**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: J11060367

**Lab Contact: Jason C Perkins** 
Date: **7/12/2011 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:

Data Flags & Calculations: **Any analytical tests or individual analytes within a test flagged with an "X" or "1" indicate a deviation from the method quality system or quality control requirement. All results are reported on a dry weight basis unless otherwise 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 **2011013564 ALLEN 27-Jun-11 8:47 AM Jeff Womack**  **FGD Purge Eff 2011013565**  **ALLEN 27-Jun-11 8:30 AM Jeff Womack EQ Tank Eff**  **2011013566 ALLEN 27-Jun-11 8:25 AM Jeff Womack**  **BioReactor 1 Inf 2011013567**  **ALLEN 27-Jun-11 9:03 AM Jeff Womack BioReactor 2 Inf**  **2011013568 ALLEN 27-Jun-11 8:35 AM Jeff Womack**  **BioReactor 2 Eff 2011013569**  **ALLEN 27-Jun-11 8:18 AM Jeff Womack Filter Blk**  **2011013570 ALLEN 21-Jun-11 11:05 AM Samantha Stowe**  **Metals 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. The Vendor Laboratories have been qualified by the**  **Analytical Laboratory Yes**  **No**



## Technical Validation Review C hecklist:

**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 Test Case Narratives**  **Analytical Laboratory QC Report Chain of Custody** 

**Reviewed By: DataBase Administrator**  **Date: 7/12/2011**  **Yes**

**Electronic Data Deliverable (EDD) Sent Separately**

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



### Order # J11060367

2011013564 **Collection Date: 27-Jun-11 8:47 AM Site:**  **FGD Purge Eff Matrix: OTHER** 

Analyte Analysis Date/Time Method Units Qualifiers RDL Result Sample #:

Analyst MERCURY (COLD VAPOR) IN WATER **Mercury (Hg)** 89.8 **ug/L EPA 245.1 01-Jul-11 12:42**  **TLINN 2.5** 
TOTAL RECOVERABLE METALS BY ICP **Boron (B)** 78.4 **mg/L EPA 200.7 30-Jun-11 14:01 DJSULL1**  **0.5**
DISSOLVED METALS BY ICP-MS **Selenium (Se)** 212 **ug/L EPA 200.8 06-Jul-11 12:26 KRICHAR**  **10**
TOTAL RECOVERABLE METALS BY ICP-MS **Arsenic (As)** 211 **ug/L EPA 200.8 05-Jul-11 13:46 KRICHAR**  **10 Chromium (Cr)**  145 **ug/L EPA 200.8**  **05-Jul-11 13:46 KRICHAR 10**  **Copper (Cu)** 174 **ug/L EPA 200.8**  **05-Jul-11 13:46 KRICHAR 10**  **Nickel (Ni)** 225 **ug/L EPA 200.8**  **05-Jul-11 13:46 KRICHAR 10**  **Selenium (Se)** 1410 **ug/L EPA 200.8**  **05-Jul-11 13:46 KRICHAR 10**  **Silver (Ag)** < 10 **ug/L EPA 200.8**  **05-Jul-11 13:46 KRICHAR 10**  **Zinc (Zn)** 224 **ug/L EPA 200.8**  **05-Jul-11 13:46 KRICHAR 20** 
SELENIUM SPECIATION **Vendor Parameter** Complete **V_AS&C**
TOTAL DISSOLVED SOLIDS **TDS** 10000 **mg/L SM2540C 28-Jun-11 11:30 TJA7067**  **200** 2011013565 **Collection Date: 27-Jun-11 8:30 AM Site:**  **EQ Tank Eff Matrix: OTHER** 

Analyte Analysis Date/Time Method Units Qualifiers RDL Result Sample #:

Analyst MERCURY (COLD VAPOR) IN WATER **Mercury (Hg)** 67.5 **ug/L EPA 245.1 01-Jul-11 12:44**  **TLINN 2.5** 
TOTAL RECOVERABLE METALS BY ICP **Boron (B)** 81.1 **mg/L EPA 200.7 30-Jun-11 14:05 DJSULL1**  **0.5**
DISSOLVED METALS BY ICP-MS **Selenium (Se)** 114 **ug/L EPA 200.8 06-Jul-11 12:11 KRICHAR**  **10**
TOTAL RECOVERABLE METALS BY ICP-MS **Arsenic (As)** 168 **ug/L EPA 200.8 05-Jul-11 13:25 KRICHAR**  **10 Chromium (Cr)**  117 **ug/L EPA 200.8**  **05-Jul-11 13:25 KRICHAR 10**  **Copper (Cu)** 141 **ug/L EPA 200.8**  **05-Jul-11 13:25 KRICHAR 10**  **Nickel (Ni)** 186 **ug/L EPA 200.8**  **05-Jul-11 13:25 KRICHAR 10** 

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



### Order # J11060367

2011013565 **Collection Date: 27-Jun-11 8:30 AM Site:**  **EQ Tank Eff Matrix: OTHER** 

Analyte Analysis Date/Time Method Units Qualifiers RDL Result Sample #:

Analyst TOTAL RECOVERABLE METALS BY ICP-MS **Selenium (Se)** 1160 **ug/L EPA 200.8 05-Jul-11 13:25 KRICHAR**  **10 Silver (Ag)**  < 10 **ug/L EPA 200.8**  **05-Jul-11 13:25 KRICHAR 10**  **Zinc (Zn)** 181 **ug/L EPA 200.8**  **05-Jul-11 13:25 KRICHAR 20**  2011013566 **Collection Date: 27-Jun-11 8:25 AM Site:**  **BioReactor 1 Inf Matrix: OTHER** 

Analyte Analysis Date/Time Method Units Qualifiers RDL Result Sample #:

Analyst TOTAL RECOVERABLE METALS BY ICP **Boron (B)** 81.4 **mg/L EPA 200.7 30-Jun-11 14:09 DJSULL1**  **0.5**
DISSOLVED METALS BY ICP-MS **Selenium (Se)** 108 **ug/L EPA 200.8 06-Jul-11 12:06 KRICHAR**  **10**
TOTAL RECOVERABLE METALS BY ICP-MS **Arsenic (As)** < 10 **ug/L EPA 200.8 05-Jul-11 13:12 KRICHAR**  **10 Chromium (Cr)**  < 10 **ug/L EPA 200.8**  **05-Jul-11 13:12 KRICHAR 10**  **Copper (Cu)** 12.2 **ug/L EPA 200.8**  **05-Jul-11 13:12 KRICHAR 10**  **Nickel (Ni)** < 10 **ug/L EPA 200.8**  **05-Jul-11 13:12 KRICHAR 10**  **Selenium (Se)** 108 **ug/L EPA 200.8**  **05-Jul-11 13:12 KRICHAR 10**  **Silver (Ag)** < 10 **ug/L EPA 200.8**  **05-Jul-11 13:12 KRICHAR 10**  **Zinc (Zn)** < 20 **ug/L EPA 200.8**  **05-Jul-11 13:12 KRICHAR 20** 
SELENIUM SPECIATION **Vendor Parameter** Complete **V_AS&C** 2011013567 **Collection Date: 27-Jun-11 9:03 AM Site:**  **BioReactor 2 Inf Matrix: OTHER** 

Analyte Analysis Date/Time Method Units Qualifiers RDL Result Sample #:

Analyst TOTAL RECOVERABLE METALS BY ICP **Boron (B)** 80.5 **mg/L EPA 200.7 30-Jun-11 14:13 DJSULL1**  **0.5**
TOTAL RECOVERABLE METALS BY ICP-MS **Arsenic (As)** < 10 **ug/L EPA 200.8 05-Jul-11 13:07 KRICHAR**  **10 Chromium (Cr)**  < 10 **ug/L EPA 200.8**  **05-Jul-11 13:07 KRICHAR 10**  **Copper (Cu)** < 10 **ug/L EPA 200.8**  **05-Jul-11 13:07 KRICHAR 10**  **Nickel (Ni)** 88.6 **ug/L EPA 200.8**  **05-Jul-11 13:07 KRICHAR 10**  **Selenium (Se)** < 10 **ug/L EPA 200.8**  **05-Jul-11 13:07 KRICHAR 10**  **Silver (Ag)** < 10 **ug/L EPA 200.8**  **05-Jul-11 13:07 KRICHAR 10**  **Zinc (Zn)** < 20 **ug/L EPA 200.8**  **05-Jul-11 13:07 KRICHAR 20** 

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



### Order # J11060367

2011013568 **Collection Date: 27-Jun-11 8:35 AM Site:**  **BioReactor 2 Eff Matrix: OTHER** 

Analyte Analysis Date/Time Method Units Qualifiers RDL Result Sample #:

Analyst MERCURY (COLD VAPOR) IN WATER **Mercury (Hg)** < 1 **ug/L EPA 245.1 01-Jul-11 12:47**  **TLINN 1** 
TOTAL RECOVERABLE METALS BY ICP **Boron (B)** 59.5 **mg/L EPA 200.7 30-Jun-11 14:17 DJSULL1**  **0.5**
TOTAL RECOVERABLE METALS BY ICP-MS **Arsenic (As)** < 5 **ug/L EPA 200.8 05-Jul-11 13:02 KRICHAR**  **5 Chromium (Cr)**  < 5 **ug/L EPA 200.8**  **05-Jul-11 13:02 KRICHAR 5**  **Copper (Cu)** < 5 **ug/L EPA 200.8**  **05-Jul-11 13:02 KRICHAR 5**  **Nickel (Ni)** < 5 **ug/L EPA 200.8**  **05-Jul-11 13:02 KRICHAR 5**  **Selenium (Se)** < 5 **ug/L EPA 200.8**  **05-Jul-11 13:02 KRICHAR 5**  **Silver (Ag)** < 5 **ug/L EPA 200.8**  **05-Jul-11 13:02 KRICHAR 5**  **Zinc (Zn)** < 10 **ug/L EPA 200.8**  **05-Jul-11 13:02 KRICHAR 10** 
SELENIUM SPECIATION **Vendor Parameter** Complete **V_AS&C** 2011013569 **Collection Date: 27-Jun-11 8:18 AM Site:**  **Filter Blk Matrix: OTHER** 

Analyte Analysis Date/Time Method Units Qualifiers RDL Result Sample #:

Analyst DISSOLVED METALS BY ICP-MS **Selenium (Se)** < 2 **ug/L EPA 200.8 06-Jul-11 11:52 KRICHAR**  **2** 2011013570 **Collection Date: 21-Jun-11 11:05 AM Site:**  **Metals Trip Blank Matrix: OTHER** 

Analyte Analysis Date/Time Method Units Qualifiers RDL Result Sample #:

Analyst TOTAL RECOVERABLE METALS BY ICP **Boron (B)** < 0.05 **mg/L EPA 200.7 30-Jun-11 13:44 DJSULL1**  **0.05**
TOTAL RECOVERABLE METALS BY ICP-MS **Arsenic (As)** < 1 **ug/L EPA 200.8 05-Jul-11 12:57 KRICHAR**  **1 Chromium (Cr)**  < 1 **ug/L EPA 200.8**  **05-Jul-11 12:57 KRICHAR 1**  **Copper (Cu)** < 1 **ug/L EPA 200.8**  **05-Jul-11 12:57 KRICHAR 1**  **Nickel (Ni)** < 1 **ug/L EPA 200.8**  **05-Jul-11 12:57 KRICHAR 1**  **Selenium (Se)** < 1 **ug/L EPA 200.8**  **05-Jul-11 12:57 KRICHAR 1**  **Silver (Ag)** < 1 **ug/L EPA 200.8**  **05-Jul-11 12:57 KRICHAR 1**  **Zinc (Zn)** < 2 **ug/L EPA 200.8**  **05-Jul-11 12:57 KRICHAR 2** 
SELENIUM SPECIATION

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



### Order # J11060367

2011013570 **Collection Date: 21-Jun-11 11:05 AM Site:**  **Metals Trip Blank Matrix: OTHER** 

Analyte Analysis Date/Time Method Units Qualifiers RDL Result Sample #:

Analyst SELENIUM SPECIATION **Vendor Parameter** Complete **V_AS&C**

### Ju ly 8 , 201 1

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 (Bi-Weekly Sampling) (LIMS # J11060367 )

Dear Mr. Perkins, Attached is the report associated with four (4 ) aqueous samples submitted for selenium speciation analysis on June 29 , 2011. The samples were received in a sealed cooler at -0. 3 o 

### C on June 30, 2011. 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,

Ben Wozniak Project Manager 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 (Bi-Weekly Sampling) (LIMS # J11060367)

Ju ly 8 , 201 1

1. Sample Reception Four (4 ) aqueous samples in 125mL HDPE bottles (provided by Applied Speciation and Consulting) were submitted for selenium speciation analysi s on June 2 9 , 2011 . The samples were received on June 30, 2011 in a sealed co ntainer at -0.3 o 

### C. The samples were received in a laminar flow clean hood void of trace metals contamination and ultra-violet radiation. Upon reception, the samples were designated discrete sample identifiers. An aliquot of each sample was filtered (0.45μm) and these filtrates were 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 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 the samples 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 minimal interval of every ten analytical runs. Selenium Speciation Analysis by IC -ICP-DRC

- MS All samples for selenium speciation analysis were analyzed by ion chromatography inductively coupled plasma dynamic reaction cell mass spectrometry (IC-ICP-DRC-MS) on Ju ly 8 , 2011 . 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 specific reactive 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 very well and no significant analytical issues were encountered. All sample results have been corrected in accordance with the continuing calibration verification recoveries to account for perceived instrument bias. All quality control parameters associated with these samples were within acceptance limits with the following exceptions: The recoveries associated with the matrix spike (MS) and matrix spike duplicate (MSD) performed on the sample identified as BioReactor 2 Eff were below the established control limit of 75% for selenocyanate (17.1 % and 18.1%, respectively). The MS and MSD also included selenite in the spiking solution which yielded elevated recoveries (167.6% and 1 68.6%, respectively). The low recoveries for selenocyanate correlate with the elevated recoveries of selenite suggesting that the sample matrix induces species conversion. The fact that no species conversion was observed in the ICV or CCVs, which contain both selenite and selenocyanate, demonstrates that the applied method stabilizes these selenium species in solution. Since the conversion of selenocyanate to selenite in the MS and MSD is a function of the sample matrix and the recoveries confirm a mass balance, no corrective action was

### required. The reported results are deemed representative of the supplied samples and suggest

that selenocyanate is not stable in the spiked sample matrix. 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,

Ben Wozniak Project Manager Applied Speciation and Consulting, LLCSample Results
Sample ID Se(IV) Se(VI) SeCN MeSe(IV) SeMe Unknown Se Species (n) FGD Purge Eff 124 65.8 ND (<4.4) 5.5 ND (<4.8) 0 (0) BioReactor 1 Inf 13.1 66.5 ND (<1.1) 1.9 ND (<1.2) 0 (0) BioReactor 2 Eff 3.3 ND (<1.0) ND (<1.1) ND (<1.2) ND (<1.2) 0 (0) Metals Trip Blk ND (<0.30) ND (<0.20) ND (<0.22) ND (<0.24) ND (<0.24) 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: Ben Wozniak Applied Speciation and Consulting, LLC Selenium Speciation Results for Duke Energy Project Name: Allen - FGD WWTS (Bi-Weekly Sampling)

Contact: Jay Perkins

Date: July 8, 2011 LIMS #J11060367Quality 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 0.030 0.30 1.5 5.9 Se(VI) 0.000 0.000 0.000 0.000 0.000 0.000 0.020 0.20 1.0 4.1 SeCN 0.000 0.000 0.000 0.000 0.000 0.000 0.022 0.22 1.1 4.4 MeSe(IV) 0.000 0.000 0.000 0.000 0.000 0.000 0.024 0.24 1.2 4.8 SeMe 0.000 0.000 0.000 0.000 0.000 0.000 0.024 0.24 1.2 4.8 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 9.521 99.5 Se(VI) LCS 9.48 9.571 101.0 SeCN LCS 8.92 9.126 102.3 MeSe(IV) LCS 6.47 5.809 89.8 SeMe LCS 9.32 8.865 95.1 LIMS #J11060367 Date: July 8, 2011 Report Generated by: Ben Wozniak Applied Speciation and Consulting, LLC Selenium Speciation Results for Duke Energy Project Name: Allen - FGD WWTS (Bi-Weekly Sampling)

Contact: Jay PerkinsQuality Control Summary - Matrix Duplicates Analyte (μg/L) Sample ID Rep 1 Rep 2 Mean RPD Se(IV) BioReactor 2 Eff 3.3 3.0 3.1 9.2 Se(VI) BioReactor 2 Eff ND (<1.0) ND (<1.0) NC NC SeCN BioReactor 2 Eff ND (<1.1) ND (<1.1) NC NC MeSe(IV) BioReactor 2 Eff ND (<1.2) ND (<1.2) NC NC SeMe BioReactor 2 Eff ND (<1.2) ND (<1.2) 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) BioReactor 2 Eff 278.0 469.1 167.6* 278.0 471.8 168.6* 0.6 Se(VI) BioReactor 2 Eff 252.3 258.4 102.4 252.3 252.5 100.1 2.3 SeCN BioReactor 2 Eff 228.8 39.09 17.1* 228.8 41.42 18.1* 5.8 * The recovery is outside the established control limit of 75-125%; please see narrative Contact: Jay Perkins LIMS #J11060367 Date: July 8, 2011 Report Generated by: Ben Wozniak Applied Speciation and Consulting, LLC Selenium Speciation Results for Duke Energy Project Name: Allen - FGD WWTS (Bi-Weekly Sampling)