NC0003433_J15070268F_20150902

+ DUKE Analytical Laboratory
ENERGY
13339 Hagers Ferry Road
Huntersville, NC 28078-7929
McGuire Nuclear Complex - MG03A2
Phone:[phone] Fax:[phone]
Order Summary Report
Order Number: J15070268
Project Name: CAPE FEAR - AB GW ASSESSMENT SPECIATION
Customer Name(s): Tim Hunsucker, Chris Suttell, Kathy Webb, John Toepfer
Customer Address:
Lab Contact: Peggy Kendall e kendall ?hpne:
P ggy Cl
Report Authorized By: cuke-energy.com Date:
(signature)-201507.31
Peggy Kendall 11:48:49-04'00'
Program Comments:
Please contact the Program Manager (Peggy Kendall) with any questions regarding this report.
Data Flags & Calculations:
7/31 /2015
Page 1 of 23
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:
Collection
Sample ID Plant/Station Date and Time
Collected By
Sample Description
2015022752
Cape Fear
30-Jun-15 11:05 AM
Synterra
MW-15SL
2015022753
Cape Fear
30-Jun-15 9:30 AM
Synterra
MW-15BR
2015022754
Cape Fear
30-Jun-15
Synterra
MW-6BR
3 Total Samples
Page 2 of 23

Page 3 of 23
Technical Validation Review
Checklist:
COC and .pdf report are in agreement with sample totals Yes No
and analyses (compliance programs and procedures).
All Results are less than the laboratory reporting limits. ❑ Yes❑ No
All laboratory QA/QC requirements are acceptable.❑ Yes ❑ No
Report Sections Included:
U Job Summary Report
❑ Sample Identification
n Technical Validation of Data Package
❑ Analytical Laboratory Certificate of Analysis
❑ Analytical Laboratory QC Report
Sub -contracted Laboratory Results
❑ Customer Specific Data Sheets, Reports, & Documentation
❑ Customer Database Entries
66 Chain of Custody
[I/0] Electronic Data Deliverable (EDD) Sent Separately
Reviewed By: Peggy Kendall Date: 7/31/2015

Certificate of Laboratory Analysis
This report shall not be reproduced, except in full.
Order # J15070268
Site: MW-15SL
Collection Date: 30-Jun-15 11:05 AM
Analyte Result Units Qualifiers RDL DF
Speciation of an Element - (Analysis Performed by Brooks Rand Labs LLC)
Vendor Parameter Complete
Sample #: 2015022752
Matrix: GW WW
Page 4 of 23
Method Analysis Date/Time Analyst
Vendor Method V_BRAND

Certificate of Laboratory Analysis Page 5 of 23
This report shall not be reproduced, except in full.
Order # J15070268
Site: MW-15BR
Collection Date: 30-Jun-15 9:30 AM
Analyte Result Units Qualifiers RDL DF
Speciation of an Element - (Analysis Performed by Brooks Rand Labs LLC)
Vendor Parameter Complete
Sample #: 2015022753
Matrix: GW WW
Method Analysis Date/Time Analyst
Vendor Method V_BRAND

Site: MW-6BR
Collection Date: 30-Jun-15
Certificate of Laboratory Analysis Page 6 of 23
This report shall not be reproduced, except in full.
Order # J15070268
Sample #: 2015022754
Matrix: GW WW
Analyte Result Units Qualifiers RDL DF Method Analysis Date/Time Analyst
Speciation of an Element - (Analysis Performed by Brooks Rand Labs LLC)
Vendor Parameter Complete Vendor Method V_BRAND
-- Additional Information --
The samples were collected 6/30/15 but were not received at Brooks Rand Lab until 7/3/15. The temperature at
receipt was 11.3 degrees C with no ice present in the cooler. Brooks Rand recommends temperatures less than or
equal to 6 degrees C to maintain integrity of the samples before analysis. Iron speciation samples received and
analyzed outside 48-hr holding time.

Page 7 of 23
BRO�©KS
RAND
LABS
MEANINGFUL METALS DATA
July 30, 2015
Peggy Kendall
Duke Energy Analytical Laboratory
Mail Code MGO3A2 (Building 7405)
13339 Hagers Ferry Rd.
Huntersville, NC 28078
980-875-5848
Project: Duke Energy Cape Fear Plant (LU\4S# J15070268)
Ms. Kendall,
Attached is the report associated with three (3) aqueous samples submitted for Arsenic
speciation, iron speciation and manganese speciation analyses on June 30, 2015. The samples
were received in a sealed cooler at 11.3°C on July 3, 2015. Arsenic speciation analyses were
performed via ion chromatography inductively coupled plasma collision reaction cell mass
spectrometry (IC-ICP-CRC-MS). All samples requesting iron speciation analysis were analyzed
by spectrophotometry. Mn(II) analysis was performed via IC-ICP-CRC-MS. Mn(IV) analysis
were performed via digestion and subsequent analysis by inductively coupled plasma triple
quadrupole mass spectrometry (ICP-QQQ-MS). Any issues associated with the analyses are
addressed in the following report.
If you have any questions, please feel free to contact me at your convenience.
Sincerely,
Russell Gerads
Business Development Director
Brooks Rand Labs, LLC
3958 6th Ave NW • Seattle, WA 98107 • T: 206-632-6206 • F: 206-632-6017 • www.brooksrand.com • [e-mail]

Page 8 of 23
Brooks Rand Labs, LLC
Report prepared for:
Peggy Kendall
Duke Energy Analytical Laboratory
Mail Code MGO3A2 (Building 7405)
13339 Hagers Ferry Rd.
Huntersville, NC 28078
Project: Duke Energy Cape Fear Plant (LIIVIS# J15070268)
July 30, 2015
1. Sample Reception
Three (3) aqueous samples were submitted for arsenic speciation, iron speciation, and
manganese speciation analyses on June 30, 2015. The samples were received in acceptable
condition on July 3, 2015 in a sealed container at a temperature of 11.3*C.
Brooks Rand Labs highly recommends maintaining a sample temperature of 40C during
shipping to mitigate molecular conversions which may bias results.
The sample fractions requesting iron speciation analysis were stored in a secure, monitored
refrigerator (maintained at a temperature of <6°C) until the analyses could be performed.
An aliquot of each sample submitted for arsenic speciation analysis was filtered (0.45µm)
into a polypropylene centrifuge tube; all filtrates and original bottles were then stored in a
secure, monitored refrigerator (maintained at a temperature of <6°C) until the analyses could
be performed.
An aliquot of each filtered sample submitted for manganese speciation analysis was decanted
into a polypropylene centrifuge tube for Mn(II) analysis. These fractions were stored in a
secure, monitored refrigerator (maintained at a temperature of <6°C) until the analyses could
be performed. Subsequently, the original bottles (filtered and unfiltered fractions) intended
for Mn speciation were preserved to pH < 2 with concentrated HNO3 and then stored in a
secure polyethylene container, known to be free from trace metals contamination, until the
digestion could be performed.
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.

Page 9 of 23
Arsenic Speciation Analysis by IC-ICP-CRC-MS An aliquot of each sample was filtered
directly into a sealed autosampler vial. No further sample preparation was performed as a
buffered EDTA solution was provided by Brooks Rand Labs for field -preservation of the
submitted samples.
Iron Speciation Analysis by Spectrophotometry No sample preparation was required as a de -
gassed HCL solution was provided by Brooks Rand Labs for field -preservation of the
submitted samples.
Manganese Mn(II Analysis by IC-ICP-CRC-MS An aliquot of each sample was filtered
(0.45µm) directly into an autosampler vial for Mn(II) analysis. No additional sample
preparation was performed as any chemical alteration of the samples may shift the
equilibrium of the system resulting in changes in speciation ratios.
Manganese Mn (I ' Anal sy is by ICP-QQQ-MS Each filtered and unfiltered sample submitted
for Mn speciation analysis was preserved with 1 % HNO3 (v/v) upon sample receipt. Each
sample fraction was then further digested on a hotblock apparatus with aliquots of 50%
HNO3 (v/v) and 50% HCl (v/v), in accordance with the digestion procedure specified in EPA
Method 200.8. All resulting sample digests were analyzed for total manganese via
inductively coupled plasma triple quadrupole mass spectrometry (ICP-QQQ-MS).
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 standards
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.
Arsenic Speciation Anal sy is by IC-ICP-CRC-MS Each sample was analyzed for arsenic
speciation via ion chromatography inductively coupled plasma collision reaction cell mass
spectrometry (IC-ICP-CRC-MS) on July 10, 2015. Aliquots of each sample are injected onto
an anion exchange column and eluted isocratically. The eluting arsenic 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 specific collision gas. Polyatomic interferences, due to their inherently larger
size, collide more frequently with the collision gas and therefore may be separated from the

Page 10 of 23
analyte of interest via kinetic energy discrimination (KED). A solid-state detector detects
ions transmitted through the mass analyzer on the basis of their mass -to -charge ratio (m/z),
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.
Iron speciation Anal sy is b�Spectrophotomet�y All samples submitted for Fe speciation
quantification were analyzed on July 3, 2015 and in accordance with the scientifically
accepted method outlined by:
Stookey, L.L., (1970). "Ferrozine - A new spectrophotometric reagent for iron",
Anal.Chem., 42:779-81.
Manganese Mn(II) Analysis by IC-ICP-CRC-MS All samples for Mn(II) analysis were
analyzed by ion chromatography inductively coupled plasma collision reaction cell mass
spectrometry (IC-ICP-CRC-MS) on July 9, 2015. Aliquots of each sample are injected onto
an anion exchange column and mobilized by an acidic (pH < 7) gradient. An ion pairing
agent provides a dynamic ion exchange mechanism for the cationic manganese species on the
chromatographic column. The differences in the affinity of manganese species towards the
ion pair agent and the column results in separation. 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.
Manganese Mn(IV) Analysis by ICP-QQQ-MS All samples submitted for Mn speciation
quantitation were analyzed by inductively coupled plasma triple quadrupole mass
spectrometry (ICP-QQQ-MS) on July 7, 2015. Aliquots of each sample digest are 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 an initial quadrupole (Q1), which filters the
target masses prior to their entrance into a second chamber. The second chamber contains
specific reactive gasses or collision gasses that preferentially react either with interfering ions
of the same target mass to charge ratios (m/z) or with the target analyte, producing an
entirely different mass to charge ratio (m/z) which can then be differentiated from the initial
interferences. The ions then exit the collision/reaction cell into and additional quadrupole
(Q2). A solid-state detector detects ions transmitted through the mass analyzer, on the basis
of their mass -to -charge ratio (m/z), and the resulting current is processed by a data handling
system.

Page 11 of 23
4. Analytical Issues
No significant analytical issues were encountered. All quality control parameters associated
with the samples were within acceptance limits.
Mn(IV) is quantified by analyzing the water samples for total Mn and dissolved Mn. Mn(IV)
is operationally defined as the difference between the filtered and unfiltered total Mn
concentrations, since it is thermodynamically favored to be in the form of a precipitate.
The eMDL value for Fe(II) and total recoverable Fe was set at 5 based on the sensitivity of
the instrument.
The eMDL for Mn(II) has been generated from replicate analyses of the lowest standard in
the calibration curve.
The eMDL values for Mn(IV) been calculated using the standard deviation of the method
blanks prepared and analyzed concurrently with the submitted samples.
If you have any questions or concerns regarding this report, please feel free to contact me.
Sincerely,
Russell Gerads
Business Development Director
Brooks Rand Labs, LLC

Page 12 of 23
Speciation Results for Duke Energy
Project Name: Duke Energy Asheville Plant
Contact: Peggy Kendall
LIMS# J15070268
Date: July 30, 2015
Report Generated by: Russell Gerads
Brooks Rand Labs, LLC
Sample Results (1)
Sample ID
As(III)
As(V)
MW-15SL
14.0
3.75
MW-15BR
11.2
61.1
MW-6BR
0.582
1.57
All results reflect the applied dilution and are reported in pg/L

Page 13 of 23
Speciation Results for Duke Energy
Project Name: Duke Energy Asheville Plant
Contact: Peggy Kendall
LIMS# J15070268
Date: July 30, 2015
Report Generated by: Russell Gerads
Brooks Rand Labs, LLC
Sample Results (1
Sample ID
Fe(II)
Fe(III)*
Mn (II)
Mn(IV)**
MW-15SL
22600
16200
4170
205
MW-15BR
ND(<5.0)
9.3
72.0
3.00
MW-6BR
176
6.1
827
ND(<0.12)
All results reflect the applied dilution and are reported in tag/L
ND = Not detected at the applied dilution
*Fe(III) defined as the difference between total recoverable Fe and Fe(II)
**Mn(IV) operationally defined as the difference between total and dissolved Mn

Page 14 of 23
Speciation Results for Duke Energy
Project Name: Duke Energy Asheville Plant
Contact: Peggy Kendall
LIMS# J15070268
Date: July 30, 2015
Report Generated by: Russell Gerads
Brooks Rand Labs, LLC
Quality Control Summary - Preparation Blank Summary (1)
Analvte (ua/L) PBW1 PBW2 PBW3 PBW4 Mean StdDev eMDL* eMDL 10x RL 10x
As(III) 0.000 0.000 0.000 0.000 0.000 0.000 0.006 0.065 0.20
As(y) 0.000 0.000 0.000 0.000 0.000 0.000 0.009 0.088 0.20
eMDL = Estimated Method Detection Limit; RL = Reporting Limit
*Please see narrative regarding eMDL calculations

Page 15 of 23
Speciation Results for Duke Energy
Project Name: Duke Energy Asheville Plant
Contact: Peggy Kendall
LIMS# J15070268
Date: July 30, 2015
Report Generated by: Russell Gerads
Brooks Rand Labs, LLC
Quality Control Summary - Preparation Blank Summary (2
Analyte (lag/L) PBW1 PBW2 PBW3 PBW4
Mean
StdDev
eMDL**
eMDL 1x
RL 1x
Fe(II) 0.0 0.0 0.0 0.0
0.0
0.0
5.0
5.0
20
Total Fe 0.0 0.0 0.0 0.0
0.0
0.0
5.0
5.0
20
eMDL = Estimated Method Detection Limit; RL = Reporting Limit
**Please see narrative regarding eMDL calculations
Quality Control Summary - Preparation Blank Summary
(3)
Analyte (lag/L) PBW1 PBW2 PBW3 PBW4
Mean
StdDev
eMDL*
eMDL 10x
RL 10x eMDL 25x RL 25x
Mn (II) -0.601 -0.601 -0.601 -0.601
-0.601
0.00
0.046
0.46
5.0 - -
Total Mn -0.329 -0.354 -0.304 -0.337
-0.329
0.021
0.002
-
- 0.06 1.0
Diss Mn -0.336 -0.281 -0.380 -0.343
-0.332
0.041
0.005
-
- 0.12 1.0
eMDL = Estimated Method Detection Limit; RL = Reporting Limit
*Please see narrative regarding eMDL calculations

Page 16 of 23
Speciation Results for Duke Energy
Project Name: Duke Energy Asheville Plant
Contact: Peggy Kendall
LIMS# J15070268
Date: July 30, 2015
Report Generated by: Russell Gerads
Brooks Rand Labs, LLC
Quality Control Summary - Certified Reference Materials (1
Analyte (Ng/L)
CRM
True Value
Result
Recovery
As(III)
LCS
5.000
4.976
99.5
As(V)
LCS
5.000
5.266
105.3
Quality Control Summary
- Certified Reference Materials (2)
Analyte (pg/L)
CRM
True Value
Result
Recovery
Fe(II)
ICV
500.0
487.3
97.5
Total Fe
TMDA-70
376.0
424.2
112.8
Mn (II)
LCS
10.00
10.35
103.5
Total Mn
TMDA-70.2
312
322
103.3
Diss Mn
TMDA-70.2
312
322
103.3

Page 17 of 23
Speciation Results for Duke Energy
Project Name: Duke Energy Asheville Plant
Contact: Peggy Kendall
LIMS# J15070268
Date: July 30, 2015
Report Generated by: Russell Gerads
Brooks Rand Labs, LLC
Quality Control Summary - Matrix Duplicates (1)
Analyte (pg/L)
Sample ID
Rep 1
Rep 2 Mean RPD
As(III)
Batch QC
ND (<0.065)
ND (<0.065) NC NC
As(V)
Batch QC
ND (<0.088)
ND (<0.088) NC NC
ND = Not detected at the applied dilution
NC = Value was not calculated due to one or more concentrations below the eMDL

Page 18 of 23
Speciation Results for Duke Energy
Project Name: Duke Energy Asheville Plant
Contact: Peggy Kendall
LIMS# J15070268
Date: July 30, 2015
Report Generated by: Russell Gerads
Brooks Rand Labs, LLC
Qualitv Control Summary - Matrix Duplicates (2
Analyte (pg/L)
Sample ID
Rep 1
Rep 2
Mean
RPD
Fe(II)
Batch QC
39.8
37.5
38.7
6.1
Total Fe
Batch QC
44.3
44.3
44.3
0.0
Mn (II)
MW-6BR
826.8
820.1
823.4
0.8
Total Mn
Batch QC
3581
3594
3587
0.4

Page 19 of 23
Speciation Results for Duke Energy
Project Name: Duke Energy Asheville Plant
Contact: Peggy Kendall
LIMS# J15070268
Date: July 30, 2015
Report Generated by: Russell Gerads
Brooks Rand Labs, LLC
Qualitv Control Summary - Matrix Spike/Matrix Spike Duplicate 0
Analyte (lag/L)
Sample ID
Spike Conc
MS Result
Recovery
Spike Conc
MSD Result
Recovery
RPD
As(III)
As(V)
Batch QC
Batch QC
20.00
20.00
22.98
22.83
114.9
114.2
20.00
20.00
22.51
22.85
112.6
114.2
2.1
0.1
Quality Control Summary - Matrix Spike/
Matrix Spike Duplicate
(2)
Analyte (lag/L)
Sample ID
Spike Conc
MS Result
Recovery
Spike Conc
MSD Result
Recovery
RPD
Fe(II)
Total Fe
Batch QC
Batch QC
500.0
500.0
541.2
538.4
100.5
98.8
500.0
500.0
536.5
540.8
99.6
99.3
0.9
0.4
Mn (II)
Total Mn
MW-6BR
Batch QC
50.00
1000
904.6
4503
162.4*
91.6
50.00
1000
859.3
4269
71.7*
68.1 *
0.8
5.3
*Ambient analyte concentration greater than spiking level

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