### 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: J12100064

Lab Contact: Jason C Perkins


### Date: 10/16/2012 Customer Address: 253 Plant Allen Road Customer Name(s): Don Scruggs, Robbin Jolly, Ray Lidke, Bill Kennedy

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 2012020952 ALLEN 28-Sep-12 9:00 AM Matt Campbell FGD Purge Eff 2012020953 ALLEN 28-Sep-12 9:10 AM Matt Campbell EQ Tank Eff 2012020954 ALLEN 28-Sep-12 9:15 AM Matt Campbell BioReactor 1 Inf 2012020955 ALLEN 28-Sep-12 9:20 AM Matt Campbell BioReactor 2 Inf 2012020956 ALLEN 28-Sep-12 9:25 AM Matt Campbell BioReactor 2 Eff 2012020957 ALLEN 28-Sep-12 9:45 AM Matt Campbell Filter Blk 6 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: 

### 10/16/2012 Electronic Data Deliverable (EDD) Sent Separately

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



### Order # J12100064

2012020952 Collection Date: 28-Sep-12 9:00 AM 

### Site: FGD Purge Eff Matrix: OTHER

Analyte Analysis Date/Time Method Units Qualifiers RDL Result 

### Sample #:

Analyst DF INORGANIC IONS BY IC Bromide 410 mg/L EPA 300.0 10/09/2012 09:29 JAHERMA 50 500 Chloride 1100 mg/L EPA 300.0 10/09/2012 09:29 JAHERMA 50 500 MERCURY (COLD VAPOR) IN WATER Mercury (Hg) 16.2 ug/L EPA 245.1 10/04/2012 14:48 AGIBBS 2.5 50
TOTAL RECOVERABLE METALS BY ICP Boron (B) 28.9 mg/L EPA 200.7 10/04/2012 09:49 MHH7131 0.5 10
DISSOLVED METALS BY ICP-MS Selenium (Se) 2420 ug/L EPA 200.8 10/04/2012 11:26 KRICHAR 10 10
TOTAL RECOVERABLE METALS BY ICP-MS Arsenic (As) 196 ug/L EPA 200.8 10/04/2012 10:30 KRICHAR 10 10 Chromium (Cr) 172 ug/L EPA 200.8 10/04/2012 10:30 KRICHAR 10 10 Copper (Cu) 182 ug/L EPA 200.8 10/04/2012 10:30 KRICHAR 10 10 Nickel (Ni) 251 ug/L EPA 200.8 10/04/2012 10:30 KRICHAR 10 10 Selenium (Se) 3650 ug/L EPA 200.8 10/04/2012 10:30 KRICHAR 10 10 Silver (Ag) < 10 ug/L EPA 200.8 10/04/2012 10:30 KRICHAR 10 10 Zinc (Zn) 240 ug/L EPA 200.8 10/04/2012 10:30 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 6100 mg/L SM2540C 10/03/2012 15:30 TJA7067 200 1



### 2012020953 Collection Date: 28-Sep-12 9:10 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) 10.5 ug/L EPA 245.1 10/04/2012 14:51 AGIBBS 2.5 50
TOTAL RECOVERABLE METALS BY ICP Boron (B) 34.4 mg/L EPA 200.7 10/04/2012 09:53 MHH7131 0.5 10
DISSOLVED METALS BY ICP-MS Selenium (Se) 1790 ug/L EPA 200.8 10/04/2012 11:29 KRICHAR 10 10

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



### Order # J12100064

2012020953 Collection Date: 28-Sep-12 9:10 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) 85.1 ug/L EPA 200.8 10/04/2012 10:33 KRICHAR 10 10 Chromium (Cr) 88.9 ug/L EPA 200.8 10/04/2012 10:33 KRICHAR 10 10 Copper (Cu) 96.2 ug/L EPA 200.8 10/04/2012 10:33 KRICHAR 10 10 Nickel (Ni) 172 ug/L EPA 200.8 10/04/2012 10:33 KRICHAR 10 10 Selenium (Se) 2390 ug/L EPA 200.8 10/04/2012 10:33 KRICHAR 10 10 Silver (Ag) < 10 ug/L EPA 200.8 10/04/2012 10:33 KRICHAR 10 10 Zinc (Zn) 138 ug/L EPA 200.8 10/04/2012 10:33 KRICHAR 10 10



### 2012020954 Collection Date: 28-Sep-12 9:15 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) 38.0 mg/L EPA 200.7 10/04/2012 10:04 MHH7131 0.5 10
DISSOLVED METALS BY ICP-MS Selenium (Se) 1430 ug/L EPA 200.8 10/04/2012 11:33 KRICHAR 10 10
TOTAL RECOVERABLE METALS BY ICP-MS Arsenic (As) < 10 ug/L EPA 200.8 10/04/2012 10:36 KRICHAR 10 10 Chromium (Cr) < 10 ug/L EPA 200.8 10/04/2012 10:36 KRICHAR 10 10 Copper (Cu) < 10 ug/L EPA 200.8 10/04/2012 10:36 KRICHAR 10 10 Nickel (Ni) < 10 ug/L EPA 200.8 10/04/2012 10:36 KRICHAR 10 10 Selenium (Se) 1560 ug/L EPA 200.8 10/04/2012 10:36 KRICHAR 10 10 Silver (Ag) < 10 ug/L EPA 200.8 10/04/2012 10:36 KRICHAR 10 10 Zinc (Zn) < 10 ug/L EPA 200.8 10/04/2012 10:36 KRICHAR 10 10 SELENIUM SPECIATION - (Analysis Performed by Applied Speciation and Consulting, LLC) Vendor Parameter Complete Vendor Method V_AS&C



### 2012020955 Collection Date: 28-Sep-12 9:20 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) 46.0 mg/L EPA 200.7 10/04/2012 10:08 MHH7131 0.5 10

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



### Order # J12100064

2012020955 Collection Date: 28-Sep-12 9:20 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 10/04/2012 10:39 KRICHAR 10 10 Chromium (Cr) < 10 ug/L EPA 200.8 10/04/2012 10:39 KRICHAR 10 10 Copper (Cu) < 10 ug/L EPA 200.8 10/04/2012 10:39 KRICHAR 10 10 Nickel (Ni) < 10 ug/L EPA 200.8 10/04/2012 10:39 KRICHAR 10 10 Selenium (Se) 65.5 ug/L EPA 200.8 10/04/2012 10:39 KRICHAR 10 10 Silver (Ag) < 10 ug/L EPA 200.8 10/04/2012 10:39 KRICHAR 10 10 Zinc (Zn) < 10 ug/L EPA 200.8 10/04/2012 10:39 KRICHAR 10 10



### 2012020956 Collection Date: 28-Sep-12 9:25 AM 

### Site: BioReactor 2 Eff Matrix: OTHER

Analyte Analysis Date/Time Method Units Qualifiers RDL Result 

### Sample #:

Analyst DF INORGANIC IONS BY IC Bromide 470 mg/L EPA 300.0 10/09/2012 09:46 JAHERMA 50 500 Chloride 1400 mg/L EPA 300.0 10/09/2012 09:46 JAHERMA 50 500
TOTAL RECOVERABLE METALS BY ICP Boron (B) 67.3 mg/L EPA 200.7 10/04/2012 10:12 MHH7131 0.5 10
TOTAL RECOVERABLE METALS BY ICP-MS Arsenic (As) < 5 ug/L EPA 200.8 10/04/2012 10:43 KRICHAR 5 5 Chromium (Cr) < 5 ug/L EPA 200.8 10/04/2012 10:43 KRICHAR 5 5 Copper (Cu) < 5 ug/L EPA 200.8 10/04/2012 10:43 KRICHAR 5 5 Nickel (Ni) < 5 ug/L EPA 200.8 10/04/2012 10:43 KRICHAR 5 5 Selenium (Se) 10.2 ug/L EPA 200.8 10/04/2012 10:43 KRICHAR 5 5 Silver (Ag) < 5 ug/L EPA 200.8 10/04/2012 10:43 KRICHAR 5 5 Zinc (Zn) < 5 ug/L EPA 200.8 10/04/2012 10:43 KRICHAR 5 5 SELENIUM SPECIATION - (Analysis Performed by Applied Speciation and Consulting, LLC) Vendor Parameter Complete Vendor Method V_AS&C



### 2012020957 Collection Date: 28-Sep-12 9:45 AM 

### 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 10/04/2012 11:11 KRICHAR 1 1

## October 1 5 , 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 #J12100064 )

Dear Mr. Perkins, Attached is the report associated with three (3 ) aqueous samples submitted for selenium speciation analysis on October 4 , 2012

. The samples were received in a sealed cooler at 0. 6 ° C on October 5, 2012

. 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: Allen - FGD WWTS (2010, Bi-Monthly Sampling) (LIMS #J12100064)

October 1 5 , 2012

1. Sample Reception Three (3 ) aqueous samples in 125mL HDPE bottles (provided by Applied Speciation and Consulting) were submitted for selenium speciation analysi s on October 4, 2012 . The samples were received on October 5 , 201 2 in a sealed container at 0.6 ° 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 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.

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 v erification standards (CCV) and continuing calibration blanks (CCB) at a minimal 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 October 8-9, 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 ( 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 th e 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 430 1610 20.0 ND (<1.4) ND (<1.4) 40.9 (1) BioReactor 1 Inf 33.8 1290 ND (<0.17) 0.55 ND (<0.35) 0.0 (0) BioReactor 2 Eff 0.64 ND (<0.57) ND (<0.17) ND (<0.35) ND (<0.35) 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: Allen - FGD WWTS (2010, Bi-Monthly Sampling)

Contact: Jay Perkins

Date: October 15, 2012 LIMS #J12100064

### Quality Control Summary - Preparation Blank Summary

Analyte (μg/L) PBW1 PBW2 PBW3 PBW4 Mean StdDev eMDL* eMDL 250x Se(IV) 0.000 0.000 0.000 0.000 0.000 0.000 0.0012 0.30 Se(VI) 0.000 0.000 0.000 0.000 0.000 0.000 0.0023 0.57 SeCN 0.000 0.000 0.000 0.000 0.000 0.000 0.0007 0.17 MeSe(IV) 0.000 0.000 0.000 0.000 0.000 0.000 0.0014 0.35 SeMe 0.000 0.000 0.000 0.000 0.000 0.000 0.0014 0.35 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 9.48 99.0 Se(VI) LCS 9.48 9.42 99.4 SeCN LCS 8.92 8.79 98.5 MeSe(IV) LCS 6.47 6.40 99.0 SeMe LCS 9.32 8.81 94.5 LIMS #J12100064 Date: October 15, 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) BioReactor 1 Inf 33.83 34.21 34.02 1.1 Se(VI) BioReactor 1 Inf 1293 1298 1295 0.3 SeCN BioReactor 1 Inf ND (<0.17) ND (<0.17) NC NC MeSe(IV) BioReactor 1 Inf 0.55 0.42 0.48 27.4* SeMe BioReactor 1 Inf ND (<0.35) ND (<0.35) NC NC 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 10 times the MDL
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) BioReactor 1 Inf 1390 1526 107.4 1390 1527 107.4 0.1 Se(VI) BioReactor 1 Inf 1261 2749 115.2 1261 2568 100.9 6.8 SeCN BioReactor 1 Inf 1144 1168 102.1 1144 1175 102.7 0.6 Applied Speciation and Consulting, LLC Selenium Speciation Results for Duke Energy Project Name: Allen - FGD WWTS (2010, Bi-Monthly Sampling)

Contact: Jay Perkins LIMS #J12100064 Date: October 15, 2012 Report Generated by: Russell Gerads