**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: J11060301 **Project Name: WWTS - Biweekly** 

**L ab Contact:**  **Jason C Perkins**
Date: **7/5/2011 Customer Address: 3195 Pine Hall Rd**  **Customer Name(s): Bill Kennedy, Melonie Martin, Wayne Chapman, Tom Johnson**

**Mailcode: Belews Steam Station Belews Creek, 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 **2011013305 BELEWS 22-Jun-11 9:35 AM W. B. WORKMAN FGD Purge Eff**  **2011013309 BELEWS 22-Jun-11 9:40 AM W. B. WORKMAN EQ TANK EFF.**  **2011013310 BELEWS 22-Jun-11 9:45 AM W. B. WORKMAN BIOREACTOR 1 INF.**  **2011013311 BELEWS 22-Jun-11 9:50 AM W. B. WORKMAN BIOREACTOR 2 INF.**  **2011013312 BELEWS 22-Jun-11 9:55 AM W. B. WORKMAN BIOREACTOR 2 EFF.**  **2011013313 BELEWS 14-Jun-11 10:00 AM S.S.**  **Trip Blank 2011013314 BELEWS 22-Jun-11 9:30 AM W. B. WORKMAN**  **FILTER 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: 7/5/2011**  **Yes**

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

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



### Order # J11060301

2011013305 **Collection Date: 22-Jun-11 9:35 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)** 208 **ug/L EPA 245.1 24-Jun-11 14:15**  **TLINN 5** 
TOTAL RECOVERABLE METALS BY ICP **Boron (B)** 142 **mg/L EPA 200.7 27-Jun-11 12:43 DJSULL1**  **0.5**
DISSOLVED METALS BY ICP-MS **Selenium (Se)** 242 **ug/L EPA 200.8 28-Jun-11 12:11 KRICHAR**  **10**
TOTAL RECOVERABLE METALS BY ICP-MS **Arsenic (As)** 229 **ug/L EPA 200.8 27-Jun-11 15:12 KRICHAR**  **10 Chromium (Cr)**  188 **ug/L EPA 200.8**  **27-Jun-11 15:12 KRICHAR 10**  **Copper (Cu)** 147 **ug/L EPA 200.8**  **27-Jun-11 15:12 KRICHAR 10**  **Nickel (Ni)** 175 **ug/L EPA 200.8**  **27-Jun-11 15:12 KRICHAR 10**  **Selenium (Se)** 4930 **ug/L EPA 200.8**  **27-Jun-11 15:12 KRICHAR 10**  **Silver (Ag)** < 10 **ug/L EPA 200.8**  **27-Jun-11 15:12 KRICHAR 10**  **Zinc (Zn)** 271 **ug/L EPA 200.8**  **27-Jun-11 15:12 KRICHAR 20** 
SELENIUM SPECIATION **Vendor Parameter** Complete **V_AS&C**
TOTAL DISSOLVED SOLIDS **TDS** 17000 **mg/L SM2540C 23-Jun-11 16:00 TJA7067**  **200** 2011013309 **Collection Date: 22-Jun-11 9:40 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)** 150 **ug/L EPA 245.1 24-Jun-11 14:17**  **TLINN 2.5** 
TOTAL RECOVERABLE METALS BY ICP **Boron (B)** 132 **mg/L EPA 200.7 27-Jun-11 12:47 DJSULL1**  **0.5**
DISSOLVED METALS BY ICP-MS **Selenium (Se)** 158 **ug/L EPA 200.8 28-Jun-11 10:46 KRICHAR**  **10**
TOTAL RECOVERABLE METALS BY ICP-MS **Arsenic (As)** 165 **ug/L EPA 200.8 27-Jun-11 15:07 KRICHAR**  **10 Chromium (Cr)**  141 **ug/L EPA 200.8**  **27-Jun-11 15:07 KRICHAR 10**  **Copper (Cu)** 109 **ug/L EPA 200.8**  **27-Jun-11 15:07 KRICHAR 10**  **Nickel (Ni)** 137 **ug/L EPA 200.8**  **27-Jun-11 15:07 KRICHAR 10** 

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



### Order # J11060301

2011013309 **Collection Date: 22-Jun-11 9:40 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)** 3830 **ug/L EPA 200.8 27-Jun-11 15:07 KRICHAR**  **10 Silver (Ag)**  < 10 **ug/L EPA 200.8**  **27-Jun-11 15:07 KRICHAR 10**  **Zinc (Zn)** 208 **ug/L EPA 200.8**  **27-Jun-11 15:07 KRICHAR 20**  2011013310 **Collection Date: 22-Jun-11 9:45 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)** 128 **mg/L EPA 200.7 27-Jun-11 12:51 DJSULL1**  **0.5**
DISSOLVED METALS BY ICP-MS **Selenium (Se)** 140 **ug/L EPA 200.8 28-Jun-11 10:30 KRICHAR**  **10**
TOTAL RECOVERABLE METALS BY ICP-MS **Arsenic (As)** < 10 **ug/L EPA 200.8 27-Jun-11 15:02 KRICHAR**  **10 Chromium (Cr)**  < 10 **ug/L EPA 200.8**  **27-Jun-11 15:02 KRICHAR 10**  **Copper (Cu)** < 10 **ug/L EPA 200.8**  **27-Jun-11 15:02 KRICHAR 10**  **Nickel (Ni)** 12.0 **ug/L EPA 200.8**  **27-Jun-11 15:02 KRICHAR 10**  **Selenium (Se)** 152 **ug/L EPA 200.8**  **27-Jun-11 15:02 KRICHAR 10**  **Silver (Ag)** < 10 **ug/L EPA 200.8**  **27-Jun-11 15:02 KRICHAR 10**  **Zinc (Zn)** < 20 **ug/L EPA 200.8**  **27-Jun-11 15:02 KRICHAR 20** 
SELENIUM SPECIATION **Vendor Parameter** Complete **V_AS&C** 2011013311 **Collection Date: 22-Jun-11 9:50 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)** 125 **mg/L EPA 200.7 27-Jun-11 12:55 DJSULL1**  **0.5**
TOTAL RECOVERABLE METALS BY ICP-MS **Arsenic (As)** < 10 **ug/L EPA 200.8 27-Jun-11 14:57 KRICHAR**  **10 Chromium (Cr)**  < 10 **ug/L EPA 200.8**  **27-Jun-11 14:57 KRICHAR 10**  **Copper (Cu)** < 10 **ug/L EPA 200.8**  **27-Jun-11 14:57 KRICHAR 10**  **Nickel (Ni)** < 10 **ug/L EPA 200.8**  **27-Jun-11 14:57 KRICHAR 10**  **Selenium (Se)** < 10 **ug/L EPA 200.8**  **27-Jun-11 14:57 KRICHAR 10**  **Silver (Ag)** < 10 **ug/L EPA 200.8**  **27-Jun-11 14:57 KRICHAR 10**  **Zinc (Zn)** < 20 **ug/L EPA 200.8**  **27-Jun-11 14:57 KRICHAR 20** 

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



### Order # J11060301

2011013312 **Collection Date: 22-Jun-11 9:55 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 24-Jun-11 14:19**  **TLINN 1** 
TOTAL RECOVERABLE METALS BY ICP **Boron (B)** 126 **mg/L EPA 200.7 27-Jun-11 12:59 DJSULL1**  **0.5**
TOTAL RECOVERABLE METALS BY ICP-MS **Arsenic (As)** < 5 **ug/L EPA 200.8 27-Jun-11 14:53 KRICHAR**  **5 Chromium (Cr)**  < 5 **ug/L EPA 200.8**  **27-Jun-11 14:53 KRICHAR 5**  **Copper (Cu)** < 5 **ug/L EPA 200.8**  **27-Jun-11 14:53 KRICHAR 5**  **Nickel (Ni)** < 5 **ug/L EPA 200.8**  **27-Jun-11 14:53 KRICHAR 5**  **Selenium (Se)** < 5 **ug/L EPA 200.8**  **27-Jun-11 14:53 KRICHAR 5**  **Silver (Ag)** < 5 **ug/L EPA 200.8**  **27-Jun-11 14:53 KRICHAR 5**  **Zinc (Zn)** < 10 **ug/L EPA 200.8**  **27-Jun-11 14:53 KRICHAR 10** 
SELENIUM SPECIATION **Vendor Parameter** Complete **V_AS&C** 2011013313 **Collection Date: 14-Jun-11 10:00 AM Site:**  **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 27-Jun-11 12:39 DJSULL1**  **0.05**
TOTAL RECOVERABLE METALS BY ICP-MS **Arsenic (As)** < 1 **ug/L EPA 200.8 27-Jun-11 14:48 KRICHAR**  **1 Chromium (Cr)**  < 1 **ug/L EPA 200.8**  **27-Jun-11 14:48 KRICHAR 1**  **Copper (Cu)** < 1 **ug/L EPA 200.8**  **27-Jun-11 14:48 KRICHAR 1**  **Nickel (Ni)** < 1 **ug/L EPA 200.8**  **27-Jun-11 14:48 KRICHAR 1**  **Selenium (Se)** < 1 **ug/L EPA 200.8**  **27-Jun-11 14:48 KRICHAR 1**  **Silver (Ag)** < 1 **ug/L EPA 200.8**  **27-Jun-11 14:48 KRICHAR 1**  **Zinc (Zn)** < 2 **ug/L EPA 200.8**  **27-Jun-11 14:48 KRICHAR 2** 
SELENIUM SPECIATION **Vendor Parameter** Complete **V_AS&C** 2011013314 **Collection Date: 22-Jun-11 9:30 AM Site:**  **FILTER BLANK Matrix: OTHER** 

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

Analyst DISSOLVED METALS BY ICP-MS

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



### Order # J11060301

2011013314 **Collection Date: 22-Jun-11 9:30 AM Site:**  **FILTER BLANK 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 28-Jun-11 10:13 KRICHAR**  **2**

### Ju ly 4 , 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: Belews - FGD (WWTS Bi -Monthly Sampling) (LIMS # J11060301 )

Dear Mr. Perkins, Attached is the report associated with four (4 ) aqueous samples submitted for selenium speciation analysis on June 23, 2011. The samples were received in a sealed cooler at -0.3 o 

### C on June 24 , 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: Belews - FGD (WWTS Bi -Monthly Sampling) (LIMS # J11060301)

Ju ly 4 , 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 3 , 2011 . The samples were received on June 2 4, 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 June 24 , 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. 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 standa rds 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 162 115 ND (<3.1) ND (<3.0) ND (<3.0) 0 (0) BioReactor 1 Inf 46.4 87.5 ND (<0.78) 4.31 ND (<0.75) 0 (0) BioReactor 2 Eff ND (<0.58) ND (<0.88) ND (<0.78) ND (<0.75) ND (<0.75) 0 (0) Metals Trip Blk ND (<0.12) ND (<0.18) ND (<0.16) ND (<0.15) ND (<0.15) 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: Belews - FGD (WWTS Bi-Monthly Sampling)

Contact: Jay Perkins
Date: July 4, 2011 LIMS #J11060301Quality 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 0.012 0.12 0.58 2.3 Se(VI) 0.000 0.000 0.000 0.000 0.000 0.000 0.018 0.18 0.88 3.5 SeCN 0.000 0.000 0.000 0.000 0.000 0.000 0.016 0.16 0.78 3.1 MeSe(IV) 0.000 0.000 0.000 0.000 0.000 0.000 0.015 0.15 0.75 3.0 SeMe 0.000 0.000 0.000 0.000 0.000 0.000 0.015 0.15 0.75 3.0 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 10.10 105.6 Se(VI) LCS 9.48 9.524 100.5 SeCN LCS 8.92 9.223 103.4 MeSe(IV) LCS 6.47 7.730 119.5 SeMe LCS 9.32 9.563 102.6 Selenium Speciation Results for Duke Energy Project Name: Belews - FGD (WWTS Bi-Monthly Sampling)

Contact: Jay Perkins LIMS #J11060301 Date: July 4, 2011 Report Generated by: Ben Wozniak Applied Speciation and Consulting, LLCQuality Control Summary - Matrix Duplicates Analyte (μg/L) Sample ID Rep 1 Rep 2 Mean RPD Se(IV) FGD Purge Eff 162.0 159.5 160.8 1.6 Se(VI) FGD Purge Eff 114.5 104.4 109.5 9.3 SeCN FGD Purge Eff ND (<3.1) ND (<3.1) NC NC MeSe(IV) FGD Purge Eff ND (<3.0) ND (<3.0) NC NC SeMe FGD Purge Eff ND (<3.0) ND (<3.0) 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) FGD Purge Eff 1112 1369 108.7 1112 1363 108.1 0.4 Se(VI) FGD Purge Eff 1009 1063 94.5 1009 1111 99.3 4.5 SeCN FGD Purge Eff 915.0 766.2 83.7 915.0 812.4 88.8 5.8 Applied Speciation and Consulting, LLC Selenium Speciation Results for Duke Energy Project Name: Belews - FGD (WWTS Bi-Monthly Sampling)

Contact: Jay Perkins LIMS #J11060301 Date: July 4, 2011 Report Generated by: Ben Wozniak