### 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: J11020228 Project Name: WWTS - Biweekly

L ab Contact: Jason C Perkins


## Date: 2/25/2011 Customer Address: 253 Plant Allen Road Customer Name(s): Robbin Jolly

Belmont, NC 28012

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



### Program Comments: FGD BiWeekly - 2/10
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 2011003122 ALLEN 10-Feb-11 8:30 AM Chris Williams FGD Purge Eff 2011003126 ALLEN 10-Feb-11 8:20 AM Chris Williams EQ Tank Eff 2011003127 ALLEN 10-Feb-11 8:25 AM Chris Williams BioReactor 1 Inf 2011003128 ALLEN 10-Feb-11 8:35 AM Chris Williams BioReactor 2 Inf 2011003129 ALLEN 10-Feb-11 8:22 AM Chris Williams BioReactor 2 Eff 2011003130 ALLEN 10-Feb-11 1:30 PM C. KNOX TRIP BLANK 2011003131 ALLEN 10-Feb-11 8:42 AM Chris Williams Filter Blk 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: 

### 2/25/2011 Yes

Electronic Data Deliverable (EDD) Sent Separately

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



## Order # J11020228

2011003122 Collection Date: 10-Feb-11 8:30 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) 81.8 ug/L EPA 245.1 17-Feb-11 15:45 2.5 TLINN
TOTAL RECOVERABLE METALS BY ICP Boron (B) 71.8 mg/L EPA 200.7 21-Feb-11 09:10 0.5 DJSULL1
DISSOLVED METALS BY ICP-MS Selenium (Se) 238 ug/L EPA 200.8 16-Feb-11 12:42 10 KRICHAR
TOTAL RECOVERABLE METALS BY ICP-MS Arsenic (As) 153 ug/L EPA 200.8 21-Feb-11 11:54 10 KRICHAR Chromium (Cr) 158 ug/L EPA 200.8 21-Feb-11 11:54 10 KRICHAR Copper (Cu) 174 ug/L EPA 200.8 21-Feb-11 11:54 10 KRICHAR Nickel (Ni) 244 ug/L EPA 200.8 21-Feb-11 11:54 10 KRICHAR Selenium (Se) 1650 ug/L EPA 200.8 21-Feb-11 11:54 10 KRICHAR Silver (Ag) 16.0 ug/L EPA 200.8 21-Feb-11 11:54 10 KRICHAR Zinc (Zn) 244 ug/L EPA 200.8 21-Feb-11 11:54 20 KRICHAR
SELENIUM SPECIATION Vendor Parameter Complete V_AS&C
TOTAL DISSOLVED SOLIDS TDS 12000 mg/L SM2540C 16-Feb-11 13:02 10 CLEEMAN 

## 2011003126 Collection Date: 10-Feb-11 8:20 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) 64.9 ug/L EPA 245.1 17-Feb-11 15:48 2.5 TLINN
TOTAL RECOVERABLE METALS BY ICP Boron (B) 72.1 mg/L EPA 200.7 21-Feb-11 09:14 0.5 DJSULL1
DISSOLVED METALS BY ICP-MS Selenium (Se) 106 ug/L EPA 200.8 16-Feb-11 12:45 10 KRICHAR
TOTAL RECOVERABLE METALS BY ICP-MS Arsenic (As) 129 ug/L EPA 200.8 21-Feb-11 11:50 10 KRICHAR Chromium (Cr) 122 ug/L EPA 200.8 21-Feb-11 11:50 10 KRICHAR Copper (Cu) 136 ug/L EPA 200.8 21-Feb-11 11:50 10 KRICHAR Nickel (Ni) 192 ug/L EPA 200.8 21-Feb-11 11:50 10 KRICHAR Selenium (Se) 1180 ug/L EPA 200.8 21-Feb-11 11:50 10 KRICHAR

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



## Order # J11020228

2011003126 Collection Date: 10-Feb-11 8:20 AM 

## Site: EQ Tank Eff Matrix: OTHER

Analyte Analysis Date/Time Method Units Qualifiers RDL Result 

## Sample #:

Analyst TOTAL RECOVERABLE METALS BY ICP-MS Silver (Ag) 24.1 ug/L EPA 200.8 21-Feb-11 11:50 10 KRICHAR Zinc (Zn) 193 ug/L EPA 200.8 21-Feb-11 11:50 20 KRICHAR 

## 2011003127 Collection Date: 10-Feb-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) 68.1 mg/L EPA 200.7 21-Feb-11 09:18 0.5 DJSULL1
DISSOLVED METALS BY ICP-MS Selenium (Se) 66.5 ug/L EPA 200.8 16-Feb-11 12:49 10 KRICHAR
TOTAL RECOVERABLE METALS BY ICP-MS Arsenic (As) < 10 ug/L EPA 200.8 21-Feb-11 11:45 10 KRICHAR Chromium (Cr) < 10 ug/L EPA 200.8 21-Feb-11 11:45 10 KRICHAR Copper (Cu) 10.7 ug/L EPA 200.8 21-Feb-11 11:45 10 KRICHAR Nickel (Ni) 25.5 ug/L EPA 200.8 21-Feb-11 11:45 10 KRICHAR Selenium (Se) 57.7 ug/L EPA 200.8 21-Feb-11 11:45 10 KRICHAR Silver (Ag) < 10 ug/L EPA 200.8 21-Feb-11 11:45 10 KRICHAR Zinc (Zn) < 20 ug/L EPA 200.8 21-Feb-11 11:45 20 KRICHAR
SELENIUM SPECIATION Vendor Parameter Complete V_AS&C 

## 2011003128 Collection Date: 10-Feb-11 8:35 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) 69.9 mg/L EPA 200.7 21-Feb-11 09:22 0.5 DJSULL1
TOTAL RECOVERABLE METALS BY ICP-MS Arsenic (As) < 10 ug/L EPA 200.8 21-Feb-11 11:40 10 KRICHAR Chromium (Cr) < 10 ug/L EPA 200.8 21-Feb-11 11:40 10 KRICHAR Copper (Cu) < 10 ug/L EPA 200.8 21-Feb-11 11:40 10 KRICHAR Nickel (Ni) 25.9 ug/L EPA 200.8 21-Feb-11 11:40 10 KRICHAR Selenium (Se) < 10 ug/L EPA 200.8 21-Feb-11 11:40 10 KRICHAR Silver (Ag) 19.5 ug/L EPA 200.8 21-Feb-11 11:40 10 KRICHAR Zinc (Zn) < 20 ug/L EPA 200.8 21-Feb-11 11:40 20 KRICHAR

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



## Order # J11020228

2011003129 Collection Date: 10-Feb-11 8:22 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 17-Feb-11 15:50 1 TLINN
TOTAL RECOVERABLE METALS BY ICP Boron (B) 78.4 mg/L EPA 200.7 21-Feb-11 09:26 0.5 DJSULL1
TOTAL RECOVERABLE METALS BY ICP-MS Arsenic (As) < 5 ug/L EPA 200.8 21-Feb-11 11:26 5 KRICHAR Chromium (Cr) < 5 ug/L EPA 200.8 21-Feb-11 11:26 5 KRICHAR Copper (Cu) < 5 ug/L EPA 200.8 21-Feb-11 11:26 5 KRICHAR Nickel (Ni) < 5 ug/L EPA 200.8 21-Feb-11 11:26 5 KRICHAR Selenium (Se) < 5 ug/L EPA 200.8 21-Feb-11 11:26 5 KRICHAR Silver (Ag) < 5 ug/L EPA 200.8 21-Feb-11 11:26 5 KRICHAR Zinc (Zn) < 10 ug/L EPA 200.8 21-Feb-11 11:26 10 KRICHAR
SELENIUM SPECIATION Vendor Parameter Complete V_AS&C 

## 2011003130 Collection Date: 10-Feb-11 1:30 PM 

## 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 21-Feb-11 09:06 0.05 DJSULL1
TOTAL RECOVERABLE METALS BY ICP-MS Arsenic (As) < 1 ug/L EPA 200.8 21-Feb-11 11:21 1 KRICHAR Chromium (Cr) < 1 ug/L EPA 200.8 21-Feb-11 11:21 1 KRICHAR Copper (Cu) < 1 ug/L EPA 200.8 21-Feb-11 11:21 1 KRICHAR Nickel (Ni) < 1 ug/L EPA 200.8 21-Feb-11 11:21 1 KRICHAR Selenium (Se) < 1 ug/L EPA 200.8 21-Feb-11 11:21 1 KRICHAR Silver (Ag) < 1 ug/L EPA 200.8 21-Feb-11 11:21 1 KRICHAR Zinc (Zn) < 2 ug/L EPA 200.8 21-Feb-11 11:21 2 KRICHAR
SELENIUM SPECIATION Vendor Parameter Complete V_AS&C 

## 2011003131 Collection Date: 10-Feb-11 8:42 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 16-Feb-11 12:52 2 KRICHAR

# February 25, 2011 Jay Perkins Duke Energy Analytical Laboratory Mail Code MGO3A2 (Building 7405) 13339 Hagers Ferry Rd. Huntersville, NC 28078 (704) 875-5245 Project: Allen – FGD WWTS (2010, Bi -Weekly Sampling) (LIMS # J11020228)

Dear Mr. Perkins, Attached is the report associat ed with four (4) aqueous sa mples submitted for selenium speciation analysis on February 14, 2011. Th e samples were recei ved on February 15, 2011 in a sealed cooler at 0.1 o 

# C. Selenium speciation analysis was performed via ion chromatography inductively coupled plasma dynamic reaction cell mass spectrometry (IC-ICP-DRC-MS). Any analytical issues asso ciated with the analysis are addressed in the following report. If you have any questions, please feel fr ee 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 -Weekly Sampling) (LIMS # J11020228)

February 25, 2011

1. Sample Reception Four (4) aqueous samples in 125mL HDPE bottles (provided by Applied Speciation and Consulting) were submitted for selenium speciation analysis on February 14, 2011. The samples were received on February 15, 2011 in a sealed container at 0.1 o 

# C. The samples were received in a lamina r flow clean hood void of trace metals contamination and ultra-violet radiat ion. 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 speciat ion analysis could be performed via ion chromatography inductive ly 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 a pplied water for dilutions and sample preservatives are monitored for contamina tion 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 filt er (0.45μm) and inject ed directly into a sealed autosampler vial. No further sa mple 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 precluded by a minimum of a five-poi nt calibration curve spanning the entire concentrati on range of interest. Calibration curves are performed at the beginning of each analytical day. All calibration curves, associated with each species of interest, are sta ndardized by linear regression re sulting 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 ve rified using second source standards which are identified as initial calibration verification standards (ICV). Ongoing instrument performance is iden tified 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 Anal ysis 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 February 16, 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 whic h 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 analytical issues were encountered. All quality control parameters associated with these samples were within acceptance limits.
The estimated method detection limits (eMDLs) for selen ite, selenate, and selenocyanate are generated from replicate analyses of the lowest standard in the calibration curve. Not all selenium speci es are present in preparation blanks; therefore, eMDL calculations based on preparat ion 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, LLCSample ResultsSample IDSe(IV) Se(VI) SeCN MeSe(IV) SeMeUnknown SeSpecies (n)FGD Purge Eff18937.222.52.9 ND (<1.9) 8.9 (2)BioReactor 1 Inf11.333.7 ND (<0.35) 0.97 ND (<0.48) 0 (0)BioReactor 2 Eff ND (<0.72) ND (<0.38) ND (<0.35) ND (<0.48) ND (<0.48) 0 (0)Metals Trip BlkND (<0.14) ND (<0.076) ND (<0.070) ND (<0.097) ND (<0.097) 0 (0)All results reflect the applied dilution and are reported in μg/LND = Not detected at the applied dilutionSeCN = SelenocyanateMeSe(IV) = Methylseleninic acidSeMe = SelenomethionineUnknown Se Species = Total concentration of all unknown Se species observed by IC-ICP-MSn = number of unknown Se species observedReport Generated by: Russell GeradsApplied Speciation and Consulting, LLCSelenium Speciation Results for Duke EnergyProject Name: Allen - FGD WWTS (2010, Bi-Weekly Sampling)Contact: Jay PerkinsDate: February 25, 2011LIMS #J11020228Quality Control Summary - Preparation Blank SummaryAnalyte (μg/L) PBW1 PBW2 PBW3 PBW4 Mean StdDev eMDL* eMDL 10x eMDL 50x eMDL 200xSe(IV) 0.000 0.000 0.000 0.000 0.000 0.000 0.014 0.14 0.72 2.9Se(VI) 0.000 0.000 0.000 0.000 0.000 0.000 0.008 0.076 0.38 1.5SeCN 0.000 0.000 0.000 0.000 0.000 0.000 0.007 0.070 0.35 1.4MeSe(IV) 0.000 0.000 0.000 0.000 0.000 0.000 0.010 0.097 0.48 1.9SeMe 0.000 0.000 0.000 0.000 0.000 0.000 0.010 0.097 0.48 1.9eMDL = Estimated Method Detection Limit*Please see narrative regarding eMDL calculationsQuality Control Summary - Certified Reference MaterialsAnalyte (μg/L) CRM True Value Result RecoverySe(IV) ICV 9.57 9.71 101.4Se(VI) ICV 9.48 9.34 98.5SeCN ICV 8.92 9.06 101.5MeSe(IV) ICV 6.47 5.65 87.4SeMe ICV 9.32 8.41 90.3LIMS #J11020228Date: February 25, 2011Report Generated by: Russell GeradsApplied Speciation and Consulting, LLCSelenium Speciation Results for Duke EnergyProject Name: Allen - FGD WWTS (2010, Bi-Weekly Sampling)Contact: Jay PerkinsQuality Control Summary - Matrix DuplicatesAnalyte (μg/L) Sample ID Rep 1 Rep 2 Mean RPDSe(IV) BioReactor 2 Eff ND (<0.72) ND (<0.72) NC NCSe(VI) BioReactor 2 Eff ND (<0.38) ND (<0.38) NC NCSeCN BioReactor 2 Eff ND (<0.35) ND (<0.35) NC NCMeSe(IV) BioReactor 2 Eff ND (<0.48) ND (<0.48) NC NCSeMe BioReactor 2 Eff ND (<0.48) ND (<0.48) NC NCND = Not detected at the applied dilutionNC = Value was not calculated due to one or more concentrations below the eMDLQuality Control Summary - Matrix Spike/ Matrix Spike DuplicateAnalyte (μg/L)Sample ID Spike Conc MS Result Recovery Spike Conc MSD Result Recovery RPDSe(IV)BioReactor 2 Eff 278.0 260.5 93.7 278.0 266.5 95.9 2.3Se(VI)BioReactor 2 Eff 252.3 241.0 95.5 252.3 240.8 95.5 0.1SeCNBioReactor 2 Eff 228.8 201.6 88.1 228.8 198.1 86.6 0.0LIMS #J11020228Date: February 25, 2011Report Generated by: Russell GeradsApplied Speciation and Consulting, LLCSelenium Speciation Results for Duke EnergyProject Name: Allen - FGD WWTS (2010, Bi-Weekly Sampling)Contact: Jay Perkins