NC0000396_J15060087F_Speciation_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: J15060087
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 a kendall@duhke
pggy
ne:
j-energy.com
Report Authorized By: 2015.06.23 11:58:26 Date:
(Signature) - 4'DO`
Peggy Kendall
Program Comments:
Please contact the Program Manager (Peggy Kendall) with any questions regarding this report.
Data Flags & Calculations:
6/23/2015
Page 1 of 16
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:
Sample ID Plant/Station
2015017103 ASHEVILLE
1 Total Samples
Collection
Date and Time Collected By
01 -Jun -15 8:58 AM Synterra
Page 2 of 16
Sample Description
MW -24D

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 16
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: 6/23/2015

Certificate of Laboratory Analysis Page 4 of 16
This report shall not be reproduced, except in full.
Order # J15060087
Site: MW -24D
Collection Date: 01 -Jun -15 8:58 AM
Analyte Result Units Qualifiers RDL DF
Speciation of an Element - (Analysis Performed by Brooks Rand Labs LLC)
Vendor Parameter Complete
Sample #: 2015017103
Matrix: GW WW
Method Analysis Date/Time Analyst
Vendor Method V_BRAND

Page 5 of 16
BRO�©KS
RAND
LABS
MEANINGFUL METALS DATA
June 19, 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 Asheville Plant (LIMS# J15060087)
Mr. Perkins,
Attached is the report associated with one (1) aqueous sample submitted for iron speciation and
manganese speciation analyses on June 1, 2015. The sample was received in a sealed cooler at
0.5°C on June 2, 2015. Iron speciation analysis was performed by spectrophotometry. Mn(II)
analysis was performed via ion chromatography inductively coupled plasma collision reaction
cell mass spectrometry (IC -ICP -CRC -MS). Mn(IV) analysis was 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,
r�
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 Energy Asheville Plant (LIMS# J15060087)
June 19, 2015
1. Sample Reception
Page 6 of 16
One (1) aqueous sample was submitted for iron speciation and manganese speciation
analyses on June 1, 2015. The sample was received in acceptable condition on June 2, 2015
in a sealed container at 0.5°C.
All samples are received in a laminar flow clean hood, void of trace metals contamination
and ultra -violet radiation, and are designated discrete sample identifiers. The sample fraction
requesting iron speciation analysis was field filtered by the client. Two containers were
submitted for the client sample requesting manganese speciation, one field filtered fraction
and one unfiltered fraction. The sample fraction requesting iron speciation analysis was
stored in a secure, monitored refrigerator (maintained at a temperature of <6°C) until the
analyses could be performed.
An aliquot of the field filtered sample submitted for manganese speciation analysis was
decanted into a polypropylene centrifuge tube for Mn(II) analysis. This fraction was 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 7 of 16
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(LI) 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 MnaV Analysis 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.
Iron Speciation Analysis by Spectrophotometry The sample fraction submitted for iron
speciation was analyzed for iron speciation quantification on June 2, 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 The fraction for Mn(II) analysis was
analyzed by ion chromatography inductively coupled plasma collision reaction cell mass
spectrometry (IC -ICP -CRC -MS) on June 5, 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

Page 8 of 16
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(ID 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 June 9, 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. 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 estimated method detection limits (eMDL) for Fe(II) and Fe(III) were set at 1/3 the value
of the associated reporting limit since the standard deviation associated with the replicate
analyses of the lowest standard in the calibration curve was zero.
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.

Page 9 of 16
If you have any questions or concerns regarding this report, please feel free to contact me.
Sincerely,
it L7S�--
Jeremy Maute
Project Manager
Brooks Rand Labs, LLC

Page 10 of 16
Speciation Results for Duke Energy
Project Name: Duke Energy Asheville Plant
Contact: Peggy Kendall
LIMS# J15060087
Date: June 19, 2015
Report Generated by: Jeremy Maute
Brooks Rand Labs, LLC
Sample Results
Sample ID Fe(II) Fe(III)* Mn (II) Mn(IV)**
MW -24D 39.5 19.8 133 2.07
All results reflect the applied dilution and are reported in pg/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 11 of 16
Speciation Results for Duke Energy
Project Name: Duke Energy Asheville Plant
Contact: Peggy Kendall
LIMS# J15060087
Date: June 19, 2015
Report Generated by: Jeremy Maute
Brooks Rand Labs, LLC
Qualitv Control Summary - Preparation Blank Summar
Analyte (Ng/L) PBW1 PBW2 PBW3 PBW4 Mean StdDev eMDL* eMDL 2x RL 2x
Fe(II) 0.0 0.0 0.0 0.0 0.0 0.0 6.7 13 40
Total Fe 2.5 2.5 2.5 2.5 2.5 0.0 6.7 13 40
eMDL = Estimated Method Detection Limit; RL = Reporting Limit
*Please see narrative regarding eMDL calculations
Qualitv Control Summary - Preparation Blank Summa
Analyte (lag/L)
PBW1
PBW2
PBW3
PBW4
Mean
StdDev
eMDL* eMDL 10x RL 10x eMDL 25x RL 25x
Mn (11)
-0.66
-0.79
-0.66
-0.75
-0.70
0.07
0.086 0.86 5.0 - -
Total Mn
0.05
-0.06
0.02
0.05
0.00
0.05
0.006 - - 0.16 1.0
Diss Mn
0.00
0.10
-0.06
-0.01
0.01
0.07
0.008 - - 0.20 1.0
eMDL = Estimated Method Detection Limit; RL = Reporting Limit
*Please see narrative regarding eMDL calculations

Page 12 of 16
Speciation Results for Duke Energy
Project Name: Duke Energy Asheville Plant
Contact: Peggy Kendall
LIMS# J15060087
Date: June 19, 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
100.0
106.2
106.2
Total Fe
LCS
100.0
103.7
103.7
Mn (II)
LCS
1.00
1.053
105.3
Total Mn
TMDA-70.2
312
326.6
104.7

Page 13 of 16
Speciation Results for Duke Energy
Project Name: Duke Energy Asheville Plant
Contact: Peggy Kendall
LIMS# J15060087
Date: June 19, 2015
Report Generated by: Jeremy Maute
Brooks Rand Labs, LLC
Quality Control Summary - Matrix Duplicates
Analyte (fag/L)
Sample ID
Rep 1
Rep 2
Mean
RPD
Fe(II)
MW -24D
40
35
37
13.3
Total Fe
MW -24D
59
59
59
0.0
Mn (II) Batch QC 51.73 50.31 51.02 2.8
Total Mn Batch QC 717.7 693.2 705.5 3.5
ND = Not detected at the applied dilution
NC = Value was not calculated due to one or more concentrations below the eMDL

Page 14 of 16
Speciation Results for Duke Energy
Project Name: Duke Energy Asheville Plant
Contact: Peggy Kendall
LIMS# J15060087
Date: June 19, 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)
MW -24D
200.0
237.1
100.0
200.0
242.0
102.5
2.1
Total Fe
MW -24D
200.0
261.8
101.3
200.0
261.8
101.3
0.0
Mn (II)
Batch QC
50.00
98.35
94.7
50.00
101.7
101.3
3.3
Total Mn
Batch QC
1000
1837
113.2
1000
1812
110.7
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1881 4 \orthcreck Parkway
Bothell, W.\ 98011
Phone [phone]
Fax [phone]
Com anv Name
M-
]i RI. Project Manager: -lererny MaUIC
Contact Person:
0.
B% submitting of samples the client agrees to all terms and conditions set forth
in the quotation provided by the BRL project manager. If you are not familiar
with the term and conditions associated with vour project, please contact tour
liM, representative as soon as possible [phone].
Address: V¢ Y' t< t 220
(L3eUvc �l SC 01
Phone Number: (t - ctki 'I
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Method of Sample Debven-:
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(:untirmation „i Sample Reception: Yes
® No
P() Number:
Sample 11)
bottle 11) 1),uc and •Time•
Mairl\
Volume
Presrtti;t I%r
Initial~
Requested Analytes ane] Methods
Comments
w
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; z 7
125-
EDTA - 1
NH4OH/NH4SO4
Degassed HCI
None
None
None
e T) L-'
;3.z> , ti;
i3101,;
As Spec
Cr(VI)
Fe Spec
Mn Spec
Mn Spec
Se Spec
field filtered
field filtered
field filtered
field filtered
unfiltered
field filtered
AA G- z y D cry
!3 3( 5 `i (v i -IS , 'jk
Is ,i i~)7 ,f i7 L C ti-( '5 VISS-L
EDTA - 1
NH4OH/NH4SO4
Degassed HCl
None
None
None
As Spec
Cr(VI)
Fe Spec
Mn Spec
Mn Spec
Se Spec
field filtered
field filtered
field filtered
field filtered
unfiltered
field filtered
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Please account for each sample bottle as a seperate line item for verification purposes.
%latrix:.\ir, Freshwater (I. V), scrwater (SW), bmantdwater ((Akl, wastewater AVW), soil (SI.), sediment (tit)), tissue (PS), product (P), other (0)
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