EPA/600/R-14/052
December 2013
Environmental Technology
Verification Report
ANDALYZE LEAD 100 TEST KIT AND
AND1000 FLUORIMETER
Prepared by
Baiieiie
The Business of Innovation
Under a cooperative agreement with
^kif ClTr\ U.S. Environmental Protection Agency
ET1/ET1/ET1/
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December 2013
Environmental Technology Verification
Report
ETV Advanced Monitoring Systems Center
ANDALYZE LEAD 100 TEST KIT AND AND1000
FLUORIMETER
by
Brian Yates and Amy Dindal, Battelle
John McKernan and Doug Grosse, U.S. EPA
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Notice
The U.S. Environmental Protection Agency, through its Office of Research and Development,
partially funded and collaborated in the research described herein. This report has been
subjected to the Agency 'speer and administrative review. Any opinions expressed in this report
are those of the author (s) and do not necessarily reflect the views of the Agency, therefore, no
official endorsement should be inferred. Any mention of trade names or commercial products
does not constitute endorsement or recommendation for use.
11
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Foreword
The U.S. Environmental Protection Agency (EPA) is charged by Congress with protecting the
nation's air, water, and land resources. Under a mandate of national environmental laws, the
Agency strives to formulate and implement actions leading to a compatible balance between
human activities and the ability of natural systems to support and nurture life. To meet this
mandate, the EPA's Office of Research and Development provides data and science support that
can be used to solve environmental problems and build the scientific knowledge base needed to
manage our ecological resources wisely, understand how pollutants affect our health, and prevent
or reduce environmental risks.
The Environmental Technology Verification (ETV) Program has been established by the EPA to
verify the performance characteristics of innovative environmental technology across all media
and report this objective information to permitters, buyers, and users of the technology, thus
substantially accelerating the entrance of new environmental technologies into the marketplace.
Verification organizations oversee and report verification activities based on testing and quality
assurance protocols developed with input from major stakeholders and customer groups
associated with the technology area. ETV consists of six environmental technology centers.
Information about each of these centers can be found on the Internet at http://www.epa.gov/etv/.
Effective verifications of monitoring technologies are needed to assess environmental quality
and to supply cost and performance data to select the most appropriate technology for that
assessment. Under a cooperative agreement, Battelle has received EPA funding to plan,
coordinate, and conduct such verification tests for "Advanced Monitoring Systems for Air,
Water, and Soil" and report the results to the community at large. Information concerning this
specific environmental technology area can be found on the Internet at
http ://www. epa.gov/etv/centers/centerl .html.
in
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Acknowledgments
The authors wish to acknowledge the contribution of the many individuals without whom this
verification testing would not have been possible. Quality assurance (QA) oversight was
provided by Holly Ferguson, EPA, and Rosanna Buhl and Betsy Cutie, Battelle. We gratefully
appreciate the accommodation of DHL Analytical, Inc. Finally, we want to thank Randy Gottler
of the City of Phoenix and John Consolvo of the Philadelphia Water Department for their review
of the Quality Assurance Project Plan (QAPP) and this verification report.
IV
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Contents
Page
Notice ii
Foreword iii
Acknowledgments iv
List of Abbreviations viii
Chapter 1 Background 1
Chapter 2 Technology Description 2
Chapters Test Design and Procedures 4
3.1 Test Overview 4
3.2 Test Site Description 7
3.2.1 Battelle Headquarters and Environmental Treatability Laboratory 8
3.2.2 Well Water 8
3.2.3 SciotoRiver 8
3.2.4 Griggs Reservoir 8
3.2.5 West Palm Beach, FL 9
3.2.6 Southerly Wastewater Treatment Plant 9
3.2.7 Jackson Pike Wastewater Treatment Plant 9
3.2.8 Metal Finishing Plant 9
3.3 Experimental Design 9
3.3.1 Performance Testing 11
3.3.2 Analysis of Finished Drinking Water Samples 13
3.3.3 Analysis of Environmental Water Samples 13
3.3.4 Analysis of Wastewater Effluent Samples 14
3.4 Experimental Procedures 18
3.4.1 General Procedures and Reference analysis 18
3.4.2 IDC Testing 19
3.4.3 TPC Testing 19
3.4.4 ICC Testing 19
3.4.5 DLOD Testing 19
3.4.6 DLR Testing 20
3.4.7 DEI Testing 20
3.4.8 Finished Drinking Water Testing 21
3.4.9 Environmental Water Testing 22
3.4.10 Wastewater Effluent Testing 23
3.5 Operational Factors 25
Chapter 4 Quality Assurance/Quality Control 26
4.1 Data Collection Quality Control 26
4.1.1 Quality Control Overview 26
4.1.2 Acceptance Criteria and Root Cause Analysis 27
4.1.3 Control Charts 28
4.1.4 Equipment Test, Inspection, and Maintenance 29
4.1.5 Calibration and Verification of Test Procedures 29
4.1.6 Inspection and Acceptance of Supplies and Consumables 29
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4.1.7 Data Management 30
4.2 Audits 31
4.2.1 Performance Evaluation Audit 31
4.2.2 Technical Systems Audit 31
4.2.3 Data Quality Audit 32
4.3 Quality Assurance/Quality Control Deviations 32
Chapters Statistical Methods 34
5.1 Accuracy 34
5.2 Precision 35
5.3 Linearity of Response 35
5.4 Limit of Detection 36
5.5 Operational Factors 36
Chapter 6 Test Results 37
6.1 Accuracy 37
6.1.1 Percent Recovery 37
6.2 Precision 43
6.3 Linearity of Response 44
6.4 Limit of Detect!on 45
6.5 Qualitative Results 46
6.6 Operational Factors 46
Chapter 7 Performance Summary for the Lead 1007AND 1000 47
7.1 Performance Summary for the Lead 1007AND 1000 47
Chapter 8 References 49
Appendices
Summary of Deviations from the QAPP
QAPP Document Replacement Appendices (C and D) and Additional
Appendices (I and J)
Round 1 Testing Results
Round 1 Control Charts
Round 2 Testing Results
Round 2 Control Charts
APPENDIX A:
APPENDIX B:
APPENDIX C:
APPENDIX D:
APPENDIX E:
APPENDIX F:
APPENDIX G: Temperature and Barometric Pressure Data
VI
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Tables
Table 1. Summary of Verification Tests and Performance Parameters 7
Table 2. DEI Water Sample Composition 12
Table 3. Overview of the Tests Performed for this Verification 15
Table 4. Experimental Test Matrix^ 17
Table 5. Consumables Used for Verification Testing 30
Table 6. Percent Recovery for IDC and ICC 38
Table 7. Percent Recovery for DLOD and DLR 39
Table 8. Percent Recovery for DEI 40
Table 9. Percent Recovery for Environmental Water 41
Table 10. Percent Recovery for Finished Drinking Water 42
Table 11. Percent Recovery for Wastewater Effluent 43
Table 12. Precision of Samples Analyzed in Triplicate 44
Table 13. Results ofDLOD Testing 45
Table 14. Precision of Seawater Testing 46
Figures
Figure 1. ANDalyze AND 1000 2
Figure 2. ANDalyze Lead 100 3
Figure 3. Site Map Showing the Locations of River Water, Reservoir Water, Municipal
Wastewater Effluent #1, and Municipal Wastewater Effluent #2 10
Figure 4. Site Map Showing the Location of the Seawater Sample 11
Figure 5. Observations from DLR Sample Testing versus Reference Concentrations 45
vn
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List of Abbreviations
ADQ Audit of Data Quality
AMS Advanced Monitoring Systems
BW bottled water
CFR Code of Federal Regulations
CV coefficient of variation
DEI determination of the effects of interferences
DI deionized
DLOD determination of the limit of detection
DLR determination of linear range
DQO data quality objective
EPA Environmental Protection Agency
ETL Environmental Treatability Laboratory
ETV Environmental Technology Verification
FCU failure cause unknown
Fe iron
FWW finished well water
FIDPE high density polyethylene
viii
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HFe
HTDS
ICC
ICP-MS
IDC
IFE
IFM
IOFM
LFM
LFMD
LOD
LRB
LTDS
MFWWE
MOD
MWWE
Pb
high iron
high total dissolved solid
Initial Calibration Check
inductively-coupled plasma mass spectroscopy
initial demonstration of capability
instrument failure electrical
instrument failure mechanical
instrument operator failure to follow method
laboratory-fortified matrix
laboratory-fortified matrix duplicate
limit of detection
laboratory record book
low total dissolved solid
metal finishing wastewater effluent
million gallons per day
municipal wastewater effluent
lead
IX
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PEA performance evaluation audit
ppb parts per billion
PT performance testing
QA quality assurance
QAPP quality assurance project plan
QC quality control
QCS quality control standard
QM Quality Manager
QMP Quality Management Plan
KB reagent blank
RCA root cause analysis
ReW reservoir water
RiW river water
RMO Records Management Office
RPD relative percent difference
RWW raw well water
SD standard deviation
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SFC sensor failure chemical
SFM sensor failure mechanical
SOP standard operating procedure
SW seawater
IDS total dissolved solid
TPC three point calibration
TSA technical systems audit
VTC Verification Test Coordinator
WF water fountain
XI
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Chapter 1
Background
EPA supports the ETV Program to facilitate the deployment of innovative environmental
technologies through performance verification and dissemination of information. The goal of the
ETV Program is to further environmental protection by accelerating the acceptance and use of
improved and cost-effective technologies. ETV seeks to achieve this goal by providing high-
quality, peer-reviewed data on technology performance to those involved in the design,
distribution, financing, permitting, purchase, and use of environmental technologies.
ETV works in partnership with recognized testing organizations; with stakeholder groups
consisting of buyers, vendor organizations, and permitters; and with the full participation of
individual technology developers. The program evaluates the performance of innovative
technologies by developing test plans that are responsive to the needs of stakeholders,
conducting field or laboratory bench tests (as appropriate), collecting and analyzing data, and
preparing peer-reviewed reports. All evaluations are conducted in accordance with rigorous QA
protocols to ensure that data of known and adequate quality are generated and that the results are
defensible. The definition of ETV is to establish or prove the truth of the performance of a
technology under specific, pre-determined criteria or protocols and a strong quality management
system. High-quality data are assured through implementation of the ETV Quality Management
Plan (QMP). ETV does not endorse, certify, or approve technologies.
EPA's National Risk Management Research Laboratory and its verification organization partner,
Battelle, operate the Advanced Monitoring Systems (AMS) Center under ETV. The AMS
Center recently evaluated the performance of the combined ANDalyze lead (Pb) detection
technologies: AND 1000 handheld fluorimeter and accompanying Lead 100 consumable test kit
(Lead 100/AND1000).
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Chapter 2
Technology Description
This report provides results for the verification testing of the Lead 100/AND 1000. The following
is a description of the technology based on information provided by the vendor. The information
provided below was not verified in this test.
The ANDalyze Lead 100/AND 1000 was designed to detect the presence of and measure the
concentration of Pb in drinking water and environmental waters. Testing is intended to take
place onsite at the source of collection or in a temperature controlled facility without sample
preservation. The test makes use of two primary components: a handheld fluorimeter
(AND 1000) and a consumable test kit (Lead 100) specific to each metal or target (in the present
case, Pb).
Figure 1. ANDalyze AND1000
Figure 1 presents a picture of the ANDalyze AND 1000 fluorimeter. The AND 1000 fluorimeter
is specifically designed to provide an interactive experience and allow testing, data storage, and
signal output without the use of a separate computational device. The fluorimeter has the
capability to analyze multiple targets with the appropriate test kit, though the sole target
discussed in this method is aqueous Pb in drinking water, wastewater effluent, and
environmental waters. The AND 1000 fluorimeter enables field testing to be performed in two
steps. ANDalyze's catalytic DNA sensors use a metal-specific DNAzyme reaction that leads to
an increase in fluorescence in the presence of a target contaminant substance (i.e., aqueous Pb).
The fluorescence of the reaction is measured by a fluorimeter to determine the concentration of
the target heavy metal and is reported in parts per billion (ppb). The product is a quantitative test
that is intended to detect metals in a linear range of 2 to 100 ppb at and below EPA standards
for drinking water. The test is performed by injecting a buffered 1 mL water sample through the
sensor and into the AND 1000 fluorimeter. This sample is then automatically analyzed and
results are reported in less than 2 minutes.
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The second component is the LeadlOO test kit which is specific to Pb. The test kit provides all
necessary materials for in-field instrument calibration and sample testing. This kit contains the
DNA sensors specific to the given analyte. The kit is color coded to facilitate use and avoid
measurement error. In addition, a product manual is provided with step-by-step instructions
including photographs. It should be noted that laboratory evaluation may require additional
supplies and standard laboratory glassware. Figure 2 presents a picture of the ANDalyze
LeadlOO disposable test kit.
The total cost of the ANDalyze AND 1000 fluorimeter used for testing was $3,000. The
AND 1000 fluorimeter package includes the fluorimeter, USB to MINI-B cable, 100 uL fixed
volume pipette and tips, and pH test strips. The cost of each LeadlOO disposable test kit used for
testing was $15. Each kit includes 25 tests and/or calibrations, 25 sensor bags with sensor and
cuvette, 25 sample tubes (with buffer), 25 1 mL syringes, 25 disposable transfer pipettes, 8 mL
analyte standard solution, instruction manuals, and material safety data sheets.
Figure 2. ANDalyze LeadlOO
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Chapter 3
Test Design and Procedures
3.1 Test Overview
This verification test was conducted according to procedures specified in the QAPP,1 including
deviations as described in Appendix A, and adhered to the quality system defined in the ETV
AMS Center QMP2. A technical panel of stakeholders was specifically assembled for the
preparation of the QAPP. A list of participants in the technical panel is presented in the QAPP.
The panel included representatives from industry associations, as well as local and federal
governments. The responsibilities of verification test stakeholders and/or peer reviewers
included:
Participate in technical discussions to provide input to the test design;
Review and provide input to the QAPP; and
Review and provide input to the verification report/verification statement.
The QAPP and this verification report were reviewed by experts in the fields related to
contaminant detection in aqueous media and statistics. The following experts provided peer
review:
Randy Gottler, City of Phoenix, Arizona
Julius Enriquez, EPA
Edward Askew, Askew Scientific Consulting
Battelle conducted this verification test with funding support from the technology vendor, and
analytical support from DHL Analytical, Inc.
This verification test assessed the performance of the Lead 100/AND 1000 relative to key
verification parameters including accuracy, precision, sample throughput, and ease of use. These
performance parameters were evaluated using multiple variables that challenged the
Lead 100/AND 1000's ability to detect Pb in a variety of aqueous matrices. The
Lead 1007AND 1000 technology evaluation was organized as four main tests. Each test evaluated
the performance of Lead 1007AND 1000 operating under different laboratory and field conditions.
The four tests were:
1. Initial demonstration of capability (IDC) and performance testing (PT) including
determination of the limit of detection (DLOD), determination of linear range (DLR), and
determination of the effects of interferences (DEI)
2. Testing accuracy and precision of the instrument for the analysis of finished drinking
water samples (bottled water, municipal drinking water, treated groundwater)
3. Testing accuracy and precision of the instrument for the analysis of environmental water
samples (surface water, groundwater and seawater)
4. Testing accuracy and precision of the instrument for the analysis of wastewater effluent
samples (municipal wastewater effluent, metal finishing wastewater effluent)
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ANDalyze, Inc. chose to have its technologies tested as described in the QAPP for Pb detection
in aqueous media. The verification testing was conducted in the field and at the Environmental
Treatability Laboratory (ETL) at Battelle's Main Campus in Columbus, OH between July 10 and
July 27, 2012 (Round 1) and between February 11 and March 13, 2013 (Round 2). The
technology was challenged with aqueous samples from a wide range of sources spiked with
different Pb concentrations. The resulting observations were used to calculate the accuracy,
precision, limit of detection, linear range, and determination of interferences, where appropriate.
Operational factors such as maintenance needs, data output, ease of use, and repair requirements
were also assessed based on technical staff observations. These performance parameters were
evaluated quantitatively using the statistical methods described in Chapter 5 of this document
and qualitatively through recorded observations. All tests were performed with the
Lead 100/AND 1000 operating according to the vendor's recommended procedures as described
in the user's manuals and during training provided to the operator. Select sections of the user
manuals were updated after Round 1 testing to clarify sample preparation procedures for specific
samples. All samples analyzed with the Lead 1007AND 1000 were also collected, stored,
transferred, and analyzed in a certified laboratory using industry accepted analytical methods.
Select aspects of certain analytical methods were modified after Round 1 testing as per vendor
recommendations and requests. Results from the technologies being verified were recorded in
laboratory record books (LRBs) and transferred to an appropriate electronic format (i.e.,
Microsoftฎ Excel). Table 1 presents a summary of the tests performed as part of this
verification, and Section 3.3 presents the experimental design.
Testing was completed according to the QAPP between July 10 and July 27, 2012 as Round 1.
Review of the data and methodology revealed the need for deviations from the QAPP for a more
appropriate verification. Specifically, concern was raised regarding the effect of the sample
preparation methodology on the apparently low recoveries of lead by the certified laboratory
compared to both target and detected concentrations by the technology. Round 2 testing was
completed between February 11 and March 13, 2013 according to deviations in the QAPP
Deviation Report3 summarized in Appendix A.
The first set of tests (IDC and PT) was performed in a highly-controlled environment within
Battelle's ETL. IDC required the detection of a Pb spike (25 ppb) in reagent grade water.
DLOD was performed by measuring seven replicates of Pb spiked at 10 ppb, five times the
purported limit of detection (2 ppb). The DLR was carried out by measuring the
Lead 100/AND 1000's ability to precisely and accurately measure seven samples with Pb
concentrations of 0 ppb, 5 ppb, 15 ppb, 25 ppb, 50 ppb, 75 ppb, and 100 ppb. The samples were
analyzed in triplicate and the coefficient of determination was used to assess the linearity of the
response of the instrument within this range. Finally, DEI was determined using three synthetic
water samples with differing characteristics: low total dissolved solids concentration (LTDS),
high total dissolved solids concentration (HTDS), and high iron (Fe) concentration and other
dissolved solids (HFe). Each of these synthetic water samples was split into required 100 mL
subsamples and received a Pb spike of 25 ppb and 50 ppb before Pb was measured in triplicate
from each subsample by Lead 1007AND 1000. Normal sample preparation procedures were
followed for the LTDS and HTDS water, and a special sample preparation procedure for the
removal of Fe interference was used to prepare the HFe sample for Pb analysis.
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The next set of tests determined the accuracy and precision of the Lead 100/AND1000 in
recovery of Pb spikes in finished drinking water. Three sets of samples were prepared with Pb
spikes of 25 ppb: finished drinking water samples collected from a water fountain (WF), bottled
mineral water purchased from a local supermarket (Bottled Water [BW]), and finished drinking
water collected from the effluent of a local water treatment facility treating groundwater
(Finished Well Water [FWW]). All samples were freshly collected during both Round 1 and
Round 2 testing, as agreed upon by the vendor. All waters were analyzed without a Pb spike and
in triplicate with a Pb spike of 25 ppb.
The third series of tests aimed at determining the accuracy and precision of the
Lead 100/AND 1000 in recovering Pb spikes in environmental water samples. The environmental
water samples for this study included samples collected from both freshwater and saltwater
sources. Three freshwater sources were sampled including water collected from the reach of a
freshwater river just outside and upstream of Columbus, OH (River Water [RiW]), samples
collected from a freshwater reservoir near the same location (Reservoir Water [ReW]), and raw
groundwater collected at the source of a drinking water treatment facility just outside Plain City,
OH (Raw Well Water [RWW]), which was collected from the source that feeds the facility from
which the Finished Well Water was collected. In addition, one seawater sample was collected in
West Palm Beach, FL (Seawater [SW]) to determine the accuracy and precision of the
Lead 100/AND 1000 in testing natural waters with high salinity. All samples were collected fresh
for both rounds of testing except for Seawater, which was collected during Round 1 testing and
retained in proper storage conditions for Round 2 testing as agreed upon by the vendor. All four
environmental samples were analyzed with no spike and in triplicate after the addition of a Pb
spike to 25 ppb. Performance of tests on Seawater differ from the performance of tests on
freshwater in that seawater was diluted tenfold before being subjected to Lead 100/AND 1000
testing and results are analyzed qualitatively, not quantitatively as with freshwater samples.
The final series of tests aimed at determining the accuracy and precision of the
Lead 100/AND 1000 in recovering Pb spikes in wastewater effluent samples. Three samples were
analyzed during this series of tests: two effluent samples collected from two separate traditional
activated sludge treatment facilities treating domestic wastewater in Columbus, OH (Municipal
Wastewater Effluent [MWWE] #1 and Municipal Wastewater Effluent #2) and a sample
collected from the effluent of a metal finishing works (Metal Finishing Wastewater Effluent
[MFWWE]). The Metal Finishing Wastewater Effluent was collected from a facility conforming
to 40 CFR 433 and/or 40 CFR 413 after all on-site pretreatment. All samples were freshly
collected during both Round 1 and Round 2 testing, except for Metal Finishing Wastewater
Effluent, which was collected during Round 1 testing and retained in proper storage conditions
for Round 2 testing, as agreed upon by the vendor.
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Table 1. Summary of Verification Tests and Performance Parameters
Test
la: Initial
Demonstration of
Capability
Ib: Three Point
Calibration
Ic: Initial Calibration
Check
Id: Determination of
Limit of Detection
le: Determination of
Linear Range
If: Determination of
Effects of
Interferences
2: Finished Drinking
Water Samples
3: Environmental
Water Samples
4: Wastewater
Effluent Samples
Test Description
Analysis of reagent grade deionized
(DI) water spiked with Pb
Analysis of three reagent grade
water samples spiked with Pb as
part of a three point calibration
Analysis of reagent grade DI water
spiked with Pb
Analysis of reagent grade DI water
spiked with Pb concentration 5
times the vendor estimated
detection limit repeated 7 times
Analysis of reagent grade DI water
spiked with Pb in 6 concentrations
within vendor-estimated detection
limits (0-100 ppb), each in triplicate
Analysis of laboratory prepared
samples of LTDS, HTDS, and HFe
water, each spiked with Pb at two
different concentrations measured
in triplicate
Analysis of Water Fountain,
Bottled, and Finished Well Water
spiked with Pb, each in triplicate
Analysis of Raw Well, River, and
Reservoir Water spiked with Pb,
and Seawater spiked with two
concentrations of Pb, each in
triplicate
Analysis of Wastewater Effluent 1,
Wastewater Effluent 2, and Metal
Finishing Wastewater Effluent
spiked with Pb, each in triplicate
Performance
Parameter
Accuracy
Precision
Operational
factors
Accuracy
Precision
Operational
factors
Accuracy
Precision
Operational
factors
Limit of
Detection
Accuracy
Precision
Operational
factors
Linearity of
Response
Accuracy
Precision
Operational
factors
Accuracy
Precision
Operational
factors
Accuracy
Precision
Operational
factors
Accuracy
Precision
Operational
factors
Accuracy
Precision
Operational
factors
Independent Variables
Pb concentration
Pb concentration
Pb concentration
Pb concentration
Pb concentration
Pb concentration
Water quality
parameters
Pb concentration
Drinking water source
Pb concentration
Environmental water
source
Pb concentration
Wastewater effluent
source
3.2 Test Site Description
PT (including DLOD, DLR, and DEI) was completed at Battelle's ETL according to the QAPP
and QAPP Deviation Report. Finished drinking water was collected from three different
sources: a WF located within Battelle headquarters in Columbus, OH; bottled water available
from a local supermarket, in Columbus, OH; and finished well water from a small water
treatment facility located outside in Plain City, OH. Environmental samples were collected from
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four different sources: river water was collected from the Scioto River in Columbus, OH;
reservoir water was collected from Griggs Reservoir in Columbus, OH; raw well water was
collected from a well located outside Plain City, OH; and seawater was collected from the
Atlantic Ocean off West Palm Beach, FL. Wastewater effluent was collected from three sources:
Southerly Wastewater Treatment Plant in Columbus, OH; Jackson Pike Wastewater Treatment
Plant in Columbus, OH; and a metal finishing plant. Detailed descriptions of the research test
site and equipment items are provided below.
3.2.1 Battelle Headquarters and Environmental Treatability Laboratory
The Battelle ETL is an operational environmental laboratory centrally located on the Battelle
Memorial Institute Main Campus in Columbus, OH. Battelle receives its finished drinking water
from the Dublin Road Water Purification Plant in Columbus, OH, which treats raw water from
the Scioto River within the city limits and select groundwater wells. The Battelle ETL offers
highly controlled laboratory conditions for performing testing, storage facilities for samples and
reagents, access to calibrated standard laboratory equipment (scales, pipettes, volumetric flasks,
etc.), production of DI water, and established laboratory protocols for the acquisition of reagents
and disposal of performance testing waste.
3.2.2 Well Water
Raw and finished well water was collected from a small water treatment facility located in Plain
City, OH. The treatment system operating is an on-demand coagulation/filtration system treating
approximately 10 gallons per minute.
3.2.3 Scioto River
River water was collected from the east bank of the Scioto River in Columbus, OH, no more than
5 miles north of Griggs Reservoir as indicated on Figure 3. The Scioto River is one of the
longest rivers in Ohio as it runs over 230 miles from Auglaize County, in the western part of the
state, through Columbus to Portsmouth where it empties into the Ohio River. Two dams have
been built on the Scioto River, both in Columbus, for drinking water and recreation purposes4.
River water was collected from the surface of the river no more than 1 ft below the water surface
and no more than 20 ft from the eastern shoreline.
3.2.4 Griggs Reservoir
Griggs Dam was the first dam to be built on the Scioto River in Columbus, Ohio in 1908, which
forms the Griggs Reservoir. Griggs Reservoir is a long, narrow body of water at almost 6 miles
long and 500 feet wide with a 1.2 million gallon capacity. The Reservoir is a major drinking
water source for Columbus. Reservoir water was sampled from within the boundaries of Griggs
Reservoir, and, identically to River Water, it was sampled from the surface, no more than 1 ft
below the water surface and no more than 20 ft from the eastern shore of the reservoir, as
indicated on Figure 3.
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3.2.5 West Palm Beach, FL
Seawater was collected from the Atlantic Ocean off West Palm Beach, FL as indicated on Figure
4. Seawater was collected from the surface of the ocean no more than 1 ft below the water
surface and no more than 20 ft from the shoreline.
3.2.6 Southerly Wastewater Treatment Plant
The Southerly Wastewater Treatment Plant (Southerly), built in 1967, is one of two treatment
plants servicing Columbus, OH, located south of the city in Lockbourne, Ohio as indicated on
Figure 3. Southerly receives and treats influent from the northeast and eastern half of Franklin
County through a series of physical and biological processes. Southerly has the capacity to treat
114 million gallons per day (MGD) and discharges into the Scioto River.
3.2.7 Jackson Pike Wastewater Treatment Plant
The Jackson Pike Wastewater Treatment Plant (Jackson Pike), built in 1935, is the original
treatment plant servicing Columbus, OH and is located on the southern limit of the city as
indicated on Figure 3. Jackson Pike receives and treats influent from the northwestern and
western half of Franklin County through a series of physical and biological processes. Jackson
Pike has the capacity to treat 68 MGD and, like Southerly, discharges into the Scioto River.
3.2.8 Metal Finishing Plant
Metal Finishing Wastewater Effluent was collected by the vendor from an undisclosed facility
conforming to 40 CFR 433 and/or 40 CFR 413 (electroplating, electroless plating, anodizing,
coating [chromating, phospating and coloring], chemical etching and milling, and printed circuit
board manufacturing).
3.3 Experimental Design
This verification test was designed to evaluate the accuracy, precision, functionality, and ease-of-
use of the Lead 100/AND 1000 in detecting Pb in laboratory, environmental, waste, and drinking
water effluent samples including DI water with and without interfering species. The
characteristics of independent variables were selected and established during the runs to
determine the response of the dependent variables. Performance parameters were evaluated
based on the responses of the dependent variables (i.e., comparison of the Lead 100/AND 1000
performance to reference method performance) and used to characterize the Lead 100/AND 1000
performance.
Dependent Variable Responses. The Lead 100/AND 1000 was evaluated with respect to its
ability to accurately and precisely determine aqueous Pb concentrations in a variety of water
samples. Detection of aqueous Pb concentration thus represents the only quantitative dependent
variable included in the test. In addition, functionality and ease of use were evaluated on a
subjective basis.
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Figure 3. Site Map Showing the Locations of River Water, Reservoir Water, Municipal
Wastewater Effluent #1, and Municipal Wastewater Effluent #2
Independent Variable Levels. The levels of the independent variables with respect to water
samples that were tested were the following: (1) prevailing water quality characteristics dictated
by environmental conditions (e.g., pH, major anions, major cations); and/or (2) water quality
characteristics artificially imparted on synthetic environmental or laboratory samples including
synthetic matrices and Pb spikes. Additionally, other qualitative independent variables included
operator ability and prevailing field conditions.
The verification test consisted of four portions (in addition to QA testing): (1) performance
testing (including DLOD, DLR and DEI); (2) finished drinking water sample testing; (3)
environmental water sample testing; and (4) wastewater effluent water sample testing. The
verification test was conducted in phases as indicated in the QAPP Deviation Report: Phase 1
consisting of performance testing, Phase 2 consisting of finished drinking water and
environmental water sample testing, and Phase 3 consisting of wastewater effluent water sample
testing.
10
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Figure 4. Site Map Showing the Location of the Seawater Sample
The four tests are described in further detail in the following subsections. Table 4 presents an
overview of the testing matrix. Table 3 presents a complete list of water samples that were
collected for analysis.
3.3.1 Performance Testing
PT was focused on IDC and determination of the inherent features and limitations of
Lead 1007AND 1000. In addition to the IDC and three point calibration (TPC), PT tests also
included DLR, DLOD, and DEI. In all cases, the tests were designed to determine the
instrument response to a known concentration of aqueous Pb contamination in controlled
laboratory samples (both DI and DI with added interferences). Instrument accuracy, precision,
and ease of use during aqueous Pb detection in the laboratory samples were determined during
these tests. Before a new sample matrix was analyzed, the Lead 100/AND 1000 was subjected to
on-site calibration as outlined in the vendor instrument manuals. An experimental matrix for PT
is presented as Table 4.
IDC was aimed at demonstrating the technology with clean samples spiked with a known
concentration of Pb. DI was spiked with 25 ppb Pb before being analyzed with the
11
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Lead 100/AND 1000. Further, these analyses were carried out in triplicate to assess the precision
of the LeadlOO/ANDlOOO.
TPC was carried out to provide a baseline calibration in DI water. Subsequent calibrations (on-
site calibrations) augmented this TPC and corrected measurements for matrix effects. The TPC
was stored in the Lead 1007AND 1000 and was augmented each time Pb was measured in a new
matrix (on-site calibration). The TPC consisted of analyzing one sample each of DI spiked with
Pb at 25 ppb, 50 ppb, and 75 ppb. Initial calibration check (ICC) served to confirm calibration
accuracy.
DLR of the instrument was accomplished through a series of triplicate tests on DI spiked with Pb
at six different concentrations within the purported linear range of the Lead 100/AND 1000 (0 to
100 ppb). The six Pb concentrations specified for the DLR experiments were 0 ppb, 5 ppb, 15
ppb, 25 ppb, 50 ppb, 75 ppb, and 100 ppb. The accuracy and precision of the instrument as well
as the linearity of the concentration curve were the performance metrics for the DLR tests.
Limit of detection (LOD) of the Lead 1007AND 1000 has been reported by the vendor as 2 ppb Pb
and was confirmed through a series of seven replicate tests of DI samples spiked with one
concentration of Pb at five times the purported detection limit (10 ppb) in accordance with 40
Code of Federal Regulations (CFR) Part 136.
The final aspect of PT was the DEI on the instrument's ability to accurately and precisely
measure Pb in aqueous samples with added interferences. Triplicate interference tests were
carried out each on three samples of DI not only with added interferences (referred to as LTDS,
HTDS, and HFe) but also spiked with Pb in the amount of 50 ppb. The ability of the
Lead 1007AND 1000 to accurately and precisely measure Pb at the specified concentration was
the performance metric for the interference tests. The first two samples were analyzed after
pretreatment with only the vendor-recommended buffer (required for all samples), while the
third was pretreated with both the vendor-recommended buffer and a special vendor-provided
pretreatment method for the removal of effects of Fe interference. An on-site calibration was
performed separately for each of the two samples (i.e., one on-site calibration for the untreated
sample and one on-site calibration for the treated sample). A series of three measurements were
also made on the HFe with only the vendor-provided buffer to assess the utility of the additional
pretreatment method for removal of the effects of Fe interference. The specific water makeup of
the three samples is specified in Table 2.
Table 2. DEI Water Sample Composition
Constituent
NaHCO3
CaS04
MgSO4
KC1
Glucose
Fe
NaCl
LTDS (ppm)
95
50
60
4
10
NS
NS
HTDS (ppm)
380
200
240
16
100
NS
NS
High Iron Water (ppm)
NS
0.142
NS
NS
NS
1
o
6
NS - Not Spiked
12
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The tests outlined in this section do not explicitly include the QC samples required (see Chapter
4). Data collected during the PT included concentration of Pb reported by the
Lead 1007AND 1000 and the reference method and qualitative data collected regarding ease of
operation.
3.3.2 Analysis of Finished Drinking Water Samples
Analyses of finished drinking water samples were aimed at determining the accuracy and
precision of the Lead 100/AND 1000 in measuring soluble Pb in water matrices other than highly
controlled, "clean" laboratory samples, but not as complex as environmental samples. Three
samples were analyzed with no spike and in triplicate each spiked with 25 ppb Pb: WF, Bottled
Water, and Finished Well Water. In addition, Finished Well Water was not only analyzed in
triplicate at ETL with a Pb spike of 25 ppb, but also once in the field with no spike. Samples
collected from the treatment facility in Plain City, OH were transferred to the ETL and analyzed
with Lead 100/AND 1000 under highly-controlled laboratory conditions to determine the
differences between the Lead 100/AND 1000 performance in the field and in the laboratory. The
tests outlined in this section were in addition to QC samples required (see Chapter 4). Data
collected during this test included concentration of Pb reported by Lead 100/AND 1000 and the
reference method and qualitative data collected regarding ease of operation, especially
differences in ease of use between field and laboratory analyses and difficulties encountered in
field analyses.
3.3.3 Analysis of Environmental Water Samples
The analysis of environmental water samples was aimed at determining the accuracy and
precision of the Lead 100/AND 1000 in measuring soluble Pb in water matrices naturally
occurring in the environment. Three samples (River Water, Reservoir Water and Raw Well
Water) each spiked with 25 ppb Pb were analyzed in triplicate and also analyzed with no spike.
River Water was collected from a reach of the Scioto River and Reservoir Water was collected
from south of the River Water sampling location in Grigg's Reservoir (see Figure 3 for a map of
sampling locations). Both samples were collected from the shore of the water bodies (less than
20 ft from shore). The samples were collected from the surface of the water bodies (less than 1 ft
depth). The Raw Well Water was collected from the raw water intake tap at a small water
treatment facility at the Plainview Christian School located in Plain City, OH; note that this is the
same facility from which the Finished Well Water was collected. All samples were filtered with
0.20 um nylon syringe filter before analysis. The freshwater environmental samples were
analyzed in the field without a Pb spike to determine the ability of the Lead 100/AND 1000 to
detect background Pb levels in the samples. In addition to field analyses, both freshwater
environmental samples were transferred to the ETL, subsequently spiked to 25 ppb Pb and
analyzed with Lead 100/AND 1000 identically as in the field under highly-controlled laboratory
conditions to determine differences between Lead 100/AND 1000 performance in the field and in
the laboratory. The tests outlined in this section were in addition to QC samples required (see
Chapter 4). Data collected during this phase of the test included concentration of Pb reported by
Lead 100/AND1000 and the reference method and qualitative data collected regarding ease of
operationespecially differences in ease of use between field and laboratory analyses and
difficulties encountered in field analyses.
13
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In addition to the two freshwater samples, one additional sample (Seawater) was collected from a
location off West Palm Beach, FL (see Figure 4 for the Seawater sampling location). The
Seawater sample was collected in the same manner as the two freshwater samples (i.e., less than
20 ft from the shoreline and less than 1 ft depth). The Seawater sample was shipped by
overnight services to ETL where two samples were separately spiked with 25 ppb Pb and 50 ppb
Pb and analyzed by the Lead 1007AND 1000 in triplicate each to determine the accuracy of the
Lead 100/AND 1000 in recovering the Pb spike as well as the precision of the instrument. All
samples were filtered with 0.20 um nylon syringe filter before analysis. In addition to spiked
samples, Seawater was also analyzed without a Pb spike to determine the ability of the
Lead 100/AND 1000 to detect background Pb levels in the samples. Due to the high dissolved
solids anticipated in Seawater, the results of the analysis of Seawater (both spiked and unspiked)
were qualitative in nature, indicating whether the Seawater samples had low, medium or high
concentrations of Pb.
3.3.4 Analysis of Wastewater Effluent Samples
The final series of tests for the verification were the analysis of three effluent water samples
collected from wastewater treatment operations. Two samples (Municipal Wastewater Effluent
#1 and Municipal Wastewater Effluent #2) were collected from two separate domestic
wastewater treatment facilities in Columbus, OH (see Figure 3 for the locations of the treatment
facilities). Due to the nature of the Lead 100/AND 1000 and the high levels of interferences in the
municipal wastewater effluent samples, all samples were filtered with 0.20 um nylon syringe
filter and diluted ten-fold with DI water before any sample preparation (i.e., Pb spike) or
analysis. Note that dilution of Municipal Wastewater Effluent #1 raised the LOD from 2 ppb Pb
to 20 ppb Pb for these samples. After dilution, the samples were analyzed in the field without a
Pb spike. Samples were then transferred to the ETL where they were analyzed in triplicate after
spiking to 25 ppb Pb.
In addition to the two municipal wastewater effluent samples (i.e., Municipal Wastewater
Effluent #1 and Municipal Wastewater Effluent #2), one industrial wastewater effluent sample
(Metal Finishing Wastewater Effluent) was supplied by the vendor. The industrial wastewater
effluent sample was collected from a metal finishing operation conforming to 40 CFR 433 and/or
40 CFR 413. Due to the nature of the Lead 1007 AND 1000 and the anticipated high levels of
interferences in the industrial wastewater effluent samples, Metal Finishing Wastewater Effluent
was filtered with 0.20 um nylon syringe filter and diluted ten-fold with DI water before any
sample preparation (i.e., Pb spike) or analysis. Metal Finishing Effluent was collected by the
vendor after all on-site pretreatment and shipped to ETL where it was spiked with 25 ppb Pb and
analyzed by the Lead 100/AND 1000 in triplicate to determine the accuracy of the
Lead 100/AND 1000 in recovering the Pb spike as well as the precision of the instrument. One
additional aliquot of unspiked effluent from each facility was analyzed to determine the ability of
the Lead 1007AND 1000 to detect potential background Pb levels in each of the samples. Note
that dilution of the Metal Finishing Wastewater Effluent raised the limit of detection from 2 ppb
Pb to 20 ppb Pb for these samples.
14
-------
Other Monitoring Data. Other variables may influence the operability of the
Lead 1007AND 1000 and information on these other variables was collected during the tests but
not controlled. Monitoring data that were recorded included field and laboratory temperature,
field and laboratory barometric pressure, and general field conditions (e.g., inclement weather).
There were no adverse field conditions encountered during testing. Appendix G contains
barometric pressure and temperature data for Columbus, Ohio obtained from the Battelle
Weather Station at Battelle Headquarters.
Table 3. Overview of the Tests Performed for this Verification
Test
Analysis of Laboratory-
Prepared Solutions
Analysis of Finished
Drinking Water
Samples
Test Sample
DI
HTDS
LTDS
HFe
WF
Bottled Watei
Finished Well
Water
Performance Parameter
Percent recovery of 5, 15,25,
50, 75, andlOOppbPb
spikes
Standard deviation and
coefficient of variation of
triplicate analyses
Limit of detection
Linearity of response
Percent recovery of 25 and
50 ppb Pb spikes
Standard deviation and
coefficient of variation of
triplicate analyses
Percent recovery of 25 and
50 ppb Pb spikes
Standard deviation and
coefficient of variation of
triplicate analyses
Percent recovery of 25 and
50 ppb Pb spikes
Standard deviation and
coefficient of variation of
triplicate analyses
Percent recovery of 25 ppb
Pb spike
Standard deviation and
coefficient of variation of
triplicate analyses
Percent recovery of 25
ppb Pb spike
Standard deviation and
coefficient of variation of
triplicate analyses
Percent recovery of 25 ppb
Pb spike
Standard deviation and
coefficient of variation of
triplicate analyses
Independent Variables
Lead concentration
Prevailing field conditions
(e.g., temperature)
Lead concentration
Water composition
(metals and anions)
Prevailing field conditions
(e.g., temperature)
Lead concentration
Water composition
(metals and anions)
Prevailing field conditions
(e.g., temperature)
Lead concentration
Water composition
(metals and anions)
Pretreatment effectiveness
Prevailing field conditions
(e.g., temperature)
Water composition
(metals and anions)
Prevailing field conditions
(e.g., temperature)
Water composition
(metals and anions)
Prevailing field conditions
(e.g., temperature)
Water composition
(metals and anions)
Prevailing field conditions
(e.g., temperature)
# of Analyses
34 (three 5 ppb spikes;
seven 10 ppb spikes; three
15 ppb spikes; ten 25 ppb
spikes; four 50 ppb spikes;
four 75 ppb spikes; three 100
ppb spikes)
7 (three 25 ppb spikes;
three 50 ppb spikes; 1
unspiked)
7 (three 25 ppb spikes;
three 50 ppb spikes; 1
unspiked)
14 (three 25 ppb spikes;
three 50 ppb spikes; 1
unspiked; each with and
without pretreatment)
4 (three 25 ppb spikes;
1 unspiked)
4 (three 25 ppb spikes;
1 unspiked)
4 (three 25 ppb spikes; 1
without a Pb spike)
15
-------
Table 3. Overview of the Tests Performed for this Verification (Continued)
Test
Analysis of
Environmental Water
Samples
Analysis of
Wastewater Effluent
Samples
Test Sample
River Water
Reservoir
Water
Seawater(a)
Municipal
Wastewater
Effluent
#1
Municipal
Wastewater
Effluent
#2
Metal
Finishing
Wastewater
Effluent
Performance Parameter
Percent recovery of 25
ppb Pb spike
Standard deviation and
coefficient of variation of
triplicate analyses
Percent recovery of 25
ppb Pb spike
Standard deviation and
coefficient of variation of
triplicate analyses
Percent recovery of 25
ppb Pb spike
Standard deviation and
coefficient of variation of
triplicate analyses
Percent recovery of 25
ppb Pb spike
Standard deviation and
coefficient of variation of
triplicate analyses
Percent recovery of 25
ppb Pb spike
Standard deviation and
coefficient of variation of
triplicate analyses
Percent recovery of 25
ppb Pb spike
Standard deviation and
coefficient of variation of
triplicate analyses
Independent Variables
Water composition
(metals and anions)
Prevailing field conditions
(e.g., temperature)
Water composition
(metals and anions)
Prevailing field conditions
(e.g., temperature)
Water composition
(metals and anions)
Prevailing field conditions
(e.g., temperature)
Water composition
(metals and anions)
Prevailing field conditions
(e.g., temperature)
Water composition
(metals and anions)
Prevailing field conditions
(e.g., temperature)
Water composition
(metals and anions)
Prevailing field
conditions (e.g.,
temperature)
# of Analyses
4 (three 25 ppb spikes; 1
without a Pb spike)
4 (three 25 ppb spikes; 1
without a Pb spike)
7 (three 25 ppb spikes;
three 50 ppb spikes; 1
unspiked at ETL)
4 (three 25 ppb spikes; 1
without a Pb spike)
4 (three 25 ppb spikes; 1
without a Pb spike)
4 (three 25 ppb spikes;
1
unspiked at ETL)
(a) Samples were diluted tenfold before any sample preparation or analysis.
16
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Table 4. Experimental Test Matrix(a)
Phase
1
2
3
Test Name
IDC
TPC
ICC
DLOD
DLR
DEI
Finished Drinking
Water Samples
Environmental
Water Samples
Waste water
Effluent Water
Samples(d)
Sample Name
IDC-25
TPC-25
TPC-50
TPC-75
ICC-25
DLOD- 10
DLR-5
DLR- 15
DLR-25
DLR-50
DLR-75
DLR- 100
HTDS-0
HTDS-25
HTDS-50
LTDS-0
LTDS-25
LTDS-50
HFe-0
HFe-25
HFe-50
WF-0
WF-25
BW-0
BW-25
FWW-0
FWW-25
RWW-0
RWW-25
ReW-0
ReW-25
RiW-0
RiW-25
SW-0
SW-25
SW-50
MWWE#1-0
MWWE#l-25
MWWE#2-0
MWWE#2-25
MFWWE-0
MFWWE-25
Matrix
DI
DI
DI
DI
DI
HTDS
LTDS
HFe
WF
Bottled Water
Finished Well
Water
Raw Well Water
Reservoir Water
River Water
Seawater
Municipal
Wastewater
Effluent #l(e)
Municipal
Wastewater
Effluent #2(f)
Metal Finishing
Wastewater
Effluent(g)
Pb Spike
(ppb)
25
25
50
75
25
10
5
15
25
50
75
100
0
25
50
0
25
50
0
25
50
0
25
0
25
0
25
0
25
0
25
0
25
0
25
50
0
25
0
25
0
25
AND1000
Analyses
3
1
1
1
3
7
3
3
3
3
3
3
1
3
3
1
3
3
2(v>
6(b)
6(b)
1
3
1
3
2(c)
3
2w
3
2w
3(c)
2(c)
3w
1
3
3
2(0
3
2(c)
3
1
3
Pb
Reference
Analyses
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
Cations,
Anions,
Alkalinity
Reference
Analyses
0
0
0
0
0
0
0
0
0
0
0
0
1
0
0
1
0
0
1
0
0
1
0
1
0
1
0
1
0
1
0
1
0
1
0
0
1
0
1
0
1
0
(a) Does not include all required QC samples. Required QC samples are discussed in Chapter 4.
(b) Three samples analyzed by LeadlOO/ANDlOOO with special pretreatment procedure for the removal of the effects
of Fe interference and three additional samples analyzed by LeadlOO/ANDlOOO without the special pretreatment
procedure.
(c) Two sets of samples analyzed by LeadlOO/ANDlOOO each in the field and at ETL.
-------
Table4. Experimental Test Matrix (Continued)
(d) All Wastewater Effluent Samples diluted 1:10 in DI water and filtered through a 0.20 |im nylon filter before addition
of Pb spike.
(e) Obtained from Jackson Pike Wastewater Treatment Plant (Columbus, OH).
(f) Obtained from Southerly Wastewater Treatment Plant (Columbus, OH).
(g) Provided by vendor from 40 CFR 433/413 facility after all on-site treatment, properly labeled and preserved sample
bottle provided by DHL Analytical and properly stored until are sent for Pb reference analysis.
3.4 Experimental Procedures
3.4.1 General Procedures and Reference analysis
The Lead 100/AND 1000 were operated exactly as specified in the vendor-provided "AND 1000
Fluorimeter for Water Testing User Manual" (AND-prod-1000-2-2012) and the "Lead Testing
and On-Site Calibration for Water Testing" (AND-Lead-100-02-2012) (see QAPP for original
documentation). In addition, environmental water testing, use of the iron interference
pretreatment and TPC was carried out as described in the appropriate solution notes (see QAPP
for original documentation).
All Lead 100/AND 1000 equipment serial numbers and chemical lot numbers were recorded in
the LRB, along with any subjective data concerning ease of use in the field compared to ETL and
general operations of the Lead 100/AND 1000 such as calibration or battery replacement.
Preparation of stock solutions was undertaken as directed by the QAPP and detailed procedures
(such as accurate component weights) were recorded in the LRB.
All samples analyzed by Lead 100/AND 1000 were also analyzed by a reference method to
determine the accuracy of the Lead 100/AND 1000 in recovering Pb spikes. Pb was measured by
inductively-coupled plasma mass spectroscopy (ICP-MS) by EPA Method 200.8 (Pb Reference
Method) with supplementary quality control (QC) requirements and procedures indicated in the
QAPP Deviation Report, summarized in Appendix A. In addition, each of the finished drinking
water, environmental water and wastewater effluent samples was analyzed once for metals and
cations by EPA Method 200.8 (Cation Reference Method), major anions by EPA Method 300.1
(Anion Reference Method), and alkalinity (including total, carbonate, bicarbonate and hydroxide
alkalinity) by Standard Method 2320B (Alkalinity Reference Method). The Cation Reference
Method reports the concentrations of the following species: aluminum, antimony, arsenic,
barium, beryllium, cadmium, chromium, cobalt, copper, lead, manganese, mercury,
molybdenum, nickel, selenium, silver, thallium, thorium, uranium, vanadium, and zinc. The
Anion Reference Method reports the concentrations of the following species: bromide, chloride,
fluoride, nitrate, nitrite, ortho-phosphate, and sulfate. All samples except Seawater were
preserved in the field as per the methods indicated and sent at 4ฑ2ฐC to DHL Analytical (Round
Rock, TX) for analysis within the hold times specified by the reference methods. The Seawater
samples were preserved in the laboratory as per the methods indicated and sent at 4ฑ2ฐC to DHL
Analytical for analysis within the hold times specified by the reference methods.
All tests were conducted in Round 1 testing according to the QAPP; issues encountered in Round
1 testing necessitated the implementation of several changes that were documented in the QAPP
Deviation Report summarized in Appendix A. The results and control charts of Round 1 testing
are presented in Appendices C and D, respectively. Round 2 testing was conducted according
18
-------
the QAPP Deviation Report and all procedures, analyses, and results discussed in this report
reflect Round 2 testing unless otherwise indicated.
3.4.2 IDC Testing
IDC testing was carried out at ETL. IDC-25 was prepared by spiking DI water to 25 ppb Pb
before it was analyzed in triplicate by the Lead 100/AND 1000 as per vendor-provided manuals
and guidance given during training. Results obtained from the Lead 100/AND 1000 analysis were
promptly recorded in the LRB. The remainder of the IDC-25 sample was filtered through a
0.20 um nylon filter into a properly labeled and preserved sample bottle provided by DHL
Analytical and stored at 4ฑ2ฐC until it was sent for Pb Reference analysis.
3.4.3 TPC Testing
TPC testing was carried out at ETL. TPC-25 was prepared by spiking DI water to 25 ppb Pb.
Similarly, TPC-50 and TPC-75 were prepared by spiking DI water to 50 ppb Pb and 75 ppb Pb,
respectively. Each of the TPC samples were analyzed once by the Lead 100/AND 1000 and
results recorded in LRB. If TPC samples had a recovery within 85 to 115 %, then a TPC was
stored in the AND 1000 and factory calibration was used for ICC, DLOD, DLR tests. If recovery
was outside this range, then TPC was not stored in AND 1000 as per vendor provided literature.
Results obtained from the Lead 100/AND 1000 analysis were promptly recorded in the LRB. The
remainder of the TPC samples was filtered through a 0.20 um nylon syringe filter into a properly
labeled and preserved sample bottles provided by DHL Analytical and properly stored until they
were sent for Pb Reference analysis.
3.4.4 ICC Testing
ICC testing was carried out at ETL. ICC-25 was prepared by spiking DI water to 25 ppb Pb
before it was analyzed in triplicate by the Lead 100/AND 1000 as per vendor-provided manuals
and guidance given during training. Results obtained from the Lead 100/AND 1000 analysis were
promptly recorded in the LRB. The remainder of the ICC-25 sample was filtered through a 0.20
um nylon syringe filter into a properly labeled and preserved sample bottle provided by DHL
Analytical and properly stored until they were sent for Pb Reference analysis.
3.4.5 DLOD Testing
DLOD testing was carried out at ETL. DLOD-10 was prepared by spiking DI water to 10 ppb
Pb before it was analyzed in septuplet by the Lead 1007AND 1000 per vendor-provided manuals
and guidance given during training. Results obtained from the Lead 100/AND 1000 analysis were
promptly recorded in the LRB. The remainder of the DLOD-10 sample was filtered through a
0.20 um nylon filter into a properly labeled and preserved sample bottle provided by DHL
Analytical and properly stored until it was sent for Pb Reference analysis. Note that the reported
LOD is applicable only for the matrix under investigation and does not necessarily apply to the
other matrices evaluated in this verification.
19
-------
3.4.6 DLR Testing
DLR testing was carried out at ETL. DLR-5 was prepared by spiking DI water to 5 ppb Pb.
Similarly, DLR-15, DLR-25, DLR-50, DLR-75, and DLR-100 were prepared by spiking DI
water to 15 ppb Pb, 25 ppb Pb, 50 ppb Pb, 75 ppb, and 100 ppb Pb, respectively. Each of the
DLR samples was analyzed in triplicate by the Lead 100/AND 1000 as per vendor-provided
manuals and guidance given during training. Results obtained from the Lead 100/AND 1000
analysis were promptly recorded in the LRB. The remainders of the DLR samples were
separately filtered through a 0.20 um nylon filter into a properly labeled and preserved sample
bottle provided by DHL Analytical and properly stored until they were sent for Pb Reference
analysis.
3.4.7 DEI Testing
DEI testing included testing the accuracy and precision of Lead 100/AND 1000 on three different
synthetic waters (HTDS, LTDS and HFe). These waters were prepared with compositions
indicated in Table 2.
DEI testing on HTDS was carried out at ETL. HTDS-25 and HTDS-50 were prepared by
spiking HTDS to 25 ppb Pb and 50 ppb Pb, respectively, before they were analyzed in triplicate
by the Lead 1007AND 1000 as per vendor-provided manuals and guidance given during training.
Results obtained from the Lead 100/AND 1000 analysis were promptly recorded in the LRB. The
remainder of the HTDS-25 and HTDS-50 samples were filtered through a 0.20 um nylon filter
into two separate properly labeled and preserved sample bottles provided by DHL Analytical and
stored at 4ฑ2ฐC until they were sent for Pb Reference analysis, Cation Reference analysis,
Anion Reference analysis, and Alkalinity Reference analysis.
DEI testing on LTDS was carried out at ETL. LTDS-25 and LTDS-50 were prepared by spiking
LTDS to 25 ppb Pb and 50 ppb Pb, respectively, before they were analyzed in triplicate by the
Lead 100/AND1000 as per vendor-provided manuals and guidance given during training. Results
obtained from the Lead 100/AND 1000 analysis were promptly recorded in the LRB. The
remainders of the LTDS-25 and LTDS-50 samples were separately filtered through a 0.20 um
nylon filter into two separate properly labeled and preserved sample bottles provided by DHL
Analytical and stored at 4ฑ2ฐC until they were sent for Pb Reference analysis, Cation Reference
analysis, Anion Reference analysis, and Alkalinity Reference analysis.
DEI testing on HFe was carried out at ETL. HFe-25 and HFe-50 were prepared by spiking HFe
to 25 ppb Pb and 50 ppb, respectively, before they were analyzed in triplicate each by the
Lead 100/AND 1000 as per vendor-provided manuals and guidance given during training. Two
sets of triplicate experiments were carried out: one using a special vendor-recommended
pretreatment method for removal of Fe interference and one using the standard pretreatment
method. Results obtained from the Lead 100/AND 1000 analysis were promptly recorded in the
LRB. The remainders of the HFe-25 and HFe-50 samples were separately filtered through a 0.20
um nylon filter into two separate properly labeled and preserved sample bottles provided by
DHL Analytical and stored at 4ฑ2ฐC until they were sent for Pb Reference analysis, Cation
Reference analysis, Anion Reference analysis, and Alkalinity Reference analysis.
20
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3.4.8 Finished Drinking Water Testing
Finished drinking water testing included testing the accuracy and precision of the
Lead 100/AND 1000 on three different finished drinking waters (WF, Bottled Water and Finished
Well Water). WF was collected from a WF within Battelle. The WF was activated and water
was allowed to flow through the tap for 60 seconds (1-2 L throughput) before samples were
collected in a 1 L high-density polyethylene (HDPE) container. WF was collected in a manner
to avoid sample agitation and entrainment of air. The 1 L sample collection container was sealed
and transported to ETL where it was divided into two 100 mL volumetric flasks. WF-25 was
prepared by spiking WF to 25 ppb Pb before it was analyzed in triplicate by the
Lead 100/AND 1000 as per vendor-provided manuals and guidance given during training. Results
obtained from the Lead 100/AND 1000 analysis were promptly recorded in the LRB. The
remainder of the WF- 25 sample was filtered through a 0.20 um nylon filter into a properly
labeled and preserved sample bottle provided by DFIL Analytical and stored at 4ฑ2ฐC until it
was sent for Pb Reference analysis. In addition, the 100 mL sample without the Pb spike (WF-0)
was analyzed once by the Lead 100/AND 1000 and the remainder of the sample was filtered
through a 0.20 um nylon filter into two separate properly labeled and preserved sample bottles
provided by DFIL Analytical and stored at 4ฑ2ฐC until they were sent for Pb Reference analysis,
Cation Reference analysis, Anion Reference analysis, and Alkalinity Reference analysis.
Bottled Water was a 1 gal sample of spring water obtained from a local supermarket in
Columbus, OH. The 1 gal Bottled Water sample was transported to ETL where it was divided
into two 100 mL volumetric flasks. BW-25 was prepared by spiking one of the 100 mL samples
to 25 ppb Pb before it was analyzed in triplicate by the Lead 1007AND 1000 as per vendor-
provided manuals and guidance given during training. Results obtained from the
Lead 100/AND 1000 analysis were promptly recorded in the LRB. The remainder of the BW-25
sample was filtered through a 0.20 um nylon filter into a properly labeled and preserved sample
bottle provided by DHL Analytical and stored at 4ฑ2ฐC until it was sent for Pb Reference
analysis. In addition, the 100 mL sample without the Pb spike (BW-0) was analyzed once by the
Lead 100/AND 1000 and the remainder of the sample was filtered through a 0.20 um nylon filter
into two separate properly labeled and preserved sample bottles provided by DHL Analytical and
stored at 4ฑ2ฐC until they were sent for Pb Reference analysis, Cation Reference analysis, Anion
Reference analysis, and Alkalinity Reference analysis.
Finished Well Water was collected from the effluent sample tap at a small water treatment
facility located outside Plain City, OH. The effluent sample tap was opened and water was
allowed to flow through the tap for 60 seconds (approximately 40 L throughput) before samples
were collected in a 1 L HDPE container. Finished Well Water was collected in a manner to
avoid sample agitation and entrainment of air. FWW-0 (Finished Well Water with no Pb spike)
was analyzed onsite once by the Lead 1007AND 1000 as per vendor-provided manuals and
guidance given during training. Results obtained from the Lead 100/AND 1000 analysis were
promptly recorded in the LRB. The remainder of the FWW-0 sample was filtered through a 0.20
um nylon filter into a properly labeled and preserved sample bottle provided by DHL Analytical
and stored at 4ฑ2ฐC until it was sent for Pb Reference analysis, Cation Reference analysis, Anion
Reference analysis, and Alkalinity Reference analysis. The remainder of the 1 L sample was
transported to ETL where FWW-0 was analyzed once by Lead 1007AND 1000 and FWW-25 was
prepared and analyzed in triplicate. The remainder of the FWW-25 sample was filtered through
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a 0.20 um nylon filter into a properly labeled and preserved sample bottle provided by DHL
Analytical and stored at 4ฑ2ฐC until it was sent for Pb Reference analysis. Any differences in
results between field and ETL measurements as well as any subjective data concerning ease of
use in the field compared to ETL were noted in the LRB.
3.4.9 Environmental Water Testing
Environmental water testing included testing the accuracy and precision of Lead 100/AND 1000
on four different environmental waters (Raw Well Water, Reservoir Water, River Water and
Seawater).
Raw Well Water was collected from the raw water intake tap at a small water treatment facility
located outside Plain City, OH; note that this is the same facility from which the Finished Well
Water was collected. The raw water intake was activated and water was allowed to flow through
the tap for 60 seconds (approximately 40 L throughput) before samples were collected in a 1 L
HOPE container. Raw Well Water was collected in a manner to avoid sample agitation and
entrainment of air. RWW-0 (Raw Well Water with no Pb spike) was analyzed onsite once by the
Lead 100/AND 1000 as per vendor-provided manuals and guidance given during training. Results
obtained from the Lead 100/AND 1000 analysis were promptly recorded in the LRB. The
remainder of the RWW-0 sample was filtered through a 0.20 um nylon filter into a properly
labeled and preserved sample bottle provided by DHL Analytical and stored at 4ฑ2ฐC until it
was sent for Pb Reference analysis, Cation Reference analysis, Anion Reference analysis, and
Alkalinity Reference analysis. The remainder of the 1 L sample was transported to ETL and
filtered through a 0.20 um nylon filter before RWW-0 was analyzed once by Lead 100/AND 1000
and RWW-25 was prepared and analyzed in triplicate. The remainder of the RWW-25 sample
was filtered through a 0.20 um nylon filter into a properly labeled and preserved sample bottle
provided by DHL Analytical and stored at 4ฑ2ฐC until it was sent for Pb Reference analysis.
Any differences in results between field and ETL measurements as well as any subjective data
concerning ease of use in the field compared to ETL were noted in the LRB.
Reservoir Water was collected from the surface of Grigg's Reservoir on the Scioto River in
Columbus, OH (see Figure 3 for sampling location). The sample was collected by means of a
retractable pole with an attached 1 L HOPE sample collection container. The sample pole was
extended to its full length (-20 ft) and a sample was collected from the surface (no more than 1 ft
below water surface) of the reservoir. The sample pole was then retracted and brought to the
reservoir shore. ReW-0 (Reservoir Water with no Pb spike) was analyzed onsite once by the
Lead 1007AND 1000 as per vendor-provided manuals and guidance given during training. Results
obtained from the Lead 100/AND 1000 analysis were promptly recorded in the LRB. The
remainder of the ReW-0 sample was filtered through a 0.20 um nylon filter into a properly
labeled and preserved sample bottle provided by DHL Analytical and stored at 4ฑ2ฐC until it
was sent for Pb Reference analysis, Cation Reference analysis, Anion Reference analysis, and
Alkalinity Reference analysis. The remainder of the 1 L sample was transported to ETL and
filtered through a 0.20 um nylon filter before ReW-0 was analyzed once by Lead 100/AND 1000
and ReW-25 was prepared and analyzed in triplicate. The remainder of the ReW-25 sample was
filtered through a 0.20 um nylon filter into a properly labeled and preserved sample bottle
provided by DHL Analytical and stored at 4ฑ2ฐC until it was sent for Pb Reference analysis.
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Any differences in results between field and ETL measurements as well as any subjective data
concerning ease of use in the field compared to ETL were noted in the LRB.
River Water was collected from the surface of the Scioto River in Columbus, OH (see Figure 3).
The sample was collected in a manner identical to that for the Reservoir Water sample by means
of a retractable pole with an attached 1 L HDPE sample collection container. RiW-0 (River
Water with no Pb spike) was analyzed onsite once by the Lead 100/AND 1000 as per vendor-
provided manuals and guidance given during training. Results obtained from the
Lead 100/AND 1000 analysis were promptly recorded in the LRB. The remainder of the RiW-0
sample was filtered through a 0.20 um nylon filter into a properly labeled and preserved sample
bottle provided by DHL Analytical and stored at 4ฑ2ฐC until it was sent for Pb Reference
analysis, Cation Reference analysis, Anion Reference analysis, and Alkalinity Reference
analysis. The remainder of the 1 L sample was transported to ETL and filtered through a 0.20
um nylon filter before RiW-0 was analyzed once by Lead 100/AND 1000 and RiW-25 was
prepared and analyzed in triplicate. The remainder of the RiW-25 sample was filtered through a
0.20 um nylon filter into a properly labeled and preserved sample bottle provided by DHL
Analytical and stored at 4ฑ2ฐC until it was sent for Pb Reference analysis. Any differences in
results between field and ETL measurements as well as any subjective data concerning ease of
use in the field compared to ETL were noted in the LRB.
Seawater was collected in two separate 1 L HDPE sample bottles from the shore of West Palm
Beach, FL (see Figure 4 for sampling location) no more than 20 ft from the shoreline and no
more than 1 ft depth. Two Seawater samples were collected for redundancy; however, only one
of the samples was used for testing. The samples were sealed and placed in a cooler with ice and
transported to ETL. Upon receipt, the Seawater sample was opened and the temperature
measured to ensure that the sample remained at 4ฑ2ฐC during transit. The sample was then
allowed to warm to ambient temperature before further testing. Seawater samples were diluted
1:10 in DI water and filtered through a 0.20 um nylon filter before analysis.
SW-25 and SW-50 were prepared by spiking Seawater to 25 ppb Pb and 50 ppb Pb, respectively,
before they were analyzed in triplicate each by the Lead 1007AND 1000 as per vendor-provided
manuals and guidance given during training. Results obtained from the Lead 100/AND 1000
analysis were promptly recorded in the LRB. The remainders of both the SW-25 and SW-50
samples were separately filtered through a 0.20 um nylon filter into separate properly labeled and
preserved sample bottles provided by DHL Analytical and stored at 4ฑ2ฐC until they were sent
for Pb Reference Analyses. In addition, a 100 mL sample without the Pb spike (SW-0) was
analyzed once by the Lead 100/AND 1000 and the remainder of the sample were filtered through
a 0.20 um nylon filter into two separate properly labeled and preserved sample bottles provided
by DHL Analytical and stored at 4ฑ2ฐC until they were sent for Pb Reference analysis, Cation
Reference analysis, Anion Reference analysis, and Alkalinity Reference analysis. The
Lead 100/AND 1000 analyses of Seawater samples were considered a qualitative test and were
not subjected to the rigorous statistical analysis of the other samples.
3.4.10 Wastewater Effluent Testing
Wastewater effluent testing included testing the accuracy and precision of Lead 100/AND 1000
on three different wastewater effluent waters (Municipal Wastewater Effluent #1, Municipal
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Wastewater Effluent #2, and Metal Finishing Wastewater Effluent). All three of the wastewater
effluent water samples were filtered through a 0.20 urn nylon filter before being diluted 1:10 in
DI water.
Municipal Wastewater Effluent #1 was collected from the effluent sampling location tap at
Jackson Pike (see Figure 3 for facility location) in a 1 L HOPE container. AIL volumetric flask
was filled halfway with DI water and 100 mL of the filtered Municipal Wastewater Effluent #1
sample was then pipetted to the volumetric flask; the flask was then filled to the line resulting in
a 1:10 dilution of Municipal Wastewater Effluent #1. Note that dilution of Municipal
Wastewater Effluent #1 raised the limit of detection from 2 ppb Pb to 20 ppb Pb for these
samples. MWWE#1-0 (Municipal Wastewater Effluent with no Pb spike) was analyzed onsite
once by the Lead 100/AND 1000 as per vendor-provided manuals and guidance given during
training. Results obtained from the Lead 100/AND 1000 analysis were promptly recorded in the
LRB. The remainder of the MWWE#1-0 sample was filtered through a 0.20 um nylon filter into
a properly labeled and preserved sample bottle provided by DHL Analytical and stored at 4ฑ2ฐC
until it was sent for Pb Reference analysis, Cation Reference analysis, Anion Reference analysis,
and Alkalinity Reference analysis. The remainder of the 1 L sample was transported to ETL
where MWWE#1-0 was analyzed once by Lead 1007AND 1000 and MWWE#l-25 was prepared
and analyzed in triplicate. The remainder of the MWWE#l-25 sample was filtered through a
0.20 um nylon filter into a properly labeled and preserved sample bottle provided by DFIL
Analytical and stored at 4ฑ2ฐC until it was sent for Pb Reference analysis. Any differences in
results between field and ETL measurements as well as any subjective data concerning ease of
use in the field compared to ETL were noted in the LRB.
Municipal Wastewater Effluent #2 was collected from the effluent sampling location tap at the
Southerly Wastewater Treatment Plant in Columbus, OH (see Figure 3) in a 1 L HOPE
container. AIL volumetric flask was filled halfway with DI water and 100 mL of the filtered
Municipal Wastewater Effluent #2 sample was then pipetted to the volumetric flask; the flask
was then filled to the line resulting in a 1:10 dilution of the Municipal Wastewater Effluent #2.
Note that dilution of Municipal Wastewater Effluent #2 raised the limit of detection from 2 ppb
Pb to 20 ppb Pb for these samples. MWWE#2-0 (Municipal Wastewater Effluent with no Pb
spike) was analyzed onsite once by the Lead 100/AND 1000 as per vendor-provided manuals and
guidance given during training. Results obtained from the Lead 100/AND 1000 analysis were
promptly recorded in the LRB. The remainder of the MWWE#2-0 sample was filtered through a
0.20 um nylon filter into a properly labeled and preserved sample bottle provided by DHL
Analytical and stored at 4ฑ2ฐC until it was sent for Pb Reference analysis, Cation Reference
analysis, Anion Reference analysis, and Alkalinity Reference analysis. The remainder of the 1 L
sample was transported to ETL where MWWE#2-0 was analyzed once by Lead 100/AND 1000
and MWWE#2-25 was prepared and analyzed in triplicate. The remainder of the MWWE#2-25
sample was filtered through a 0.20 um nylon filter into a properly labeled and preserved sample
bottle provided by DHL Analytical and stored at 4ฑ2ฐC until it was sent for Pb Reference
analysis. Any differences in results between field and ETL measurements as well as any
subjective data concerning ease of use in the field compared to ETL were noted in the LRB.
Metal Finishing Wastewater Effluent was collected by the vendor from a metal finishing facility
conforming to 40 CFR 433 and/or 40 CFR413 in a 1 L HOPE sample collection bottle and sent
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on ice to ETL. The method of sampling was documented by the vendor and provided to Battelle.
Upon arrival, the sample bottle was opened and the temperature of the sample was confirmed.
The sample was filtered through a 0.20 um nylon filter before sample preparation. MFWWE-25
was prepared by spiking Metal Finishing Wastewater Effluent to 25 ppb Pb before it was
analyzed in triplicate by the Lead 100/AND 1000 as per vendor-provided manuals and guidance
given during training. Results obtained from the Lead 100/AND 1000 analysis were promptly
recorded in the LRB. The remainder of the MFWWE-25 sample was filtered through a 0.20 um
nylon filter into a properly labeled and preserved sample bottle provided by DFIL Analytical and
stored at 4ฑ2ฐC until it was sent for Pb Reference analysis. In addition a sample of Metal
Finishing Wastewater Effluent without the Pb spike (MFWWE-0) was analyzed twice (once with
a pretreatment method for the removal of Fe interference and once without) by the
Lead 100/AND 1000 and the remainder of the sample was filtered through a 0.20 um nylon filter
into two separate properly labeled and preserved sample bottles provided by DHL Analytical and
stored at 4ฑ2ฐC until they were sent for Pb Reference analysis, Cation Reference analysis, Anion
Reference analysis, and Alkalinity Reference analysis.
3.5 Operational Factors
Operational factors such as maintenance needs, data output, and sustainability factors such as
ease of use and repair requirements were noted when observed. Battelle testing staff
documented observations in the LRB and directly into the control charts (MS Excelฎ).
Examples of recorded information included recalibration, replacement of batteries, vendor effort
(e.g., time on site for training), the duration and causes of any technology downtime or data
acquisition failure and operator observations on many other related items (e.g., ease of use).
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Chapter 4
Quality Assurance/Quality Control
QA/ QC procedures were performed in accordance with the QMP for the AMS Center and the
QAPP for this verification test. QA/QC procedures and results are described in the following
sub chapters.
4.1 Data Collection Quality Control
4.1.1 Quality Control Overview
Steps were taken to maintain the quality of data collected during this verification test. QC
samples (including quality control standard [QCS], laboratory-fortified matrix [LFM] samples
and reagent blank [KB] samples) were incorporated into the sampling and analysis design to
assess the quality of the method of assessment.
Prepared QC samples included both KB and LFM. The KB samples were prepared from DI
water and exposed to identical handling and analysis procedures as other prepared samples,
including the addition of all reagents. These samples were used to help ensure that no sources of
contamination were introduced in the sample handling and analysis procedures. Acceptance
criteria for KB are discussed in the next section.
The LFM and LFM duplicate [LFMD] samples were prepared as aliquots of environmental
samples and spiked in the field to increase the Pb concentration of the samples to 25 ppb. The
Pb standard solution used for the LFM was prepared in the laboratory and brought to the field
site. These samples were used to help identify whether matrix effects had any influence on the
analytical results. At least 10% of all the prepared samples to be analyzed were RBs, and at least
two samples taken from each sampling site were LFM and LFMD. The following samples
satisfy the LFM requirements for field-collected samples: WF-25, BW-25, FWW-25, RWW-25,
ReW-25, RiW-25, SW-25, MWWE#l-25, MWWE#2-25, and MFWWE-25. Acceptance criteria
for LFM and LFMD are discussed in the next section.
QCSs were used as a calibration check to verify that Lead 1007AND 1000 and the reference
instruments were properly calibrated and reading within defined control limits. QCS is defined
as 30 ppb Pb. These standards were purchased from Fisher Scientific and were subject only to
dilution by DI water. The calibration of all instruments was verified using a QCS before and
after each testing day, as well as after every tenth sample. In addition, instruments and
equipment used for this verification were operated at the expected ranges and calibration records
were verified and kept for all monitoring instruments and equipment used during this verification
test.
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4.1.2 Acceptance Criteria and Root Cause Analysis
Acceptance criteria for QC samples varied depending on the sample(s) being analyzed. For each
set of samples a root cause analysis (RCA) might have been required before testing began (see
Appendices F, G and H of the original QAPP document for root cause analysis flow-charts).
For IDC, an initial on-site calibration must have been passed before LFM and LFMD samples
were analyzed. If on-site calibration was not passed the first time it was repeated and if a second
failure occurred, a RCA was performed and the vendor was contacted. If on-site calibration was
passed either during the first or (if necessary) the second attempt, LFM and LFMD samples were
analyzed. The acceptance criteria for the LFM and LFMD were recovery of the target Pb spike
of 75 to 125% and an RPD of less than 30%. If these criteria were not met, on-site calibration
was repeated. Analysis of the remaining samples for that specific matrix was initiated only when
LFM and LFMD criteria were met.
For ICC and TPC, an initial on-site calibration must have been passed before LFM and LFMD
samples were analyzed. If on-site calibration was not passed the first time it was repeated and if
a second failure occurred, a RCA was performed and the vendor was contacted. If on-site
calibration was passed either during the first or (if necessary) the second attempt, LFM and
LFMD samples were analyzed. The acceptance criteria for the LFM and LFMD were recovery
of the Pb spike of 85 to 115% and a standard deviation of ฑ15% of the expected Pb value. If
these criteria were not met, on-site calibration was repeated. Analysis of the remaining samples
for that specific matrix was initiated only when LFM and LFMD criteria were met.
For DEI, finished drinking water, environmental waters, and wastewater effluents an initial on-
site calibration must have been passed before LFM and LFMD samples were analyzed. If on-site
calibration was not passed the first time it was repeated and if a second failure occurred, a RCA
was performed and the vendor was contacted for collaborative analysis with information
regarding the samples (e.g., pH, color, turbidity, conductivity). If on-site calibration was passed
either during the first or (if necessary) the second attempt, LFM and LFMD samples were
analyzed. The acceptance criteria for the LFM and LFMD were recovery of the Pb spike of 75
to 125% and RPD of less than 30%. If these criteria were not met, on-site calibration was
repeated. Analysis of the remaining samples for that specific matrix was initiated only when
LFM and LFMD criteria were met.
Acceptance criteria for RB were set at less than the vendor-reported method detection limit of 2
ppb Pb, making the method detection limit and reporting limit identical. If Lead 100/AND 1000
reported values of Pb equal to or greater than 2 ppb Pb, a second RB was analyzed and if
Lead 1007AND 1000 indicated a value equal to or greater than 2 ppb Pb, on-site calibration was
repeated before analysis was continued. A value of less than 2 ppb Pb was indicated by the
AND1000 displaying the message "*BELOW LIMIT*" while values measured equal to or
greater than 2 ppb Pb were indicated by AND 1000 as a quantitative result.
Acceptance criteria for QCS were set at ฑ25% of the expected Pb concentration (i.e., 30 ppb Pb)
in QCS samples for both Lead 100/AND 1000 and reference methods.
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In the cases that a RCA was completed, the laboratory analyst performed a RCA collaboratively
with the vendor. The analysis had at a minimum the following areas described in detail:
1. Identification of the problem: the QC failure, including instrument, reagent, sampling,
personnel, and any other problems, was identified.
2. Investigation to identify the root cause: it was determined how each identified problem
interacted with each other to create the QC problem.
3. Solution: an encompassing solution was developed to address all problems that created
the QC failure.
4. Implementation of the solution: an implementation plan was developed which included
all components of the developed solution and was implemented by laboratory
management.
5. Documentation of the solution: all corrective action steps taken were documented under
laboratory management implementation of the corrective action.
6. Communication of the solution: training and management programs were developed to
communicate with and evaluate all personnel included in the corrective action solution.
7. Evaluation of the effectiveness of the solution: QC results were documented in trend
charts and laboratory staff performances were documented to validate corrective action
solution.
The following RCA QC identifiers were used:
Instrument Failure Mechanical (IFM)
Instrument Failure Electrical (IFE)
Instrument Operator Failure to Follow Method (IOFM)
Sensor Failure Chemical (SFC)
Sensor Failure Mechanical (SFM)
Failure Cause Unknown (FCU)
4.1.3 Control Charts
Control charts were maintained throughout the entire verification testing process as per Standard
Methods Section 10205. Control limits were calculated after the first five samples and after
every 10 samples thereafter. If analysis of the control charts indicated non-conformance as
described in Standard Methods Section 1020 B, the sample in question was rerun and in the
event of a second non-conformance sample, the vendor was contacted to determine the cause of
the problem, which included a RCA.
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4.1.4 Equipment Test, Inspection, and Maintenance
The instruments used during the verification test were inspected and maintained according to the
instrument manuals or the laboratory standard operating procedures of DHL Analytical.
Operation of the Lead 100/AND 1000 during the verification test was performed by Battelle
technical staff as directed by the vendor user manuals and during on-site training.
4.1.5 Calibration and Verification of Test Procedures
The instruments used during the verification test (i.e., Lead 100/AND 1000 and reference
instruments) were calibrated per the instrument manual, the methods being used to make each
measurement, or the Standard Operating Procedures (SOPs) of the analysis laboratory. For each
measurement, the equipment calibration was verified. Calibration procedures, checks, and
results were documented in the project files. Testing did not occur until instrument calibration
results met the acceptance criteria as defined in the RCAs.
All calibrations performed were documented by the verification staff in the project LRB. The
Lead 100/AND 1000 technology vendor provided the Battelle verification staff with the necessary
training/information to properly calibrate and maintain Lead 100/AND 1000. Calibration of
Lead 100/AND 1000 was performed as often as indicated in the Lead 100/AND 1000 user manual
and as suggested by the vendors. Vendors were required to describe the necessary calibration
procedures specific to Lead 100/AND 1000.
4.1.6 Inspection and Acceptance of Supplies and Consumables
All materials, supplies, and consumables used to establish the test conditions were ordered by
Battelle. Where possible, Battelle relied on sources of materials and consumables that have been
used previously without problems as part of past ETV verification testing. Table 4 provides a
list of all reagents used in this testing.
Supplies met the following criteria:
Solvent and reagent grades are based on the intended use. All reagents were of >96%
purity (Table 4).
Equipment used to generate data must provide appropriate sensitivity.
A certificate of analysis must be provided and retained for reagents and standards.
The quality and purity of expendable materials must be documented and adequate to meet
the data quality objectives (DQOs) of the client.
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Table 5. Consumables Used for Verification Testing
Reagent
NIST-Traceable
Lead Solution
Sodium
Bicarbonate
Anhydrous
Calcium Sulfate
Hemihydrate
Magnesium
Sulfate
Anhydrous
Potassium
Chloride
Anhydrous
Sodium Chloride
Anhydrous
Glucose aqueous
solution
Iron Solution
CAS Number
10099-74-8
144-55-8
10034-76-1
7487-88-9
7447-40-7
7647-14-5
50-99-7
7437-89-6
Description of Use
Preparing lead spikes;
preparing calibration
standards; preparing PEA
standards
Preparing Low IDS and
High
IDS synthetic Waters
Preparing Low TDS and
High
TDS and High Fe synthetic
Waters
Preparing Low TDS and
High
TDS synthetic Waters
Preparing Low TDS and
High
TDS synthetic Waters
Preparing Low TDS, High
TDS and High Fe synthetic
Waters
Preparing Low TDS and
High
TDS synthetic waters
Preparing HFe
Purity/
Concentration
l,000ppm
>99.7%
97%
>97%
>99%
>99%
20%w/v
l,000ppm
Mass/Volume
100 mL
500 g
100 g
500 g
500 g
500 g
100 mL
100 mL
Vendor
Fisher
Scientific
Fisher
Scientific
Fisher
Scientific
Fisher
Scientific
Fisher
Scientific
Fisher
Scientific
Ricca
Chemical
Acros
Organics
Catalogue
Number
SL21-100
S233500
AC38535-1000
AC4 1348-5000
P2 17-500
S271500
R3254000100
AC19605-1000
4.1.7 Data Management
Various types of data were acquired and recorded electronically or manually by verification staff
during this verification test. All data and observations for the operation of the
Lead 100/AND 1000 were documented by the vendor or verification staff in LRBs, data forms or
electronically. Results from the laboratory analytical instruments were compiled by laboratory
staff in electronic format and submitted to the Verification Test Coordinator (VTC) upon
obtaining results. Hand-transcribed data were 100% verified by a second person.
Records received or generated by any of the verification staff during the verification test were
reviewed within 2 weeks of receipt of generation before the records were used to calculate,
evaluate, or report verification results. The review was documented as the dated initials of the
reviewer. If a Battelle staff member generated the record, this review was performed by a
Battelle technical staff member involved in the verification test, but not the staff member that
originally received or generated the record. The review was documented by the person
performing the review by adding his/her initials and date to the hard copy of the record being
reviewed. In addition, at least 10% of data calculations performed by verification staff were
checked by Battelle technical staff to ensure that calculations were performed correctly and
results were correct. Calculations checked also included any statistical calculations described in
the QAPP. The data obtained from this verification test were compiled and reported.
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All electronic testing records and documents were stored on a test-specific networked ETV
SharePoint site and common drive within Battelle's network. Testing data were uploaded to the
SharePoint site within 2 days of receipt. This site is within the protected Battelle network and is
backed up regularly. The goal of this data delivery schedule was prompt identification and
resolution of any data collection or recording issues.
In addition, once this verification report is complete, all testing records and documents will be
sent to Battelle's Records Management Office (RMO) for archival within 2 months of project
close-out.
4.2 Audits
Three types of audits were performed during the verification test: a performance evaluation audit
(PEA) of the analytical methods, a technical systems audit (TSA) of the verification test
procedures, and a data quality audit. Audit procedures are described further below.
4.2.1 Performance Evaluation Audit
PEAs for the Lead 100/AND 1000 were conducted by having two analysts independently taking
triplicate measurements for a 25 ppb Pb standard (in DI water). To be considered acceptable, the
average of the two analysts' results should agree within 20% and coefficient of variation (CV) of
each analysts triplicate measurements should be no more than 20%. The PEA results were
determined to be acceptable.
4.2.2 Technical Systems Audit
The Battelle Quality Manager (QM) performed a TSA during performance evaluation activities.
The purpose of the TSA is to ensure that the verification tests are being performed in accordance
with the AMS Center QMP1 and the project QAPP. The Battelle QM compared actual test
procedures to those specified or referenced in the QAPP, and reviewed data acquisition and
handling procedures. In preparation of the TSA, a project-specific checklist based on the QAPP
requirements was prepared to guide the TSA, which included a review of the test locations and
general testing conditions; observation of the testing activities; and review test documentation.
Data acquisition procedures were also verified. The Battelle QM prepared an initial TSA report.
No findings were recorded during the TSA, however, several observations were made. The TSA
observations were communicated to technical staff at the time of the audit and documented in the
TSA reports. The observations were acknowledged by the VTC and responses were recorded in
the final TSA document.
The Battelle AMS Center QA Officer for this verification test performed a TSA during Day 1
testing of Round 1 to ensure that the verification test was performed in accordance with the QMP
for the AMS Center and the QAPP. On July 10 and 18, 2012, the QM conducted the TSA to
verify that field testing was being conducted according to the QAPP requirements. The TSA on
July 10 was conducted at Battelle ETL to observe IDC testing. The TSA included a review of
documents available at the test site for reference and records being maintained by the testing
staff; observations of the testing equipment; the initiation of IDC testing; and the real-time data
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recording practices during each run. Verification testing was halted prematurely on July 10 due
to the implementation of a RCA. On July 18, 2012, a ISA was again conducted. A debriefing
was conducted with the Battelle VTC, Battelle Verification Testing Leader, Battelle AMS Center
Manager, and EPA AMS Center Project Officer and QM.
Five observations were noted during the audit: (1) the vendor-supplied lead calibration standard
solution was labeled with a different lot number than its outer bag; (2) IDC-25 (replicate 1)
percent recovery did not meet the QAPP requirement for the LFM sample; (3) IDC-25 (replicate
2) percent recovery after recalibration did not meet the QAPP requirement for the LFM sample;
(4) IDC-25-2 was prepared and percent recovery did not meet the QAPP requirement for the
LFM sample, initiating RCA; and (5) Day 1 testing was repeated over two separate days rather
than on the same day as stated in the QAPP. Responses to these observations were prepared and
recorded by the VTC.
Battelle's assessment was that the noted deviations did not negatively impact the quality of data
being generated for Round 2 testing.
4.2.3 Data Quality Audit
The Battelle QM, or designee, audited at least 10% of the sample results data acquired in the
verification tests and 100% of the calibration and QC data versus the QAPP requirements. One
audits of data quality (ADQ) was conducted for this project. Data were audited at the conclusion
of testing using a project-specific checklist and completed within 10 business days of receipt of
all test data. During this audit, the Battelle QM, traced the data from initial acquisition (as
received from the vendor's technology), through reduction and statistical comparisons, to final
reporting. Calculations performed on the data undergoing the ADQ were checked. Data
underwent a 100% validation and verification by technical staff (i.e., VTC, or designee) before
being assessed as part of the data quality audit. All QC data and all calculations performed on
the data undergoing the audit were checked by the Battelle QM. Results of the ADQ were
documented using the checklist and reported to the VTC and EPA within 10 business days after
completion of the audit. The ADQ which assessed overall data quality, including accuracy and
completeness of the technical report, was prepared as a narrative and distributed to the VTC and
EPA within 10 business days of completion of the audit.
4.3 Quality Assurance/Quality Control Deviations
Appendix A presents a list of all deviations found during the QA/QC checks performed. Round
1 testing was found to be inadequate for this verification and required deviation. Five causes for
deviation were indicated: (1) sample preparation procedures were modified, (2) on-site
calibration procedures were modified, (3) additional QA/QC requirements were included for
ICP-MS analysis, (4) high iron sample treatment procedures were clarified, and (5) phased
sample testing scheme was implemented. These deviations were applied in Round 2 testing.
Specific deviations are discussed throughout this verification report where appropriate. The
remaining deviations related to QA/QC are discussed below.
Deviation Number 3 stated that the root cause of low recoveries determined by ICP-MS
32
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pertained to the QA/QC procedures employed by the commercial laboratory. Utilizing the
requirements for QA/QC samples detailed in Standard Methods for the Examination of Water
and Wastewater5 and 40 CFR Part 136.7, the following QA/QC requirements were added to
standard QA/QC requirements of EPA Method 200.8:
QC Failure Requirements:
If the analyst reaches the point where a RCA must be performed, the analyst would contact
Battelle. All RCA results must be recorded and submitted for approval by Battelle prior to
restarting the ICP-MS analyses.
Understanding between commercial laboratory, Battelle and ANDalyze:
A conference call was held between the lab manager of the commercial lab, Battelle, and
ANDalyze to discuss these requirements. A statement of understanding outlining these
requirements was developed after the call and circulated to affected parties to ensure all were
aware of these specific requirements.
Note that addition of this language to the QAPP did not replace Sections B4 and B5, but were
used by the commercial lab as a SOP for this project, supplementing QA/QC requirements
specified in EPA Method 200.8. All QA sample preparation and preservation (i.e., RBs, QC
samples, and LFM and LFMDs and the PEA) were executed as described in Section B5.1 of the
original QAPP. In the event that a RCA was conducted, it was conducted exactly as described in
Section B5.2 of the original QAPP. Control charts were maintained and reviewed exactly as
described in Section B5.3 of the original QAPP.
Flow charts were prepared for easy interpretation of the additional QA/QC requirements for EPA
Method 200.8 (that were included as Appendix F, G and H of the original QAPP document).
These flowcharts were not used in isolation but supplemented detailed procedures described in
the QAPP deviation.
33
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Chapter 5
Statistical Methods
The statistical methods used to evaluate the quantitative performance factors listed in Section 3.3
are presented in this chapter. Qualitative observations were also used to evaluate verification test
data. The following subchapters describe each performance parameter evaluated.
5.1 Accuracy
Accuracy of the Lead 100/AND 1000 was assessed by comparing Pb values obtained from the
Lead 1007AND 1000 (PbANo) and those reported by the Pb reference analysis (PbREr) on the same
samples. The relative percent difference (RPD) between the two measurements serves as a
quantitative measure of the accuracy of the Lead 100/AND 1000 as detailed in Equation 1.
\PbAND ~ PbREF\
RDP = . * 100
Equation 1
RPD is reported for all Lead 100/AND 1000 and Pb reference measurement pairs of data and are
summarized by an average value; however, results from Seawater are reported qualitatively as
high, medium or low Pb concentrations.
RPD was also calculated between the LFM and LFMD when determining whether to accept an
on-site calibration according to the control charts. RPD as defined by Equation 2 provides a
measure of the agreement between the LFM and LFMD.
\rbjpM PbjfMDl
RPD = LFMD * 100
(PbLFM + PbLFMD)/2
Equation 2
Percent recovery was also calculated for the LFM and LFMD when determining whether to
accept an on-site calibration according to the control charts. Percent recovery was calculated as
shown in Equation 3 for the LFM.
(PbLFM -s* Pb0}
Percent Recovery (LFM) = * 100
Equation 3
where s is a dilution correction, Pb^pM is the ANDalyze meter reading for the LFM, and Pbo is
the ANDalyze meter reading for the unspiked sample (if the reading is "Below Limit" a value of
0 ppb was used). The LFM spike is 25 ppb Pb.
34
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5.2 Precision
Precision of the Lead 1007AND 1000 was assessed by comparing the spread of Pb concentration
data obtained by Lead 1007AND 1000 on triplicate samples. Precision was expressed
quantitatively through the standard deviation (SD) and the CV.
The SD of triplicate samples Si, 82 and 83 were computed as expressed in Equation 4.
Iv1
SD = X '
N 1=1
Equation 4
where n is the mean value of the three samples expressed in Equation 5.
3
" = 3i=i
Equation 5
The CV of triplicate samples Si, 82, and 83 was computed as expressed in Equation 6.
SD
CV =
V-
Equation 6
The mean, SD, and CV was reported for all triplicate samples analyzed by Lead 1007AND 1000.
5.3 Linearity of Response
During the DLR testing, a series of samples with known concentrations of Pb were analyzed in
triplicate by Lead 1007AND 1000 (0 ppb, 5 ppb, 15 ppb, 25 ppb, 50 ppb, 75 ppb and 100 ppb). In
addition to the accuracy and precision of the instrument for these tests, linearity was assessed by
linear regression, with the analyte concentration measured by the reference method as the
independent variable and the reading from Lead 100/AND 1000 as the dependent variable.
Linearity is expressed in terms of slope, intercept, and the square of the correlation coefficient
(r2) as calculated by Microsoftฎ Excel standard computation tools.
35
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5.4 Limit of Detection
The LOD for the Lead 100/AND 1000 was assessed from seven replicate analyses of a fortified
sample with an analyte concentration of five times the vendor's estimated detection limit. In the
case of the Lead 100/AND 1000, the vendor's estimated detection limit is 2 ppb. Thus, the LOD
tests were carried out on 10 ppb Pb samples. The LOD is calculated from Equation 7.
LOD = t*SD
Equation 7
where t is the Student's t-test value for a 99% confidence interval (i.e., Student's t-test value for
a of 0.01 and 6 degrees of freedom) and SD is the standard deviation of the replicate samples.
5.5 Operational Factors
Operational factors such as maintenance needs, calibration frequency, data output, ease of use,
and repair requirements were evaluated and summarized based on technical staff observations for
all runs.
36
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Chapter 6
Test Results
This chapter provides results of the quantitative and qualitative evaluations of this verification
test for the ANDalyze LeadlOO/ANDlOOO. Appendix E presents the Round 2 run data that were
collected and used to provide these results. Appendix F presents Round 2 control charts which
were constructed according to Standard Methods5. There are a few important aspects of the
control charts which should be noted. Firstly, the observation number on the x-axis refers to the
65 observations of Phase 1 and the 51 observations of Phase 2 in Tables 5 through 10 of Section
6. Upper control limit (UCL), lower control limit (LCL), upper warning limit (UWL), lower
warning limit (LWL), positive standard deviation (+SD), negative standard deviation (-SD) and
mean were calculated after the first 15 samples and then recalculated after each additional 5
samples. Further details of control charts including equations for the calculation of required
variables can be found in Standard Methods5.
6.1 Accuracy
6.1.1 Percent Recovery
Percent recovery was used for all Lead 100/AND 1000 observations to verify acceptability of on-
site calibration using control charts. Percent recovery was also used for IDC, ICC, DEI, finished
drinking water testing, environmental water testing, and wastewater effluent testing as
acceptance criteria for observations as described in Section 4.1.2. During testing, reference data
were not available, and expected concentration was used as acceptance criteria.
Table 5 presents the expected concentrations, observations, reference concentrations, and percent
recovery values for IDC and ICC testing and associated quality control standard (QCS). Control
charts for these observations are presented in Appendix F; no QC issues were indicated on
control charts for this set of observations. Retesting was performed four times on IDC and ICC
related samples. On-site recalibration was performed once during IDC and ICC testing. After
on-site recalibration, two IDC samples still did not meet criteria for percent recovery when
compared to reference concentrations (TDC-25-2-RR2 and IDC-25-3). Thus on-site recalibration
did not seem to improve data quality compared to the reference concentration, although it did
appear to improve data quality when compared to the target concentration. Discussion of the
precision of triplicate samples for IDC and ICC is presented in Section 6.2.
37
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Table 6. Percent Recovery for IDC and ICC
Phase 1
Sample
Number
1
2
3
4
5
6
7
8
9
10
11
12
Sample Name
QCS-1
IDC-25-1
IDC-25-2
IDC-25-2-RR1
IDC-25-2-RR2
IDC-25-3
IDC-25-3-RR1
ICC-25-1
ICC-25-2
ICC-25-3
QCS-2
QCS-2-RR1
Sample
Type
QCS
IDC
IDC
IDC
IDC
IDC
IDC
ICC
ICC
ICC
QCS
QCS
Expected
Concentration
(ug/LPb)
30
25
25
25
25
25
25
25
25
25
30
30
Measured
Concentratio
n (ug/LPb)
31
20
18
16
19
18
21
20
25
21
20
25
ICP-MS
Concentratio
n (ug/LPb)
30
27
22
31
Percent
Recovery
to Target
103
80
72
64
76
72
84
80
100
84
67
83
Percent
Recovery
to ICP-MS
103
74
67
59
70
67
78
91
114
95
65
81
Percent recovery values that do not meet criteria are shaded and bold font.
Table 6 presents the expected concentrations, observations, reference concentrations, and percent
recovery values for DLOD and DLR testing and associated QCS. Control charts for these
observations are presented in Appendix F. Several QC issues were indicated on control charts
for observations corresponding to DLR: two consecutive samples were above the upper warning
limit, four out of five consecutive samples were outside one standard deviation, and six
consecutive samples were above the mean. For each of these QC issues, samples were
reanalyzed as described in the original QAPP document and QC issues were resolved.
Therefore, the QC issues identified had a minimal impact on data quality. Although on-site
recalibration was not required for DLOD and DLR testing, all samples met criteria for percent
recovery when compared to reference concentrations. Discussion of limit of detection is
presented in Section 6.4. Discussion of the precision of triplicate samples for DLR is presented
in Section 6.2. Discussion of linearity of response is presented in Section 6.3.
38
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Table 7. Percent Recovery for DLOD and DLR
Phase 1
Sample
Number
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
Sample Name
DLOD-10-1
DLOD- 10-2
DLOD-10-3
DLOD- 10-4
DLOD-10-5
DLOD-10-6
DLOD- 10-7
DLR-5-1
DLR-5-2
DLR-5-3
QCS-3
DLR-15-1
DLR- 15-2
DLR- 15-3
DLR-25-1
DLR-25-2
DLR-25-3
DLR-50-1
DLR-50-2
DLR-50-3
QCS-4
DLR-75-1
DLR-75-2
DLR-75-3
DLR- 100-1
DLR-100-2
DLR-100-3-RR1
QCS-5
Sample
Type
DLOD
DLOD
DLOD
DLOD
DLOD
DLOD
DLOD
DLR
DLR
DLR
QCS
DLR
DLR
DLR
DLR
DLR
DLR
DLR
DLR
DLR
QCS
DLR
DLR
DLR
DLR
DLR
DLR
QCS
Expected
Concentration
(ug/LPb)
10
10
10
10
10
10
10
5
5
5
30
15
15
15
25
25
25
50
50
50
30
75
75
75
100
100
100
30
Measured
Concentration
(Mg/LPb)
8
8
9
8
8
8
9
4
4
5
24
12
14
12
20
19
22
51
46
46
28
77
78
73
105
91
83
34
ICP-MS
Concentration
(ug/LPb)
9
5
32
14
29
53
29
83
109
34
Percent
Recovery
to Target
80
80
90
80
80
80
90
80
80
100
80
80
93
80
80
76
88
102
92
92
93
103
104
97
105
91
83
113
Percent
Recovery
to ICP-MS
89
89
100
89
89
89
100
80
80
100
75
86
100
86
69
66
76
96
87
87
97
93
94
88
96
83
76
100
Percent recovery values that do not meet criteria are shaded and bold font.
Table 7 presents the expected concentrations, observations, reference concentrations, and percent
recovery values for DEI consisting of Low IDS (LTDS), High IDS (HTDS), and High Fe (HFe)
testing and associated QCS. Control charts for these observations are presented in Appendix F.
One QC issue was indicated on control charts for observations corresponding to DEI: seven
consecutive observations indicated an increasing trend. Retesting was performed on four
samples during DEI. On-site recalibration was not required for DEI as all re-run samples (i.e.,
LTD-25-2-RR1, HTDS-25-1-RR1 and HFe-25-2-RRl) met criteria for percent recovery when
compared to reference concentrations. Discussion of the precision of triplicate samples for DEI
is presented in Section 6.2.
39
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Table 8. Percent Recovery for DEI
Phase 1
Sample
Number
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
61
62
63
64
65
Sample
Name
QCS-6
QCS-6-RR1
LTDS-25-1
LTDS-25-2
LTDS-25-2-
RR1
LTDS-25-3
LTDS-50-1
LTDS-50-2
LTDS-50-3
HTDS-25-1
HTDS-25-1-
RR1
HTDS-25-2
HTDS-25-3
QCS-7
HTDS-50-1
HTDS-50-2
HTDS-50-3
HFe-25-1
HFe-25-2
HFe-25-2-
RR1
HFe-25-3
HFe-50-1
HFe-50-2
HFe-50-3
QCS-8
Sample Type
Quality Control
Quality Control
Low IDS
Low IDS
Low IDS
Low IDS
Low IDS
Low IDS
Low IDS
High IDS
High IDS
High IDS
High IDS
Quality Control
High IDS
High IDS
High IDS
High Fe
High Fe
High Fe
HighFe
High Fe
High Fe
HighFe
Quality Control
Expected
Concentration
(ug/LPb)
30
30
25
25
25
25
50
50
50
25
25
25
25
30
50
50
50
25
25
25
25
50
50
50
30
Measured
Concentration
(ug/LPb)
20
27
19
17
23
25
46
38
41
18
26
22
24
26
46
41
47
24
18
19
20
42
44
45
33
ICP-MS
Concentration
(Ug/LPb)
27
25
47
21
31
49
22
45
31
Percent
Recovery
to Target
67
90
76
68
92
100
92
76
82
72
104
88
96
87
92
82
94
96
72
76
80
84
88
90
110
Percent
Recovery
to ICP-MS
74
100
76
68
92
100
98
81
87
86
124
105
114
84
94
84
96
109
82
86
91
93
98
100
106
Percent recovery values that do not meet criteria are shaded and bold font.
Table 8 presents the expected concentrations, observations, reference concentrations, and percent
recovery values for environmental water testing and associated QCS. Observations for Seawater
are discussed in Section 6.5. Control charts for these observations are presented in Appendix F.
Two QC issues were indicated on control charts for observations corresponding to environmental
samples: one observation was below the lower control limit and two consecutive samples
(including that observation mentioned) were below the lower warning limit. However, the QCS
observation conducted immediately after reaffirmed QC standards and these samples were
retested following the iron interference procedure. Retesting was performed on four samples
during environmental sample testing. On-site recalibration was required and a RCA was
performed for raw well water samples suspected of containing high levels of Fe that interfered
with the test. Five observations did not meet criteria for percent recovery when compared to
reference concentrations. These observations were for matrices raw well water both without and
with Fe removal pretreatment. This indicates that accurate measurement of Pb in this matrix is
difficult even with Fe removal pretreatment. This could be because of other interferences which
have not been identified. Discussion of the precision of triplicate samples for DEI is presented in
Section 6.2.
40
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Table 9. Percent Recovery for Environmental Water
Phase 2
Sample
Number
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
Sample Name
QCS-9
RiW-25-1
RiW-25-2
RiW-25-3
RiW-25-3-
RR1
ReW-25-1
ReW-25-2
ReW-25-3
RWW-25-1
RWW-25-1-
RR1
QCS-10
RWW-25-1-
RR2
RWW-25-1-
RR3
RWW-25-2
RWW-25-2-
RR1
RWWPT-25-1
RWWPT-25-2
RWWPT-25-3
RWWPT-25-
3-RR1
Sample Type
Quality Control
River Water
River Water
River Water
River Water
Reservoir
Water
Reservoir
Water
Reservoir
Water
Raw Well
Water
Raw Well
Water
Quality Control
Raw Well
Water
Raw Well
Water
Raw Well
Water
Raw Well
Water
Raw Well
Water
Pretreated
Raw Well
Water
Pretreated
Raw Well
Water
Pretreated
Raw Well
Water
Pretreated
Expected
Concentration
(ug/LPb)
30
25
25
25
25
25
25
25
25
25
30
25
25
25
25
35
35
35
35
Measured
Concentration
(ug/LPb)
24
21
24
16
23
23
20
23
13
12
24
16
21
18
14
43
32
26
31
ICP-MS
Concentration
(ug/LPb)
29
20
21
18
26
18
21
Percent
Recovery
to Target
80
84
96
64
92
92
80
92
52
48
80
64
84
72
56
123
91
74
89
Percent
Recovery
to ICP-
MS
83
105
120
80
115
110
95
110
72
67
92
89
117
100
78
205
152
124
148
Percent recovery values that do not meet criteria are shaded and bold font.
Table 9 presents the expected concentrations, observations, reference concentrations, and percent
recovery values for finished drinking water testing and associated QCS. Control charts for these
observations are presented in Appendix F. Two QC issues were indicated on control charts for
observations corresponding to drinking water samples related to QCS testing: one observation
was above the upper control limit and two consecutive samples were above the upper warning
limit. Furthermore, many of these QCS observations did not meet percent recovery criteria.
However, the only finished drinking water sample tested during this time resulted in an average
percent recovery. Additionally, the last QCS was retested and resulted in an acceptable percent
recovery, and no QC issues were identified in the following control charts. Retesting was
performed on three samples during drinking water sample testing. On-site recalibration was
required twice during drinking water testing. During testing, Bottled Water did not appear to
41
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meet QC criteria and a RCA was performed. It was determined that these observations were in
fact within QC criteria once reference data were received. Four observations related to the QCS
testing did not meet criteria for percent recovery when compared to reference concentrations.
This result was unexpected as QCS samples were prepared in DI water. It is possible that
analysis of FWW conducted immediately before the QCS samples had a negative impact on
subsequent analysis of QCS samples. Discussion of the precision of triplicate samples for DEI is
presented in Section 6.2.
Table 10. Percent Recovery for Finished Drinking Water
Phase 2
Sample
Number
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
Sample
Name
FWW-25-1
FWW-25-2
QCS- 11
QCS-11-RR1
FWW-25-3
QCS-12
QCS-12-RR1
QCS-12-RR2
QCS- 13
WF-25-1
WF-25-2
WF-25-3
BW-25-1
BW-25-1-
RR1
BW-25-1-
RR2
BW-25-1-
RR3
BW-25-1-
RR4
Sample Type
Finished Well
Water
Finished Well
Water
Quality Control
Quality Control
Finished Well
Water
Quality Control
Quality Control
Quality Control
Quality Control
WF
WF
WF
Bottled Water
Bottled Water
Bottled Water
Bottled Water
Bottled Water
Expected
Concentration
(ug/LPb)
25
25
30
30
25
30
30
30
30
25
25
25
25
25
25
25
25
Measured
Concentration
(ug/LPb)
23
21
43
37
19
40
46
33
27
19
24
25
18
17
16
17
18
ICP-MS
Concentration
(Ug/LPb)
24
28
24
28
29
21
20
Percent
Recovery
to Target
92
84
143
123
76
133
153
110
90
76
96
100
72
68
64
68
72
Percent
Recovery
to ICP-MS
96
88
154
132
79
143
164
118
93
90
114
119
90
85
80
85
90
Percent recovery values that do not meet criteria are shaded and bold font.
Table 10 presents the expected concentrations, observations, reference concentrations, and
percent recovery values for wastewater effluent testing and associated QCS. Control charts for
these observations are presented in Appendix F. No QC issues were indicated on control charts
for observations corresponding to wastewater effluent samples. Retesting was performed on two
samples during wastewater effluent testing, and on-site recalibration was required once.
Nevertheless, five observations did not meet criteria for percent recovery when compared to
reference concentrations which were all associated with MWWE#2. It is unknown why
measurement of Pb in MWWE#2 did not meet the percent recovery criterion, however, it is
possible that some unidentified interference was present in this matrix. Discussion of the
precision of triplicate samples for DEI is presented in Section 6.2.
42
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Table 11. Percent Recovery for Wastewater Effluent
Phase 2
Sample
Number
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
Sample Name
MWWE#l-25-l
MWWE#l-25-2
MWWE#l-25-3
MWWE#l-25-3-
RR1
QCS-14
MWWE#2-25-l
MWWE#2-25-2
MWWE#2-25-2-
RR1
MWWE#2-25-2-
RR2
MWWE#2-25-3
MWWE#2-25-4
MFWWE-25-1
MFWWE-25-2
MFWWE-25-3
QCS-15
Sample Type
Wastewater 1
Wastewater 1
Wastewater 1
Wastewater 1
Quality
Control
Wastewater 2
Wastewater 2
Wastewater 2
Wastewater 2
Wastewater 2
Wastewater 2
Metal
Finishing
Metal
Finishing
Metal
Finishing
Quality
Control
Expected
Concentration
(ug/LPb)
25
25
25
25
30
25
25
25
25
25
25
25
25
25
30
Measured
Concentration
(ug/LPb)
20
19
17
21
23
28
34
33
26
23
26
22
21
23
31
ICP-MS
Concentration
(ug/LPb)
19
30
20
24
30
Percent
Recovery
to Target
80
76
68
84
77
112
136
132
104
92
104
88
84
92
103
Percent
Recovery
to ICP-
MS
105
100
89
111
77
140
170
165
130
115
130
92
88
96
103
Percent recovery values that do not meet criteria are shaded and bold font.
6.2 Precision
Table 11 presents the mean observation values, SDs, and CVs for all samples analyzed in
triplicate. Although Seawater was analyzed in triplicate, quantitative analysis of accuracy and
precision is not presented in Table 11 as described in the original QAPP document. Discussion
of Seawater results is presented in Section 6.5. The majority of the tested samples had CV
values <0.10. The triplicate measurements which had CV values >0.10 are IDC-25, DLR-5,
DLR-100, LTDS-25, LTDS-50, HFe-25, RWWPT-25, FWW-25, WF-25 and MWWE#2-25 the
these are shaded in Table 12. It is unclear why IDC and LTDS samples had CV > 0.10 as these
were DI water and relatively simple matrices, respectively. DLR-5 and DLR-100 are at the
bottom and top of the limits of detection, respectively and may have spread the data. HFe and
RWWPT samples required pretreatment of the samples and may have spread the data. FWW
contained Fe, but was not pretreated and this may have spread the data for this sample. It is
unclear why WF and MWWE#2 samples have CV > 0.10.
43
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6.3 Linearity of Response
Figure 5 presents observations from DLR sample testing plotted against reference concentrations
from ICP-MS analysis. The x-axis of Figure 5 is the ICP-MS reference concentration and the y-
axis is the corresponding measured mean concentration. The error bars represent the standard
deviation of the measured concentration which are provided in Table 9. Linearity was calculated
in terms of slope, intercept, and the the square of the correlation coefficient (r2) as 0.8841, -
0.8418, and 0.9927, respectively.
Table 12. Precision of Samples Analyzed in Triplicate
Sample Name
IDC-25
ICC-25
DLR-5
DLR-15
DLR-25
DLR-50
DLR-75
DLR- 100
LTDS-25
LTDS-50
HTDS-25
HTDS-50
HFe-25
HFe-50
RiW-25
ReW-25
RWWPT-25
FWW-25
WF-25
BW-25
MWWE#l-25
MWWE#2-25
MFWWE-25
Sample Type
IDC
ICC
DLR
DLR
DLR
DLR
DLR
DLR
Low IDS
Low IDS
High IDS
High IDS
High Fe
High Fe
River Water
Reservoir Water
Raw Well Water
Pretreated
Finished Well Water
WF
Bottled Water
Wastewater 1
Wastewater 2
Metal Finishing
ICP-MS
Concentration
(Mg/LPb)
27
22
5
14
29
53
83
109
25
47
21
49
22
45
20
21
21
24
21
20
19
20
24
Mean
Observation
(Mg/LPb)
20
22
4
13
20
48
76
93
22
42
24
45
21
44
23
22
35
21
23
18
20
26
22
Standard
Deviation
1.00
2.65
0.58
1.15
1.53
2.89
2.65
11.14
3.06
4.04
2.00
3.21
2.65
1.53
1.53
1.73
6.66
2.00
3.21
0.58
1.00
2.52
1.00
cv
0.05
0.12
0.13
0.09
0.08
0.06
0.03
0.12
0.14
0.10
0.08
0.07
0.13
0.03
0.07
0.08
0.19
0.10
0.14
0.03
0.05
0.10
0.05
Shaded values indicate CV >0.10
44
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120
-a 100
Q-
c
5
T3
(11
80
60 -
20
1:1 Relation
= 0.8841x-0.8418
R2 = 0.9927
20
40 60 80 100
ICP-MS Reference Concentration (fig/Las Pb)
120
Figure 5. Observations from DLR Sample Testing versus Reference Concentrations
6.4 Limit of Detection
Table 12 presents the results of DLOD testing in addition to some statistical analyses. The
Student's t-test value for a of 0.01 and 6 degrees of freedom is 3.143. The LOD of the
Lead 100/AND 1000 was determined by Equation 7 to be 1.534 ug/L Pb, which is below the
vendor's estimated detection limit.
Table 13. Results of DLOD Testing
Sample Name
DLOD- 10-1
DLOD- 10-2
DLOD- 10-3
DLOD- 10-4
DLOD- 10-5
DLOD- 10-6
DLOD- 10-7
Sample Type
DLOD
DLOD
DLOD
DLOD
DLOD
DLOD
DLOD
ICP-MS
Concentration
(MS/LPb)
9
Observation
(Mg/LPb)
8
8
9
8
8
8
9
Mean
Observation
8.3
Standard
Deviation
0.488
45
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6.5 Qualitative Results
Table 13 presents precision results for Seawater samples. The coefficients of variation for
Seawater observations were significantly higher than those associated with any other test. This
was expected due to the high salinity of the samples as communicated by the vendor prior to
testing. However, observations aligned with reference concentrations (i.e., no observations for
samples prepared with 20 ug/L Pb were greater than any observations for samples prepared with
40 ug/L Pb). This demonstrates that the Lead 100/AND 1000 is capable of indicating whether
seawater has a high or low concentration of Pb, despite its low precision when analyzing
seawater samples.
Table 14. Precision of Seawater Testing
Sample Name
SW-25
SW-50
Sample Type
Seawater
Seawater
ICP-MS
Concentration
(Mg/LPb)
20
40
Mean
Observation
(Mg/LPb)
24
60
Standard
Deviation
9.84
18.93
CV
0.42
0.32
6.6 Operational Factors
In general, the ease of use of the Lead 100/AND 1000 was high. In several cases, the
rechargeable battery provided with the AND 1000 lost power after less than 8 hours. In addition,
in one instance, the instrument displayed a screen that was foreign to the user making the
instrument unusable. Simply turning the instrument off and rebooting retuned the AND 1000 to
normal working order. The Lead 100 test kits generate a significant amount of solid waste if
many tests are performed; this could make field measurements under some conditions difficult,
although this claim is specific to field testing conditions and not an issue when testing under
laboratory conditions.
46
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Chapter 7
Performance Summary for the Lead 100/AND1000
7.1 Performance Summary for the Lead 100/AND 1000
The performance of the Lead 100/AND 1000 was evaluated for its accuracy, precision, linearity of
response, LOD, and other operational factors. Prevailing water quality characteristics dictated
by environmental conditions (e.g., pH, major anions, major cations) and water quality
characteristics artificially imparted on synthetic environmental or laboratory samples, including
synthetic matrices and Pb spikes, were varied to challenge the Pb detection technology under a
variety of conditions.
The accuracy of the Lead 100/AND 1000 was evaluated by comparing percent recovery to
reference observations for samples with a variety of prevailing water quality characteristics and
characteristics artificially imparted on the laboratory samples. Average percent recoveries for
IDC and ICC testing were determined to be 74% and 100%, respectively. Average percent
recoveries for DLOD and DLR testing were determined to be 92% and 86%, respectively.
Average percent recovery for DEI testing was determined to be 96%. Average percent
recoveries for River Water, Reservoir Water, and Raw Well Water were determined to be 113%,
105%, and 168%, respectively. Average percent recoveries for Finished Well Water, WF, and
Bottled Water were determined to be 88%, 108%, and 88%, respectively. Average percent
recoveries for Wastewater Effluent and Metal Finishing Wastewater Effluent were determined to
be 117% and 92%, respectively.
The precision of the Lead 100/AND 1000 was evaluated by statistical analysis of triplicate
observations, summarized by the mean value, SD, and CV presented in Table 12. Average CV
across all triplicate samples was determined to be 0.09. Moreover, the greatest CV determined
for triplicate observations was 0.19 (for pretreated Raw Well Water), indicating that SD of less
than 20% of the mean value should be expected during proper operation of the
Lead 100/AND 1000 within its reported operating range by a trained individual.
The linearity of response of the Lead 100/AND 1000 was evaluated by statistical analysis of DLR
testing observations, summarized by the linear regression equation. Linearity was calculated in
terms of slope, intercept, and the square of the correlation coefficient (r2) as 0.8841, -0.8418, and
0.9927, respectively. This is indicative of a nearly linear response across the reported operating
range of the Lead 100/AND 1000 for synthetic samples prepared with reagent grade water.
The LOD of the Lead 100/AND 1000 was evaluated by statistical analysis of DLOD testing
observations. The LOD of the Lead 100/AND 1000 was determined to be 1.534 ug/L Pb, which
is below the vendor's estimated detection limit of 2 |ig/L.
Observations of Seawater testing were evaluated qualitatively rather than quantitatively.
Average percent recovery for Seawater was determined to be 131% and CV was reported as high
as 0.42 for Seawater samples. However, high Pb observations in Seawater samples coincided
directly with high Pb reference concentrations. This verifies that the Lead 100/AND 1000 is
47
-------
capable of indicating high or low Pb concentrations in seawater, albeit with less precision and
accuracy than in other matrices.
Operational factors were also evaluated for the Lead 100/AND 1000. Observations of short
battery life (i.e., power loss after less than 8 hours of operation) were recorded, as well as
observations of unexplained errors necessitating device restart. However, these observations
were infrequent. In addition, if it were necessary to conduct many tests over a short period of
time, a significant amount of waste would be generated. Recalibration was necessary for 5 LFM
and LFMD samples and retesting was required for 17 LFM and LFMD samples during Round 2
testing due to QC inconsistencies. However, in some instances, QC inconsistencies were
misidentified during testing due to actual spike concentrations being outside of acceptable
ranges. Total training time for the VTC included three days of vendor training between Rounds
1 and 2 and one week of vendor observation during Round 2 testing to ensure proper sample
preparation and preservation due to Round 1 retesting.
Other general limitations were identified during the performance evaluation. The
Lead 100/AND 1000 detects only lead in the dissolved phase. Water treatment systems are
required to monitor for total (paniculate and dissolved) lead under the Lead and Copper Rule and
research indicates that a significant proportion of lead in drinking water systems at the customer
tap may be particulate lead. Secondly pH is an important parameter to measure when using the
technology because samples must be in a limited pH range to ensure accurate results, according
to vendor specifications..
48
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Chapter 8
References
1. Quality Assurance Project Plan for Verification ofANDalyze LeadlOO Test Kit and
AND1000 Fluorimeter. U.S. Environmental Technology Verification Program, Battelle,
2012.
2. Quality Management Plan for the ETV Advanced Monitoring Systems Center, Version 8.
U.S. EPA Environmental Technology Verification Program, Battelle, April 2011.
3. Quality Assurance Project Plan Deviation Report: "Verification ofANDalyze LeadlOO
Test Kit and AND 1000 Fluorimeter" (July 3, 2012). U.S. Environmental Technology
Verification Program, Battelle, 2012.
4. Touring Ohio Magazine. 2012. Scioto River. Available at: http://www.touring-
ohio.com/central/columbus/scioto-river.html.
5. Standard Methods for the Examination of Water and Wastewater, 22nd Edition,
American Public Heath Association/American Water Works Association, Rice, E.W.,
Baird, R.B., Eaton, A.D. and Clesceri, L.S. (ed.).
49
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Appendix A
Summary of Deviations from the QAPP
-------
Deviation
(Date)
Description
Cause
ETV Report
Location
Original
QAPP
Location
No. 1
(11/13/12)
In order to ensure that lead-spiked samples
used for ANDalyze tests and ICP-MS were
identical in treatment, lead spikes were made
after specific sample matrices have been
filtered to remove suspended material (the
putative sequestration phase).
ANDalyze analysis is designed to
detect only dissolved lead for this
verification. During the previous
testing Battelle and ANDalyze
discovered that matrix composition
(especially environmental waters) can
have a significant effect on lead
partitioning between bioavailable and
sequestered phases, which can lead to
low recoveries compared to expected
values. This deviation was to clarify
experimental procedures which were
believed to lead to low recovery of Pb
using both ICP-MS and
LeadlOO/ANDlOOO during testing
conducted according to procedures
described in the original QAPP
Section 3.3
Section B 1.1
No. 2
(11/13/12)
ANDalyze document AND-Sol-Env-02-2012
("Environmental Water Testing: Surface
Water, Groundwater, Hard Water, Wastewater,
& Seawater") was revised to clarify the
specific protocol for on-site calibration of
environmental samples (to be included as a
replacement to Appendix C of the QAPP; see
below). Specifically, this document was
revised to include filtration and incubation
requirements for environmental samples.
ANDalyze analysis is designed to
detect only dissolved lead for this
verification. During the previous
testing Battelle and ANDalyze
discovered that matrix composition
(especially environmental waters) can
have a significant effect on lead
partitioning between bioavailable and
sequestered phases, which can lead to
low recoveries compared to expected
values. This deviation was to clarify
experimental procedures which were
believed to lead to low recovery of Pb
using both ICP-MS and
LeadlOO/ANDlOOO during testing
conducted according to procedures
described in the original QAPP.
Section 3.3
Section B 1.1
and Appendix
C
No. 3
(11/13/12)
Utilizing the requirements for QA/QC samples
detailed in Standard Methods for the
Examination of Water and Wastewater, 22nd
Edition 1020 B and 40 CFR part 136.7,
QA/QC requirements have been added to
standard QA/QC requirements of EPA Method
200.8. These requirements are discussed in
detail in Section 4.3 of this document.
It was believed that the root cause of
low recoveries determined by ICP-MS
lied in the QA/QC procedures
employed by the commercial
laboratory.
Section 4.3
Section B5.2
and Appendix
J
Procedures for preparation of the HFe sample
were clarified. As stated in ANDalyze
document AND-Sol-Lead-05-2012 ("Iron
No. 4 Interference with LeadlOO Sensor"), pH must
be adjusted carefully to 6.5-8.0 using a pH
(11/13/12) meter before lead is spiked. It is important to
carefully adjust pH with constant stirring and
to wait two minutes and re-test the pH to
ensure no drift has occurred.
In prior sample testing the Battelle-
prepared HFe sample had a starting pH
~ 3 due to the acidic iron solution that
was used in their preparation. This is
not typical for natural ground water
samples that have high iron content.
Section 3.3
Section B 1.1
and Appendix
D
A-l
-------
Deviation
(Date)
No. 5
(11/13/12)
Description
Battelle and ANDalyze agreed that the tests
would be conducted in three phases. The test
results, which include ANDalyze sensor test
results, root cause analyses (if applicable), and
the ICP-MS results were reviewed by
ANDalyze and discussed with Battelle at the
end of each phase or during each phase before
commencement of the next phase.
The three phases are described as:
Phase 1 : Performance testing
Phase 2: Finished drinking water
testing and environmental water
testing
Phase 3: Wastewater testing
Cause
Testing was not able to be completed
in the timeframe allotted by the QAPP
when root cause analyses were
required. Communication between
phases of testing reduces the risk of
repeating large portions of testing due
to unforeseen QA/QC issues.
ETV Report
Location
Section 3.1
Original
QAPP
Location
SectionB 1.1
A-2
-------
Appendix B
QAPP Document Replacement Appendices (C and D) and Additional
Appendices (I and J)
-------
Document: AND-Sol-Env-02-2012
Environmental Water Testing: Surface Water, Groundwater, Hard Water,
Wastewater, & Seawater
and for
1. ANDalyze metal test kits are designed for use out of the box with drinking water; however they can be
used for environmental water analysis with some minor protocol modifications.
2. Below are instructions for testing samples obtained from sources such as:
Surface Water (rivers, lakes, ponds)
Ground Water (wells, aquifers)
Hard or Very Hard Water (multiple sources)
Treated Wastewater - Finished or treated and diluted tenfold
Seawater (from the surface, not the sediment/water column interface)
Each matrix type may require one or more of the following pre-treatment kits. Read guidelines for each
matrix. Kits may be purchased from ANDalyze wherever indicated or individual components for pre-
treatment may be purchased through a scientific supply company.
ANDalyze Dilution Kit
50 ml Self-standing sample tube
5 ml Fixed Volume Pipette
Reagent grade water
ANDalyze pH Adjustment Kit
Sodium Hydroxide Neutralization Solution, 1% (w/w) sodium hydroxide in a dropper bottle
Nitric Acid Neutralization Solution, 1.5% (v/v) nitric acid in a dropper bottle
pH paper
ANDalyze Iron Interference Kit
Sodium Hydroxide Neutralization Solution, 1% (w/w) sodium hydroxide in a dropper bottle
Hydrogen Peroxide Solution, 30% (w/w) hydrogen peroxide in a dropper bottle
ANDalyze Filtration Kit (Available now from ANDalyze)
0.2 u.m Nylon filter, 25 mm diameter (Nalgene)
20 ml Syringe
50 ml Self-standing sample tube
B~1 ฉ ANDalyze Inc., 2012. A!! rights reserved.
-------
Solution Note for Environmental Water Testing February 2, 2012
ANDalyze kits may be used to test many different environmental waters. Each matrix may require different
pretreatment steps. Please see the general protocols below for: (1) Dilution, (2) pH Adjustment, (3)
Filtration, and (4) Environmental Water On-site Calibration. Matrix-specific instructions, including necessary
protocols, are presented following the protocols.
Note: Our tests have shown that the percent recovery for lead in environmental samples is ~60 % for less than 25 ppb lead and 75-
125 % for 25-100 ppb lead. The percent recovery for uranium in environmental samples is > 60% for less than 30 ppb uranium and
75 - 125 % for 30 - 60 ppb uranium. Copper is less well characterized in environmental matrices, though the copper sensor is
tolerant of high salt conditions.
(1)
Dilution is needed for accurate readings if the target metal ion is present at a concentration higher than the
linear detection range stated in the Testing and Calibration manual. Linear detection ranges are noted
below:
LeadlOO sensor - 2-100 ppb Lead
UraniumlOO sensor - 2-60 ppb Uranium
Copper High Range - 0.6-3 ppm Copper
Copper Low Range - 40-200 ppb Copper
MercurylOO Range - 2-50 ppb Mercury
The ANDalyze Copper sensor is available in two ranges and therefore dilution is usually not required.
1. Dilution is best performed using standard laboratory glassware and reagent grade water - one
volume sample to nine volumes reagent grade water.
2. Dilution may also be performed in the field, with a decrease in accuracy, by withdrawing 5 mL
sample with a 5 mL fixed volume pipette, adding the aliquot to a 50 mL self-standing tube, and filling
to the 50 mL mark with reagent grade water. Shake well.
3. If the sample is diluted, on-site calibration must be performed with the diluted sample.
ANDalyze inc. 2109 S, Oak Street, Suite 102, Champaign, it 61820 USA Tel, +1 217,328,0045 www.andalyze.corn
B-2
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Solution Note for Environmental Water Testing February 2, 2012
(2) pH
ANDalyze Lead, Mercury and Copper sensors perform best when the sample pH is between 5 and 8 (pH 4-7
for Uranium). Samples with a pH greater than 8 or below 5 will not test reliably for Lead, Mercury, or Copper
(greater than 7 or below 4 for Uranium). It is required to adjust the pH into this range before sample
preparation steps and testing can continue. Samples above pH 10 should not be tested even with pH
adjustment.
1. Check the sample pH using pH paper.
2. Prepare the following solutions if pH adjustment is required
1. Sodium Hydroxide Neutralization Solution, 1% (w/w) sodium hydroxide
2. Nitric Acid Neutralization Solution, 1.5% (v/v) nitric acid
3. Adjust the sample pH
1. If the sample is below pH 5 (or pH 4 for U) addition of a dilute sodium hydroxide solution is
necessary. To a 50 mL volume of sample add the Sodium Hydroxide Neutralization Solution
dropwise with stirring or with shaking between addition of each drop. Do not titrate beyond pH
5 for Lead, Mercury, and Copper and pH 4 for Uranium.
Note: pH change from 4-5 is rapid, requiring a half drop or less. Check the pH multiple times during titration. The
number of drops required depends heavily on matrix constituents. As few as four drops may be sufficient to increase
pH from 3 to 4, or many more may be required.
2. If the sample is above pH 8 for Lead, Mercury, and Copper (above pH 7 for Uranium) addition
of a dilute nitric acid (1.5 %) solution is necessary. Samples above pH may be unsuitable for
testing even with pH adjustment as metal ion may have already precipitated out.
Note: pH change from 9-8 is rapid, requiring a half drop or less depending on matrix. Check the pH multiple times
during titration. The number of drops required depends heavily on matrix constituents. As few as four drops may be
sufficient to decrease pH from 10 to 7, or many more may be required.
Note: For highly basic water samples, acidification may be insufficient to solubilize precipitated metals.
-------
Solution Note for Environmental Water Testing
February 2, 2012
(3) - General Protocol - Filtration
1. Obtain an ANDalyze Filtration Kit. Before testing or spiking any environmental water sample, it must be
filtered to remove suspended solids.
2. Filter the water sample. Draw ~20 ml water sample into a 20 ml syringe, securely attach the filter, and
dispense into the self-standing vial.
Note: If the sample is collected off-site and transported to a laboratory for testing, ensure that the sample is stirred (e.g., stir-
bar in the bottom of a 1 L HOPE Nalgene bottle filled with sample on a stir plate) while filling the syringe to ensure
homogeneity.
3. The sample should be clear and the filter may no longer be white.
Note: If a sample contains a great deal of suspended solids the syringe filter may clog after elution of 10-20 ml sample. In this
case, discard the clogged filter and use a fresh filter to continue filtering the sample.
ANDalyze Inc. 2109 S. Oak Street, Suite 102, Champaign, IL 61820 USA Tel. +1 217.328.0045 www.andalyze.com
B-4
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Solution Note for Environmental Water Testing February 2, 2012
(4)
On-site calibration is performed for all new samples and any time a matrix may have changed, e.g. new
sampling day, change in matrix composition, new sensor batch, temperature change, etc. If in doubt,
perform On-site Calibration.
Important: For environmental samples, filtration (with 0.2 u.m Nylon filter) is required before the 100 ul
standard metal solution spike. After filtration and spiking, it is required to incubate the calibration spike
with the sample for at least 5 minutes as the spiked metal takes some time to reach equilibrium between
dissolved and bound states. Failure to allow spike incubation in the sample will lead to lower recovery.
1. Perform on-site calibration as described in the Product Manual. After adding the 100 ul standard
metal solution spike as per the instructions in the product manual, shake, and let it sit for ~ 5 minutes
before the analysis is performed.
2. Use all spiked solutions within 15 minutes.
Note: The ANDalyze test kit is designed to test for bioavailable metals and not total metals without acid digestion, which is beyond
the scope of this procedure.
ANDalyze inc. 2109 S, Oak Street, Suite 102, Champaign, it 61820 USA Tel, +1 217,328,0045 www.andalyze.corn
B-5
-------
Solution Note for Environmental Water Testing February 2, 2012
ANDalyze has performed extensive testing of our kits in surface waters such as rivers, lakes, and streams.
Some surface waters, such as runoff from industrial sites, heavily contaminated bodies of water, mine
runoff, or areas affected by acid rain may exceed interference levels and the acceptable pH range. Special
care may be needed in handling as well as testing these samples. Please contact ANDalyze with any
questions.
Important: Testing of surface waters from rivers, lakes, and streams usually does not require dilution, pH
adjustment, or iron interference removal. If required, perform those steps as stated in the protocols.
Filtration, however, is always required.
Follow this order of steps:
1. Check the pH using pH paper and adjust if required.
2. Filtration is required as per the Filtration Protocol.
3. Perform Environmental Water On-site Calibration following the Environmental Water On-site
Calibration Protocol (with incubation of calibration spike) and instructions in the Testing and On-site
Calibration manual.
ANDalyze inc. 2109 S, Oak Street, Suite 102, Champaign, IL 61820 USA Tel, +1 217,328,0045 www.andalyze.com
B-6
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Solution Note for Environmental Water Testing February 2, 2012
Important: Testing of raw or treated groundwater usually does not require dilution or pH adjustment. If
required, perform those steps as stated in the protocols. Iron interference may be an issue and the solution
color should be noted - yellow/orange color may be indicative of iron. Filtration is always required.
Follow this order of steps:
1. Check the pH using pH paper and adjust if required.
2. Verify that iron interference is not an issue. If interference is suspected, follow the Iron Interference
Solution Note.
3. Filtration is required as per the Filtration Protocol.
4. Perform Environmental Water On-site Calibration following the Environmental Water On-site
Calibration Protocol (with incubation of calibration spike) and instructions in the Testing and On-site
Calibration manual.
Note: ANDalyze has performed extensive testing of our kits in ground waters from across the U.S.A as well as in artificial matrices
based on those in Standard Methods for the Examination of Water & Wastewater, Centennial Edition. As a general rule,
performance in <;nft watpn: pyrpprk that nf wpry harH watpn: whirh arp murh mnrp likely to exceed the interference level or pH
range.
-------
Solution Note for Environmental Water Testing February 2, 2012
I lard
ANDalyze, Inc. has performed extensive testing of our kits in simulated hard waters, including hard and
moderately hard waters according to Standard Methods for the Examination of Water & Wastewater,
Centennial Edition.
Important: Testing of hard waters usually does not require dilution, pH adjustment, or iron interference
removal. If required, perform those steps as stated in the protocols. Filtration, however, may be required.
Follow this order of steps:
1. Check the pH using pH paper and adjust if required.
2. Filtration is required as per the Filtration Protocol IF the water is cloudy.
3. Perform Environmental Water On-site Calibration following the Environmental Water On-site
Calibration Protocol (with incubation of metal spike) and instructions in the Testing and On-site Calibration
manual.
-------
Solution Note for Environmental Water Testing February 2, 2012
Important: ANDalyze has tested multiple finished or treated wastewater matrices and analysis can be
challenging depending on matrix constituents. Raw wastewater is NOT suitable for testing. Dilution of the
sample (1:10) is absolutely required, which increases the effective detection range tenfold, e.g. the
detection range for Lead after dilution is 20-1000 ppb. Analyte concentrations measured at the low end of
the sensor ranges are qualitative rather than quantitative and the relative standard deviation of results is
larger than experienced in drinking water.
Follow this order of steps:
1. Precautions! Wastewaters are complicated matrices and may contain interferences beyond other metal
ions.
- Chelators such as EDTA will cause false negatives. Chelators are present in many cleaning products
and industrial processes, so check wastewater components carefully.
- Fluorescent compounds will give a high background signal and results may be unreliable
- Very high concentration of other metal ions - Example: Known metals from a metal finisher plant
- Wear personal protective equipment. Wastewaters may have extreme pH values and contain
hazardous components. Wear appropriate laboratory attire and use a fume hood as appropriate.
2. Follow the Dilution Protocol to dilute the sample tenfold. Remember that your effective detection
range has increased tenfold.
3. Check the pH using pH paper and adjust if required.
4. Verify that iron interference is not an issue. If interference is suspected, follow the Iron Interference
Solution Note.
5. Filtration is required as per the Filtration Protocol. If filters clog rapidly then pre-filtration through
Whatman 3MM paper or acid digestion may be necessary.
6. Perform Environmental Water On-site Calibration following the Environmental Water On-site
Calibration Protocol and instructions in the Testing and On-site Calibration manual.
1. If on-site calibration fails, repeat.
2. If on-site calibration fails again, further dilution may be necessary. Dilute the sample another
tenfold (total 100-fold dilution). Be aware that the analyte concentration may be out of the linear
detection range upon 100-fold (total) dilution.
Note: Some waste water matrices have many interferences and cannot be effectively analyzed without acid digestion or other
treatment procedures, which are beyond the scope of this solution note.
ANDalyze Inc. 2109 S, Oak Street, Suite 102, Champaign, IL 61820 USA Tel, +1 217,328,0045 www.andalyze.corn
B-9
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Solution Note for Environmental Water Testing February 2, 2012
Important: Sample preparation steps for seawater are normally not necessary beyond filtration unless the
sample is taken from a polluted area. This protocol is intended for analysis of seawater from the surface or
water column with minimal sediment. Analyte concentrations measured are qualitative/ semi quantitative
rather than quantitative and the relative standard deviations of results are larger than experienced in
drinking water.
Follow this order of steps:
1. Follow the Dilution protocol to dilute the sample tenfold. Remember that your effective detection
range has increased
2. Filtration is required as per the Filtration Protocol.
3. Perform Environmental Water On-site Calibration following the Environmental Water On-site
Calibration Protocol and instructions in the Testing and On-site Calibration manual.
Note: Bittern Water is a concentrated solution left over after crystallization of NaCI from seawater. It contains very high
concentrations of interfering ions, notably magnesium. ANDalyze test kits may work in bittern water upon dilution of the sample by
at least ten-fold if not 100-fold. Contact ANDalyze for further details.
ANDalyze Inc. 2109 5, Oak Street, Suite 102, Champaign, IL 61820 USA Tel, +1 217,328,0045 www.andalyze.corn
B-10
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flNDalyze
Document: AND-Sol-Lead-05-2012
Iron Interference with the LeadlOO Sensor
of in
The presence of soluble iron has a negative effect on sensor performance. The interference level for the
ANDalyze Lead sensor is defined as the level of an ion at which the signal of a 30 ppb Pb2+ solution is
changed by ฑ10%. The interference level for soluble Fe(lll) is 40 ppb. Insoluble iron in the form of
precipitates may be removed, at least in part, through natural settling or filtration. Steps to minimize
interference are provided below.
ANDalyze pH Adjustment Kit
Sodium Hydroxide Neutralization Solution, 1% (w/w) sodium hydroxide in a dropper bottle
Nitric Acid Neutralization Solution, 1.5% (v/v) nitric acid in a dropper bottle
pH paper
ANDalyze Iron Interference Kit
Sodium Hydroxide Neutralization Solution, 1% (w/w) sodium hydroxide in a dropper bottle
Sodium Hydroxide Neutralization Solution, 0.1% (w/w) sodium hydroxide in a dropper bottle
Hydrogen Peroxide Solution, 30% (w/w) hydrogen peroxide in a dropper bottle
ANDalyze Filtration Kit (Available now from ANDalyze)
0.2 u.m Nylon filter, 25 mm diameter (Nalgene)
20 ml Syringe
50 ml Self-standing sample tube
Important: Ground water samples visibly orange in color are likely to contain high levels of iron (low ppm),
though lower levels may not be easily detected with the naked eye. If it is suspected that the water sample
to be tested contains interfering levels of iron, it may be prudent to test the iron concentration using a
commercial iron test kit.
Important Safety Note: Refer to the product manual for general guidelines on safety, proper use, and
general sample testing procedures before using the testing protocol listed in this solution note. Be very
careful when handling the sodium hydroxide solution and the hydrogen peroxide solution. Wear gloves and
eye protection. Exposure to concentrated hydrogen peroxide will result in burns. See the manufacturer
Material Safety Data Sheet for further information.
B"11 ฉ Inc., 2011, AH
-------
Note: Although no individual ion may exceed the interference levels, a combination of many interfering ions close to the maximum
levels may have an effect meeting or exceeding that of a single ion at the interference level.
pH for
ANDalyze Lead sensors perform best when the sample pH is between 5 and 8. Samples with a pH greater
than 8 or below 5 will not test reliably for Lead. Iron interference removal requires a narrower pH range of
pH 6.5 to pH 8. It is required to adjust the pH into this range before sample preparation steps and testing
can continue. Samples above pH 10 should not be tested for Lead, even with pH adjustment.
1. Check the sample pH using pH paper.
1. Prepare or purchase from ANDalyze the following solutions if pH adjustment is required
2. Sodium Hydroxide Neutralization Solution, 1% (w/w) sodium hydroxide
3. Sodium Hydroxide Neutralization Solution, 0.1% (w/w) sodium hydroxide
4. Nitric Acid Neutralization Solution, 1.5% (v/v) nitric acid
2. Adjust the sample pH
1. If the sample is below pH 6.5 addition of a dilute sodium hydroxide solution is necessary. This
is a strict limit and use of a pH meter instead of pH paper will ensure that the sample is at least
pH 6.5. To a 50 mL volume of sample add the Sodium Hydroxide Neutralization Solution
dropwise with stirring or with shaking between addition of each drop. Do not titrate beyond pH
8 for Lead as it will precipitate out of solution. Once the correct pH has been achieved, wait 2
minutes and re-check to ensure that pH has stabilized
Note: The number of drops required depends heavily on matrix constituents. As few as four drops of 1% (w/w)
sodium hydroxide solution may be sufficient to increase pH from 3 to 4, or many more may be required. pH change
from 4-6.5 is rapid; add 0.1% (w/w) sodium hydroxide solution to avoid over titration. Check the pH multiple times
during titration.
2. If the sample is above pH 8 for Lead, addition of a dilute nitric acid (1.5 %) solution is
necessary. Samples above pH 10 should not be tested even with pH adjustment.
Note: pH change from 9-8 is rapid, requiring a half drop or less depending on matrix. Check the pH multiple times
during titration. The number of drops required depends heavily on matrix constituents.
Note: For highly basic water samples, acidification may be insufficient to solubilize precipitated metals.
The addition of hydrogen peroxide converts soluble iron to insoluble iron which can then be removed by
filtration.
1. Hydrogen peroxide addition. Add 4 drops of the hydrogen peroxide solution to each ~50 mL water
sample using a dropper, replace cap on the sample tube, mix well by inversion, then let sit on the
bench for 20 min.
ANDalyze Inc. 2109 S. Oak Street, Suite 102, Champaign, IL 61S20 USA Tel. +1 217,328.0045 www.andalyze.com
-------
Solution Note for Iron Interference with LeadlOO sensor
August 15, 2011
2. After the 20 min incubation continue with the Filtration Protocol described below.
Filtration Protocol
1. Obtain an ANDalyze Filtration Kit. Before
testing or spiking any environmental water
sample, it must be filtered to remove
suspended solids.
2. Filter the water sample. Draw ~20 ml water sample into a 20 ml syringe, securely attach the filter, and
dispense into the self-standing vial.
Note: If the sample is collected off-site and transported to a laboratory for testing, ensure that the sample is stirred (e.g., stir
bar in the bottom of a 1 L HOPE Nalgene bottle filled with sample on a stir plate) while filling the syringe to ensure
homogeneity.
3. The sample should be clear and the filter may no longer be
white.
Note: If a sample contains a great deal of suspended solids the syringe
filter may clog after elution of 10-20 ml sample. In this case, discard the
clogged filter and use a fresh filter to continue filtering the sample.
After completion of the Filtration Protocol continue with On-site
Calibration as described in the Testing and On-site Calibration
manual.
Summary/Notes/References
ANDalyze Inc. 2109 S. Oak Street, Suite 102, Champaign, IL ง1,|820 USA Tel. +1 217.328.0045 www.andalyze.com
-------
It is expected that, upon completion of this procedure, the interference from Iron will be greatly reduced
and that a more accurate reading of Lead concentration will be obtained. It should be noted that some co-
precipitation of Iron and Lead may be possible.
-------
Appendix 1
QAPP Deviation -1
Flowchart for sample preparation,
ANDalyze analysis, ICP analysis
Prepared by: Dr. Priya Mazumdar
(ANDalyze)
B-15
-------
IDC Testing (page 47, section Bl.1.8.1)
Collect Dl water
*
Use for ANDalyze on
site calibration
->
Record ANDalyze
measurement of
unspiked sample
Spike the water with lead
stock to make 25 ppb Pb
sample
Use for ANDalyze IDC
tests with the
calibrated site field
Preserve in acid and
send for ICP
See RCA for
recovery criteria
B-16
-------
TPC (page 47, section Bl.1.8.2)
Collect the Dl water
Spike the water with lead
stock to make 25, 50, 75
ppb Pb sample
Use for ANDalyze 3- point
calibration. Accept new
calibration
Preserve in acid and
send for ICP
Use for ANDalyze TPC tests
using site field "None" for
the new 3 point calibration
i
See RCA for
recovery criteria
B-17
-------
ICC (page 49, section Bl.1.8.3)
Collect the Dl water
Spike the water with lead
stock to make 25 ppb Pb
sample
Preserve in acid and
send for ICP
Use for ANDalyze ICC tests
using site field "None"
See RCA for
recovery criteria
B-18
-------
DLOD (page 49, section Bl.1.8.4)
Collect the Dl water
Spike the water with lead
stock to make 10 ppb Pb
sample
Preserve in acid and
send for ICP
Use for ANDalyze DLOD tests
using site field "None"
B-19
-------
DLR (page 50, section Bl.1.8.5)
Collect the Dl water
Spike the water with lead
stock to make 5, 15, 25,
50, 75, 100 Pb sample
Preserve in acid and
send for ICP
Use for ANDalyze DLR tests
using site field "None".
B-20
-------
DEI Testing - for high IDS, low IDS, High Fe Water (page 50, section Bl.1.8.1)
Filter the Battelle
prepared DEI water
Use for ANDalyze on
site calibration
Record ANDalyze
measurement of
unspiked sample
Note: Filter into 100 ml volumetric flask for preparing each lead spiked
solution. Filter into 50 ml plastic tubes for use in on site calibration
and testing unspiked samples
Spike the filtered water
with lead stock to make
25 and 50 ppb Pb sample
Use for ANDalyze tests
with the calibrated
site field
Preserve in acid and
send for ICP
See RCA for
recovery criteria
B-21
-------
DEI Testing- High Fe Water (page 50, section Bl.1.8.1) with ANDalyze iron interference
treatment
Take the prepared High
Fe water
Perform ANDalyze iron removal
treatment as stated in Iron
Interference solution note (pH
adjustment, then peroxide
precipitation, then filtration)
k
Use for ANDalyze on
site calibration
Record ANDalyze
measurement of
unspiked sample
Note: Filter into 100 ml volumetric flask for preparing each lead
spiked solution. Filter into 50 ml plastic tubes for use in on site
calibration and testing unspiked samples
Spike the water with lead stock
to make 25, 50 ppb Pb sample
Use for ANDalyze tests
with the calibrated
site field
Preserve in acid and
send for ICP
See RCA for
recovery criteria
-------
Finished drinking Water (page 51, section Bl.1.8.7) - Field test + Lab test
Collect the environmental
water and filter
Use for ANDalyze on site
calibration in the field -
(Call)
Record ANDalyze
measurement of
unspiked sample in field
Note: Filter into 100 ml volumetric flask for preparing each lead spiked
solution. Filter into 50 ml plastic tubes for use in on site calibration
and testing unspiked samples
Use for ANDalyze on-site
calibration in the lab -
(Cal2)
Spike the filtered water with lead
stock to make 25 ppb sample in lab
Use for ANDalyze tests
with the calibrated
site field (Cal2)
Preserve in acid and
send for ICP
See RCA for
recovery criteria
Note: For bottled water, fountain water: data will be collected in lab only. No field tests
For each sample that is to be tested both in the field and in the lab, two on-site calibrations
will be performed -one in the field (call) and one in the lab (ca!2).
-------
Environmental Water (page 53, section Bl. 1.8.8), except sea water - Field test + Lab test
Collect the environmental
water and filter
Use for ANDalyze on-site
calibration in the lab -
(Cal2)
Use for ANDalyze on site
calibration in the field -
(Call)
Record ANDalyze
measurement of
unspiked sample
Note: Filter into 100 ml volumetric flask for preparing each lead spiked
solution. Filter into 50 mL plastic tubes for use in on site calibration
and testing unspiked samples
Spike the filtered water with lead
stock to make 25 ppb sample
Use for ANDalyze tests
with the calibrated
site field (Cal2)
Preserve in acid and
send for ICP
See RCA for
recovery criteria
Note: For each sample that is to be tested both in the field and in the lab, two on-site
calibrations will be performed - one in the field (call) and one in the lab (ca!2).
-------
Seawater (page 55, section Bl.1.8.8)
Collect the seawater and
dilute 1:10. Then filter
Use for ANDalyze on-site
calibration
Note: Filter into 100 ml volumetric flask for preparing each lead spiked
solution. Filter into 50 ml plastic tubes for use in on site calibration
and testing unspiked samples
Spike the filtered water with
lead stock to make 25 and 50
ppb Pb sample
Use for ANDalyze tests
with the calibrated
site field
Preserve in acid and
send for ICP
See RCA for
recovery criteria
B-25
-------
Wastewater (page 56, section Bl.1.8.9) - Field test + Lab test
Collect the wastewater and
dilute 1:10 and filter
Use for ANDalyze on-site
calibration in the lab -
(Cal2)
Use for ANDalyze on site
calibration in the field -
(Call)
Record ANDalyze
measurement of
unspiked sample
Note: Filter into 100 mL volumetric flask for preparing each lead spiked
solution. Filter into 50 mL plastic tubes for use in on site calibration
and testing unspiked samples
Spike the filtered water with lead
stock to make 25 ppb sample
Use for ANDalyze tests
with the calibrated
site field (Cal2)
Preserve in acid and
send for ICP
See RCA for
recovery criteria
Note: For each sample that is to be tested both in the field and in the lab, two on-site
calibrations will be performed - one in the field (call) and one in the lab (ca!2).
-------
Appendix 2
ICP-MS Quality Control Requirements for
ANDalyze Instrument ETV Study
Edward F. Askew
Askew Scientific Consulting
Updated November 8, 2012
B-27
-------
Table of Figures 3
Introduction 4
Definitions 6
Quality Control Requirements for the ICP-MS 7
Analytical Batch 7
QC Failure Requirements: 7
B-28
-------
Table of Figures
Figure A: DHL QCS Percent recoveries 4
Figure B: DFIL vs. ANDalyze Different Aqueous Sample Matrix Recoveries 5
Figure C: Initial ICP-MS Calibration and QC 8
Figure D; ICP-MS ongoing Calibration and QC 9
Figure E: Calibration Performance Flow Chart 10
Figure F: Laboratory reagent Blank (LRB) QC Flowchart 11
Figure G: Laboratory Formulation Blank (LFB) QC Flowchart 12
Figure H: Laboratory Formulation Matrix Spike 7 Duplicate (LFM/LFMD) QC Flowchart 13
B-29
-------
Introduction
ANDalyze has contracted with Battelle Laboratories through the EPA Environmental
Technology Verification Program to evaluate the ANDalyze instrument for the determination of
lead in aqueous matrixes. A Quality Assurance Project plan (QAPP) was developed by Battelle
to perform the ETV project.
The initial ICP-MS data received from the 3r party contract laboratory, DHL Analytical, for QC
samples and aqueous matrix samples prepared by Battelle did not show acceptable agreement
between the expected value and the experimental value.
ICP-MS Pb QCS Recoveries
DHL Analytical
LCS Lower Control Limit from DHL
LCS Upper Control Limit from DHL
O
Figure A: DHL QCS Percent recoveries
Figure A summarizes the quality control samples (QCS) prepared by Battelle consisting of 25
PPB lead. These samples should be accurate and are the analog of the LCS (laboratory control
sample) prepared by DHL. In DHLs report, they have set the recovery limits for their LCS to
85% and 115%. These control limits were used to evaluate the QCS recoveries. As can be seen
in the Figure A, there are disturbing trends on DHL's QCS recoveries by ICP-MS. Their
recoveries are very low to start with and only twice did they exceed 100%.
As per Standard Methods for the Examination of Water and Wastewater 19th Edition, 1020 B(7)
these QCS recoveries must vary above or below the true value when plotted. Ideally, the
variation of the analytical results must occur such that over a 5 sample sequential sequence the
observed (determined) value must vary on either side of the 100% true value indicates that the
B-30
-------
bias is random and not due to a correctable analyst or instrument error. This has not happened
with the DHL reported values and indicates a correctable bias is present.
Andalyze vs. ICP-MS
Percent Recovery Comparison
t Recovery from Andalyze
I Recovery from ICP-MS
Figure B: DHL vs. ANDalyze Different Aqueous Sample Matrix Recoveries
Figure B summarizes the ANDalyze vs. ICP-MS recoveries for samples prepared in DI water.
The control range limits of 80% and 120% emphasizes the difference between the Andalyze
instrument recoveries and supposedly the more accurate ICP-MS. It is evident the DHL samples
did not have acceptable recoveries when compared to the ANDalyze instrument or to the
maximum recoveries acceptable for an ICP-MS instrument. This points to the samples analyses
bias.
The final area of concern is the DHL concentrations used for lead in the following QC samples.
They are:
ICV
ccv
LCS
MS and MSD
PDS
100PPB
200 PPB
200 PPB
200 PPB
200 PPB
The Andalyze samples had spike concentrations for the majority of the samples in the range of
25-30 PPB lead. The DHL concentrations of the MS, MSD, and PDS were 6-8 times higher than
the actual sample concentration. Referring to the current EPA method 200.8, the MS/MSD only
has to be at the concentration of the LFB (LCS). But, if this concentration is too high, it fails to
show the effect of the matrix on the sample analyse.
Standard Methods for the Examination of Water and Wastewater, 22nd Edition 1020 B (7)
provides more guidance in this area: "Add a concentration that is at least 10 times the MRL,
B-31
-------
less than or equal to the midpoint of the calibration curve, or method-specified level to the
selected sample(s). Preferably use the same concentration as for the LFB to allow analysts to
separate the matrix's effect from laboratory performance. Prepare the LFMfrom the same
reference source used for the LFB/LCS. Make the addition such that sample background levels
do not adversely affect recovery (preferably adjust LFM concentrations if the known sample is
more than five times the background level). For example, if the sample contains the analyte of
interest, then add approximately as much analyte to the LFM sample as the concentration
found in the known sample. "
So, the MRL reported by DHL is 1 PPB for lead. Utilizing Standard Methods, the LCS, MS,
MSD, and PDS should have been between 10 PPB lead and no higher than the 25-30 PPB QCS
spike.
Definitions
Calibration Blank: A volume of reagent water with the same sample preparation matrix as in the
calibration standards.
Calibration Standard: A solution prepared from the dilution of stock standard solutions. These
solutions are used to calibrate the instrument response with respect to analyte concentration
Continuing Calibration Standard Check: Analyte standard that has a concentration between the
lower calibration standard and upper calibration standard. A continuing calibration standard
check will be run at least once per batch.
Control Charts: Graphical charts that contain the expected value (the central line) and the
acceptable range of occurrence. The acceptable range is determined from the control limits and
warning limits. Refer to Part 1000 of Standard Methods for the Examination of Water and
Wastewater for further explanation and guidance.
Laboratory Fortified Blank (LFB): An aliquot of analyte free reagent water to which known
quantities of analyte is added in the laboratory. The LFB is analyzed exactly like a sample, and
its purpose is to determine whether the methodology is in control and whether the laboratory is
capable of making accurate and precise measurements.
Laboratory Fortified Sample Matrix/Duplicate (LFM/LFMD) also called a Matrix
Spike/Duplicate (MS/MSD): An aliquot of an environmental sample to which known quantities
of analyte is added in the laboratory. The LFM/LFMD are analyzed exactly like a sample, and
there purpose is to determine whether the sample matrix contributes bias to the analytical results.
The background concentrations of the analytes in the sample matrix must be determined in a
separate aliquot and the measured values in the LFM/LFMD corrected for background
concentrations.
Laboratory Reagent Blank (LRB): An aliquot of reagent water or other blank matrices that are
treated exactly as a sample including exposure to all glassware, equipment, solvents, reagents,
B-32
-------
and internal standards that are used with other samples. The LRB is used to determine if method
analytes or other interferences are present in the laboratory environment, reagents or apparatus.
Ongoing Demonstration of Capability (ODC) also called Ongoing Precision and Recovery
(OPR): ODC/OPR is performed at least once per sample batch to demonstrate proficiency with
the method. Reagent water is spiked with known quantities of analyte. Its purpose is to assure
that the results produced by the laboratory remain within the limits specified in this method for
precision and recovery.
Sample Batch: A group of samples which behave similarly with respect to the sampling or the
testing procedures being employed and which are processed as a unit. For QC purposes, if the
number of samples in a group is greater than 20, then each group of 20 samples or less will all be
handled as a separate batch. A batch cannot span between laboratory work days (24 hrs). New
batches must be started each laboratory work day.
Quality Control Requirements for the ICP-MS
Utilizing the requirements for QC samples detailed in Standard Methods for the Examination of
Water and Wastewater, 22nd Edition 1020 B and 40 CFR part 136.7, the following QC analysis
per batch will be performed for the ICP-MS analysis of the ANDalyze samples;
Analytical Batch
1. Initial Calibration and QC. (Figure C)
a. Meet the QC requirements Figures E-H
2. 10 unique ANDalyze analytical samples.
3. Ongoing Calibration and QC.(Figure D)
a. Meet the QC requirements Figures E-H
4. 10 unique ANDalyze analytical samples.
5. Continue sequence of 10 samples until end of batch with Ongoing QC .(Figure D) until
end of sample batch.
QC Failure Requirements:
If by following the flow charts in Figures E-H, the analyst reaches the point where a Root Cause
Analyses, RCA, must be performed, contact Battelle. All RCA results must be recorded and
submitted for approval by Battelle prior to restarting the ICP-MS analyses.
B-33
-------
ICP-MS
Calibration and Initial QC
Initial
Calibration
Initial Cal.
Performance
Initial LRB
Performance
Initial LFB
Performance
Calibration Standards=Minimum 5 concentrations between 1-250
PPB Lead and calibration zero.
Non-linear Calibration.
Calibration Standard Check run at % and % points in the calibration
range. Recovery will not vary more than 90-110%
Laboratory Reagent Blank: Lead concentration must not exceed /2
the MDL. The LRB will be prepared by the ICP-MS laboratory and
will be independent from the LCS samples being prepared by
Battelle
Laboratory Formulation Blank: Recovery will not vary more than
90-110%. The concentration of the LFB will be 25 PPB lead for all
batches. The LFB will be prepared by the ICP-MS laboratory and
will be independent from the LCS samples being prepared by
Battelle
Initial
LFM/LFMD
Laboratory Formulation Matrix Spike/Duplicate: Recovery will not
vary more than 90-110%. The concentration of the LFM/LFMD
spike will be 25 PPB lead for all batches. The LFM/LFMD will be
prepared by the ICP-MS laboratory and will be independent from
samples being prepared by Battelle.
Figure C: Initial ICP-MS Calibration and QC
B-34
-------
ICP-MS
Ongoing Calibration and QC
Cont.
Calibration
Check
Continuing
LFM/LFMD
Continuing Calibration Standard Check run at % and % points in
the calibration range. Recovery will not vary more than 90-110%
Continuing Laboratory Reagent Blank: Lead concentration must
not exceed 1/2 the MDL. The LRB will be prepared by the ICP-MS
laboratory and will be independent from the LCS samples being
prepared by Battelle
Continuing Laboratory Formulation Blank: Recovery will not vary
more than 90-110%. The concentration of the LFB will be 25 PPB
lead for all batches. The LFB will be prepared by the ICP-MS
laboratory and will be independent from the LCS samples being
prepared by Battelle
Laboratory Formulation Matrix Spike/Duplicate: Recovery will not
vary more than 90-110%. The concentration of the LFM/LFMD
spike will be 25 PPB lead for all batches. The LFM/LFMD will be
prepared by the ICP-MS laboratory and will be independent from
samples being prepared by Battelle.
Figure D; ICP-MS ongoing Calibration and QC
B-35
-------
ICP-MS
Calibration QC Performance Flow Chart
Redo Non-linear Calibration
has correlation value < 0.99
Analyses halts and RCA is
performed
Non-linear Calibration has
correlation value > 0.99.
NO
T
Redo Initial
Calibration
Initial rrr
Calibration /
Non-linear Calibration has
correlation value < 0.99.
r
Non-linear Calibration has
correlation value > 0.99.
YES
Redo Continuing
Calibration has
recovery value
outside of 90-110%
Analyses halts and
RCA is performed
Continuing Calibration
Standard Check run at %
and % points in the
calibration range.
Recovery will not vary
more than 90-110%
Figure E: Calibration Performance Flow Chart
B-36
-------
ICP-MS
LRB QC Performance Flow Chart
RedoLRB>50%oftheRL
Analyses halts and RCA is
performed
Redo LRB > 50%
percent of the RL.
Analyses halts and
RCA is performed
NO
Recovery will not be more
than 50% of the Reporting
Limit (RL).
Redo LRB < 50% of the RL
Continuing LRB is run at
least every 20 samples.
Recovery will be < 50% of
theRL
LRB < 50% of theRL
YES
Continue
;/ \-ui ILII me \
Batch
Figure F: Laboratory reagent Blank (LRB) QC Flowchart
B-37
-------
ICP-MS
LFB QC Performance Flow Chart
Redo LFB outside the 90-110%
percent recovery.
Analyses halts and RCA is
performed
Redo LFB inside the 90-110%
percent recovery.
NO
Recovery will not vary more
than 90-110%. The
concentration of the LFB will
be 25 PPB lead for all batches
Redo LFB outside
the 90-110%
percent recovery.
Analyses halts and
RCA is performed
Continuing LFB is run at
least every 20 samples.
Recovery will not vary
more than 90-110%
Recovery within
90-110%
YES
Continue
;/ \-ui ILII me \
Batch
Figure G: Laboratory Formulation Blank (LFB) QC Flowchart
B-38
-------
ICP-MS
LFM/LFMD QC Performance Flow Chart
Redo LFM or LFMD outside
the 90-110% percent
recovery.
Analyses halts and RCA is
performed
Redo LFM/LFMD inside the
90-110% percent recovery.
NO
Recovery will not vary more
than 90-110%. The
concentration of the LFM/
LFMD spike will be 25 PPB
lead for all batches.
Redo LFM/LFMD
outside the 90-
110% percent
recovery.
Analyses halts and
RCA is performed
Continuing LFM/LFMD is
run at least every 20
samples. Recovery will
not vary more than 90-
110%
Recovery within
90-110%
YES
Continue
;/ \-ui ILII me \
Batch
Figure H: Laboratory Formulation Matrix Spike 7 Duplicate (LFM/LFMD) QC Flowchart
B-39
-------
Appendix C
Round 1 Testing Results
-------
o
Date
7/10/2012
7/13/2012
Sample
Number
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
Sample
Name
QCS-1
IDC-25-1
IDC-25-1-
RR1
IDC-25-1-
RR2
IDC-25-2
IDC-25-2-
RR2
QCS-1
QCS-1 -RR1
IDC-25-1
IDC-25-2
IDC-25-3
TPC-25
TPC-25-RR1
TPC-50
TPC-50-RR1
TPC-75
Expected
Concentration
(ug/LPb)
30
25
25
25
25
25
30
30
25
25
25
25
25
50
50
75
Measured
Concentration
(ug/LPb)
27
18
16
22
16
18
22
27
24
31
24
36
22
65
50
61
ICP-MS
Concentration
(ug/LPb)
Not Analyzed
Not Analyzed
Not Analyzed
Not Analyzed
Not Analyzed
Not Analyzed
18
18
17
17
17
17
17
46
46
58
Abnormal Anticipated
Percent
Recovery/Control Chart
Result (vs. Expected
Results)
None
Percent recovery < 75%
Percent recovery < 75%
None
Percent recovery < 75%
Percent recovery < 75%
Percent recovery < 75%
None
None
Sample above UCL
None
Percent recovery > 125%
None
Percent recovery > 125%
None
None
Resolution
Perform on-site
calibration and rerun
sample
Root cause analysis.
Reprepare IDC-25
sample and repeat
onsite calibration
Repeat on-site
calibration and rerun
sample
pH and temperature
of each sample
measured (6.92-
6.94)
Repeat on-site
calibration and rerun
sample
Three point
calibration (25, 50
and 75 ppb)
completed and
saved to AND 1000
Repeat on-site
calibration and rerun
sample
Comments
Reanalysis of IDC-25-1
Assume sample preparation
error for IDC-25
Contacted ANDalyze and
agreed that ANDalyze will be
present to observe only a
repeat of the performance
testing on 7/1 3/1 2
Failed first on-site calibration
Reanalysis of QCS-1
Sample should have been
reanalyzed
Reanalysis of TPC-25
Reanalysis of TPC-50
-------
Date
Sample
Number
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
Sample
Name
ICC-25-1
ICC-25-2
ICC-25-3
QCS-2
DLOD-10-1
DLOD-10-2
DLOD-10-3
DLOD-10-4
DLOD-10-5
DLOD-10-6
DLOD-10-7
DLR-5-1
DLR-5-2
DLR-5-3
QCS-3
QCS-3-RR1
Expected
Concentration
(ug/LPb)
25
25
25
30
10
10
10
10
10
10
10
5
5
5
30
30
Measured
Concentration
(ug/LPb)
26
23
22
27
11
12
11
8
11
7
8
6
6
7
35
22
ICP-MS
Concentration
(ug/LPb)
19
19
19
25
6
6
6
6
6
6
6
4
4
4
23
23
Abnormal Anticipated
Percent
Recovery/Control Chart
Result (vs. Expected
Results)
None
None
None
None
None
None
None
None
None
None
None
None
None
None
Four out of five samples
are outside one standard
deviation of the mean
percent recovery
Percent recovery < 75%.
Four out of five samples
are outside one standard
deviation of the mean
percent recovery
Resolution
QCS-3 reanalyzed
QCS-3 reanalyzed
Comments
RB-1 analyzed (below limit
reported)
DLOD has no explicit QC
requirement for percent
recovery. These samples
must conform to the control
chart
DLR has no explicit QC
requirement for percent
recovery. These samples
must conform to the control
chart
This sample was mistakenly
observed above the UCL and
reanalyzed. Reanalysis
unnecessary and results of
reanalysis results not reported
RB-2 analyzed: first reading 3
ppb. RB-2 reanalyzed:
second reading below limit
Reanalysis of QCS-3
-------
o
OJ
Date
7/18/2012
Sample
Number
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
Sample
Name
QCS-3-RR2
DLR-15-1
DLR-15-1-
RR1
DLR-15-2
DLR-15-3
DLR-25-1
DLR-25-2
DLR-25-3
DLR-50-1
DLR-50-2
DLR-50-3
DLR-75-1
DLR-75-2
DLR-75-3
QCS-4
DLR- 100-1
DLR- 100-2
DLR- 100-3
HTDS-25-1
HTDS-25-1 -
RR1
HTDS-25-1 -
RR2
HTDS-25-2
HTDS-25-3
Expected
Concentration
(ug/LPb)
30
15
15
15
15
25
25
25
50
50
50
75
75
75
30
100
100
100
25
25
25
25
25
Measured
Concentration
(ug/LPb)
29
18
15
14
14
25
21
23
50
51
45
83
60
63
35
141
105
95
19
14
27
25
33
ICP-MS
Concentration
(ug/LPb)
23
12
12
12
12
22
22
22
41
41
41
66
66
66
29
81
81
81
21
21
21
21
21
Abnormal Anticipated
Percent
Recovery/Control Chart
Result (vs. Expected
Results)
None
Four out of five samples
are outside one standard
deviation of the mean
percent recovery
None
None
None
None
None
None
None
None
None
None
None
None
None
None
None
None
Four out of five
measurements in
decreasing order
Percent recovery < 75%
None
None
Percent recovery > 125%
Resolution
DLR-15-2
reanalyzed
Reanalyze HTDS-
25-1
Repeat on-site
calibration and
reanalyze HTDS-25-
1
Repeat on-site
Comments
ReanalysisofQCS-3
ReanalysisofDLR-15-3
RB-2 analyzed (below limit
reported)
This sample was mistakenly
observed above the UCL and
reanalyzed. Reanalysis
unnecessary and results of
reanalysis results not reported
Reanalysis of HTDS-25-1
Reanalysis of HTDS-25-1
-------
Date
Sample
Number
56
57
58
59
60
61
62
63
64
65
66
67
68
69
70
71
Sample
Name
HTDS-25-3-
RR1
HTDS-50-1
HTDS-50-2
HTDS-50-3
QCS-5
LTDS-25-1
LTDS-25-2
LTDS-25-3
LTDS-50-1
LTDS-50-2
LTDS-50-3
LTDS-50-3-
RR1
QCS-6
HFe-25-PT-l
HFe-25-PT-
1-RR1
HFe-50-PT-l
Expected
Concentration
(ug/LPb)
25
50
50
50
30
25
25
25
50
50
50
50
30
25
25
50
Measured
Concentration
(ug/LPb)
19
52
45
40
29
20
21
19
53
41
33
50
35
2
2
3
ICP-MS
Concentration
(ug/LPb)
21
43
43
43
25
19
19
19
39
39
39
39
30
27
27
51
Abnormal Anticipated
Percent
Recovery/Control Chart
Result (vs. Expected
Results)
None
None
None
None
None
None
None
None
None
None
Percent recovery < 75%
None
None
Percent recovery < 75%.
Sample is below LCL
Percent recovery < 75%.
Sample is below LCL
Percent recovery < 75%.
Sample is below LCL.
Resolution
calibration and
reanalyze HTDS-25-
3
Repeat on-site
calibration and
reanalyze LTDS-50-
3
Repeat on-site
calibration and
reanalyze HFe-25-
PT-1
HFe-25 analysis
terminated
Repeat on-site
calibration and
Comments
Reanalysis of HTDS-25-3
RB-4 analyzed (2 ppb
reported). RB-4 reanalyzed
(below limit reported)
Reanalysis of LTDS-50-3
HFe water analyzed with and
without pretreatment.
Samples without pretreatment
do not have explicit percent
recovery QC criteria nor are
they reported in the control
chart. RB-5 analyzed (below
limit reported)
Reanalysis of HFe-25-1
-------
o
Date
7/19/2012
Sample
Number
72
73
74
75
76
77
78
79
80
81
82
83
84
85
86
Sample
Name
HFe-50-PT-
1-RR1
QCS-7
QCS-7-RR1
QCS-8
WF-25-1
WF-25-2
WF-25-2-
RR1
WF-25-2-
RR2
WF-25-2-
RR3
WF-25-3
BW-25-1
BW-25-2
BW-25-3
BW-25-3-
RR1
QCS-9
Expected
Concentration
(ug/LPb)
50
30
30
30
25
25
25
25
25
25
25
25
25
25
30
Measured
Concentration
(ug/LPb)
4
38
36
23
21
16
14
12
19
19
20
21
18
25
32
ICP-MS
Concentration
(ug/LPb)
51
29
29
28
15
15
15
15
15
15
16
16
16
16
28
Abnormal Anticipated
Percent
Recovery/Control Chart
Result (vs. Expected
Results)
Fourth out of five
samples outside of one
standard deviation from
mean percent recovery
Percent recovery < 75%.
Sample is below LCL
Percent recovery > 125%
None
None
None
Percent recovery < 75%
Percent recovery < 75%.
LFM/LFMD RPD > 30 %
Percent recovery < 75%.
LFM/LFMD RPD > 30 %
None
None
None
None
Percent recovery < 75%
None
None
Resolution
reanalyze HFe-50-
PT-1
HFe-50 analysis
terminated.
Reanalyze QCS-7
Repeat on- site
calibration and
reanalyze WF-25-2
Repeat on-site
calibration and
reanalyze WF-25-2
Repeat on-site
calibration and
reanalyze WF-25-2
Repeat on-site
calibration and
reanalyze BW-25-3
Comments
ReanalysisofHFe-50-1. RB-
6 analyzed (below limit
reported)
Reanalysis of QCS-7
This sample was mistakenly
observed as the fourth out of
five samples outside of one
standard deviation from mean
percent recovery. Reanalysis
unnecessary and results of
reanalysis results not reported
Repeated on-site calibration 3
times as the readings did not
seem correct (12 ppb and 29
ppb) for WF water
Reanalysis of WF-25-2.
Testing should have been
abandoned at this point
Reanalysis of WF-25-2.
Reanalysis of WF-25-2.
Reanalysis of BW-25-3. RB-
7 analyzed (below limit
reported)
This sample was mistakenly
-------
o
Date
7/24/2012
Sample
Number
87
88
89
90
91
92
93
94
95
96
97
98
99
100
101
Sample
Name
FWW-25-1
RWW-25-1
RWW-25-2
RWW-25-3
QCS-10
QCS-11
QCS-12
ReW-25-1
ReW-25-1-
RR1
ReW-25-1-
RR2
RiW-25-1
RiW-25-1-
RR1
RiW-25-2
RiW-25-3
RiW-25-3-
RR1
Expected
Concentration
(ug/LPb)
25
25
25
25
30
30
30
25
25
25
25
25
25
25
25
Measured
Concentration
(ug/LPb)
15
23
21
19
32
25
35
3
9
0
9
22
19
13
13
ICP-MS
Concentration
(ug/LPb)
23
7
7
7
29
27
28
8
8
8
4
4
4
4
4
Abnormal Anticipated
Percent
Recovery/Control Chart
Result (vs. Expected
Results)
Percent recovery < 75%
None
None
None
None
None
None
Percent recovery < 75%
Percent recovery < 75%.
LFM/LFMD RPD > 30 %
Percent recovery < 75%.
LFM/LFMD RPD > 30 %
Percent recovery < 75%.
LFM/LFMD RPD > 30 %
None
None
Percent recovery < 75%
Percent recovery < 75%
Resolution
Repeat on-site
calibration and
reanalyze FWW-25-
1
Repeat on-site
calibration and
reanalyze ReW-25-1
Repeat on-site
calibration and
reanalyze ReW-25-1
Reservoir water
analysis terminated
Repeat on-site
calibration and
reanalyze RiW-25-1
Repeat on-site
calibration and
reanalyze RiW-25-3
River water analysis
terminated
Comments
observed as the fourth out of
five samples in increasing
order. Reanalysis
unnecessary and results of
reanalysis results not reported
Attempted recalibration,
however, AND 1000 reported
that the test water was not
suitable for accurate analysis
and to contact the vendor. As
a result, FWW analysis was
terminated
RB-8 analyzed (below limit
reported)
Reanalysis of ReW-25-1.
Reanalysis of ReW-25-1.
Reanalysis of RiW-25-1
Reanalysis of RiW-25-3
-------
o
Date
7/25/2012
Sample
Number
102
103
104
105
106
107
108
109
110
111
112
113
114
115
116
Sample
Name
SW-25-1
SW-25-2
SW-25-3
SW-50-1
SW-50-2
SW-50-3
QCS-13
QCS-14
QCS-15
MWWE#1-
25-1
MWWE#1-
25-2
MWWE#1-
25-3
MWWE#1-
25-3-RR1
QCS-16
MWWE#2-
Expected
Concentration
(ug/LPb)
25
25
25
50
50
50
30
30
30
25
25
25
25
30
25
Measured
Concentration
(ug/LPb)
23
30
18
48
42
51
32
29
25
22
20
17
22
30
21
ICP-MS
Concentration
(ug/LPb)
20
20
20
46
46
46
29
27
25
19
19
19
19
28
17
Abnormal Anticipated
Percent
Recovery/Control Chart
Result (vs. Expected
Results)
None
None
None
None
None
None
None
None
None
None
None
Percent recovery < 75%
None
None
None
Resolution
Repeat on-site
calibration and
reanalyze
MWWE# 1-25-3
Comments
Seawater samples were
diluted 10:1 and filtered
through 0.20 |im Nylon filter
before any further analysis or
manipulation. Seawater
samples required pH
adjustment. Seawater
samples have no explicit QC
requirement for percent
recovery. These samples
must conform to the control
chart.
RB-9 analyzed (below limit
reported)
RB-10 analyzed (below limit
reported)
All wastewater samples were
diluted 10:1 and filtered
through 0.20 |im Nylon filter
before any further analysis or
manipulation
Reanalysis of MWWE#l-25-3
RB-1 1 analyzed (below limit
reported)
All wastewater samples were
-------
o
oo
Date
7/27/2012
Sample
Number
117
118
119
120
121
122
Sample
Name
25-1
MWWE#2-
25-2
MWWE#2-
25-3
MWWE#2-
25-3-RR1
QCS-18
QCS-18-RR1
QCS-19
Expected
Concentration
(ug/LPb)
25
25
25
30
30
30
Measured
Concentration
(ug/LPb)
20
15
12
22
29
26
ICP-MS
Concentration
(ug/LPb)
17
17
17
29
29
31
Abnormal Anticipated
Percent
Recovery/Control Chart
Result (vs. Expected
Results)
None
Percent recovery < 75%
Percent recovery < 75%
Percent recovery < 75%
None
None
Resolution
Repeat on-site
calibration and
reanalyze
MWWE#2-25-3
MWWE#2 analysis
terminated
Reanalyze QCS-18
Comments
diluted 10:1 and filtered
through 0.20 urn Nylon filter
before any further analysis or
manipulation
Reanalysis of MWWE#2-25-3
MFWWE analysis attempted
on 7/26/12 however, operator
failure to follow QAPP
resulted in reanalysis on
7/27/12
Reanalysis of QCS-18
Attempted recalibration,
however, AND 1000 reported
that the test water was not
suitable for accurate analysis
and to contact the vendor. As
a result, MFWWE analysis
was terminated. RB-12
analyzed (below limit
reported)
-------
Appendix D
Round 1 Control Charts
-------
o
i in
Recovery
h
2 I
k.
Percent 1
^
A
<
^V* ^B-ป
>
J
-^_ซ ^BVT-
^
k
^ ^^
k
^
^ ^^
<
k
^ ^
, -^
^
k
^
<
<
^
>
>
^B ^^
<
<
^ ^^ป
>
>
-) ^^r-
<
^mt ^_ซ
^
-UWL
-LWL
+SD
-SD
1 2 3 4 5 6 7 8 9 10 11 12 13 14
Observation Number
-------
O
1 1f\
1 ^c\
ljU
i ^n
1 1 f\
t>
o
u
U
C* 90
S
c <
OJ
&
^7A
^n
ir\
in -
^B ^B ^^L.
<
^
^B ^ ^^
.^^ ^ ^m
>
~^ ^ ^H
^ ^
4
^^ ^^
^ ^B
<
^^ ^
^ ^B ^^
^ ^ ^^r
_^ ^B ^
<
~^ ^ ^
1 ^ ^ 1
>
1 ^^ ^^ I
^ ^ ^B_
^
^ ^ ^^r~
.^ ^ ^^
>
^ ^ ^^
^ -UWL
-LWL
+SD
-SD
16 17 18 19 20 21 22 23 24 25
Observation Number
-------
O
1 f*f\
1 A(\
i on
t>
O 1 AA
Percent Rec
h-
c c
<
/:A
/] A
on
M ^ ^B~
^^^^^^^^^^^
^
~^m ^m ^
^ ^
^ ^m
^m ^m ^r
4
-^ ^
k
s ^m ^m i
^
^ ^ ^B~
^
^B ^ ^m
-UWL
^ -LWL
+SD
-SD
26 27 28 29 30 31 32 33 34 35
Observation Number
-------
o
1 7(\
i ^n
ฃ? i in -
33 nu
o
u
g <
aj QA _
PH
^7A
^ <
<
>
4
^
ป
^
^
^
>
>
4
-UWL
-LWL
+SD
-SD
36 37 38 39 40 41 42 43 44 45
Observation Number
-------
O
1 7(\
i ^n
1 7n
ฃ? i in -
3 ill)
>
o
u
s
g
aj QA _
PH
<
^7A
^n
7H
B__^B__^B_
J
>
<
_^H_^B_^
L
>
_^B_^B_S
<
B_^B_^B_
>
<
^B_^B_^B.
1
_^B_^B_^
>
<
>__^B__^B_S
4
>
B_^B_^B_
S
<
.^B_^B_^
<
>
>
-UWL
-LWL
+SD
-SD
46 47 48 49 50 51 52 53 54 55
Observation Number
-------
O
C3N
1 1f\
i ^n
i ^n
&* 1 1A _
ircent Recove
h-
^ c
fi
<
^7A
^n
7fป
^m ^B ^^ป-
<
-^ ^B ^H
>
^ ^M
^ ^ ^
^ ^ ^M-
^M ^ ^
1 ^ ^ 1
^ ^M ^^B
-^ ^ ^^
\^
p
<
>
<
^
^
>
^
f
^ -UWL
^ -LWL
> +SD
-SD
56 57 58 59 60 61 62 63 64 65
Observation Number
-------
O
1 Gn
1 AH
1 A(\
i on
t>
y inn -
o
O
3
g
W on -
0)
0.
<
/Tfl
40
OH
n -
a5 aa aa~
>
BBB ^^B ^^B-
~^B ^B SB
4
-^ ^m
as aa a
k
^^ ^^B
a aa aa
ป ^
aa aa aa~
^ ^BV-
<
~aa aa ai
^am ^B* ^
[
ป aa aa i
1
1 ^BK- ^BB) I
as aa aa~
>
BB ^BB) ^BB>
~aa aa aa
A
-^BB) ^BB) ^BB)
^ -UWL
> -LWL
+SD
-SD
66 67 68 69 70 71 72 73 74 75
Observation Number
-------
O
i^n
i An
i in
IzU
, i nn
fe* 1UU
0)
>
o
u
s <
+-
fi Ofl _
g oU -
a
0>
&
/:A
/] A
^>n
ZU
n -
^ ^B ^B~
~^B ^B ^
^B BB a
m ^S ^B
B BB BB"
~BB BB Si
4
i BB SB i
B SB BB~~
BB BB BB
-UWL
-LWL
+SD
-SD
76 77 78 79 80 81 82 83 84 85
Observation Number
-------
O
i /in
i on
<
o>
o
o
fi on
g oU -
^n
/in
n -
^m ^M ^M-
^
-^M ^M ^H
^ ^
0
,
^ ^
^ ^ ^^B-
1
^ ^M ^
>
^
1 ^ ^ 1
^
^ ^M ^^B
-^ ^ ^^
^^^
^ -UWL
^ -LWL
+SD
-SD
86 87 88 89 90 91 92 93 94 95
Observation Number
-------
o
o
i An
i on
0)
o
u
fi Ofl
g oU -
/Tfl
/
n -
j
^ -UWL
-LWL
+SD
-SD
96 97 98 99 100 101 102 103 104 105
Observation Number
-------
O
i^n
i An
i on
, i nn
fe* 1UU
0)
>
o
u
s
-*^
fi on _
g oU -
a
0)
a.
/Tfl
/in
on
zU
^m ^B ^^k-
<
>
^ ^ ^K-
-^ ^ ^m
>
4
-^m ^ ^
^ ^B
^
4
^ ^
^B ^
^ ^ ^^
^m ^K_
^K ^ ^
^ ^B
_^ ^
^B ^ 1
^m ^ ^^
^ ^ 1
^ ^ ^B-
-^ ^B ^
-^ ^ ^
^ -UWL
^ -LWL
+SD
-SD
106 107 108 109 110 111 112 113 114 115
Observation Number
-------
o
to
140
120
o
u
$4
u
a
40
UWL
LWL
-SD
116
117
118 119
Observation Number
120
-------
Appendix E
Round 2 Testing Results
-------
Date
2/12/2013
Phase 1
Sample
Number
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
Sample
Name
QCS-1
IDC-25-1
IDC-25-2
IDC-25-
2-RR1
IDC-25-
2-RR2
IDC-25-3
IDC-25-
3-RR1
ICC-25-1
ICC-25-2
ICC-25-3
QCS-2
QCS-2-
RR1
DLOD-
10-1
DLOD-
10-2
DLOD-
10-3
DLOD-
10-4
DLOD-
10-5
DLOD-
10-6
DLOD-
10-7
Expected
Concentration
(ug/LPb)
30
25
25
25
25
25
25
25
25
25
30
30
10
10
10
10
10
10
10
Measured
Concentration
(ug/LPb)
31
20
18
16
19
18
21
20
25
21
20
25
8
8
9
8
8
8
9
ICP-MS
Concentration
(ug/LPb)
30
27
22
31
9
Percent
Recovery
to Target
(%)
103
80
72
64
76
72
84
80
100
84
67
83
80
80
90
80
80
80
90
Percent
Recovery
to ICP-
MS (%)
103
74
67
59
70
67
78
91
114
95
65
81
89
89
100
89
89
89
100
Abnormal
Anticipated Percent
Recovery/Control
Chart Result
Percent recovery <
75%
Percent recovery <
75%
Percent recovery <
75%
Percent recovery <
75%
No Percent recovery
criterion
No Percent recovery
criterion
No Percent recovery
criterion
No Percent recovery
criterion
No Percent recovery
criterion
No Percent recovery
criterion
No Percent recovery
criterion
Resolution
Rerun IDC-
2
Repeat on-
site
calibration
Continue to
TPC
Rerun
QCS-2
Comments
TPC completed
and applied.
Site "None"
used for all
remaining DI
water samples
-------
Date
Phase 1
Sample
Number
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
Sample
Name
DLR-5-1
DLR-5-2
DLR-5-3
QCS-3
DLR-15-
1
DLR-15-
2
DLR-15-
3
DLR-25-
1
DLR-25-
2
DLR-25-
3
DLR-50-
1
DLR-50-
2
DLR-50-
3
QCS-4
DLR-75-
1
DLR-75-
2
DLR-75-
3
DLR-
100-1
DLR-
100-2
DLR-
100-3-
RR1
Expected
Concentration
(ug/LPb)
5
5
5
30
15
15
15
25
25
25
50
50
50
30
75
75
75
100
100
100
Measured
Concentration
(ug/LPb)
4
4
5
24
12
14
12
20
19
22
51
46
46
28
77
78
73
105
91
83
ICP-MS
Concentration
(ug/LPb)
5
32
14
29
53
29
83
109
Percent
Recovery
to Target
(%)
80
80
100
80
80
93
80
80
76
88
102
92
92
93
103
104
97
105
91
83
Percent
Recovery
to ICP-
MS (%)
80
80
100
75
86
100
86
69
66
76
96
87
87
97
93
94
88
96
83
76
Abnormal
Anticipated Percent
Recovery/Control
Chart Result
No Percent recovery
criterion
No Percent recovery
criterion
No Percent recovery
criterion
No Percent recovery
criterion
No Percent recovery
criterion
No Percent recovery
criterion
No Percent recovery
criterion
No Percent recovery
criterion
No Percent recovery
criterion
No Percent recovery
criterion
No Percent recovery
criterion
No Percent recovery
criterion
No Percent recovery
criterion
No Percent recovery
criterion
No Percent recovery
criterion
No Percent recovery
criterion
No Percent recovery
criterion
First reading was
157 ppb and above
the UCL
Resolution
DLR-100-3
will be
rerun
Comments
-------
w
OJ
Date
2/1 3/1 3/
Phase 1
Sample
Number
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
Sample
Name
QCS-5
QCS-6
QCS-6-
RR1
LTDS-
25-1
LTDS-
25-2
LTDS-
25-2-RR1
LTDS-
25-3
LTDS-
50-1
LTDS-
50-2
LTDS-
50-3
HTDS-
25-1
HTDS-
25-1-RR1
HTDS-
25-2
HTDS-
25-3
QCS-7
HTDS-
50-1
HTDS-
50-2
HTDS-
50-3
HFe-25-1
Expected
Concentration
(ug/LPb)
30
30
30
25
25
25
25
50
50
50
25
25
25
25
30
50
50
50
25
Measured
Concentration
(ug/LPb)
34
20
27
19
17
23
25
46
38
41
18
26
22
24
26
46
41
47
24
ICP-MS
Concentration
(ug/LPb)
34
27
25
47
21
31
49
22
Percent
Recovery
to Target
(%)
113
67
90
76
68
92
100
92
76
82
72
104
88
96
87
92
82
94
96
Percent
Recovery
to ICP-
MS (%)
100
74
100
76
68
92
100
98
81
87
86
124
105
114
84
94
84
96
109
Abnormal
Anticipated Percent
Recovery/Control
Chart Result
Percent recovery <
75%
Percent recovery <
75%
Percent recovery <
75%
Resolution
rerun QCS-
6
Rerun
LTDS-25-2
Rerun
HTDS-25-1
Comments
All LTDS
samples
prefiltered
All HTDS
samples
prefiltered
After filtration,
pH adjustment
and
-------
Date
Phase 1
Sample
Number
59
60
61
62
63
64
65
Sample
Name
HFe-25-2
HFe-25-
2-RR1
HFe-25-3
HFe-50-1
HFe-50-2
HFe-50-3
QCS-8
Expected
Concentration
(ug/LPb)
25
25
25
50
50
50
30
Measured
Concentration
(ug/LPb)
18
19
20
42
44
45
33
ICP-MS
Concentration
(ug/LPb)
45
31
Percent
Recovery
to Target
(%)
72
76
80
84
88
90
110
Percent
Recovery
to ICP-
MS (%)
82
86
91
93
98
100
106
Abnormal
Anticipated Percent
Recovery/Control
Chart Result
Resolution
Comments
pretreatment
Date
3/12/2013
Phase 2
Sample
Number
1
2
3
4
5
6
7
8
9
10
11
12
Sample
Name
QCS-9
RiW-25-1
RiW-25-2
RiW-25-3
RiW-25-3-
RR1
ReW-25-1
ReW-25-2
ReW-25-3
RWW-25-1
RWW-25-
1-RR1
QCS-10
RWW-25-
1-RR2
Expected
Concentration
(ug/LPb)
30
25
25
25
25
25
25
25
25
25
30
25
Measured
Concentration
(ug/LPb)
24
21
24
16
23
23
20
23
13
12
24
16
ICP-MS
Concentration
(ug/LPb)
29
20
21
18
26
18
Percent
Recovery
to Target
( ฐ)
80
84
96
64
92
92
80
92
52
48
80
64
Percent
Recovery to
ICP-MS
( ฐ)
83
105
120
80
115
110
95
110
72
67
92
89
Anticipated
Percent
Recovery/Control
Chart Result
Percent recovery <
75%
Percent recovery <
75%
Percent recovery <
75%
Percent recovery <
75%
Resolution
Rerun RiW-
25-3
Rerun
RWW-25-1
Repeat on-
calibration
and rerun
RWW-25-1
Rerun
RWW-25-1 -
RR2
Comments
w
-------
Date
3/13/2013
Phase 2
Sample
Number
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
Sample
Name
RWW-25-
1-RR3
RWW-25-2
RWW-25-
2-RR1
RWWPT-
25-1
RWWPT-
25-2
RWWPT-
25-3
RWWPT-
25-3-RR1
FWW-25-1
FWW-25-2
QCS-11
QCS-11-
RR1
FWW-25-3
QCS-12
QCS-12-
RR1
QCS-12-
RR2
QCS-13
WF-25-1
WF-25-2
Expected
Concentration
(ug/LPb)
25
25
25
35
35
35
35
25
25
30
30
25
30
30
30
30
25
25
Measured
Concentration
(ug/LPb)
21
18
14
43
32
26
31
23
21
43
37
19
40
46
33
27
19
24
ICP-MS
Concentration
(ug/LPb)
21
24
28
24
28
29
21
Percent
Recovery
to Target
(%)
84
72
56
123
91
74
89
92
84
143
123
76
133
153
110
90
76
96
Percent
Recovery to
ICP-MS
(%)
117
100
78
205
152
124
148
96
88
154
132
79
143
164
118
93
90
114
Abnormal
Anticipated
Percent
Recovery /Control
Chart Result
Percent recovery <
75%
Percent recovery <
75%
Percent recovery <
75%
Percent Recovery >
125%
Percent Recovery >
125%
Percent Recovery >
125%
Resolution
Rerun
RWW-25-2
Proceed with
iron
interference
procedure
Rerun
RWWPT-
25-3
Rerun QCS-
11
Rerun QCS-
12
Repeat on-
site
calibration
and rerun
QCS-12-
RR1
Comments
Assume that
residual iron in
the sample is
causing the low
readings
-------
Date
Phase 2
Sample
Number
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
Sample
Name
WF-25-3
BW-25-1
BW-25-1 -
RR1
BW-25-1 -
RR2
BW-25-1 -
RR3
BW-25-1 -
RR4
MWWE#1-
25-1
MWWE#1-
25-2
MWWE#1-
25-3
MWWE#1-
25-3-RR1
QCS-14
MWWE#2-
25-1
MWWE#2-
25-2
MWWE#2-
25-2-RR1
MWWE#2-
25-2-RR2
MWWE#2-
25-3
Expected
Concentration
(ug/LPb)
25
25
25
25
25
25
25
25
25
25
30
25
25
25
25
25
Measured
Concentration
(ug/LPb)
25
18
17
16
17
18
20
19
17
21
23
28
34
33
26
23
ICP-MS
Concentration
(ug/LPb)
20
19
30
20
Percent
Recovery
to Target
(%)
100
72
68
64
68
72
80
76
68
84
77
112
136
132
104
92
Percent
Recovery to
ICP-MS
(%)
119
90
85
80
85
90
105
100
89
111
77
140
170
165
130
115
Abnormal
Anticipated
Percent
Recovery /Control
Chart Result
Percent Recovery <
75%
Percent Recovery <
75%
Percent Recovery <
75%
Percent Recovery <
75%
Percent Recovery <
75%
Percent Recovery <
75%
Percent Recovery >
125%
Percent Recovery >
125%
Resolution
Rerun BW-
25-1
Repeat on-
site
calibration
Rerun BW-
25-1-RR2
Rerun BW-
25-1-RR3 as
a final BW
sample
Rerun
MWWE#1-
25-3
Rerun
MWWE#2-
25-2
Repeat
onsite
calibration
Comments
-------
Date
Phase 2
Sample
Number
47
48
49
50
51
Sample
Name
MWWE#2-
25-4
MFWWE-
25-1
MFWWE-
25-2
MFWWE-
25-3
QCS-15
Expected
Concentration
(ug/LPb)
25
25
25
25
30
Measured
Concentration
(ug/LPb)
26
22
21
23
31
ICP-MS
Concentration
(ug/LPb)
24
30
Percent
Recovery
to Target
(%)
104
88
84
92
103
Percent
Recovery to
ICP-MS
(%)
130
92
88
96
103
Abnormal
Anticipated
Percent
Recovery /Control
Chart Result
Resolution
Comments
This sample
run because of
LFM/LFMD
requirement
after new on-
site calibration
w
-------
Appendix F
Round 2 Control Charts
-------
1 ?n -
1 m -
inn -
Qfl -
ฃ
0)
u
ce. an
+*
c
u
01
ฐ- 70
fin -
50 -
An -
3n -
>
4
1
^
^
^^^^^UCL
^^^^B i n
^ UWL
^ -LWL
+SD
-SO
6 7 8 9 10
Phase 1 Observation Number
11 12 13 14 15
-------
130
110
90
ฃ *
01
o
u
01
oe 70
01
Q.
to
50
30
10
Mean
UCL
LCL
UWL
LWL
+SD
-SD
16
17
18
19 20 21
Phase 1 Observation Number
22
23
24
25
-------
160
140
120
01
8 100
01
QC
01
Q.
80 O
60
40
20
Mean
UCL
LCL
UWL
LWL
+SD
-SD
26
27
28
29 30 31
Phase 1 Observation Number
32
33
34
35
-------
170
150
130
v 110
o
u
01
QC
= ^
01
S 90
Q.
70
50
30
Mean
UCL
LCL
UWL
LWL
+SD
-SD
36
37
38
39 40 41
Phase 1 Observation Number
42
43
44
45
-------
120 -
110 -
inn 4
QH -
ฃ- 90
0)
u
cฃ an
c
y
-------
130
120
110
100
2-
01
o
u
01
90
80
70
60
Mean
UCL
LCL
UWL
LWL
+SD
-SD
50
40
30
56
57
58
59 60 61 62
Phase 1 Observation Number
63
64
65
-------
120 -
1 m -
mn -
Qn -
ฃ
01
o
u
o: sn 4
c
u
01
ฐ- 70
fin -
50 -
An -
3n -
4
^^^^^m Mttdl 1
^^^^" LCL
^ UWL
^ LWL
+bU
-SD
6 7 8 9 10 11 12 13 14 15
Phase 2 Observation Number
-------
170
150
130
110
01
o
u
01
oe 90
01
01
0.
70
50
30
10
Mean
UCL
LCL
UWL
LWL
+SD
-SD
16
17
18
19 20 21 22
Phase 2 Observation Number
23
24
25
-------
160
140
120
01
8 100
01
QC
01
y
01
80
60
40
20
26
Mean
UCL
LCL
UWL
LWL
+SD
-SD
27
28
29 30 31
Phase 2 Observation Number
32
33
34
35
-------
170
150
130
71
^^
o
o
01
QC
01
110
90
70
Mean
UCL
LCL
UWL
LWL
+SD
-SD
50
30
36
37
38
39 40 41
Phase 2 Observation Number
42
43
44
45
-------
170
150
130
o
01
QC
01
110
90
70
i
Mean
UCL
LCL
UWL
LWL
+SD
-SD
50
30
46
47
48
49 50 51
Phase 2 Observation Number
52
53
54
55
-------
Appendix G
Temperature and Barometric Pressure Data
-------
30.80y
30.60-
30.40-
30.20
30.00
29.30
29.60--
29.40-
29.20
Baroneter (in)
2012 - 2013
-j- j
ill
yv
ilk
\ .
Th
i
, i
m
rti
r - - 1 - - i - -j- -
_ 1 _iL . _ L ^ . . J _ -
i | - -T J- p H T 1 r-
__
_
y
i
_ _ j
i
L _ _ J J. J _
l_
!
1
'
!
1
1
i-
i
-K J-L
.
!
1
r
|
Nay Jun Jul Aug Sep Oct Nov Dec Jan Feb Mar Apr
Outside Tenperature (F>
2012 - 2013
r
o.o-
1I[
iIh
I I I I I I I I I I I
May Jun Jul Aug Sep Oct Nov Dec Jan Feb Mar Apr
G-l
------- |