NC0000396_J15070455F_20150823

+ 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: J15070455
Project Name: ASHEVILLE - AB GW ASSESSMENT SPECIATION
Customer Name(s): Todd Plating, Kathy Webb, John Toepfer, Tim Hunsucker
Customer Address: 200 CP and L Drive
Arden, NC 28704
Lab Contact: Peggy Kendall kenddll@ho
Pe99yne:
uk
Report Authorized By: e-ener 9y.com
Date:
(signature) 201 -5 -0728 -
Peggy Kendall 16:02:01 -04'00'
Program Comments:
Please contact the Program Manager (Peggy Kendall) with any questions regarding this report.
Data Flags & Calculations:
7/28/2015
Page 1 of 20
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
2015023316
ASHEVILLE
08 -Jul -15 8:30 AM
Synterra
CB -3R
2015023317
ASHEVILLE
08 -Jul -15 9:00 AM
Synterra
CB -04
2015023318
ASHEVILLE
08 -Jul -15 1:22 PM
Synterra
CB -06
3 Total Samples
Page 2 of 20

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 F./] 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
Page 3 of 20
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: 7/28/2015

Certificate of Laboratory Analysis Page 4 of 20
This report shall not be reproduced, except in full.
Order # J15070455
Site: CB -3R
Collection Date: 08 -Jul -15 8:30 AM
Analyte Result Units Qualifiers RDL DF
Speciation of an Element - (Analysis Performed by Brooks Rand Labs LLC)
Vendor Parameter Complete
Sample #: 2015023316
Matrix: GW WW
Method Analysis Date/Time Analyst
Vendor Method V_BRAND

Certificate of Laboratory Analysis Page 5 of 20
This report shall not be reproduced, except in full.
Order # J15070455
Site: CB -04
Collection Date: 08 -Jul -15 9:00 AM
Analyte Result Units Qualifiers RDL DF
Speciation of an Element - (Analysis Performed by Brooks Rand Labs LLC)
Vendor Parameter Complete
Sample #: 2015023317
Matrix: GW WW
Method Analysis Date/Time Analyst
Vendor Method V_BRAND

Certificate of Laboratory Analysis Page 6 of 20
This report shall not be reproduced, except in full.
Order # J15070455
Site: CB -06
Collection Date: 08 -Jul -15 1:22 PM
Analyte Result Units Qualifiers RDL DF
Speciation of an Element - (Analysis Performed by Brooks Rand Labs LLC)
Vendor Parameter Complete
Sample #: 2015023318
Matrix: GW WW
Method Analysis Date/Time Analyst
Vendor Method V_BRAND

Page 7 of 20
BRO�©KS
RAND
LABS
MEANINGFUL METALS DATA
July 28, 2015
Peggy Kendall
Duke Energy Analytical Laboratory
Mail Code MGO3A2 (Building 7405)
13339 Hagers Ferry Rd.
Huntersville, NC 28078
980-875-5848
Project: Duke: Asheville (LIMS# J15070455)
Ms. Kendall,
Attached is the report associated with three (3) aqueous samples submitted for iron speciation
and manganese speciation analyses on July 8, 2015. The samples were received in a sealed
cooler at -0.3°C on July 10, 2015. 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,
k: �
Jeremy Maute
Project Manager
Brooks Rand Labs, LLC
3958 6th Ave NW • Seattle, WA 98107 • T: 206-632-6206 • F: 206-632-6017 • www.brooksrand.com • [e-mail]

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: Asheville (LIMS# J15070455)
July 28, 2015
1. Sample Reception
Page 8 of 20
Three (3) aqueous samples were submitted for iron speciation and manganese speciation
analyses on July 8, 2015. The samples were received in acceptable condition on July 10,
2015 in a sealed container at a temperature of -0.3°C.
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 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.
Iron Speciation Anal sis by Spectrophotometny 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.

Page 9 of 20
Manganese Mn(I ' Analysis by ICP-MQQ-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.
Iron Speciation Analysis by Spectrophotometry All samples submitted for Fe speciation
quantification were analyzed on July 10, 2015 and July 14, 2015, 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 LII 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 13, 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.

Page 10 of 20
Retention times for each eluting species are compared to known standards for species
identification.
Manganese Mn (1Q Anal sy is 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 21, 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.
4. Analytical Issues
No significant analytical issues were encountered. With the exceptions noted below, all
quality control parameters associated with the samples were within acceptance limits.
All samples were analyzed for Fe(II) outside the 48 hour holding time specified by the
method. All iron speciation sample results have been flagged to reflect the discrepancy.
Preparation blanks were not analyzed for Fe(II) analysis. No iron was detected in any of the
bracketing continuing calibration blanks (CCB) or the initial calibration blank (ICB),
demonstrating the absence of any iron contamination in the analytical run. The preparation
blanks were analyzed or Fe(III) analysis. All preparation blanks yielded non -detect results
for total iron, demonstrating the absence of iron contamination due to the containers, the
preservative employed, and the equipment used to collect the samples.
For the Fe(II) analytical run the client sample, identified as CB -3R, was analyzed as the
matrix quality control sample. The matrix spike sample and matrix spike duplicate sample
(MS/MSD) spike recoveries for Fe(II) were greater than the upper control limit of 125%, at
196.1% and 197.9%, respectively. The native Fe(II) concentration in the quality control
sample was greater than the spiking level. Acceptable spike recoveries are often not realized
when the ambient level analyte concentration is greater than the spiking level. No
qualification of data was necessary.
The Mn(II) result for the client sample, identified as CB -06, was greater than the value of the
associated high calibration standard. A linear range verification standard was analyzed at
2000 µg/L. The Mn(II) recovery for the linear range verification standard was acceptable, at
103.8%, demonstrating that the linear range of the analytical platform extended to 2000 µg/L

Page 11 of 20
for Mn(II). The Mn(II) result for the client sample CB -06 was less than 2000 µg/L with the
dilution at the instrument factored in, and thus was within the linear range demonstrated by
the linear range verification standard. No corrective actions were necessary.
For Mn(IV) analysis the client sample, identified as CB -06, was analyzed as the quality
control sample. The matrix spike duplicate sample (MSD) spike recovery for total
manganese was less than the lower control limit of 75%, at 68.1%. The native manganese
concentration in the quality control sample was greater than the spiking level. Acceptable
spike recoveries are often not realized when the ambient level analyte concentration is
greater than the spiking level. No qualification of data was necessary.
The total and dissolved manganese results for the client sample, identified as CB -06, were
greater than the value of the associated high calibration standard. A linear range verification
standard was analyzed at 2000 µg/L. The manganese recovery for the linear range
verification standard was acceptable, at 90.8%, demonstrating that the linear range of the
analytical platform extended to 2000 µg/L for manganese. The total and dissolved
manganese results for the client sample CB -06 were less than 2000 µg/L with the dilutions at
the instrument factored in, and thus was within the linear range demonstrated by the linear
range verification standard. No corrective actions were necessary.
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,
Jeremy Maute
Project Manager
Brooks Rand Labs, LLC

Page 12 of 20
Speciation Results for Duke Energy
Project Name: Duke: Asheville
Contact: Peggy Kendall
LIMS# J15070455
Date: July 28, 2015
Report Generated by: Jeremy Maute
Brooks Rand Labs, LLC
Samale Results
Sample ID
Fe(II) *
Fe(III)**
I Mn (II)
Mn(IV)**
CB -3R
258
ND (<5.0)
796
4.88
CB -04
NR
NR
771
40.7
CB -06
20300
ND (<250)
3310
20.5
All results reflect the applied dilution and are reported in tag/L
NR = Analysis not requested
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
$ Fe(II) and Fe(III) results are estimated due to holding time violations. Please see narrative.

Page 13 of 20
Speciation Results for Duke Energy
Project Name: Duke: Asheville
Contact: Peggy Kendall
LIMS# J15070455
Date: July 28, 2015
Report Generated by: Jeremy Maute
Brooks Rand Labs, LLC
Quality Control Summary - Preparation Blank Summa
Analyte (lag/L) PBW1* PBW2* PBW3* PBW4*
Mean
StdDev
eMDL**
eMDL 1x
RL 1x
eMDL 50x
RL 50x
Fe(I1)
5.0
5.0
20
250
1000
Total Fe 0.0 0.0 0.0 0.0
0.0
0.0
5.0
5.0
20
250
1000
eMDL = Estimated Method Detection Limit; RL = Reporting Limit
*Preparation blanks for Fe(II) speciation were not analyzed.
See narrative.
**Please see narrative regarding eMDL calculations
Quality Control Summary - Preparation Blank Summary
Analyte (lag/L) PBW1 PBW2 PBW3 PBW4
Mean
StdDev
eMDL*
eMDL 10x
RL 10x
eMDL 25x
RL 25x
Mn (II) -0.60 -0.60 -0.60 -0.60
-0.60
0.00
0.046
0.46
5.0
-
-
Total Mn -0.329 -0.354 -0.304 -0.337
-0.329
0.021
0.002
-
-
0.062
1.0
Diss Mn -0.34 -0.28 -0.38 -0.34
-0.33
0.04
0.005
-
-
0.12
1.0
eMDL = Estimated Method Detection Limit; RL = Reporting Limit
*Please see narrative regarding eMDL calculations

Page 14 of 20
Speciation Results for Duke Energy
Project Name: Duke: Asheville
Contact: Peggy Kendall
LIMS# J15070455
Date: July 28, 2015
Report Generated by: Jeremy Maute
Brooks Rand Labs, LLC
Quality Control Summary - Certified Reference Materials
Analyte (Ng/L)
CRM
True Value
Result
Recovery
Fe(II)
ICV
500.0
457.7
91.5
Total Fe
TMDA-70
376.0
401.7
106.8
Mn (II)
LCS
10.00
10.35
103.5
Total Mn
TMDA-70.2
312
322.3
103.3

Page 15 of 20
Speciation Results for Duke Energy
Project Name: Duke: Asheville
Contact: Peggy Kendall
LIMS# J15070455
Date: July 28, 2015
Report Generated by: Jeremy Maute
Brooks Rand Labs, LLC
Quality Control Summary - Matrix Duplicates
Analyte (pg/L)
Sample ID
Rep 1
Rep 2
Mean
RPD
Fe(II)
CB -3R
258.1
258.1
258.1
0.0
Total Fe
CB -3R
247.3
247.3
247.3
0.0
Mn (II) Batch QC 344.9 336.9 340.9 2.3
Total Mn CB -06 3581 3594 3587 0.4

Page 16 of 20
Speciation Results for Duke Energy
Project Name: Duke: Asheville
Contact: Peggy Kendall
LIMS# J15070455
Date: July 28, 2015
Report Generated by: Jeremy Maute
Brooks Rand Labs, LLC
Qualitv Control Summary - Matrix Spike/ Matrix Spike Duplicate
Analyte (lag/L)
Sample ID
Spike Conc
MS Result
Recovery
Spike Conc
MSD Result
Recovery
RPD
Fe(I1)
CB -3R
200.0
650.4
196.1*
200.0
653.8
197.9*
0.5
Total Fe
CB -3R
500.0
717.1
93.9
500.0
719.4
94.4
0.3
Mn (II)
Batch QC
50.00
390.8
99.8
50.00
398.1
114.4
0.8
Total Mn
CB -06
1000
4503
91.6*
1000
4269
68.1*
5.3

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