### 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: J13030340 Project Name: WWTS - Biweekly (2)

L ab Contact: Jason C Perkins


## Date: 4/22/2013 Customer Address: 3195 Pine Hall Rd Customer Name(s): BIll K, Wayne C, Melonie M, and T. THORNTON

Mailcode: Belews Steam Station Belews Creek, 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. Jason C Perkins

# Sample ID's & Descriptions:

Sample ID Plant/Station Collection Date and Time Collected By Sample Description 2013006360 BELEWS 28-Mar-13 8:00 AM ILLEGIBLE FGD Purge Eff 2013006361 BELEWS 28-Mar-13 8:05 AM ILLEGIBLE EQ TANK EFF. 2013006362 BELEWS 28-Mar-13 8:10 AM ILLEGIBLE BIOREACTOR 1 INF. 2013006363 BELEWS 28-Mar-13 8:15 AM ILLEGIBLE BIOREACTOR 2 INF. 2013006364 BELEWS 28-Mar-13 8:20 AM ILLEGIBLE BIOREACTOR 2 EFF. 2013006365 BELEWS 28-Mar-13 8:25 AM ILLEGIBLE FILTER BLANK 2013006366 BELEWS 21-Mar-13 7:30 AM C.KNOX 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: 

### 4/22/2013 Electronic Data Deliverable (EDD) Sent Separately

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



## Order # J13030340

2013006360 Collection Date: 28-Mar-13 8:00 AM 

## Site: FGD Purge Eff Matrix: OTHER

Analyte Analysis Date/Time Method Units Qualifiers RDL Result 

## Sample #:

Analyst DF INORGANIC IONS BY IC Bromide 220 mg/L EPA 300.0 04/16/2013 02:45 JAHERMA 5 50 MERCURY (COLD VAPOR) IN WATER Mercury (Hg) 205 ug/L EPA 245.1 04/04/2013 13:08 AGIBBS 5 100
TOTAL RECOVERABLE METALS BY ICP Boron (B) 288 mg/L EPA 200.7 04/12/2013 13:24 DJSULL1 0.5 10
DISSOLVED METALS BY ICP-MS Selenium (Se) 358 ug/L EPA 200.8 04/08/2013 14:07 KRICHAR 10 10
TOTAL RECOVERABLE METALS BY ICP-MS Arsenic (As) 276 ug/L EPA 200.8 04/10/2013 13:56 KRICHAR 10 10 Cadmium (Cd) < 10 ug/L EPA 200.8 04/10/2013 13:56 KRICHAR 10 10 Chromium (Cr) 310 ug/L EPA 200.8 04/10/2013 13:56 KRICHAR 10 10 Copper (Cu) 149 ug/L EPA 200.8 04/10/2013 13:56 KRICHAR 10 10 Nickel (Ni) 291 ug/L EPA 200.8 04/10/2013 13:56 KRICHAR 10 10 Selenium (Se) 5170 ug/L EPA 200.8 04/10/2013 13:56 KRICHAR 20 20 Silver (Ag) < 10 ug/L EPA 200.8 04/10/2013 13:56 KRICHAR 10 10 Zinc (Zn) 271 ug/L EPA 200.8 04/10/2013 13:56 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 35000 mg/L SM2540C 04/08/2013 12:43 TJA7067 200 1



## 2013006361 Collection Date: 28-Mar-13 8:05 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) 116 ug/L EPA 245.1 04/04/2013 13:11 AGIBBS 2.5 50
TOTAL RECOVERABLE METALS BY ICP Boron (B) 263 mg/L EPA 200.7 04/12/2013 13:27 DJSULL1 0.5 10
DISSOLVED METALS BY ICP-MS Selenium (Se) 343 ug/L EPA 200.8 04/08/2013 14:10 KRICHAR 10 10

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



## Order # J13030340

2013006361 Collection Date: 28-Mar-13 8:05 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) 178 ug/L EPA 200.8 04/10/2013 13:00 KRICHAR 10 10 Cadmium (Cd) < 10 ug/L EPA 200.8 04/10/2013 13:00 KRICHAR 10 10 Chromium (Cr) 229 ug/L EPA 200.8 04/10/2013 13:00 KRICHAR 10 10 Copper (Cu) 113 ug/L EPA 200.8 04/10/2013 13:00 KRICHAR 10 10 Nickel (Ni) 253 ug/L EPA 200.8 04/10/2013 13:00 KRICHAR 10 10 Selenium (Se) 3400 ug/L EPA 200.8 04/10/2013 13:00 KRICHAR 10 10 Silver (Ag) < 10 ug/L EPA 200.8 04/10/2013 13:00 KRICHAR 10 10 Zinc (Zn) 207 ug/L EPA 200.8 04/10/2013 13:00 KRICHAR 10 10



## 2013006362 Collection Date: 28-Mar-13 8:10 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) 231 mg/L EPA 200.7 04/12/2013 13:31 DJSULL1 0.5 10
DISSOLVED METALS BY ICP-MS Selenium (Se) 200 ug/L EPA 200.8 04/08/2013 14:14 KRICHAR 10 10
TOTAL RECOVERABLE METALS BY ICP-MS Arsenic (As) < 10 ug/L EPA 200.8 04/10/2013 13:03 KRICHAR 10 10 Cadmium (Cd) < 10 ug/L EPA 200.8 04/10/2013 13:03 KRICHAR 10 10 Chromium (Cr) < 10 ug/L EPA 200.8 04/10/2013 13:03 KRICHAR 10 10 Copper (Cu) < 10 ug/L EPA 200.8 04/10/2013 13:03 KRICHAR 10 10 Nickel (Ni) 54.9 ug/L EPA 200.8 04/10/2013 13:03 KRICHAR 10 10 Selenium (Se) 190 ug/L EPA 200.8 04/10/2013 13:03 KRICHAR 10 10 Silver (Ag) < 10 ug/L EPA 200.8 04/10/2013 13:03 KRICHAR 10 10 Zinc (Zn) < 10 ug/L EPA 200.8 04/10/2013 13:03 KRICHAR 10 10 SELENIUM SPECIATION - (Analysis Performed by Applied Speciation and Consulting, LLC) Vendor Parameter Complete Vendor Method V_AS&C



## 2013006363 Collection Date: 28-Mar-13 8:15 AM 

## 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) 221 mg/L EPA 200.7 04/12/2013 13:35 DJSULL1 0.5 10

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



## Order # J13030340

2013006363 Collection Date: 28-Mar-13 8:15 AM 

## 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 04/10/2013 13:07 KRICHAR 10 10 Cadmium (Cd) < 10 ug/L EPA 200.8 04/10/2013 13:07 KRICHAR 10 10 Chromium (Cr) < 10 ug/L EPA 200.8 04/10/2013 13:07 KRICHAR 10 10 Copper (Cu) < 10 ug/L EPA 200.8 04/10/2013 13:07 KRICHAR 10 10 Nickel (Ni) < 10 ug/L EPA 200.8 04/10/2013 13:07 KRICHAR 10 10 Selenium (Se) 18.0 ug/L EPA 200.8 04/10/2013 13:07 KRICHAR 10 10 Silver (Ag) < 10 ug/L EPA 200.8 04/10/2013 13:07 KRICHAR 10 10 Zinc (Zn) < 10 ug/L EPA 200.8 04/10/2013 13:07 KRICHAR 10 10



## 2013006364 Collection Date: 28-Mar-13 8:20 AM 

## Site: BIOREACTOR 2 EFF. Matrix: OTHER

Analyte Analysis Date/Time Method Units Qualifiers RDL Result 

## Sample #:

Analyst DF INORGANIC IONS BY IC Bromide 160 mg/L EPA 300.0 04/16/2013 03:04 JAHERMA 5 50
TOTAL RECOVERABLE METALS BY ICP Boron (B) 206 mg/L EPA 200.7 04/12/2013 13:39 DJSULL1 0.5 10
TOTAL RECOVERABLE METALS BY ICP-MS Arsenic (As) < 5 ug/L EPA 200.8 04/10/2013 13:10 KRICHAR 5 5 Cadmium (Cd) < 5 ug/L EPA 200.8 04/10/2013 13:10 KRICHAR 5 5 Chromium (Cr) < 5 ug/L EPA 200.8 04/10/2013 13:10 KRICHAR 5 5 Copper (Cu) < 5 ug/L EPA 200.8 04/10/2013 13:10 KRICHAR 5 5 Nickel (Ni) < 5 ug/L EPA 200.8 04/10/2013 13:10 KRICHAR 5 5 Selenium (Se) < 5 ug/L EPA 200.8 04/10/2013 13:10 KRICHAR 5 5 Silver (Ag) < 5 ug/L EPA 200.8 04/10/2013 13:10 KRICHAR 5 5 Zinc (Zn) < 5 ug/L EPA 200.8 04/10/2013 13:10 KRICHAR 5 5 SELENIUM SPECIATION - (Analysis Performed by Applied Speciation and Consulting, LLC) Vendor Parameter Complete Vendor Method V_AS&C



## 2013006365 Collection Date: 28-Mar-13 8:25 AM 

## Site: FILTER BLANK 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 04/08/2013 13:53 KRICHAR 1 1

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



## Order # J13030340

2013006366 Collection Date: 21-Mar-13 7:30 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 04/12/2013 13:16 DJSULL1 0.05 1
TOTAL RECOVERABLE METALS BY ICP-MS Arsenic (As) < 1 ug/L EPA 200.8 04/10/2013 12:50 KRICHAR 1 1 Cadmium (Cd) < 1 ug/L EPA 200.8 04/10/2013 12:50 KRICHAR 1 1 Chromium (Cr) < 1 ug/L EPA 200.8 04/10/2013 12:50 KRICHAR 1 1 Copper (Cu) < 1 ug/L EPA 200.8 04/10/2013 12:50 KRICHAR 1 1 Nickel (Ni) < 1 ug/L EPA 200.8 04/10/2013 12:50 KRICHAR 1 1 Selenium (Se) < 1 ug/L EPA 200.8 04/10/2013 12:50 KRICHAR 1 1 Silver (Ag) < 1 ug/L EPA 200.8 04/10/2013 12:50 KRICHAR 1 1 Zinc (Zn) < 1 ug/L EPA 200.8 04/10/2013 12:50 KRICHAR 1 1

# April 18 , 2013

Jay Perkins Duke Energy Analytical Laboratory Mail Code MGO3A2 (Building 7405) 13339 Hagers Ferry Rd. Huntersville, NC 28078 (704) 875-5 245 Project: Belews - FGD WWTS (Bi-Monthly Sampling) (LIMS #J13030340)

Dear Mr. Perkins, Attached is the report associated with three (3 ) aqueous samples submitted for selenium speciation on April 2, 2013

. The samples were received in a sealed cooler at-0 .5° C on April 3 , 201 3

. Selenium speciation analysis was performed via ion chromatography inductively coupled plasma collision reaction cell mass spectrometry (IC-ICP- CRC -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: Belews - FGD WWTS (Bi-Monthly Sampling) (LIMS #J13030340)
April 18 , 2013

1. Sample Reception Three (3 ) aqueous samples in 125mL HDPE bottles (provided by Applied Speciation and Consulting) were submitted for selenium speciation analysis on April 2, 2013. The samples were received on April 3, 2013 in a sealed co ntainer at -0.5 °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 collision reaction cell mass spectrometry (IC-ICP- CRC -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-CRC- MS Prior to analysis, an aliquot of each sample 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 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 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-CRC- MS Each sample for selenium speciation analysis w as analyzed by ion chromatography inductively coupled plasma collision reaction cell mass spectrometry (IC-ICP- CRC -MS) on April 17, 2013. 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.

4. Analytical Issues The overall analyses went well and no significant analytical issues were encountered. All 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 284 49.0 ND (<2.1) 8.3 ND (<2.1) 0.0 (0) BioReactor 1 Inf 116 43.6 ND (<0.52) 8.30 ND (<0.53) 2.34 (1) BioReactor 2 Eff ND (<0.72) ND (<0.35) ND (<0.52) ND (<0.53) ND (<0.53) 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 n = number of unknown Se species observed Report Generated by: Russell Gerads Applied Speciation and Consulting, LLC Selenium Speciation Results for Duke Energy Project Name: Belews - FGD WWTS (Bi-Monthly Sampling)

Contact: Jay Perkins

Date: April 18, 2013 LIMS #J13030340

## Quality Control Summary - Preparation Blank Summary

Analyte (μg/L) PBW1 PBW2 PBW3 PBW4 Mean StdDev eMDL* eMDL 250x eMDL 1000x Se(IV) -0.003 0.013 0.007 0.010 0.007 0.007 0.003 0.72 2.9 Se(VI) 0.000 0.000 0.000 0.000 0.000 0.000 0.001 0.35 1.4 SeCN 0.000 0.000 0.000 0.000 0.000 0.000 0.002 0.52 2.1 MeSe(IV) 0.000 0.000 0.000 0.000 0.000 0.000 0.002 0.53 2.1 SeMe 0.000 0.000 0.000 0.000 0.000 0.000 0.002 0.53 2.1 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 4.79 4.530 94.7 Se(VI) LCS 4.74 4.269 90.1 SeCN LCS 4.46 4.095 91.8 MeSe(IV) LCS 3.24 3.009 93.0 SeMe LCS 4.66 4.226 90.7 Applied Speciation and Consulting, LLC Selenium Speciation Results for Duke Energy Project Name: Belews - FGD WWTS (Bi-Monthly Sampling)

Contact: Jay Perkins LIMS #J13030340 Date: April 18, 2013 Report Generated by: Russell Gerads

## Quality Control Summary - Matrix Duplicates Analyte (μg/L) Sample ID Rep 1 Rep 2 Mean RPD Se(IV) Batch QC 1.46 1.69 1.58 14.6 Se(VI) Batch QC ND (<0.35) ND (<0.35) NC NC SeCN Batch QC 0.94 1.07 1.00 12.8 MeSe(IV) Batch QC ND (<0.53) ND (<0.53) NC NC SeMe Batch QC ND (<0.53) ND (<0.53) 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 1390 1570 112.9 1390 1584 113.9 0.9 Se(VI) Batch QC 1261 1235 97.9 1261 1237 98.1 0.1 SeCN Batch QC 1144 914.5 79.9 1144 921.2 80.5 0.7 Applied Speciation and Consulting, LLC Selenium Speciation Results for Duke Energy Project Name: Belews - FGD WWTS (Bi-Monthly Sampling)

Contact: Jay Perkins LIMS #J13030340 Date: April 18, 2013 Report Generated by: Russell Gerads