April 2003
Environmental Technology
Verification Report
CHEMetrics
VVR V-1000 Multi-Analyte
Photometer with
V-3803 Cyanide Module
Prepared by
Battelle
Battelle
Putting Technology To Work
Under a cooperative agreement with
SEPA U.S. Environmental Protection Agency
ETV EIVElV

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April 2003
Environmental Technology Verification
Report
ETV Advanced Monitoring Systems Center
CHEMetrics
VVR V-1000 Multi-Analyte Photometer
with V-3803 Cyanide Module
by
Ryan James
Amy Dindal
Zachary Willenberg
Karen Riggs
Battelle
Columbus, Ohio 43201

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Notice
The U.S. Environmental Protection Agency (EPA), through its Office of Research and
Development, has financially supported and collaborated in the extramural program described
here. This document has been peer reviewed by the Agency. Mention of trade names or
commercial products does not constitute endorsement or recommendation by the EPA for use.
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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 to build the scientific knowledge base needed
to manage our ecological resources wisely, to understand how pollutants affect our health, and to
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 to 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 seven 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. In 1997, through a competitive cooperative agreement, Battelle was awarded EPA
funding and support 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.
Battelle conducted this verification under a follow-on agreement to the original cooperative
agreement. Information concerning this specific environmental technology area can be found on
the Internet at http://www.epa.gov/etv/centers/centerl.html.
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Acknowledgments
The authors wish to acknowledge the support of all those who helped plan and conduct the
verification test, analyze the data, and prepare this report. We would like to thank Billy Potter,
U.S. EPA, National Exposure Research Laboratory; Ricardo DeLeon, Metropolitan Water
District of Southern California; William Burrows, U.S. Army Center for Environmental Health
Research; and Kenneth Wood, Du Pont Corporate Environmental Engineering Group, for their
technical review of the test/QA plan and for their careful review of this verification report. We
also would like to thank Allan Chouinard, City of Montpelier, VT; Gordon Brand, Des Moines,
IA, Water Works; Wylie Harper, City of Seattle, WA; John Morrill, City of Tallahassee, FL; and
Tom Scott, City of Flagstaff, AZ, water distribution facilities who provided post-treatment water
samples for evaluation.
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Contents
Page
Notice	ii
Foreword 	 iii
Acknowledgments 	 iv
List of Abbreviations 	 viii
1	Background 	 1
2	Technology Description 	2
3	Test Design and Procedures 	4
3.1	Introduction	4
3.2	Reference Method	5
3.3	Test Design	5
3.4	Test Samples 	6
3.4.1	Quality Control Samples 	6
3.4.2	Performance Test Samples	7
3.4.3	Lethal/Near-Lethal Concentrations of Cyanide in Water	8
3.4.4	Surface Water; Drinking Water from Around the U.S.;
and Columbus, OH, Area Drinking Water	8
3.5	Test Procedure	 11
3.5.1	Sample Preparation 	 11
3.5.2	Sample Identification	 11
3.5.3	Sample Analysis	 11
4	Quality Assurance/Quality Control	 13
4.1	Reference Method QC Results	 13
4.2	Audits 	 15
4.2.1	Performance Evaluation Audit		15
4.2.2	Technical Systems Audit		16
4.2.3	Audit of Data Quality		16
4.3	QA/QC Reporting 		17
4.4	Data Review 		17
5	Statistical Methods and Reported Parameters	 18
5.1	Accuracy		18
5.2	Precision 		18
5.3	Linearity 		19
5.4	Method Detection Limit. 		19
5.5	Inter-Unit Reproducibility		19
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5.6	Lethal or Near-Lethal Dose Response		19
5.7	Operator Bias	20
5.8	Field Portability	20
5.9	Ease of Use 	20
5.10	Sample Throughput	20
6	Test Results	21
6.1	Accuracy	21
6.2	Precision 	21
6.3	Linearity 	30
6.4	Method Detection Limit 	31
6.5	Inter-Unit Reproducibility	32
6.6	Lethal or Near-Lethal Dose Response	32
6.7	Operator Bias	33
6.8	Field Portability	34
6.9	Ease of Use 	35
6.10	Sample Throughput	35
7	Performance Summary	36
8	References 	39
Figures
Figure 2-1. CHEMetrics VVR Photometer	2
Figure 3-1. Sampling through Analysis Process		10
Figure 6-1. Non-Technical Operator Linearity Results	30
Figure 6-2. Technical Operator Linearity Results	30
Figure 6-3. Inter-Unit Reproducibility Results	32
Figure 6-4. Non-Technical vs. Technical Operator Bias Results 	33
Tables
Table 3-1. Test Samples 	7
Table 4-1. Reference Method QCS Results		14
Table 4-2. Reference Method LFM Analysis Results 		15
Table 4-3. Summary of Performance Evaluation Audit 		16
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Table 4-4.	Summary of Data Recording Process		17
Table 6-la.	Cyanide Results from Performance Test Samples 	22
Table 6-lb.	Cyanide Results from Surface Water	23
Table 6-lc.	Cyanide Results from U.S. Drinking Water	24
Table 6-Id.	Cyanide Results from Columbus, OH, Drinking Water	25
Table 6-2a.	Percent Accuracy of Performance Test Sample Measurements 	27
Table 6-2b.	Percent Accuracy of Surface Water Measurements 	27
Table 6-2c.	Percent Accuracy of U.S. Drinking Water Measurements	27
Table 6-2d.	Percent Accuracy of Columbus, OH, Drinking Water Measurements	28
Table 6-3a.	Relative Standard Deviation of Performance Test Sample Measurements	28
Table 6-3b.	Relative Standard Deviation of Surface Water Measurements	28
Table 6-3c.	Relative Standard Deviation of U.S. Drinking Water Measurements	29
Table 6-3d.	Relative Standard Deviation of Columbus, OH, Drinking
Water Measurements 	29
Table 6-4.	Results of Method Detection Limit Assessment 	31
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List of Abbreviations
AMS
Advanced Monitoring Systems
ASTM
American Society of Testing and Materials
ATEL
Aqua Tech Environmental Laboratories
CNC1
cyanogen chloride
DPD
n,n-diethyl-p-phenylenediamine
EPA
U.S. Environmental Protection Agency
ETV
Environmental Technology Verification
HC1
hydrochloric acid
ID
identification
KCN
potassium cyanide
L
liter
LFM
laboratory-fortified matrix
MDL
method detection limit
mg
milligram
mL
milliliter
NaOH
sodium hydroxide
PE
performance evaluation
PT
performance test
QA
quality assurance
QA/QC
quality assurance/quality control
QC
quality control
QCS
quality control standard
QMP
quality management plan
RB
reagent blank
RPD
relative percent difference
RSD
relative standard deviation
TSA
technical systems audit
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Chapter 1
Background
The U.S. Environmental Protection Agency (EPA) supports the Environmental Technology
Verification (ETV) Program to facilitate the deployment of innovative environmental tech-
nologies through performance verification and dissemination of information. The goal of the
ETV Program is to further environmental protection by substantially accelerating the acceptance
and use of improved and cost-effective technologies. ETV seeks to achieve this goal by provid-
ing 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 tech-
nologies by developing test plans that are responsive to the needs of stakeholders, conducting
field or laboratory tests (as appropriate), collecting and analyzing data, and preparing peer-
reviewed reports. All evaluations are conducted in accordance with rigorous quality assurance
(QA) protocols to ensure that data of known and adequate quality are generated and that the
results are defensible.
The EPA's National Exposure 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 CHEMetrics VVR V-1000 photometer with the V-
3803 cyanide module (referred to as the CHEMetrics VVR throughout this report) in detecting
the presence of cyanide in water. Portable cyanide analyzers were identified as a priority
technology verification category through the AMS Center stakeholder process.
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Chapter 2
Technology Description
The objective of the ETV AMS Center is to verify the performance characteristics of
environmental monitoring technologies for air, water, and soil. This verification report provides
results for the verification testing of the VVR photometer by CHI- Metrics with the V-3803
cyanide module. Following is a description of the CHEMetrics VVR, based on information
provided by the vendor. The information provided below was not verified in this test.
The CHEMetrics VVR is a portable multi-analyte direct-reading photometer. It uses CHEMetrics
self-filling reagent Vacu-vial® ampoules. The cyanide Vacu-vial® test method employs the
isonicotinic-barbituric acid colorimetric chemistry. The
CHEMetrics VVR uses optical interference filters and a photodiode
detector. Test results are displayed in concentration units of
milligrams per liter (mg/L).
Most chemical reaction rates arc affected by temperature, so the
Vacu-vial® test procedure and VVR photometer factoiy-set
calibration have been established with cyanide standards at room
temperature. Consequently, colorimetric analytical methods will be
impacted by sample temperature. For this reason, sample
temperatures significantly above or below 20°C can be expected to
impact the accuracy of test results. The chemical reactions involved
in the final color development of the cyanide Vacu-vial® method
are also pH dependent. The CHEMetrics VVR factory-set
calibration is based on cyanide standards preserved at alkaline pH
conditions rather than at neutral/near neutral pH because it is
assumed that cyanide testing occurs after samples have been
preserved with base to pH values between 10.5 and 11.0.
Vacu-vials® are packaged in individual analyte modules, which
contain 30 ampoules, two accessory reagent solutions, a
25.0-milliliter (mL) sample cup, and instructions. A storage case,
dedicated filter, and a coded, sealed water-blank ampoule are included. Additionally, a test tube
is provided for photometer zeroing in situations where samples have background color.
To measure cyanide with the CHEMetrics VVR, a 10.0-mL sample is measured in the sample
cup, two reagent solutions are added to the sample, the sample is stirred with the tip of the
Figure 2-1. CHEMetrics
VVR Photometer
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ampoule, and then the tip of the Vacu-vial® is snapped, allowing the sample to be drawn into the
ampoule. If any cyanide is present in the water sample, it will react with the chlorine reagent
solution to form cyanogen chloride (CNC1), which in turn reacts with the reagent in the ampoule
to form a blue complex in direct proportion to the cyanide concentration. The ampoules are read
in the CHEMetrics VVR after a 15-minute color development time. The CHEMetrics VVR
operates on four AA batteries, has dimensions of 10 inches by 2 inches by 3 inches, and weighs
16 ounces. The list prices are $612.90 for the photometer, $54.10 for the cyanide module, and
$20.10 for the Vacu-vial® refill (which contains 30 ampoules). Accessory solution replenishment
packs are available (six bottles/pack).
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Chapter 3
Test Design and Procedures
3.1 Introduction
Cyanide can be present in various forms in water. This verification test focuses on the detection
of the free cyanide ion prepared using potassium cyanide (KCN) and referred to as simply
"cyanide" in this report. At high doses, this form of cyanide inhibits cellular respiration and, in
some cases, can result in death. Because of the toxicity of cyanide to humans, the EPA has set
0.2 mg/L as the maximum concentration of cyanide that can be present in drinking water. In
drinking and surface water under ambient conditions, cyanide evolves from aqueous hydrogen
cyanide, sodium cyanide, potassium cyanide, and other metal or ionic salts where cyanide is
released when dissolved in water. Heavier cyanide complexes (e.g., iron) are bound tightly,
requiring an acid distillation to liberate the toxic free cyanide ion, a step not verified as part of
this test since field portability would have been eliminated. Because disassociation of the free
cyanide ion is unlikely under ambient conditions, the heavier complexes are considered much
less toxic than simple cyanide salts such as potassium and sodium cyanide.
This verification test was conducted according to procedures specified in the Test/QA Plan for
Verification of Portable Analyzers for Detection of Cyanide in Water.(1) The verification was
based on comparing the cyanide concentrations of water samples analyzed using the
CHEMetrics VVR with cyanide concentrations analyzed using a laboratory-based reference
method. The reference method used during this verification test was EPA Method 335.1,
Cyanides Amenable to ChlorinationP This method was selected because it measures the
concentration of the cyanide ion in water samples under ambient conditions, which is the same
form of cyanide that the participating technologies are designed to measure. The CHEMetrics
VVR V-1000 photometer with the V-3803 cyanide module was verified by analyzing
performance test (PT), surface, and drinking water samples. A statistical comparison of the
analytical results from the CHEMetrics VVR and the reference method provided the basis for
the quantitative performance evaluations.
The CHEMetrics VVR's performance was evaluated in terms of
¦	Accuracy
¦	Precision
¦	Linearity
¦	Method detection limit
¦	Inter-unit reproducibility
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¦	Lethal or near-lethal dose response
¦	Operator bias
¦	Field portability
¦	Ease of use
¦	Sample throughput.
3.2 Reference Method
Aqua Tech Environmental Laboratories (ATEL) in Marion, OH, performed the reference
analyses of all test samples. ATEL received the samples from Battelle labeled with an
identification number meaningful only to Battelle, performed the analyses, and submitted to
Battelle the results of the analyses without knowledge of the prepared or fortified concentration
of the samples.
The analytical results for the CHEMetrics VVR were compared with the results obtained from
analysis using semi-automated colorimetry according to EPA Method 335.1.(2) For the reference
method analyses, the concentration of free cyanide was determined by the difference of two
measurements of total cyanide. One colorimetric determination was made after the free cyanide
in the sample had been chlorinated to cyanogen chloride, which degrades quickly, and a second
was made without chlorination. Typically, samples were sent to the reference laboratory for
analysis each testing day. The reference analysis was performed within 14 days of sample
collection.
3.3 Test Design
Two CHEMetrics VVRs were tested independently between January 13 and February 4, 2003.
All preparation and analyses were performed according to the manufacturer's recommended
procedures for the CHEMetrics VVR V-1000 photometer and V-3803 cyanide module. The
verification test involved challenging the CHEMetrics VVR with a variety of test samples,
including sets of drinking and surface water samples representative of those likely to be
analyzed by the CHEMetrics VVR. The results from the CHEMetrics VVR were compared with
the reference method to quantitatively assess accuracy and linearity. Multiple aliquots of each
test sample were analyzed separately to assess the precision of the CHEMetrics VVR and the
reference method.
Each CHEMetrics VVR was tested by a technical and a non-technical operator to assess
operator bias. The non-technical operator had no previous laboratory experience. Both operators
received a brief orientation with a vendor representative to become acquainted with the basic
operation of the instrument. Both operators analyzed all of the test samples. Each operator
manipulated the water samples and reagents to generate a solution that could be probed
photometrically. Then, each operator analyzed that solution using both CHEMetrics VVRs.
Sample throughput was estimated based on the time required to prepare and analyze a sample.
Ease of use was based on documented observations by the operators and the Battelle
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Verification Test Coordinator. The CHEMetrics VVR was used in a field environment as well as
in a laboratory setting to assess the impact of field conditions on performance.
3.4 Test Samples
Test samples used in the verification test included quality control (QC) samples, PT samples,
lethal/near-lethal concentration samples, drinking water samples, and surface water samples
(Table 3-1). The QC, PT, and lethal/near-lethal samples were prepared from purchased
standards. The PT and QC sample concentrations were targeted to the EPA maximum con-
taminant level in drinking water, which for cyanide is 0.200 mg/L.(3) The PT samples ranged
from 0.030 mg/L to 0.800 mg/L. The performance of the CHEMetrics VVR also was
qualitatively evaluated with samples prepared in an American Society of Testing and Materials
(ASTM) Type II deionized water with cyanide concentrations up to 250 mg/L that could be
lethal if ingested. Two surface water sources (Olentangy River and Alum Creek Reservoir) were
sampled and analyzed. In addition, five sources of drinking water from around the United States
and two sources of Columbus, OH, drinking water were evaluated (Table 3-1).
3.4.1 Quality Control Samples
Prepared QC samples included both laboratory reagent blanks (RBs) and laboratory-fortified
matrix (LFM) samples (Table 3-1). The RB samples were prepared from ASTM Type II
deionized water and were exposed to handling and analysis procedures identical to 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 proce-
dures. One reagent blank sample was analyzed for every batch of about 12 water samples. The
LFM samples were prepared as aliquots of drinking and surface water samples spiked with KCN
as free cyanide to increase the cyanide concentration by 0.200 mg/L. Four LFM samples were
analyzed for each source of water. These samples were used to monitor the general performance
of the reference method to help determine whether matrix effects had an influence on the
analytical results.
Quality control standards (QCSs) were used to ensure the proper calibration of the reference
instrument. The reference laboratory prepared the QCSs for its use from a stock solution inde-
pendent from the one used to prepare the QCS analyzed using the CHEMetrics VVR. The QCSs
for the CHEMetrics VVR were purchased by Battelle from a commercial supplier and subject
only to dilution as appropriate. An additional independent QCS was used in a performance
evaluation (PE) audit of the reference method.
The reference method required that the concentration of each QCS be within 25% of the known
concentration. If the difference was larger that 25%, the data collected since the most recent
QCS were flagged; and proper maintenance was performed to regain accurate cyanide
measurement, according to ATEL protocols. Section 4.1 describes these samples in more detail.
The CHEMetrics VVR was factory calibrated, so no additional calibration was performed by the
operators. However, QCSs were analyzed (without defined performance expectations) by the
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Table 3-1. Test Samples
Type of Sample
Sample Characteristics
Concentration
No. of Samples
Quality Control
RB
~0
10% of all
LFM
0.200 mg/L
4 per water
source
QCS
0.200 mg/L
10% of all
Performance Test
For the determination of
method detection limit
0.200 mg/L
7
Cyanide
0.030 mg/L
4
Cyanide
0.100 mg/L
4
Cyanide
0.200 mg/L
4
Cyanide
0.400 mg/L
4
Cyanide
0.800 mg/L
4
Lethal /
Near-Lethal
Cyanide
50.0 mg/L
4
Cyanide
100 mg/L
4
Cyanide
250 mg/L
4
Surface Water
Alum Creek Reservoir
Background
4
0.200 mg/L LFM
4
Olentangy River
Background
4
0.200 mg/L LFM
4
Drinking Water
from Around the
U.S.
Northwestern U.S.
Background
1
0.200 mg/L LFM
4
Southwestern U.S.
Background
1
0.200 mg/L LFM
4
Midwestern U.S.
Background
1
0.200 mg/L LFM
4
Southeastern U.S.
Background
1
0.200 mg/L LFM
4
Northeastern U.S.
Background
1
0.200 mg/L LFM
4
Columbus, OH,
Area Drinking
Water
Residence with city water
Background
6
0.200 mg/L LFM
12
Residence with well water
Background
6
0.200 me/L LFM
12
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CHEMetrics VVR to demonstrate their proper functioning to the operator. A QCS was analyzed
before and after each sample batch (typically consisting of 12 water samples).
3.4.2	Performance Test Samples
The PT samples (Table 3-1) were prepared in the laboratory using ASTM Type II deionized
water. The samples were used to determine the CHEMetrics VVR's accuracy, linearity, and
detection limit. Seven non-consecutive replicate analyses of an 0.200-mg/L solution were made
to obtain precision data with which to determine the method detection limit (MDL).(4) Four other
solutions were prepared to assess the linearity over a 0.030- to 0.800-mg/L range of cyanide
concentrations. Four aliquots of each of these solutions were analyzed separately to assess the
precision of the CHEMetrics VVR. The concentrations of the PT samples are listed in Table 3-1.
The operators analyzed the PT samples blindly and in random order to minimize bias.
3.4.3	Lethal/Near-Lethal Concentrations of Cyanide in Water
To assess the response of the CHEMetrics VVR when cyanide is present in drinking water at
lethal and near-lethal concentrations (>50.0 mg/L), samples were prepared in ASTM Type II
deionized water at concentrations of 50.0, 100, and 250 mg/L. Qualitative observations were
made of the CHEMetrics VVR while analyzing such samples. Observations of unusual
operational characteristics (rate of color change, unusually intense color, unique digital readout,
etc.) were documented.
3.4.4	Surface Water; Drinking Water from Around the U.S.;
and Columbus, OH, Area Drinking Water
Water samples, including fresh surface water and tap water (well and local distribution sources),
were collected from a variety of sources and used to evaluate technology performance. Surface
water samples were collected from
¦	Alum Creek Reservoir (OH)
¦	Olentangy River (OH).
Drinking water samples were collected from
¦	Local distribution source water (post-treatment) from five cities (Montpelier, VT;
Des Moines, IA; Seattle, WA; Tallahassee, FL; and Flagstaff, AZ)
¦	Columbus, OH, city water
¦	Columbus, OH, well water.
The water samples collected as part of this verification test were not characterized in any way
(i.e., hardness, alkalinity, etc.) other than for cyanide concentration. Each sample was tested for
the presence of chlorine, dechlorinated if necessary, preserved with sodium hydroxide (NaOH)
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to a pH greater than 12, and split into two subsamples. Figure 3-1 is a diagram of the process
leading from sampling to aliquot analysis. One subsample was spiked with 0.200 mg/L of
cyanide to provide LFM aliquots, and the other subsample remained unspiked (background).
Four 10-mL aliquots were taken from each subsample and analyzed for cyanide by the
CHEMetrics VVR. Also taken from the background subsample were eight aliquots used for
analysis by the reference method. Four of the aliquots were left unspiked and analyzed by the
reference method, and four of the aliquots were fortified with 0.200 mg/L of KCN as free
cyanide at the reference laboratory just before the reference analyses took place. This was done
to closely mimic the time elapsed between when the LFM samples were fortified with
0.200 mg/L KCN as free cyanide and when they were analyzed during the testing of the
participating technologies.
To assess the reproducibility of background water samples, four replicates of Columbus, OH,
city and well water; Alum Creek samples; and Olentangy River samples were analyzed. None of
these samples had detectable concentrations of cyanide. Four LFM aliquots were dechlorinated,
prepared, and analyzed for every drinking and surface water source. To avoid replicating
samples with non-detectable concentrations of cyanide, only one background aliquot of the
drinking water samples from around the country was analyzed.
Surface water from the Olentangy River and Alum Creek Reservoir and drinking water samples
collected at the five U.S. cities were shipped to Battelle for use in verification testing. Surface
water was collected near the shoreline by submerging containers no more than one inch below
the surface of the water. Representatives of each city's water treatment facility provided Battelle
a sample of water that had completed the water treatment process, but had not yet entered the
water distribution system. When the samples arrived at Battelle, they were dechlorinated,
preserved, and split into background and LFM subsamples, as described above for the rest of the
water samples.
Columbus, OH, city and well water samples were used to verify the field portability of the
CHEMetrics VVR. Approximately 20 liters of water were collected from an outside spigot at
two participating residences, one with well water and one with Columbus, OH, city water, and
split into three samples. One sample was analyzed outdoors at the residence under the current
weather conditions. The weather conditions on the two days of outdoor testing happened to be
extremely cold (air temperature ~0°C, sample temperature ~4 to 6°C). A second sample was
equilibrated to room temperature inside the residence (~17°C) and analyzed inside the residence.
These two samples were preserved, split into background and LFM samples, and analyzed at the
field location as described for the other water samples (see Figure 3-1). For the third sample, the
background and LFM samples were prepared at the field location and transported to Battelle for
analysis in the laboratory two to three days later. Because these analyses were done using the
same bulk water sample, a single set of four background replicates were analyzed using the
reference method. The LFM sample fortified at the field location and the LFM sample fortified
at the reference laboratory were analyzed by the reference method (see Table 4-2). These back-
ground and LFM reference concentrations were compared with the results produced by the
CHEMetrics VVR at the indoor and outdoor field locations and the laboratory location.
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Analyze
four
aliquots by
reference
method
(background)
Spike four
aliquots with
0.2 mg/L
cyanide
at reference
laboratory
Background
Subsample
LFM
Subsample
Water
Sample
Dechlorinate
Test for
Chlorine
Preserve
with NaOH
to pH > 12
Spike four
aliquots with
0.2 mg/L
cyanide
Analyze by
reference
method
(LFM)
Adjust pH
of four
aliquots
with HCI
to between
10.5 and 11
Analyze
aliquots
by portable
cyanide
analyzer
(background)
Adjust pH
of four
aliquots
with HCI
to between
10.5 and 11
Analyze four
10-mL aliquots
by portable
cyanide
analyzer
(LFM)
Figure 3-1. Sampling through Analysis Process
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3.5 Test Procedure
3.5.1	Sample Preparation
QC and PT samples were prepared from a commercially available National Institute of
Standards and Technology-traceable standard. The standard was dissolved and diluted to
appropriate concentrations using ASTM Type II deionized water in Class A volumetric
glassware. The QC and PT samples were prepared at the start of testing, preserved with NaOH,
and stored at 4°C for the duration of the test.
Surface and drinking water samples were collected from the sources indicated in Section 3.4.4
and were stored in high-density polyethylene containers. Because free chlorine degrades cyanide
during storage, at the time of sample receipt, before NaOH preservation, all of the samples were
tested for free chlorine with potassium iodide starch paper. When the samples collected as part
of this verification test were tested in this manner, none of them changed the color of the paper,
indicating that free chlorine was not present. However, when the LFM samples were analyzed
with the colorimetric technologies being verified, non-detectable results were observed. To
further investigate the possibility of a chlorine interference, approximately 500 mL of each water
sample were added to separate beakers and one n,n-diethyl-p-phenylenediamine (DPD) chlorine
indicator tablet (Orbeco Analytical Systems, Inc.) was added and crushed with a glass stirring
rod. If the water turned pink, the presence of chlorine was indicated, and ascorbic acid was
added a few crystals at a time until the color disappeared. All the drinking water samples were
tested in this manner; and, if the presence of chlorine was indicated, approximately 60 mg of
ascorbic acid were added per liter of bulk sample to dechlorinate the sample. A separate DPD
indicator test (as described above) was done to confirm adequate dechlorination of the sample
(indicated by no color change). After dechlorination, all samples to be analyzed by the
CHEMetrics VVR were adjusted to a pH between 10.5 and 11.0, according to the
manufacturer's specifications (see Figure 3-1). All the samples to be analyzed by the reference
method were stored at 4°C and preserved with NaOH at a pH greater than 12.0.
3.5.2	Sample Identification
Aliquots to be analyzed were drawn from the prepared standard solutions or from source and
drinking water samples and placed in uniquely identified sample containers for subsequent
analysis. The sample containers were identified by a unique identification (ID) number. A
master log of the samples and sample ID numbers for each technology being verified was kept
by Battelle. The ID number, date, person collecting, sample location, and time of collection were
recorded on a chain-of-custody form for all field samples.
3.5.3	Sample Analysis
The two CHEMetrics VVRs were tested independently. Each CHEMetrics VVR analyzed the
full set of samples, and verification results were compared to assess inter-unit reproducibility. As
shown in Table 3-1, the samples included replicates of each of the PT, QC, surface water, and
drinking water samples. The complete set of samples was analyzed twice for each of the units
11

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being verified, once by a non-technical operator and once by a technical operator. The analyses
were performed according to the manufacturer's recommended procedures.
Results were recorded manually on appropriate data sheets. In addition to the analytical results,
the data sheets and corresponding laboratory notebooks included records of the time required for
sample analysis and operator observations concerning the use of the CHEMetrics VVR (i.e.,
ease of use, maintenance, etc.).
While the participating technologies were being tested, a replicate sample set was being
analyzed by the reference laboratory. The reference instrument was operated according to the
recommended procedures in the instruction manual, and samples were analyzed according to
EPA Method 335.1(2) and ATEL standard operating procedures. Results from the reference
analyses were recorded electronically and compiled by ATEL into a report, including the sample
ID and the analyte concentration for each sample.
12

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Chapter 4
Quality Assurance/Quality Control
Quality assurance/quality control (QA/QC) procedures were performed in accordance with the
quality management plan (QMP) for the AMS Center(5) and the test/QA plan for this verification
test.(1)
4.1 Reference Method QC Results
Analyses of QC samples were used to document the performance of the reference method. To
ensure that no sources of contamination were present, RB samples were analyzed. The test/QA
plan stated that if the analysis of an RB sample indicated a concentration above the MDL for the
reference method, any contamination source was to be corrected and proper blank reading
achieved before proceeding with the verification test. Six reagent blank samples were analyzed,
and all of them were reported as below the 0.005 mg/L reporting limit for the reference method.
The reference instrument was calibrated initially according to the procedures specified in the
reference method. The accuracy of the reference method was verified with QCS samples analyzed
with the sample sets. One of two QCS samples, one with a concentration of 0.150 mg/L and the
other with a concentration of 0.200 mg/L, were analyzed with each analytical batch
(approximately every 10 water samples). As required by the test/QA plan,(1) if the QCS analysis
differed by more than 25% from the true value of the standard, corrective action would be taken
before the analysis of more samples. As shown in Table 4-1, the QCS results were always within
the acceptable percent recovery range of 75 to 125% and, in fact, were always between 90 and
110%.
Reference LFM samples were analyzed to confirm the proper functioning of the reference method
and to assess whether matrix effects influenced the results of the reference method. The LFM
recovery (R) of the spiked solution was calculated from the following equation:
R = Cs~C y^JQQ	(1)
j1
where Cs is the reference concentration of the spiked sample, C is the reference concentration of
the background sample which, in this case, was always zero (results were below the MDL for the
reference method), and s is the fortified concentration of the cyanide spike. If the percent recovery
of an LFM fell outside the range of 75 to 125%, a matrix effect or some other analytical problem
was suspected. As shown in Table 4-2, only the percent recovery for the LFM from the Columbus,
OH, well water was outside the acceptable range, indicating a potential matrix effect.
13

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Table 4-1. Reference Method QCS Results
Known QCS
Date
Analysis Result
Concentration (mg/L)
% Recovery
1/13/2003
0.157
0.150
105
1/13/2003
0.203
0.200
102
1/15/2003
0.142
0.150
95
1/15/2003
0.180
0.200
90
1/16/2003
0.151
0.150
101
1/16/2003
0.194
0.200
97
1/17/2003
0.154
0.150
103
1/17/2003
0.190
0.200
95
1/20/2003
0.190
0.200
95
1/20/2003
0.158
0.150
105
1/21/2003
0.153
0.150
102
1/21/2003
0.205
0.200
103
1/27/2003
0.143
0.150
95
1/27/2003
0.187
0.200
94
1/28/2003
0.146
0.150
97
1/28/2003
0.186
0.200
93
1/29/2003
0.149
0.150
99
1/29/2003
0.189
0.200
95
1/30/2003
0.139
0.150
93
1/30/2003
0.187
0.200
94
1/30/2003
0.139
0.150
93
1/30/2003
0.188
0.200
94
1/31/2003
0.146
0.150
97
1/31/2003
0.150
0.150
100
1/31/2003
0.196
0.200
98
2/3/2003
0.152
0.150
101
2/3/2003
0.189
0.200
95
2/5/2003
0.147
0.150
98
2/5/2003
0.149
0.150
99
2/5/2003
0.194
0.200
97
2/6/2003
0.151
0.150
101
2/6/2003
0.198
0.200
99
2/7/2003
0.154
0.150
103
2/7/2003
0.199
0.200
100
2/10/2003
0.148
0.150
99
2/10/2003
0.181
0.200
90
2/11/2003
0.141
0.150
94
2/11/2003
0.180
0.200
90
2/11/2003
0.136
0.150
91
2/11/2003
0.191
0.200
96
2/12/2003
0.159
0.150
106
2/12/2003
0.211
0.200
106
2/12/2003
0.153
0.150
102
2/12/2003
0.206
0.200
103
2/13/2003
0.158
0.150
105
14

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Table 4-2. Reference Method LFM Analysis Results
Average
Fortified	Reference
Sample Description
Concentration
(mg/L)
Concentration
(mg/L)
% LFM
Recovery
Reference
RSD
Alum Creek LFM
0.200
0.168
84%
8%
Olentangy River LFM
0.200
0.175
87%
2%
Des Moines, IA, LFM
0.200
0.178
89%
3%
Flagstaff, AZ, LFM
0.200
0.153
76%
12%
Montpelier, VT, LFM
0.200
0.170
85%
2%
Seattle, WA, LFM
0.200
0.173
87%
2%
Tallahassee, FL, LFM
0.200
0.161
80%
2%
Columbus, OH, City Water LFM(a)
0.200
0.172
86%
4%
Columbus, OH, City Water LFM03'
0.200
0.152
76%
1%
Columbus, OH, Well Water LFM(a)
0.200
0.107
53%
13%
Columbus, OH, Well Water LFM®
0.200
<0.005
0%
NA(c)
(a)	Reference LFM sample spiked minutes before analysis by the reference method.
(b)	Reference LFM sample spiked 8 to 10 days before analysis by the reference method.
(C) Calculation of relative standard deviation (RSD) not appropriate for non-detectable results.
To mimic the elapsed time between fortification and analysis by the technologies being verified,
the reference LFM samples were spiked just minutes prior to analysis using the reference
method. However, because the well water LFM samples exhibited decreased cyanide concen-
trations when analyzed by the vendor technologies one to two days after fortification, the LFM
samples for the Columbus, OH, city and well water spiked in the field location were also
submitted to the reference laboratory for analysis. These samples were analyzed eight to 10 days
after initial fortification. The Columbus, OH, city reference LFM result after the eight- to 10-day
delay was within 15% of the result obtained from the LFM sample spiked just minutes before
reference analysis. However, the well water reference LFM sample fortified eight to 10 days
prior to analysis was less than the MDL for the reference method. The combination of the poor
recovery (53%) of cyanide obtained immediately upon spiking and the complete loss of the
reference method's ability to detect the cyanide fortified eight to 10 days before strongly
suggests the presence of a time-dependent matrix interference in the well water. In response to
this finding, the biases for the well water samples were calculated using the fortified
concentration of cyanide (0.200 mg/L) rather than the reference LFM result.
4.2 Audits
4.2.1 Performance Evaluation Audit
A PE audit was conducted once to assess the quality of the reference measurements made in this
verification test. For the PE audit, an independent standard was obtained from a different vendor
15

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than the one that supplied the QCSs. The relative percent difference (RPD) of the measured
concentration and the known concentration was calculated using the following equation:
M
RPD =	xlOO	(2)
A
where M is the absolute difference between the measured and known concentrations, and A is
the mean of the same two concentrations. An RPD of less than 25% was required for the
reference measurements to be considered acceptable. Failure to achieve this agreement would
have triggered a repeat of the PE comparison. As shown in Table 4-3, all the PE sample results
were well within this required range.
Table 4-3. Summary of Performance Evaluation Audit
Sample
Date of Analysis
Measured Concentration
(mg/L)
Known Concentration
(mg/L)
RPD
(%)
PE-A
2-12-2003
0.216
0.200
8
PE-B
2-12-2003
0.213
0.200
6
PE-C
2-12-2003
0.218
0.200
9
PE-D
2-12-2003
0.203
0.200
1
4.2.2	Technical Systems Audit
The Battelle Quality Manager performed a pre-verification test audit of the reference laboratory
(ATEL) to ensure that the selected laboratory was proficient in the reference analyses. This
entailed a review of the appropriate training records, state certification data, and the laboratory
QMP. The Battelle Quality Manager also conducted a technical systems audit (TSA) to ensure
that the verification test was performed in accordance with the test/QA plan(1) and the AMS
Center QMP.(5) As part of the audit, the Battelle Quality Manager reviewed the reference method
used, compared actual test procedures to those specified in the test/QA plan, and reviewed data
acquisition and handling procedures. Observations and findings from this audit were documented
and submitted to the Battelle Verification Test Coordinator for response. No findings were docu-
mented that required any corrective action. The records concerning the TSA are permanently
stored with the Battelle Quality Manager.
4.2.3	Audit of Data Quality
At least 10% of the data acquired during the verification test were audited. Battelle's Quality
Manager traced the data from the initial acquisition, through reduction and statistical analysis, to
final reporting, to ensure the integrity of the reported results. All calculations performed on the
data undergoing the audit were checked.
16

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4.3 QA/QC Reporting
Each assessment and audit was documented in accordance with Sections 3.3.4 and 3.3.5 of the
QMP for the ETV AMS Center.(5) Once the assessment report was prepared, the Battelle
Verification Test Coordinator ensured that a response was provided for each adverse finding or
potential problem and implemented any necessary follow-up corrective action. The Battelle
Quality Manager ensured that follow-up corrective action was taken. The results of the TSA were
sent to the EPA.
4.4 Data Review
Records generated in the verification test were reviewed before these records were used to
calculate, evaluate, or report verification results. Table 4-4 summarizes the types of data
recorded. The review was performed by a technical staff member involved in the verification test,
but not the staff member who originally generated the record. The person performing the review
added his/her initials and the date to a hard copy of the record being reviewed.
Table 4-4. Summary of Data Recording Process
Data to be
Recorded
Responsible
Party
Where Recorded
How Often
Recorded
Disposition of Data(a)
Dates, times of test
events
Battelle
Laboratory record
books
Start/end of test; at
each change of a
test parameter
Used to organize/
check test results;
manually incorporated
data into spreadsheets
as necessary
Test parameters
(meteorological
conditions, analyte
concentrations,
location, etc.)
Battelle
Laboratory record
books
When set or
changed, or as
needed to
document stability
Used to organize/
check test results;
manually incorporated
data into spreadsheets
as necessary
Water sampling data
Battelle
Laboratory record
books
At least at the time
of sampling
Used to organize/
check test results;
manually incorporated
data into spreadsheets
as necessary
Reference method
sample analysis,
chain of custody,
results
ATEL
Laboratory record
book/data sheets or
data acquisition
system, as
appropriate
Throughout sample
handling and
analysis process
Excel spreadsheets
(a) All activities subsequent to data recording were carried out by Battelle.
17

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Chapter 5
Statistical Methods and Reported Parameters
The statistical methods presented in this chapter were used to verify the performance parameters
listed in Section 3.1.
5.1 Accuracy
Accuracy was assessed relative to the results obtained from the reference analyses. Samples were
analyzed by both the reference method and the CHEMetrics VVR. The results for each set of
analyses were averaged, and the accuracy was expressed in terms of a relative average bias (B) as
calculated from the following equation:
where d is the average difference between the readings from the CHEMetrics VVR and those
from the reference method, and CR is the average of the reference measurements. Accuracy was
assessed independently for each CHEMetrics VVR to determine inter-unit reproducibility.
Additionally, the results were analyzed independently for the readings obtained from the two
operators to determine whether significant operator bias existed.
5.2 Precision
The standard deviation (S) of the results for the replicate samples was calculated and used as a
measure of CHEMetrics VVR precision at each concentration.
(3)
1/2
7 n	0
_n 1 k=l
(4)
18

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where n is the number of replicate samples, Ck is the concentration measured for the k'h sample,
and c is the average concentration of the replicate samples. The analyzer precision at each
concentration was reported in terms of the RSD, e.g.,
RSD =
xlOO
(5)
5.3 Linearity
Linearity was assessed by linear regression, with the analyte concentration measured by the
reference method as independent variable and the reading from the CHEMetrics VVR as
dependent variable. Linearity is expressed in terms of the slope, intercept, and the coefficient of
determination (r2).
5.4 Method Detection Limit
The MDL(4) for each CHEMetrics VVR was assessed from the seven replicate analyses of a
fortified sample with a cyanide concentration of approximately five times the vendor's estimated
detection limit (see Table 3-1). The MDL(4) was calculated from the following equation:
MDL =t xS	(6)
where t is the Student's value for a 99% confidence level, and S is the standard deviation of the
replicate samples. The MDL for each CHEMetrics VVR was reported separately.
5.5 Inter-Unit Reproducibility
The results obtained from two identical CHEMetrics VVRs were compiled independently for
each CHEMetrics VVR and compared to assess inter-unit reproducibility. The results were inter-
preted using a linear regression of one CHEMetrics VVR's results plotted against the results
produced by the other CHEMetrics VVR. If the CHEMetrics VVRs function alike, the slope of
such a regression should not differ significantly from unity.
5.6 Lethal or Near-Lethal Dose Response
The CHEMetrics VVR is not designed to quantitatively measure near-lethal or lethal
concentrations of cyanide in water. Therefore, the operators and Battelle Verification Test
Coordinator made qualitative observations of their operation while analyzing such samples.
Observations of unusual operational characteristics (rate of color change, unusually intense color,
unique digital readout, etc.) were documented and reported.
19

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5.7 Operator Bias
To assess operator bias for each technology, the results obtained from each operator were
compiled independently and subsequently compared. The results were interpreted using a linear
regression of the non-technical operator's results plotted against the results produced by the
technical operator. If the operators obtain identical results, the slope of such a regression should
not differ significantly from unity.
5.8	Field Portability
The results obtained from the measurements made on drinking water samples in the laboratory
and field settings were compiled independently for each CHEMetrics VVR and for each operator
and compared to assess the accuracy of the measurements under the different analysis conditions.
The results were interpreted qualitatively since factors such as temperature and matrix effects
largely influenced the results.
5.9	Ease of Use
Ease of use was a qualitative measure of the user friendliness of the instrument, including how
easy or hard the instruction manual was to use.
5.10 Sample Throughput
Sample throughput indicated the amount of time required to analyze a sample, including both
sample preparation and analysis.
20

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Chapter 6
Test Results
The results of the verification test of the CHEMetrics VVR are presented in this section.
6.1 Accuracy
Tables 6-la-d present the measured cyanide results from analysis of the PT samples; surface water;
drinking water from various regions of the United States; and drinking water from Columbus, OH,
respectively, for both the reference analyses and the CHEMetrics VVR. Results are shown for the
technical and non-technical operators and for both CHEMetrics VVRs that were tested (labeled as
Unit #1 and #2). The 0.800 mg/L PT samples were outside the detectable range of the CHEMetrics
VVR. When these samples were inserted into the CHEMetrics VVR, the result was reported as
"over range."
Tables 6-2a-d present the percent accuracy of the CHEMetrics VVR results. The bias values were
determined according to Equation (3), Section 5.1. Bias was not calculated for background
samples with non-detectable concentrations of cyanide. However, in instances when the LFM
samples resulted in a non-detect reading from the CHEMetrics VVR, the bias was reported as
100%. The bias values shown in Tables 6-2a-d can be summarized by the range of bias observed
with different sample sets. For example, the biases ranged from 3 to 24% for the PT samples; 4 to
17% for the surface water samples; 7 to 63% for the drinking water samples from around the
country; and 42 to 100% for the Columbus, OH, drinking water samples. Because of the low well
water reference LFM sample recovery (see Section 4.1 and Table 4-2), the well water biases were
calculated using the fortified concentration of 0.200 mg/L as the reference concentration.
6.2 Precision
Tables 6-3a-d show the RSDs of the cyanide analysis results for PT samples; surface water;
drinking water from around the U.S.; and drinking water from Columbus, OH, respectively, from
the CHEMetrics VVR and the reference method. Results are shown for the technical and non-
technical operators and for both units that were tested. RSDs were not calculated for results
reported as less than the MDL of the CHEMetrics VVR. The RSD values shown in Tables 6-3a-d
can be summarized by the range of RSDs observed with different sample sets. For example, the
RSDs ranged from 0 to 13% for the PT samples; 2 to 5% for the surface water samples; 0 to 27%
for the drinking water samples from around the country; and 5 to 13% for the Columbus, OH,
drinking water samples analyzed at the indoor field site and at the laboratory.
21

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Table 6-la. Cyanide Results from Performance Test Samples
Non-Technical Operator		Technical Operator
Prepared
Concentration
(mg/L)
Ref. Cone.
(mg/L)
Unit #1
(mg/L)
Unit #2
(mg/L)
Unit #1
(mg/L)
Unit #2
(mg/L)
0.030
0.027
0.020
0.025
0.025
0.020
0.030
0.023
0.020
0.020
0.025
0.025
0.030
0.026
0.020
0.025
0.025
0.025
0.030
0.023
0.015
0.020
0.025
0.025
0.100
0.102
0.085
0.089
0.095
0.090
0.100
0.089
0.085
0.090
0.090
0.085
0.100
0.097
0.075
0.080
0.090
0.085
0.100
0.103
0.075
0.080
0.090
0.090
0.200
0.173
0.160
0.170
0.180
0.165
0.200
0.179
0.155
0.165
0.175
0.170
0.200
0.173
0.155
0.160
0.170
0.165
0.200
0.174
0.160
0.165
0.165
0.160
0.400
0.381
0.310
0.325
0.340
0.330
0.400
0.392
0.325
0.345
0.340
0.325
0.400
0.392
0.300
0.315
0.350
0.335
0.400
0.395
0.320
0.335
0.355
0.345
0.800
0.736
OR(a)
OR
OR
OR
0.800
0.724
OR
OR
OR
OR
0.800
0.720
OR
OR
OR
OR
0.800
0.740
OR
OR
OR
OR
(a) OR = over the detectable range of the CHEMetrics VVR.
22

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Table 6-lb. Cyanide Results from Surface Water


Non-Technical Operator
Technical Operator

Ref. Cone.
Unit #1
Unit #2
Unit #1
Unit #2
Sample Description
(mg/L)
(mg/L)
(mg/L)
(mg/L)
(mg/L)
Alum Creek Background
<0.005
<0.03
<0.03
<0.03
<0.03
Alum Creek Background
<0.005
<0.03
<0.03
<0.03
<0.03
Alum Creek Background
<0.005
<0.03
<0.03
<0.03
<0.03
Alum Creek Background
<0.005
<0.03
<0.03
<0.03
<0.03
Alum Creek LFM
0.183
0.145
0.135
0.155
0.140
Alum Creek LFM
0.173
0.145
0.140
0.155
0.150
Alum Creek LFM
0.151
0.145
0.140
0.165
0.155
Alum Creek LFM
0.166
0.150
0.145
0.150
0.140
Olentangy River Background
<0.005
<0.03
<0.03
<0.03
<0.03
Olentangy River Background
<0.005
<0.03
<0.03
<0.03
<0.03
Olentangy River Background
<0.005
<0.03
<0.03
<0.03
<0.03
Olentangy River Background
<0.005
<0.03
<0.03
<0.03
<0.03
Olentangy River LFM
0.171
0.160
0.160
0.180
0.170
Olentangy River LFM
0.178
0.170
0.155
0.165
0.160
Olentangy River LFM
0.176
0.175
0.170
0.175
0.160
Olentangy River LFM
0.174
0.180
0.170
0.170
0.165
23

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Table 6-lc. Cyanide Results from U.S. Drinking Water


Non-Technical Operator
Technical Operator

Ref. Cone.
Unit #1
Unit #2
Unit #1
Unit #2
Sample Description
(mg/L)
(mg/L)
(mg/L)
(mg/L)
(mg/L)
Des Moines, IA, Background
<0.005
<0.03
<0.03
<0.03
<0.03
Des Moines, IA, LFM
0.181
0.145
0.150
0.085
0.085
Des Moines, IA, LFM
0.183
0.160
0.165
0.100
0.105
Des Moines, IA, LFM
0.173
0.170
0.175
0.120
0.115
Des Moines, IA, LFM
0.173
0.170
0.175
0.115
0.115
Flagstaff, AZ, Background
<0.005
<0.03
<0.03
<0.03
<0.03
Flagstaff, AZ, LFM
SL(a)
0.120
0.130
0.075
0.070
Flagstaff, AZ, LFM
0.132
0.130
0.140
0.090
0.085
Flagstaff, AZ, LFM
0.169
0.135
0.135
0.060
0.055
Flagstaff, AZ, LFM
0.157
0.140
0.145
0.105
0.105
Montpelier, VT, Background
<0.005
<0.03
<0.03
<0.03
<0.03
Montpelier, VT, LFM
0.168
0.100
0.100
0.105
0.105
Montpelier, VT, LFM
0.168
0.110
0.110
0.115
0.120
Montpelier, VT, LFM
0.167
0.115
0.115
0.115
0.120
Montpelier, VT, LFM
0.176
0.120
0.125
0.115
0.120
Seattle, WA, Background
<0.005
<0.03
<0.03
<0.03
<0.03
Seattle, WA, LFM
0.172
0.120
0.120
0.140
0.140
Seattle, WA, LFM
0.174
0.135
0.145
0.140
0.145
Seattle, WA, LFM
0.177
0.140
0.150
0.140
0.140
Seattle, WA, LFM
0.170
0.140
0.150
0.140
0.145
Tallahassee, FL, Background
<0.005
<0.03
<0.03
<0.03
<0.03
Tallahassee, FL, LFM
0.161
0.070
0.075
0.065
0.065
Tallahassee, FL, LFM
0.165
0.075
0.080
0.065
0.060
Tallahassee, FL, LFM
0.159
0.075
0.075
0.055
0.050
Tallahassee, FL, LFM
0.157
0.090
0.090
0.070
0.065
(a) SL = reference sample lost because of laboratory error.
24

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Table 6-Id. Cyanide Results from Columbus, OH, Drinking Water


Non-Technical Operator
Technical Operator
Sample Description
Ref. Cone.
(mg/L)
Unit #1
(mg/L)
Unit #2
(mg/L)
Unit #1
(mg/L)
Unit #2
(mg/L)
City Water Background -
Outdoor Field Site
<0.005
<0.03
<0.03
<0.03
<0.03
City Water Background - Indoor
Field Site
<0.005
<0.03
<0.03
<0.03
<0.03
City Water Background - Lab
<0.005
<0.03
<0.03
<0.03
<0.03
City Water Background - Lab
<0.005
<0.03
<0.03
<0.03
<0.03
City Water Background - Lab
<0.005
<0.03
<0.03
<0.03
<0.03
City Water Background - Lab
<0.005
<0.03
<0.03
<0.03
<0.03
City LFM - Outdoor Field Site
0.176
<0.03
<0.03
<0.03
<0.03
City LFM - Outdoor Field Site
0.167
<0.03
<0.03
<0.03
<0.03
City LFM - Outdoor Field Site
0.165
<0.03
<0.03
<0.03
<0.03
City LFM - Outdoor Field Site
0.178
<0.03
<0.03
<0.03
<0.03
City LFM - Indoor Field Site
0.176
0.070
0.075
0.070
0.065
City LFM - Indoor Field Site
0.167
0.065
0.075
0.070
0.060
City LFM - Indoor Field Site
0.165
0.060
0.070
0.080
0.075
City LFM - Indoor Field Site
0.178
0.075
0.080
0.085
0.080
City LFM - Lab
0.176
0.090
0.085
0.060
0.055
City LFM - Lab
0.167
0.095
0.090
0.060
0.060
City LFM - Lab
0.165
0.100
0.095
0.065
0.060
City LFM - Lab
0.178
0.090
0.095
0.050
0.050
25

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Table 6-ld. Cyanide Results from Columbus, OH, Drinking Water (continued)


Non-Technical Operator
Technical Operator
Sample Description
Ref. Cone.
(mg/L)
Unit #1
(mg/L)
Unit #2
(mg/L)
Unit #1
(mg/L)
Unit #2
(mg/L)
Well Water Background -
Outdoor Field Site
<0.005
<0.03
<0.03
<0.03
<0.03
Well Water Background - Indoor
Field Site
<0.005
<0.03
<0.03
<0.03
<0.03
Well Water Background - Lab
<0.005
<0.03
<0.03
<0.03
<0.03
Well Water Background - Lab
<0.005
<0.03
<0.03
<0.03
<0.03
Well Water Background - Lab
<0.005
<0.03
<0.03
<0.03
<0.03
Well Water Background - Lab
<0.005
<0.03
<0.03
<0.03
<0.03
Well Water LFM -
Outdoor Field Site
0.100
<0.03
<0.03
<0.03
<0.03
Well Water LFM -
Outdoor Field Site
0.121
<0.03
<0.03
<0.03
<0.03
Well Water LFM -
Outdoor Field Site
0.114
<0.03
<0.03
<0.03
<0.03
Well Water LFM -
Outdoor Field Site
0.091
<0.03
<0.03
<0.03
<0.03
Well Water LFM -
Indoor Field Site
0.100
0.120
0.120
0.120
0.125
Well Water LFM -
Indoor Field Site
0.121
0.105
0.110
0.105
0.110
Well Water LFM -
Indoor Field Site
0.114
0.095
0.095
0.100
0.110
Well Water LFM -
Indoor Field Site
0.091
0.105
0.110
0.115
0.120
Well Water LFM - Lab
0.100
<0.03
<0.03
<0.03
<0.03
Well Water LFM - Lab
0.121
<0.03
<0.03
<0.03
<0.03
Well Water LFM - Lab
0.114
<0.03
<0.03
<0.03
<0.03
Well Water LFM - Lab
0.091
<0.03
<0.03
<0.03
<0.03
26

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Table 6-2a. Percent Accuracy of Performance Test Sample Measurements

Non-Technical Operator
Technical Operator
Sample




Concentration
Unit #1
Unit #2
Unit #1
Unit #2
(mg/L)
(bias)
(bias)
(bias)
(bias)
0.030
24%
9%
7%
12%
0.100
18%
14%
7%
10%
0.200
10%
6%
3%
6%
0.400
20%
15%
11%
14%
0.800
NA(a)
NA
NA
NA
(a) NA = Calculation of bias not appropriate when over detectable range of the CHEMetrics VVR.

Table 6-2b. Percent Accuracy of Surface Water Measurements


Non-Technical Operator
Technical Operator
Sample Description
Unit #1 (bias)
Unit #2 (bias)
Unit #1 (bias)
Unit #2 (bias)
Alum Creek LFM
13%
17%
11%
14%
Olentangy River LFM
4%
6%
4%
6%
Table 6-2c. Percent Accuracy of U.S. Drinking Water Measurements
Sample Description
Non-Technical Operator
Technical Operator
Unit #1 (bias)
Unit #2 (bias)
Unit #1 (bias)
Unit #2 (bias)
Des Moines, IA, LFM
9%
7%
41%
41%
Flagstaff, AZ, LFM
12%
12%
59%
62%
Seattle, WA, LFM
23%
18%
19%
18%
Montpelier, VT, LFM
34%
34%
34%
32%
Tallahassee, FL, LFM
52%
50%
60%
63%
27

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Table 6-2d. Percent Accuracy of Columbus, OH, Drinking Water Measurements

Non-Technical Operator
Technical Operator
Sample Description Unit #1 (bias)
Unit #2 (bias)
Unit #1 (bias)
Unit #2 (bias)
City Water LFM - Outdoor
100%(a)
100%(a)
100%(a)
100%(a)
Field Site




City Water LFM - Indoor Field
61%
56%
56%
59%
Site




City Water LFM - Lab
45%
47%
66%
67%
Well Water LFM - Outdoor
100%(a)
100%(a)
100%(a)
100%(a)
Field Site




Well Water LFM - Indoor
47%(b)
46%(b)
45 %(b)
42%(b)
Field Site




Well Water LFM - Lab
100%(a)
100%(a)
100%(a)
100%(a)
(a) 100% bias due to non-detect reading from CHEMetrics VVR.


^ Due to an approximately 50% reference LFM recovery in the well water sample (see Table 4-2), these biases were
calculated using the fortified concentration of 0.200 mg/L as the reference concentration.

Table 6-3a. Relative Standard Deviation of Performance Test Sample Measurements

Non-Technical Operator
Technical Operator
Reference




Concentration Method
Unit #1
Unit #2
Unit #1
Unit #2
(mg/L) (RSD)
(RSD)
(RSD)
(RSD)
(RSD)
0.030 8%
13%
13%
0%
11%
0.100 7%
7%
7%
3%
3%
0.200 2%
2%
2%
4%
2%
0.400 2%
4%
4%
2%
3%
0.800 1%
NA(a)
NA(a)
NA(a)
NA(a)
(a) NA = Calculation of precision not appropriate when result was outside the detectable range of the CHEMetrics
VVR.




Table 6-3b. Relative Standard Deviation of Surface Water Measurements


Non-Technical Operator
Technical Operator
Reference




Sample Method
Unit #1
Unit #2
Unit #1
Unit #2
Description (RSD)
(RSD)
(RSD)
(RSD)
(RSD)
Alum Creek LFM 8%
2%
3%
4%
5%
Olentangy River LFM 2 %
5%
5%
4%
3%
28

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Table 6-3c. Relative Standard Deviation of U.S. Drinking Water Measurements
Non-Technical Operator
Technical Operator
Reference
Sample Method
Description	(RSD)
Unit #1
(RSD)
Unit #2
(RSD)
Unit #1
(RSD)
Unit #2
(RSD)
Des Moines, IA	3%
LFM-A
Flagstaff, AZ	12%
LFM-A
Montpelier, VT	2%
LFM-A
Seattle, WALFM- 2%
A
Tallahassee, FL	2%
LFM-A
7%
7%
8%
7%
11%
7%
5%
9%
10%
9%
15%
23%
4%
0%
10%
13%
27%
6%
2%
12%
Table 6-3d. Relative Standard Deviation of Columbus, OH, Drinking Water Measurements
Non-Technical Operator
Technical Operator
Reference
Sample Method
Description	(RSD)
Unit #1
(RSD)
Unit #2
(RSD)
Unit #1
(RSD)
Unit #2
(RSD)
City Water LFM - NA(a)
Outdoor Field Site
City Water LFM - 4%
Indoor Field Site
City Water LFM - 4%
Lab
Well Water LFM - NA
Outdoor Field Site
Well Water LFM - 13%
Indoor Field Site
Well Water LFM - 13%
Lab
NA
10%
5%
NA
10%
NA
NA
5%
5%
NA
9%
NA
NA
10%
11%
NA
8%
NA
NA
13%
9%
NA
6%
NA
(a)
Calculation of precision not appropriate when results were outside the detection range of the CHEMetrics VVR.
29

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6.3 Linearity
The linearity of the CHEMetrics VVR was assessed by using a linear regression of the PT
results against the reference method results (Table 6-la). Figures 6-1 and 6-2 show scatter plots
of the results from the non-technical and technical operator, respectively versus the reference
results. A dotted regression line with a slope of unity and intercept of zero also is shown in
Figures 6-1 and 6-2.
0.45
0.40
y = 0.8232X + 0.0051
r2 = 0.9907
0.35 -
0.30
0.25 -
0.20
0.15 -
0.10 -
0.05 -
0.00
0
0.1
0.2
0.3
0.4
0.5
Reference Method Results (mg/L)
Figure 6-1. Non-Technical Operator Linearity Results
0.45
0.40
y = 0.8627X + 0.0074
r2 = 0.9949
0.35
- 5 °-30
8 o ~
| DC 0.25
.c
o
V
I-
0.15
Q.
0.10
0.05
0.00
0
0.05
0.1
0.15
0.2
0.25
0.3
0.35
0.4
0.45
Reference Method Results (mg/L)
Figure 6-2. Technical Operator Linearity Results
30

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A linear regression of the data in Figure 6-1 for the non-technical operator gives the following
regression equation:
y (non-technical operator results in mg/L)=0.823 (± 0.030) x (reference result in mg/L)
+ 0.005 (± 0.007) mg/L with r2=0.991 and N=33.
A linear regression of the data in Figure 6-2 for the technical operator gives the following
regression equation:
y (technical operator results in mg/L)=0.863 (± 0.023) x (reference result in mg/L)
+ 0.007 (± 0.005) mg/L with r2=0.995 and N=33.
where the values in parentheses represent the 95% confidence interval of the slope and intercept.
Only the technical operator's intercept is significantly different from zero, and the r2 values are
both above 0.990. Both slopes are significantly different from unity at the 95% confidence
interval, but the slopes from each operator are statistically the same.
6.4 Method Detection Limit
The manufacturer's estimated detection limit for the CHEMetrics VVR is 0.030 mg/L cyanide.
The MDL(4) was determined by analyzing seven replicate samples at a concentration of
0.200 mg/L. Table 6-4 shows the results of the MDL assessment. The MDL determined as
described in Equation (6) of Section 5.4 was 0.034 and 0.031 mg/L for the CHEMetrics VVR
when used by the non-technical operator and 0.017 and 0.011 mg/L for the CHEMetrics VVR
when used by the technical operator.
Table 6-4. Results of Method Detection Limit Assessment

Non-Technical Operator
Technical Operator
MDL Cone.
Unit #1
Unit #2
Unit #1
Unit #2
(mg/L)
(mg/L)
(mg/L)
(mg/L)
(mg/L)
0.200
0.160
0.170
0.180
0.165
0.200
0.155
0.165
0.175
0.170
0.200
0.155
0.160
0.170
0.165
0.200
0.160
0.165
0.165
0.160
0.200
0.165
0.170
0.170
0.165
0.200
0.185
0.190
0.170
0.165
0.200
0.155
0.165
0.165
0.160
Std Dev
0.011
0.010
0.005
0.003
t (n=7)
3.140
3.140
3.140
3.140
MDL (mg/L)
0.034
0.031
0.017
0.011
31

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6.5 Inter-Unit Reproducibility
The inter-unit reproducibility of the CHEMetrics VVR was assessed by using a linear regression
of the results produced by one CHEMetrics VVR plotted against the results produced by the
other CHEMetrics VVR. The results from all of the samples that had detectable amounts of
cyanide (including the PT, surface, and drinking water samples) produced by both operators were
included in this regression. Figure 6-3 shows a scatter plot of the results from both CHEMetrics
VVRs.
0.4
0.35
y = 0.9981X + 0.0001
r2 = 0.9913
0.3
0.25
0.2
^ 0.15
c
3
0.05
0
0.05
0.1
0.15
0.2
0.25
0.3
0.35
0.4
Unit #2 (mg/L)
Figure 6-3. Inter-Unit Reproducibility Results
A lineal- regression of the data in Figure 6-3 for the inter-unit reproducibility assessment gives the
following regression equation:
y (Unit #1 result in mg/L)=0.998 (± 0.015) x (Unit #2 result in mg/L) + 0.0001 (± 0.002) mg/L
with r=0.991 and N=128.
where the values in parentheses represent the 95% confidence interval of the slope and intercept.
The slope is not significantly different from unity and the intercept is not significantly different
from zero. These data indicate that the two CHEMetrics VVRs functioned veiy similarly to one
another.
6.6 Lethal or Near-Lethal Dose Response
Samples at 50.0-, 100-, and 250-mg/L concentrations (close to what may be lethal if a volume the
size of a typical glass of water was ingested) were prepared and analyzed by the CHEMetrics
VVR. Upon breaking the ampoule in the sample, the color of the sample changed within five
seconds to brilliant purple and, after approximately 35 more seconds, to blood red. The change
was much more rapid than for any of the PT samples. The PT samples took about 30 seconds to
produce a small change in the color of the sample and took the full 15-minute reaction time to
reach its analysis color of clear, light purple. When these samples with lethal/near-lethal
concentrations were inserted into the CHEMetrics VVR after the full reaction time, the digital
readout read "over range." Even without using the CHEMetrics VVR, the reagents and
32

-------
Vacu-vials® would be useful for a first responder seeking to find out whether a toxic level of
cyanide is present in a drinking water sample. The presence of such concentrations could be
confirmed within minutes by observation of the color development process.
6.7 Operator Bias
The possible difference in results produced by the non-technical and technical operator was
assessed by using a linear regression of the results produced by the non-technical operator plotted
against the results produced by the technical operator. The results from all of the samples that had
detectable amounts of cyanide (including the PT, surface, and drinking water samples) from both
technologies were included in this regression. Figure 6-4 shows a scatter plot of the results from
both technologies.
0.400
0.350
(0
" 0.200
£ 2 0.150
O V
z Q. 0.100
o
0.050
0.000
4
Figure 6-4.
A linear regression of the data in Figure 6-4 for the inter-unit comparability assessment gives the
following regression equation:
y (non-tech result in mg/L)=0.911 (± 0.053) x (tech result in mg/L) + 0.016
(± 0.007) mg/L with r2=0.902 and N=128.
where the values in parentheses represent the 95% confidence interval of the slope and intercept.
The slope of this regression is less than 10% different from unity, indicating a slight difference in
the results produced by the operators. The relatively low coefficient of variation is due to the
samples from Flagstaff, AZ, and Des Moines, IA. The technical operator's results for these
samples were significantly less than the non-technical operator. These samples make up the
outlying data points that are above the linear regression line in the 0.050 to 0.125 mg/L range for
the technical operator. If these sixteen data points are removed from the data set, the r2 increases
to 0.950. While the difference between the operators (indicated by this slope, which deviates
from unity) is not explainable for these samples, these data should not be interpreted to conclude
that the effectiveness of the CHEMetrics VVR is dependent on the operator. In the two plots












Technical Operator Results (mg/L)
Non-Technical vs. Technical Operator Bias Results
33

-------
describing linearity in Section 6.3, the slopes for each operator are not significantly different
from one another. If one operator was consistently more accurate than the other, the slopes of the
linearity plots would be significantly different. Rather than this deviation from unity being a
result of the fact that one operator is non-technical and the other technical, it is probably a result
of the normal variability of two separate people performing the analyses. Even if both operators
had been technically trained, there would probably be a slight difference in performance because
of variations in analysis technique.
6.8 Field Portability
The CHEMetrics VVR was operated in laboratory and field settings during this verification test.
Tables 6-Id, 6-2d, and 6-3d show the results of these measurements. From an operational
standpoint, the CHEMetrics VVR was easily transported to the field setting, and the samples
were analyzed in the same fashion as they were in the laboratory. No functional aspects of the
CHEMetrics VVR were compromised by performing the analyses in the field setting. However,
performing analyses under extremely cold conditions (sample water temperatures between 4 and
6°C) negatively affected the performance of the CHEMetrics VVR reagents. The low
temperatures apparently slowed the chemical reaction rates, which caused the decreased color
change in the LFM samples.
Table 6-2d shows the bias of the samples analyzed in the field setting (indoors with sample
temperatures of approximately 16°C and outdoors with sample temperatures of 4 to 6°C) and of
the identical samples analyzed at the laboratory at approximately 20°C. The well and Columbus,
OH, city water samples were both dechlorinated as described in Section 3.5.1. In addition,
because the well water sample had a pungent odor, lead carbonate was added after NaOH
preservation to check for the presence of sulfides. The lead carbonate did not turn black. Such a
color change would have indicated the presence of sulfides. Nonetheless, there was a 56 to 61%
bias in the indoor Columbus, OH, city water measurements and a 42 to 47% bias in the indoor
well water measurements. Because there was an apparent matrix interference in the reference
measurement (see Table 4-2), the well water biases were calculated using the fortified
concentration (0.200 mg/L) as the reference concentration.
The apparent matrix interference in the well water LFM continued to mask the cyanide in the
LFM sample after it was spiked and analyzed at the indoor field setting (producing a 42 to 47%
bias from initial fortification) because, by the time the well water LFM samples were analyzed by
the CHEMetrics VVR at the laboratory two days after initial fortification, there was no detectable
cyanide (100% bias from initial fortification). These same samples were analyzed using the
reference method eight days after initial fortification, and the result was below the MDL of the
reference method (Table 4-2). Because there was an apparent time-dependent matrix interference,
the data generated from the well water samples using the CHEMetrics VVR in the field setting
cannot be meaningfully compared with the result produced from the identical samples analyzed
with the CHEMetrics VVR in the laboratory.
The bias in the Columbus, OH, city water indoor LFM sample (56 to 61%) was similar to the bias
in the Columbus, OH, city water LFM sample analyzed at the laboratory location (45 to 63%).
34

-------
The apparent matrix interference causing the large biases did not further mask the cyanide in the
LFM sample as evidenced by the similar biases at the field location and at the laboratory two
days later. These data support the qualitative assessment that the CHEMetrics VVR functions
properly when operated in field locations.
6.9 Ease of Use
The CHEMetrics VVR and associated cyanide test reagents and Vacu-vials® were easy to
operate. The instructions were clear, and the sample and reagents were easily measured using a
graduated sample cup, syringe, and a dropper bottle. It was convenient that adding reagents did
not have strict mixing and reaction time requirements. The operators only had to hold strictly to
the 15-minute color development reaction time. Not having to keep track of several short mixing/
reaction times after adding each reagent streamlined the analysis and increased sample through-
put. The CHEMetrics VVR recognized the Vacu-vials® when they were inserted and auto-
matically produced the result on the digital output. While the sample handling and analysis were
very easy, the pH of each sample had to be adjusted to between 10.5 and 11.0 using NaOH and
hydrochloric acid (HC1). This step required the availability of acid and base, pH paper or meter,
and some knowledge of pH adjustment. Instructions for pH adjustment were not provided.
Because the color change took place within the Vacu-vials® and they were disposable, cleanup
was simple and free of mess. Only the sample cup used for measuring the sample and adding
reagents had to be rinsed between samples.
6.10 Sample Throughput
Sample preparation, including accurate volume measurement and the addition of reagents, took
only one to two minutes per sample. After performing the sample preparation, a 15-minute period
of color development is required before sample analysis. Therefore, if only one sample is
analyzed, it would take approximately 17 minutes. However, both operators were able to stagger
the start of the color development period every two minutes for subsequent samples, so a typical
sample set of 12 analyses took 30 to 40 minutes.
35

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Chapter 7
Performance Summary
Biases for the CHEMetrics VVR ranged from 3 to 24% for the PT samples; 4 to 17% for the
surface water samples; 7 to 63% for the drinking water samples from around the country; and 42
to 100% for the Columbus, OH, drinking water samples.
The RSD ranged from 0 to 13% for the PT samples; 2 to 5% for the surface water samples; 0 to
27% for the drinking water samples from around the country; and 5 to 13% for the Columbus,
OH, drinking water samples analyzed at the indoor field site and at the laboratory. The
calculation of precision for all the drinking water samples analyzed outdoors and the Columbus
well water samples analyzed at the laboratory was not appropriate because the results were below
the MDL of the CHEMetrics VVR.
A linear regression of the linearity data obtained for the non-technical operator gives the
following regression equation:
y (non-technical operator results in mg/L)=0.823 (± 0.030) x (reference result in mg/L)
+ 0.005 (± 0.007) mg/L with r2=0.991 and N=33.
A linear regression of the data for the technical operator gives the following regression equation:
y (technical operator results in mg/L)=0.863 (± 0.023) x (reference result in mg/L)
+ 0.007 (± 0.005) mg/L with r2=0.995 and N=33.
where the values in parentheses represent the 95% confidence interval of the slope and intercept.
Both operators' intercepts are very close to zero, and the r2 values are both above 0.990. The
linearity of the CHEMetrics VVR was not dependent on which operator was performing the
analyses. The slope of the linear regression was significantly less than unity in both instances.
This deviation from unity indicates a low bias in the results generated by the CHEMetrics VVR
compared with the results produced by the reference method.
The MDL was determined to be 0.034 and 0.031 mg/L for the CHEMetrics VVR when used by
the non-technical operator and 0.017 and 0.011 mg/L for the CHEMetrics VVR when used by the
technical operator.
36

-------
A linear regression of the data to determine inter-unit reproducibility gives the following
regression equation:
y (Unit #1 result in mg/L)=0.998 (± 0.015) x (Unit #2 result in mg/L) + 0.0001 (± 0.002) mg/L
with 1^=0.991 and N=128.
where the values in parentheses represent the 95% confidence interval of the slope and intercept.
The slope is not significantly different from unity, and the intercept is not significantly different
from zero. These data indicate that the technologies functioned very similarly to one another.
When performing the analysis on samples containing lethal/near-lethal concentrations of cyanide,
the difference in the color development was remarkable. Upon snapping the ampoule in the
sample, the color of the sample changed within five seconds to brilliant purple and, after
approximately 35 more seconds, to blood red. The change was much more rapid than for any of
the PT samples. When the samples were inserted into the CHEMetrics VVR after the full reaction
time, the digital readout read "over range." Even without using the CHEMetrics VVR, the
reagents and Vacu-vials® would be useful for a first responder seeking to find out whether a
toxic level of cyanide is present in a drinking water sample. The presence of such concentrations
could be confirmed within minutes by visual observation of the color development process.
A linear regression of the data for the operator bias assessment gives the following regression
equation:
y (non-tech result in mg/L)=0.911 (± 0.053) x (tech result in mg/L) + 0.016
(± 0.007) mg/L with r^O.902 and N=128.
where the values in parentheses represent the 95% confidence interval of the slope and intercept.
The slope of this regression is less than 10% different from unity, indicating a difference in the
results produced by the operators. Rather than this deviation from unity being due to the fact that
one operator is non-technical and the other technical, it is probably a result of the normal varia-
bility of two separate people performing the analyses. Even if both operators had been technically
trained, there would probably be a slight difference in performance due to variations in analysis
technique.
From an operational standpoint, the CHEMetrics VVR was easily transported to the field setting,
and the samples were analyzed in the same fashion as they were in the laboratory. No functional
aspects of the CHEMetrics VVR were compromised by performing the analyses in the field
setting. However, performing analyses under extremely cold conditions (4 to 6°C) negatively
affected the performance of the CHEMetrics V-3803 reagents. The low temperatures apparently
slowed the chemical reaction rates, which caused the decreased color change in the LFM
samples.
The CHEMetrics VVR and V-3803 cyanide module were easy to operate. The instructions were
clear, and the sample and reagents were easily measured using a graduated sample cup, syringe,
and a dropper bottle. The CHEMetrics VVR recognized the Vacu-vials® when they were inserted
and automatically produced the result on the digital output. While the sample handling and
analysis were easy, the pH of each sample had to be adjusted to between 10.5 and 11 using
37

-------
NaOH and HC1. This step required the availability of acid and base, pH paper or meter, and some
knowledge of pH adjustment. Instructions for pH adjustment were not included in the
manufacturer's instructions. Because the color change took place within the Vacu-vials® and
they were disposable, cleanup was simple and free of mess. Only the sample cup used for
measuring the sample and adding reagents needed to be rinsed between samples.
Since the CHEMetrics VVR did not require strict mixing/reaction time periods after adding each
reagent, and the Vacu-vials® automatically measured the volume of sample added to the final
reaction vessel, the analysis process was conducive to analyzing large numbers of samples
consecutively. Each sample was entirely prepared within one or two minutes, and then the
15-minute color development period started. If only one sample is analyzed, sample analysis
would take approximately 17 minutes. However, both operators were able to stagger the start of
the color development period every two minutes for subsequent samples, so a typical sample set
of 12 analyses took 30 to 40 minutes.
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Chapter 8
References
1.	Test/QA Plan for Verification of Portable Analyzers for Detection of Cyanide in Water,
Battelle, Columbus, Ohio, January 2003.
2.	U.S. EPA Method 335.1, Cyanides Amenable to Chlorination, 1974, in "Methods for
Chemical Analysis of Water and Wastes," EPA/600/4-79/020, March 1983.
3.	United States Environmental Protection Agency, National Primary Drinking Water
Standards, EPA/816-F-02-013, July 2002.
4.	Code of Federal Regulations, Title 40, Part 136, Appendix B, Definition and Procedure for
the Determination of the Method Detection Limit-Revision 1.11.
5.	Quality Management Plan (QMP)for the ETV Advanced Monitoring Systems Center,
Version 4.0, U.S. EPA Environmental Technology Verification Program, Battelle, Columbus,
Ohio, December 2002.
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