486 Collection Date: 13-Nov-12 11:55 AM 

## Site: EQ Tank Eff Matrix: OTHER

Analyte Analysis Date/Time Method Units Qualifiers RDL Result 

## Sample #:

Analyst DF MERCURY (COLD VAPOR) IN WATER Mercury (Hg) 25.9 ug/L EPA 245.1 11/15/2012 14:47 AGIBBS 2.5 50
TOTAL RECOVERABLE METALS BY ICP Boron (B) 23.9 mg/L EPA 200.7 11/27/2012 09:14 MHH7131 0.5 10
DISSOLVED METALS BY ICP-MS Selenium (Se) 319 ug/L EPA 200.8 11/29/2012 12:12 DJSULL1 10 10

# Certificate of Laboratory Analysis This report shall not be reproduced, except in full.



## Order # J12110239

2012024486 Collection Date: 13-Nov-12 11:55 AM 

## Site: EQ Tank Eff Matrix: OTHER

Analyte Analysis Date/Time Method Units Qualifiers RDL Result 

## Sample #:

Analyst DF TOTAL RECOVERABLE METALS BY ICP-MS Arsenic (As) 217 ug/L EPA 200.8 11/28/2012 11:23 KRICHAR 10 10 Chromium (Cr) 199 ug/L EPA 200.8 11/28/2012 11:23 KRICHAR 10 10 Copper (Cu) 297 ug/L EPA 200.8 11/28/2012 11:23 KRICHAR 10 10 Nickel (Ni) 302 ug/L EPA 200.8 11/28/2012 11:23 KRICHAR 10 10 Selenium (Se) 6210 ug/L EPA 200.8 11/28/2012 11:23 KRICHAR 20 20 Silver (Ag) < 10 ug/L EPA 200.8 11/28/2012 11:23 KRICHAR 10 10 Zinc (Zn) 375 ug/L EPA 200.8 11/28/2012 11:23 KRICHAR 10 10



## 2012024487 Collection Date: 13-Nov-12 11:58 AM 

## Site: BioReactor 1 Inf Matrix: OTHER

Analyte Analysis Date/Time Method Units Qualifiers RDL Result 

## Sample #:

Analyst DF TOTAL RECOVERABLE METALS BY ICP Boron (B) 27.7 mg/L EPA 200.7 11/27/2012 09:18 MHH7131 0.5 10
DISSOLVED METALS BY ICP-MS Selenium (Se) 974 ug/L EPA 200.8 11/29/2012 12:15 DJSULL1 10 10
TOTAL RECOVERABLE METALS BY ICP-MS Arsenic (As) < 10 ug/L EPA 200.8 11/28/2012 10:45 KRICHAR 10 10 Chromium (Cr) < 10 ug/L EPA 200.8 11/28/2012 10:45 KRICHAR 10 10 Copper (Cu) < 10 ug/L EPA 200.8 11/28/2012 10:45 KRICHAR 10 10 Nickel (Ni) < 10 ug/L EPA 200.8 11/28/2012 10:45 KRICHAR 10 10 Selenium (Se) 1130 ug/L EPA 200.8 11/28/2012 10:45 KRICHAR 10 10 Silver (Ag) < 10 ug/L EPA 200.8 11/28/2012 10:45 KRICHAR 10 10 Zinc (Zn) < 10 ug/L EPA 200.8 11/28/2012 10:45 KRICHAR 10 10 SELENIUM SPECIATION - (Analysis Performed by Applied Speciation and Consulting, LLC) Vendor Parameter Complete Vendor Method V_AS&C



## 2012024488 Collection Date: 13-Nov-12 12:02 PM 

## Site: BioReactor 2 Inf Matrix: OTHER

Analyte Analysis Date/Time Method Units Qualifiers RDL Result 

## Sample #:

Analyst DF TOTAL RECOVERABLE METALS BY ICP Boron (B) 29.7 mg/L EPA 200.7 11/27/2012 09:22 MHH7131 0.5 10

# Certificate of Laboratory Analysis This report shall not be reproduced, except in full.



## Order # J12110239

2012024488 Collection Date: 13-Nov-12 12:02 PM 

## Site: BioReactor 2 Inf Matrix: OTHER

Analyte Analysis Date/Time Method Units Qualifiers RDL Result 

## Sample #:

Analyst DF TOTAL RECOVERABLE METALS BY ICP-MS Arsenic (As) < 10 ug/L EPA 200.8 11/28/2012 10:49 KRICHAR 10 10 Chromium (Cr) < 10 ug/L EPA 200.8 11/28/2012 10:49 KRICHAR 10 10 Copper (Cu) < 10 ug/L EPA 200.8 11/28/2012 10:49 KRICHAR 10 10 Nickel (Ni) < 10 ug/L EPA 200.8 11/28/2012 10:49 KRICHAR 10 10 Selenium (Se) 23.9 ug/L EPA 200.8 11/28/2012 10:49 KRICHAR 10 10 Silver (Ag) < 10 ug/L EPA 200.8 11/28/2012 10:49 KRICHAR 10 10 Zinc (Zn) < 10 ug/L EPA 200.8 11/28/2012 10:49 KRICHAR 10 10



## 2012024489 Collection Date: 13-Nov-12 12:07 PM 

## Site: BioReactor 2 Eff Matrix: OTHER

Analyte Analysis Date/Time Method Units Qualifiers RDL Result 

## Sample #:

Analyst DF INORGANIC IONS BY IC Bromide 730 mg/L EPA 300.0 11/20/2012 09:42 JAHERMA 10 100 MERCURY (COLD VAPOR) IN WATER Mercury (Hg) < 1 ug/L EPA 245.1 11/15/2012 14:49 AGIBBS 1 20
TOTAL RECOVERABLE METALS BY ICP Boron (B) 27.4 mg/L EPA 200.7 11/27/2012 09:26 MHH7131 0.5 10
TOTAL RECOVERABLE METALS BY ICP-MS Arsenic (As) < 5 ug/L EPA 200.8 11/28/2012 10:52 KRICHAR 5 5 Chromium (Cr) < 5 ug/L EPA 200.8 11/28/2012 10:52 KRICHAR 5 5 Copper (Cu) < 5 ug/L EPA 200.8 11/28/2012 10:52 KRICHAR 5 5 Nickel (Ni) < 5 ug/L EPA 200.8 11/28/2012 10:52 KRICHAR 5 5 Selenium (Se) 9.36 ug/L EPA 200.8 11/28/2012 10:52 KRICHAR 5 5 Silver (Ag) < 5 ug/L EPA 200.8 11/28/2012 10:52 KRICHAR 5 5 Zinc (Zn) < 5 ug/L EPA 200.8 11/28/2012 10:52 KRICHAR 5 5 SELENIUM SPECIATION - (Analysis Performed by Applied Speciation and Consulting, LLC) Vendor Parameter Complete Vendor Method V_AS&C



## 2012024490 Collection Date: 13-Nov-12 12:40 PM 

## Site: Filter Blk Matrix: OTHER

Analyte Analysis Date/Time Method Units Qualifiers RDL Result 

## Sample #:

Analyst DF DISSOLVED METALS BY ICP-MS Selenium (Se) < 1 ug/L EPA 200.8 11/29/2012 11:43 DJSULL1 1 1

# Certificate of Laboratory Analysis This report shall not be reproduced, except in full.



## Order # J12110239

2012024491 Collection Date: 18-Oct-12 8:30 AM 

## Site: TRIP BLANK Matrix: OTHER

Analyte Analysis Date/Time Method Units Qualifiers RDL Result 

## Sample #:

Analyst DF TOTAL RECOVERABLE METALS BY ICP Boron (B) < 0.05 mg/L EPA 200.7 11/27/2012 09:07 MHH7131 0.05 1
TOTAL RECOVERABLE METALS BY ICP-MS Arsenic (As) < 1 ug/L EPA 200.8 11/28/2012 10:35 KRICHAR 1 1 Chromium (Cr) < 1 ug/L EPA 200.8 11/28/2012 10:35 KRICHAR 1 1 Copper (Cu) < 1 ug/L EPA 200.8 11/28/2012 10:35 KRICHAR 1 1 Nickel (Ni) < 1 ug/L EPA 200.8 11/28/2012 10:35 KRICHAR 1 1 Selenium (Se) < 1 ug/L EPA 200.8 11/28/2012 10:35 KRICHAR 1 1 Silver (Ag) < 1 ug/L EPA 200.8 11/28/2012 10:35 KRICHAR 1 1 Zinc (Zn) < 1 ug/L EPA 200.8 11/28/2012 10:35 KRICHAR 1 1 SELENIUM SPECIATION - (Analysis Performed by Applied Speciation and Consulting, LLC) Vendor Parameter Complete Vendor Method V_AS&C

# November 2 7 , 201 2

Jay Perkins Duke Energy Analytical Laboratory Mail Code MGO3A2 (Building 7405) 13339 Hagers Ferry Rd. Huntersville, NC 28078 (704) 875-5 245 Project: Allen - FGD WWTS (2010, Bi-Monthly Sampling) (LIMS #J12110239)

Dear Mr. Perkins, Attached is the report associated with four (4 ) aqueous samples submitted for selenium speciation on November 15, 2012. The samples were received in a sealed cooler at-0. 1 ° C on November 1 6 , 2012

. Selenium speciation analysis was performed via ion chromatography inductively coupled plasma dynamic reaction cell mass spectrometry (IC-ICP-DRC-MS). Any issues associated with the analysis are addressed in the following report. If you have any questions, please feel free to contact me at your convenience.
Sincerely,

Russell Gerads Vice President Applied Speciation and Consulting, LLC

# Applied Speciation and Consulting, LLC Report prepared for: Jay Perkins Duke Energy Analytical Laboratory Mail Code MGO3A2 (Building 7405) 13339 Hagers Ferry Rd. Huntersville, NC 28078 Project: Allen - FGD WWTS (2010, Bi-Monthly Sampling) (LIMS #J12110239)

November 2 7 , 2012

1. Sample Reception Four (4 ) aqueous samples in 125mL HDPE bottles (provided by Applied Speciation and Consulting) were submitted for selenium speciation analysis on November 15 , 2012. The samples were received on November 1 6 , 201 2 in a sealed container at -0. 1°C. The 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 was filtered (0.45μm) and each filtrate w as stored in a secure, monitored cryofreezer (maintained at a temperature of -80 o 

# C) until selenium speciation analysis could be performed via ion chromatography inductively coupled plasma dynamic reaction cell mass spectrometry (IC-ICP-DRC-MS).

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. Selenium Speciation Analysis by IC -ICP-DRC

- MS Prior to analysis, an aliquot of each sa mple was filtered with a syringe filter (0.45μm) and injected directly into an 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.

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 curv es , 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 standard s 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. Selenium Speciation Analysis by IC -ICP-DRC

- MS Each sample for selenium speciation analysis w as analyzed by ion chromatography inductively coupled plasma dynamic reaction cell mass spectrometry (IC-ICP-DRC-MS) on November 19 , 2012

. 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 (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.

4. Analytical Issues The overall analyses went well and no significant analytical issues were encountered. The selenocyanate matrix spike and matrix spike duplicate sample recoveries (35.8% and 39.5%, respectively) were below the lower control limit of 75%. The spiking solution also contained selenite, and the spike recoveries for selenite (169.0% and 167.1%, respectively) were greater than the upper control limit of 125%. An acceptable mass balance of selenium species was obtained; the sum of species was calculated in each case yielding values of 103.6% and 104.6%. The apparent conversion of selenocyanate to selenite is indicative of an oxidizing matrix in the samples. Selenium species conversion was not observed in the bracketing continuing calibration verification standards (CCV), demonstrating adequate stability of selenium species within the analytical platform. No corrective actions were required. All other quality control parameters associated with the samples were within acceptance limits.

# The estimated method detection limits (eMDLs) 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 for methylseleninic acid and selenomethionine is 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. If you have any questions or concerns regarding this report, please feel free to contact me. Sincerely,

Russell Gerads Vice President Applied Speciation and Consulting, LLC

### Sample Results
Sample ID Se(IV) Se(VI) SeCN MeSe(IV) SeMe Unknown Se Species (n) FGD Purge Eff 500 112 116 25.5 ND (<1.6) 14.5 (2) BioReactor 1 Inf 713 247 ND (<0.49) 32.1 ND (<0.40) 10.1 (2) BioReactor 2 Eff ND (<0.25) ND (<0.45) ND (<0.49) ND (<0.40) ND (<0.40) 0.84 (1) Metals Trip Blk ND (<0.050) ND (<0.091) ND (<0.097) ND (<0.079) ND (<0.079) 0.0 (0) All results reflect the applied dilution and are reported in μg/L ND = Not detected at the applied dilution SeCN = Selenocyanate MeSe(IV) = Methylseleninic acid SeMe = Selenomethionine Unknown Se Species = Total concentration of all unknown Se species observed by IC-ICP-MS Report Generated by: Russell Gerads Applied Speciation and Consulting, LLC Selenium Speciation Results for Duke Energy Project Name: Allen - FGD WWTS (2010, Bi-Monthly Sampling)

Contact: Jay Perkins

Date: November 27, 2012 LIMS #J12110239

## Quality Control Summary - Preparation Blank Summary

Analyte (μg/L) PBW1 PBW2 PBW3 PBW4 Mean StdDev eMDL* eMDL 10x eMDL 50x eMDL 200x Se(IV) 0.000 0.000 0.000 0.000 0.000 0.000 0.0050 0.050 0.25 1.0 Se(VI) 0.000 0.000 0.000 0.000 0.000 0.000 0.0091 0.091 0.45 1.8 SeCN 0.000 0.000 0.000 0.000 0.000 0.000 0.0097 0.097 0.49 1.9 MeSe(IV) 0.000 0.000 0.000 0.000 0.000 0.000 0.0079 0.079 0.40 1.6 SeMe 0.000 0.000 0.000 0.000 0.000 0.000 0.0079 0.079 0.40 1.6 eMDL = Estimated Method Detection Limit *Please see narrative regarding eMDL calculations
Quality Control Summary - Certified Reference Materials Analyte (μg/L) CRM True Value Result Recovery Se(IV) LCS 9.57 9.74 101.8 Se(VI) LCS 9.48 9.48 100.1 SeCN LCS 8.92 8.98 100.6 MeSe(IV) LCS 6.47 6.43 99.3 SeMe LCS 9.32 9.09 97.5 LIMS #J12110239 Date: November 27, 2012 Report Generated by: Russell Gerads Applied Speciation and Consulting, LLC Selenium Speciation Results for Duke Energy Project Name: Allen - FGD WWTS (2010, Bi-Monthly Sampling)

Contact: Jay Perkins

## Quality Control Summary - Matrix Duplicates Analyte (μg/L) Sample ID Rep 1 Rep 2 Mean RPD Se(IV) Batch QC 23.9 20.9 22.4 13.4 Se(VI) Batch QC 73.8 72.2 73.0 2.1 SeCN Batch QC ND (<1.9) ND (<1.9) NC NC MeSe(IV) Batch QC 3.5 3.3 3.4 5.5 SeMe Batch QC ND (<1.6) ND (<1.6) 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 Spike/ Matrix Spike Duplicate Analyte (μg/L) Sample ID Spike Conc MS Result Recovery Spike Conc MSD Result Recovery RPD Se(IV) Batch QC 1112 1902 169.0 * 1112 1880 167.1 * 1.1 Se(VI) Batch QC 1009 1142 106.0 1009 1155 107.3 1.2 SeCN Batch QC 915.0 327.2 35.8 * 915.0 361.5 39.5 * 10.0 *Low/high recovery is attributed to matrix induced species conversion Applied Speciation and Consulting, LLC Selenium Speciation Results for Duke Energy Project Name: Allen - FGD WWTS (2010, Bi-Monthly Sampling)

Contact: Jay Perkins LIMS #J12110239 Date: November 27, 2012 Report Generated by: Russell Gerads