HomeMy WebLinkAboutNC0001422_ATT 5 - Speciation - J15060246F2_2015080513339 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: J15060246
Project Name:SUTTON - AB GW ASSESSMENT SPECIATION
Lab Contact:Peggy Kendall
Date:7/1/2015
Customer Address:
Customer Name(s):Perry Waldrep, Tim Hunsucker, Kathy Webb, John Toepfer
Phone:
Report Authorized By:
(Signature)
Program Comments:
Please contact the Program Manager (Peggy Kendall) with any questions regarding this report.
Data Flags & Calculations:
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.
Peggy Kendall
Page 1 of 40
Sample ID's & Descriptions:
Sample ID Plant/Station
Collection
Date and Time Collected By Sample Description
2015017791 Sutton 03-Jun-15 10:05 AM Synterra MW23B
2015017792 Sutton 03-Jun-15 11:44 AM Synterra MW23E
2015017793 Sutton 03-Jun-15 10:26 AM Synterra AW-5B
2015017794 Sutton 03-Jun-15 11:26 AM Synterra AW-5C
2015017795 Sutton 03-Jun-15 1:50 PM Synterra AW-2D
2015017796 Sutton 03-Jun-15 2:26 PM Synterra AW-2C
2015017797 Sutton 03-Jun-15 10:06 AM Synterra AW-2B
2015017798 Sutton 03-Jun-15 4:12 PM Synterra AW-5E
2015017799 Sutton 03-Jun-15 6:37 PM Synterra AW-6D
2015017800 Sutton 03-Jun-15 3:52 PM Synterra AW-6B
2015017801 Sutton 03-Jun-15 4:20 PM Synterra SMW-6D
2015017802 Sutton 03-Jun-15 4:40 PM Synterra SMW-6B
12 Total Samples
Page 2 of 40
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.
Yes No
Technical Validation Review
Checklist:
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
Analytical Laboratory QC Report
Chain of Custody
Reviewed By:Peggy Kendall Date:7/1/2015
Electronic Data Deliverable (EDD) Sent Separately
Page 3 of 40
Certificate of Laboratory Analysis
This report shall not be reproduced, except in full.
Order # J15060246
2015017791
Collection Date: 03-Jun-15 10:05 AM
Site: MW23B
Matrix: GW_WW
Analyte Analysis Date/TimeMethodUnits Qualifiers RDLResult
Sample #:
AnalystDF
Speciation of an Element - (Analysis Performed by Brooks Rand Labs LLC)
Vendor Parameter Complete Vendor Method V_BRAND
Page 4 of 40
Certificate of Laboratory Analysis
This report shall not be reproduced, except in full.
Order # J15060246
2015017792
Collection Date: 03-Jun-15 11:44 AM
Site: MW23E
Matrix: GW_WW
Analyte Analysis Date/TimeMethodUnits Qualifiers RDLResult
Sample #:
AnalystDF
Speciation of an Element - (Analysis Performed by Brooks Rand Labs LLC)
Vendor Parameter Complete Vendor Method V_BRAND
Page 5 of 40
Certificate of Laboratory Analysis
This report shall not be reproduced, except in full.
Order # J15060246
2015017793
Collection Date: 03-Jun-15 10:26 AM
Site: AW-5B
Matrix: GW_WW
Analyte Analysis Date/TimeMethodUnits Qualifiers RDLResult
Sample #:
AnalystDF
Speciation of an Element - (Analysis Performed by Brooks Rand Labs LLC)
Vendor Parameter Complete Vendor Method V_BRAND
Page 6 of 40
Certificate of Laboratory Analysis
This report shall not be reproduced, except in full.
Order # J15060246
2015017794
Collection Date: 03-Jun-15 11:26 AM
Site: AW-5C
Matrix: GW_WW
Analyte Analysis Date/TimeMethodUnits Qualifiers RDLResult
Sample #:
AnalystDF
Speciation of an Element - (Analysis Performed by Brooks Rand Labs LLC)
Vendor Parameter Complete Vendor Method V_BRAND
Page 7 of 40
Certificate of Laboratory Analysis
This report shall not be reproduced, except in full.
Order # J15060246
2015017795
Collection Date: 03-Jun-15 1:50 PM
Site: AW-2D
Matrix: GW_WW
Analyte Analysis Date/TimeMethodUnits Qualifiers RDLResult
Sample #:
AnalystDF
Speciation of an Element - (Analysis Performed by Brooks Rand Labs LLC)
Vendor Parameter Complete Vendor Method V_BRAND
Page 8 of 40
Certificate of Laboratory Analysis
This report shall not be reproduced, except in full.
Order # J15060246
2015017796
Collection Date: 03-Jun-15 2:26 PM
Site: AW-2C
Matrix: GW_WW
Analyte Analysis Date/TimeMethodUnits Qualifiers RDLResult
Sample #:
AnalystDF
Speciation of an Element - (Analysis Performed by Brooks Rand Labs LLC)
Vendor Parameter Complete Vendor Method V_BRAND
Page 9 of 40
Certificate of Laboratory Analysis
This report shall not be reproduced, except in full.
Order # J15060246
2015017797
Collection Date: 03-Jun-15 10:06 AM
Site: AW-2B
Matrix: GW_WW
Analyte Analysis Date/TimeMethodUnits Qualifiers RDLResult
Sample #:
AnalystDF
Speciation of an Element - (Analysis Performed by Brooks Rand Labs LLC)
Vendor Parameter Complete Vendor Method V_BRAND
Page 10 of 40
Certificate of Laboratory Analysis
This report shall not be reproduced, except in full.
Order # J15060246
2015017798
Collection Date: 03-Jun-15 4:12 PM
Site: AW-5E
Matrix: GW_WW
Analyte Analysis Date/TimeMethodUnits Qualifiers RDLResult
Sample #:
AnalystDF
Speciation of an Element - (Analysis Performed by Brooks Rand Labs LLC)
Vendor Parameter Complete Vendor Method V_BRAND
Page 11 of 40
Certificate of Laboratory Analysis
This report shall not be reproduced, except in full.
Order # J15060246
2015017799
Collection Date: 03-Jun-15 6:37 PM
Site: AW-6D
Matrix: GW_WW
Analyte Analysis Date/TimeMethodUnits Qualifiers RDLResult
Sample #:
AnalystDF
Speciation of an Element - (Analysis Performed by Brooks Rand Labs LLC)
Vendor Parameter Complete Vendor Method V_BRAND
Page 12 of 40
Certificate of Laboratory Analysis
This report shall not be reproduced, except in full.
Order # J15060246
2015017800
Collection Date: 03-Jun-15 3:52 PM
Site: AW-6B
Matrix: GW_WW
Analyte Analysis Date/TimeMethodUnits Qualifiers RDLResult
Sample #:
AnalystDF
Speciation of an Element - (Analysis Performed by Brooks Rand Labs LLC)
Vendor Parameter Complete Vendor Method V_BRAND
Page 13 of 40
Certificate of Laboratory Analysis
This report shall not be reproduced, except in full.
Order # J15060246
2015017801
Collection Date: 03-Jun-15 4:20 PM
Site: SMW-6D
Matrix: GW_WW
Analyte Analysis Date/TimeMethodUnits Qualifiers RDLResult
Sample #:
AnalystDF
Speciation of an Element - (Analysis Performed by Brooks Rand Labs LLC)
Vendor Parameter Complete Vendor Method V_BRAND
Page 14 of 40
Certificate of Laboratory Analysis
This report shall not be reproduced, except in full.
Order # J15060246
2015017802
Collection Date: 03-Jun-15 4:40 PM
Site: SMW-6B
Matrix: GW_WW
Analyte Analysis Date/TimeMethodUnits Qualifiers RDLResult
Sample #:
AnalystDF
Speciation of an Element - (Analysis Performed by Brooks Rand Labs LLC)
Vendor Parameter Complete Vendor Method V_BRAND
Page 15 of 40
3958 6th Ave NW • Seattle, WA 98107 • T: 206-632-6206 • F: 206-632-6017 • www.brooksrand.com • brl@brooksrand.com
June 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/Sutton Plant (LIMS# J15060246)
Mr. Perkins,
Attached is the report associated with twelve (12) aqueous samples submitted for hexavalent
chromium, selenium speciation, arsenic speciation, iron speciation, and manganese speciation
analyses on June 3, 2015. The samples were received in two sealed coolers at temperatures of
-0.3°C and -0.2°C on June 4, 2015. Hexavalent chromium analysis was performed by ion
chromatography inductively coupled plasma dynamic reaction cell mass spectrometry (IC-ICP-
DRC-MS). Selenium speciation and arsenic speciation (Batch As01616) analyses were
performed via ion chromatography inductively coupled plasma collision reaction cell mass
spectrometry (IC-ICP-CRC-MS). Arsenic speciation (Batch As00626) analyses were performed
via ion chromatography inductively coupled plasma dynamic reaction cell mass spectrometry
(IC -ICP-DRC-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,
Jeremy Maute
Project Manager
Brooks Rand Labs, LLC
Page 16 of 40
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/Sutton Plant (LIMS# J15060246)
June 30, 2015
1. Sample Reception
Twelve (12) aqueous samples were submitted for hexavalent chromium, selenium speciation,
arsenic speciation, iron speciation, and manganese speciation analyses on June 3, 2015. All
samples were received in acceptable condition on June 4, 2015 in two sealed containers at
cooler temperatures of -0.3°C and -0.2°C. The chain-of-custody forms were documented to
indicate the specific cooler in which each individual client sample was received in.
The bottle IDs on several containers did not match the corresponding bottle IDs listed on the
associated chain-of-custody (COC) forms. The cases of bottle ID disagreement are described
in the table below.
Sample ID Date/Time
Collected
Bottle ID on
Container
Bottle ID on
COC
Target Analyte
AW-5B 6/3/2015 10:26 B38460 B41698 As Spec
AW-5C 6/3/2015 11:26 B36192 B36129 Fe Spec
AW-2C 6/3/2015 14:26 B36408 B39903 Mn Spec
AW-2C 6/3/2015 14:26 B39903 Not listed on
COC
Se Spec
The container labels were adequately labeled and there was no ambiguity in terms of which
sample containers corresponded to specific entries on the associated COC forms.
All samples were received in a laminar flow clean hood, void of trace metals contamination
and ultra-violet radiation, and were designated discrete sample identifiers. Sample fractions
requesting hexavalent chromium, selenium speciation, arsenic speciation, and iron speciation
analyses were field filtered by the client. Two containers were submitted for each client
sample requesting manganese speciation, one field filtered fraction and one unfiltered
fraction. An aliquot of each sample submitted for hexavalent chromium analysis was filtered
into a clean polypropylene tube. All hexavalent chromium sample fractions were stored in a
secure refrigerator maintained at a temperature of 4oC, until the analyses could be performed.
Page 17 of 40
An aliquot of each sample requiring selenium speciation evaluation was decanted into a
polypropylene centrifuge tube and each filtrate was stored in a secure, monitored cryofreezer
(maintained at a temperature of -80°C) until selenium speciation analysis could be
performed. The original bottles were then stored in a secure, monitored refrigerator
(maintained at a temperature of ≤6oC).
An aliquot of each sample submitted for arsenic speciation analysis was decanted into a
polypropylene centrifuge tube; all fractions were then stored in a secure, monitored
refrigerator (maintained at a temperature of ≤6oC) until the analyses could be performed.
The sample fractions requesting iron speciation analysis were stored in a secure, monitored
refrigerator (maintained at a temperature of ≤6oC) 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 ≤6oC) 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.
Hexavalent Chromium 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
a sample may shift the equilibrium of the system, resulting in changes in speciation ratios.
Selenium Speciation Analysis by IC-ICP-CRC-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
a sample may shift the equilibrium of the system, resulting in changes in speciation ratios.
Arsenic Speciation Analysis by IC-ICP-CRC-MS and IC-ICP-DRC-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.
Page 18 of 40
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(IV) 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.
Hexavalent Chromium Analysis by IC-ICP-DRC-MS Each sample for hexavalent chromium
analysis was analyzed by ion chromatography inductively coupled plasma dynamic reaction
cell mass spectrometry (IC-ICP-DRC-MS) on June 6, 2015. An aliquot of each sample is
injected onto an anion exchange column and mobilized by a basic (pH > 7) gradient. The
eluting chromium 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 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.
Page 19 of 40
Selenium Speciation Analysis by IC-ICP-CRC-MS Each sample for selenium speciation
analysis was analyzed by ion chromatography inductively coupled plasma collision reaction
cell mass spectrometry (IC-ICP-CRC-MS) on June 5, 2015. 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 (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.
Arsenic Speciation Analysis by IC-ICP-CRC-MS and IC-ICP-DRC-MS All arsenic speciation
fractions associated with Batch As01616 were analyzed for arsenic speciation via ion
chromatography inductively coupled plasma collision reaction cell mass spectrometry (IC-
ICP-CRC-MS) on June 17, 2015. Arsenic speciation fractions associated with Batch
As00626 were analyzed for arsenic speciation via ion chromatography inductively coupled
plasma dynamic reaction cell mass spectrometry (IC-ICP-DRC-MS) on June 26, 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/DRC) containing a specific collision or reactive gas. In
collision mode, polyatomic interferences, due to their inherently larger size, collide more
frequently with the collision gas and therefore may be separated from the analyte of interest
via kinetic energy discrimination (KED). In reaction mode the reactive gas 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 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 Analysis by Spectrophotometry All sample fractions submitted for iron
speciation were analyzed for Fe(II) quantification on June 4, 2015. All sample fractions
submitted for iron speciation were analyzed for Fe(III) quantification on June 9, 2015. The
samples were analyzed for iron speciation 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.
Page 20 of 40
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 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
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 June 16-17, 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 exception noted below, all
quality control parameters associated with the samples were within acceptance limits.
The ferrous iron matrix spike performed on the sample identified as MW23B was above the
established control limit of 125% (125.5%). All other quality control parameters were within
acceptance limits signifying acceptable method performance. No corrective action was
necessary and all reported results are deemed representative of the submitted samples.
Page 21 of 40
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 limit (eMDL) for hexavalent chromium is generated from
replicate analyses of the lowest standard in the calibration curve.
The eMDL values 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 values for methylseleninic acid and selenomethionine are 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.
The eMDL values for arsenite, arsenate, and dimethylarsinic acid are generated using the
standard deviation of replicate analyses of the lowest standard in the calibration curve. The
eMDL for monomethylarsonic acid is calculated from the average eMDL of the three arsenic
species contained in the calibration (i.e., arsenite, arsenate, and dimethylarsinic acid); the
calibration and CCVs do not contain monomethylarsonic acid due to impurities in this
standard which would bias the results for other arsenic species.
The eMDL values for Fe(II) been generated from replicate analyses of the lowest standard in
the calibration curve. The eMDL values for total recoverable iron were set at 1/3 the value of
the associated reporting limit since the standard deviations associated with the replicate
analyses of the lowest standard in the calibration curves were 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.
The fourth preparation blank for dissolved manganese analysis was determined to be a
statistical outlier according to the Grubb’s Test. The blank was not used for the eMDL
calculations presented in this report.
Page 22 of 40
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 23 of 40
Sample Results (1)
Sample ID Cr(VI)Se(IV)Se(VI)SeCN MeSe(IV)SeMe
Unknown Se
Species (n)
MW23B 0.051 ND (< 0.080)5.29 ND (< 0.098)ND (< 0.081)ND (< 0.081)0 (0)
MW23E 0.047 ND (< 0.080)0.169 ND (< 0.098)ND (< 0.081)ND (< 0.081)0 (0)
AW-5B 0.013 ND (< 0.080)ND (< 0.065)ND (< 0.098)ND (< 0.081)ND (< 0.081)0 (0)
AW-5C 0.019 ND (< 0.080)ND (< 0.065)ND (< 0.098)ND (< 0.081)ND (< 0.081)0 (0)
AW-2D 0.017 ND (< 0.080)ND (< 0.065)ND (< 0.098)ND (< 0.081)ND (< 0.081)0 (0)
AW-2C ND (< 0.007)ND (< 0.080)ND (< 0.065)ND (< 0.098)ND (< 0.081)ND (< 0.081)0 (0)
AW-2B ND (< 0.007)ND (< 0.080)ND (< 0.065)ND (< 0.098)ND (< 0.081)ND (< 0.081)0 (0)
AW-5E 0.027 ND (< 0.080)ND (< 0.065)ND (< 0.098)ND (< 0.081)ND (< 0.081)0 (0)
AW-6D 0.022 ND (< 0.080)ND (< 0.065)ND (< 0.098)ND (< 0.081)ND (< 0.081)0 (0)
AW-6B 0.024 ND (< 0.080)ND (< 0.065)ND (< 0.098)ND (< 0.081)ND (< 0.081)0 (0)
SMW-6D 0.072 ND (< 0.080)0.142 ND (< 0.098)ND (< 0.081)ND (< 0.081)0 (0)
SMW-6B 0.022 ND (< 0.080)ND (< 0.065)ND (< 0.098)ND (< 0.081)ND (< 0.081)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: Jeremy Maute
Brooks Rand Labs, LLC
Speciation Results for Duke Energy
Project Name: Duke Energy/Sutton Plant
Contact: Peggy Kendall
Date: June 30, 2015
LIMS# J15060246
Page 24 of 40
Sample Results (2)
Sample ID Batch ID As(III)As(V)MMAs DMAs
Unknown As
Species
MW23B As01616 ND (< 0.025)ND (< 0.047)ND (< 0.042)ND (< 0.053)ND (< 0.042)
MW23E As01616 0.371 0.102 0.112 ND (< 0.053)ND (< 0.042)
AW-5B As01616 0.171 0.163 ND (< 0.042)ND (< 0.053)ND (< 0.042)
AW-5C As01616 ND (< 0.025)ND (< 0.047)ND (< 0.042)ND (< 0.053)ND (< 0.042)
AW-2D As01616 0.431 ND (< 0.047)ND (< 0.042)ND (< 0.053)ND (< 0.042)
AW-2C As00626 ND (< 0.049)ND (< 0.028)ND (< 0.053)ND (< 0.083)ND (< 0.053)
AW-2B As01616 0.110 ND (< 0.047)ND (< 0.042)ND (< 0.053)ND (< 0.042)
AW-5E As01616 0.333 0.312 0.343 ND (< 0.053)ND (< 0.042)
AW-6D As00626 ND (< 0.049)ND (< 0.028)ND (< 0.053)ND (< 0.083)ND (< 0.053)
AW-6B As01616 ND (< 0.025)ND (< 0.047)ND (< 0.042)ND (< 0.053)0.659
SMW-6D As00626 0.072 0.115 0.069 ND (< 0.083)ND (< 0.053)
SMW-6B As01616 ND (< 0.025)ND (< 0.047)ND (< 0.042)ND (< 0.053)ND (< 0.042)
All results reflect the applied dilution and are reported in µg/L
ND = Not detected at the applied dilution
MMAs = monomethylarsonic acid
DMAs = dimethylarsinic acid
Unknown As Species = Total concentration of all unknown As species observed by IC-ICP-MS
Brooks Rand Labs, LLC
Speciation Results for Duke Energy
Project Name: Duke Energy/Sutton Plant
Contact: Peggy Kendall
LIMS# J15060246
Date: June 30, 2015
Report Generated by: Jeremy Maute
Page 25 of 40
Sample Results (3)
Sample ID Fe(III)Fe(III)*Mn (II)Mn(IV)**
MW23B ND (< 8.4)18 1.88 5.09
MW23E 28.1 ND (< 13)1.51 3.61
AW-5B 33.8 ND (< 13)18.1 6.25
AW-5C 16.9 ND (< 13)20.7 1.19
AW-2D 175 41 65.7 0.268
AW-2C 6000 580 58.4 1.26
AW-2B 1580 ND (< 13)215 5.89
AW-5E 61.9 ND (< 13)5.29 6.26
AW-6D 11.3 ND (< 13)16.6 1.97
AW-6B 16.9 ND (< 13)16.5 0.154
SMW-6D 67.6 ND (< 13)33.9 3.49
SMW-6B 22.5 ND (< 13)29.8 0.872
All results reflect the applied dilution and are reported in µg/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
Brooks Rand Labs, LLC
Speciation Results for Duke Energy
Project Name: Duke Energy/Sutton Plant
Contact: Peggy Kendall
LIMS# J15060246
Date: June 30, 2015
Report Generated by: Jeremy Maute
Page 26 of 40
Quality Control Summary - Preparation Blank Summary (1)
Analyte (µg/L)PBW1 PBW2 PBW3 PBW4 Mean StdDev eMDL*eMDL 5x RL 5x eMDL 50x RL 50x
Cr(VI)0.014 0.004 0.011 0.008 0.009 0.004 0.001 0.007 0.050 --
Se(IV)0.000 0.000 0.000 0.000 0.000 0.000 0.002 --0.080 0.50
Se(VI)0.000 0.000 0.000 0.000 0.000 0.000 0.001 --0.065 0.50
SeCN 0.000 0.000 0.000 0.000 0.000 0.000 0.002 --0.098 0.46
MeSe(IV)0.000 0.000 0.000 0.000 0.000 0.000 0.002 --0.081 0.49
SeMe 0.000 0.000 0.000 0.000 0.000 0.000 0.002 --0.081 0.49
eMDL = Estimated Method Detection Limit; RL = Reporting Limit
*Please see narrative regarding eMDL calculations
Quality Control Summary - Preparation Blank Summary (2)
Analyte (µg/L)Batch ID PBW1 PBW2 PBW3 PBW4 Mean StdDev eMDL*eMDL 10x RL 10x
As(III)As01616 0.000 0.000 0.000 0.000 0.000 0.000 0.002 0.025 0.20
As(V)As01616 0.00 0.00 0.00 0.00 0.00 0.00 0.005 0.047 0.20
MMAs As01616 0.000 0.000 0.000 0.000 0.000 0.000 0.004 0.042 0.20
DMAs As01616 0.000 0.000 0.000 0.000 0.000 0.000 0.005 0.053 0.21
As(III)As00626 0.000 0.000 0.000 0.000 0.000 0.000 0.005 0.049 0.20
As(V)As00626 0.000 0.000 0.000 0.000 0.000 0.000 0.003 0.028 0.20
MMAs As00626 0.000 0.000 0.000 0.000 0.000 0.000 0.005 0.053 0.20
DMAs As00626 0.000 0.000 0.000 0.000 0.000 0.000 0.008 0.083 0.21
eMDL = Estimated Method Detection Limit; RL = Reporting Limit
*Please see narrative regarding eMDL calculations
Brooks Rand Labs, LLC
Speciation Results for Duke Energy
Project Name: Duke Energy/Sutton Plant
Contact: Peggy Kendall
LIMS# J15060246
Date: June 30, 2015
Report Generated by: Jeremy Maute
Page 27 of 40
Quality Control Summary - Preparation Blank Summary (3)
Analyte (µg/L)PBW1*PBW2*PBW3*PBW4*Mean StdDev eMDL*eMDL 2x RL 2x eMDL 10x RL 10x
Fe(II)0.0 -2.8 -2.8 -2.8 -2.1 1.4 4.2 8.4 40 42 200
Total Fe 0.0 0.0 0.0 0.0 0.0 0.0 6.7 13 40 67 200
eMDL = Estimated Method Detection Limit; RL = Reporting Limit
*Please see narrative regarding eMDL calculations
Quality Control Summary - Preparation Blank Summary (3)
Analyte (µg/L)PBW1 PBW2 PBW3 PBW4 Mean StdDev eMDL*eMDL 10x RL 10x eMDL 25x RL 25x
Mn (II)-0.59 -0.74 -0.15 -0.88 -0.49 0.32 0.086 0.86 5.0 --
Total Mn -0.183 -0.227 -0.171 -0.201 -0.194 0.024 0.003 --0.072 1.0
Diss Mn -0.095 -0.114 -0.086 **-0.098 0.014 0.002 --0.043 1.0
eMDL = Estimated Method Detection Limit; RL = Reporting Limit
*Please see narrative regarding eMDL calculations
**Preparation blank is a statistical outlier according to the Grubb's Test. Please see narrative.
Speciation Results for Duke Energy
Brooks Rand Labs, LLC
Project Name: Duke Energy/Sutton Plant
Contact: Peggy Kendall
LIMS# J15060246
Date: June 30, 2015
Report Generated by: Jeremy Maute
Page 28 of 40
Quality Control Summary - Certified Reference Materials (1)
Analyte (µg/L)CRM True Value Result Recovery
Cr(VI)LCS 2.002 1.781 89.0
Se(IV)LCS 10.00 10.03 100.3
Se(VI)LCS 10.00 10.32 103.2
SeCN LCS 8.92 8.821 98.9
MeSe(IV)LCS 6.47 6.709 103.7
SeMe LCS 9.32 9.547 102.4
Quality Control Summary - Certified Reference Materials (2)
Analyte (µg/L)Batch ID CRM True Value Result Recovery
As(III)As01616 LCS 5.00 5.143 102.9
As(V)As01616 LCS 5.00 4.983 99.7
MMAs As01616 LCS 5.07 5.668 111.7
DMAs As01616 LCS 3.63 3.504 96.7
As(III)As00626 LCS 5.00 5.043 100.9
As(V)As00626 LCS 5.00 4.581 91.6
MMAs As00626 LCS 5.07 5.732 113.0
DMAs As00626 LCS 3.63 3.509 96.8
Speciation Results for Duke Energy
Project Name: Duke Energy/Sutton Plant
Contact: Peggy Kendall
LIMS# J15060246
Date: June 30, 2015
Report Generated by: Jeremy Maute
Brooks Rand Labs, LLC
Page 29 of 40
Quality Control Summary - Certified Reference Materials (3)
Analyte (µg/L)CRM True Value Result Recovery
Fe(II)ICV 500.0 481.3 96.3
Total Fe LCS 500.0 499.5 99.9
Mn (II)LCS 1.00 1.053 105.3
Total Mn TMDA-70.2 312 301.3 96.6
Diss Mn TMDA-70.2 312 305.8 98.0
Report Generated by: Jeremy Maute
Brooks Rand Labs, LLC
Speciation Results for Duke Energy
Project Name: Duke Energy/Sutton Plant
Contact: Peggy Kendall
LIMS# J15060246
Date: June 30, 2015
Page 30 of 40
Quality Control Summary - Matrix Duplicates (1)
Analyte (µg/L)Sample ID Rep 1 Rep 2 Mean RPD
Cr(VI)SMW-6B 0.022 0.018 0.020 20.1
Se(IV)Batch QC ND (< 0.080)ND (< 0.080)NC NC
Se(VI)Batch QC ND (< 0.065)ND (< 0.065)NC NC
SeCN Batch QC ND (< 0.098)ND (< 0.098)NC NC
MeSe(IV)Batch QC ND (< 0.081)ND (< 0.081)NC NC
SeMe Batch QC ND (< 0.081)ND (< 0.081)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 Duplicates (2)
Analyte (µg/L)Batch ID Sample ID Rep 1 Rep 2 Mean RPD
As(III)As01616 SMW-6B ND (< 0.025)ND (< 0.025)NC NC
As(V)As01616 SMW-6B ND (< 0.047)ND (< 0.047)NC NC
MMAs As01616 SMW-6B ND (< 0.042)ND (< 0.042)NC NC
DMAs As01616 SMW-6B ND (< 0.053)ND (< 0.053)NC NC
As(III)As00626 Batch QC 0.352 0.411 0.382 15.6
As(V)As00626 Batch QC 0.116 0.123 0.120 6.0
MMAs As00626 Batch QC ND (< 0.053)ND (< 0.053)NC NC
DMAs As00626 Batch QC ND (< 0.083)ND (< 0.083)NC NC
ND = Not detected at the applied dilution
NC = Value was not calculated due to one or more concentrations below the eMDL
Speciation Results for Duke Energy
Project Name: Duke Energy/Sutton Plant
Contact: Peggy Kendall
LIMS# J15060246
Date: June 30, 2015
Report Generated by: Jeremy Maute
Brooks Rand Labs, LLC
Page 31 of 40
Quality Control Summary - Matrix Duplicates (3)
Analyte (µg/L)Sample ID Rep 1 Rep 2 Mean RPD
Fe(II)MW23B ND (< 8.4)ND (< 8.4)NC NC
Total Fe MW23B 18 18 18 0.0
Mn (II)AW-5E 5.29 5.44 5.37 2.8
Total Mn Batch QC 72.97 72.14 72.55 1.1
Diss Mn Batch QC 69.47 71.97 70.72 3.5
ND = Not detected at the applied dilution
NC = Value was not calculated due to one or more concentrations below the eMDL
Report Generated by: Jeremy Maute
Brooks Rand Labs, LLC
Speciation Results for Duke Energy
Project Name: Duke Energy/Sutton Plant
Contact: Peggy Kendall
LIMS# J15060246
Date: June 30, 2015
Page 32 of 40
Quality Control Summary - Matrix Spike/ Matrix Spike Duplicate (1)
Analyte (µg/L)Sample ID Spike Conc MS Result Recovery Spike Conc MSD Result Recovery RPD
Cr(VI)SMW-6B 5.000 4.870 97.0 5.000 4.831 96.2 0.8
Se(IV)Batch QC 251.0 263.3 104.9 251.0 265.6 105.8 0.9
Se(VI)Batch QC 250.0 260.7 104.3 250.0 260.8 104.3 0.1
SeCN Batch QC 228.8 236.1 103.2 228.8 236.8 103.5 0.3
Quality Control Summary - Matrix Spike/ Matrix Spike Duplicate (2)
Analyte (µg/L)Batch ID Sample ID Spike Conc MS Result Recovery Spike Conc
MSD
Result Recovery RPD
As(III)As01616 SMW-6B 20.00 17.60 88.0 20.00 17.93 89.6 1.8
As(V)As01616 SMW-6B 20.00 17.42 87.1 20.00 17.86 89.3 2.5
DMAs As01616 SMW-6B 20.98 18.30 87.2 20.98 18.28 87.1 0.1
As(III)As00626 Batch QC 20.00 19.31 94.6 20.00 19.69 96.6 2.0
As(V)As00626 Batch QC 20.00 18.97 94.3 20.00 19.37 96.2 2.1
DMAs As00626 Batch QC 20.98 19.33 92.1 20.98 19.40 92.4 0.4
Quality Control Summary - Matrix Spike/ Matrix Spike Duplicate (3)
Analyte (µg/L)Sample ID Spike Conc MS Result Recovery Spike Conc MSD Result Recovery RPD
Fe(II)MW23B 1000 1250 125.0 1000 1255 125.5*0.4
Total Fe MW23B 1000 1031 101.3 1000 1036 101.7 0.4
Mn (II)AW-5E 50.00 61.26 111.8 50.00 62.02 113.3 1.2
Total Mn Batch QC 1000 1049 97.6 1000 1019 94.7 2.9
Diss Mn Batch QC 1000 1060 98.9 1000 1056 98.5 0.4
*Spike recovery is greater than the upper control limit of 125%. Please see narrative.
Speciation Results for Duke Energy
Project Name: Duke Energy/Sutton Plant
Contact: Peggy Kendall
LIMS# J15060246
Date: June 30, 2015
Report Generated by: Jeremy Maute
Brooks Rand Labs, LLC
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