April 2003
Environmental Technology
Verification Report
LaMotte
1919 SMART 2 COLORIMETER
with 3660-SC Reagent System
Prepared by
Battelle
Battelle
. . . Putting Technology To Work
Under a cooperative agreement with
SEPA U.S. Environmental Protection Agency
ETV ElV ElV
-------
April 2003
Environmental Technology Verification
Report
ETV Advanced Monitoring Systems Center
LaMotte
1919 SMART 2 Colorimeter
with 3660-SC Reagent System
by
Ryan James
Amy Dindal
Zachary Willenberg
Karen Riggs
Battelle
Columbus, Ohio 43201
-------
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.
ii
-------
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 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.
iii
-------
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.
iv
-------
Contents
Page
Notice ii
Foreword iii
Acknowledgments iv
List of Abbreviations viii
1 Background 1
2 Technology Description 2
3 Test Design and Procedures 3
3.1 Introduction 3
3.2 Reference Method 4
3.3 Test Design 4
3.4 Test Samples 4
3.4.1 Quality Control Samples 5
3.4.2 Performance Test Samples 7
3.4.3 Lethal/Near-Lethal Concentrations of Cyanide in Water 7
3.4.4 Surface Water; Drinking Water from Around the U.S.;
and Columbus, OH, Drinking Water 7
3.5 Test Procedure 10
3.5.1 Sample Preparation 10
3.5.2 Sample Identification 10
3.5.3 Sample Analysis 10
4 Quality Assurance/Quality Control 12
4.1 Reference Method QC Results 12
4.2 Audits 15
4.2.1 Performance Evaluation Audit 15
4.2.2 Technical Systems Audit 15
4.2.3 Audit of Data Quality 16
4.3 QA/QC Reporting 16
4.4 Data Review 16
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
v
-------
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 29
6.3 Linearity 31
6.4 Method Detection Limit 32
6.5 Inter-Unit Reproducibility 33
6.6 Lethal or Near-Lethal Dose Response 34
6.7 Operator Bias 34
6.8 Field Portability 35
6.9 Ease of Use 36
6.10 Sample Throughput 37
7 Performance Summary 38
8 References 41
Figures
Figure 2-1. LaMotte SMART 2 Colorimeter 2
Figure 3-1. Sampling Through Analysis Process 8
Figure 6-1. Non-Technical Operator Linearity Results 31
Figure 6-2. Technical Operator Linearity Results 32
Figure 6-3. Inter-Unit Reproducibility Results 33
Figure 6-4. Non-Technical vs. Technical Operator Bias Results 35
Tables
Table 3-1. Test Samples 6
Table 4-1. Reference Method QCS Results 13
Table 4-2. Reference Method LFM Analysis Results 14
vi
-------
Table 4-3. Summary of Performance Evaluation Audit 15
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 26
Table 6-2a. Percent Accuracy of Performance Test Sample Measurements 28
Table 6-2b. Percent Accuracy of Surface Water Measurements 28
Table 6-2c. Percent Accuracy of U.S. Drinking Water Measurements 28
Table 6-2d. Percent Accuracy of Columbus, OH, Drinking Water Measurements 29
Table 6-3a. Relative Standard Deviation of Performance Test Sample Measurements 30
Table 6-3b. Relative Standard Deviation of Surface Water Measurements 30
Table 6-3c. Relative Standard Deviation of U.S. Drinking Water Measurements 30
Table 6-3d. Relative Standard Deviation of Columbus, OH,
Drinking Water Measurements 31
Table 6-4. Results of Method Detection Limit Assessment 33
vii
-------
List of Abbreviations
AMS
Advanced Monitoring Systems
ASTM
American Society of Testing and Materials
ATEL
Aqua Tech Environmental Laboratories
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
viii
-------
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 LaMotte 1919 SMART 2 colorimeter with the 3660-
SC Reagent System 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.
1
-------
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 1919 SMART 2 colorimeter by LaMotte with the 3660-
SC reagent system. Following is a description of the SMART 2, based on information provided
by the vendor. The information provided below was not verified in this test.
The LaMotte SMART 2 is a portable colorimeter in which a sample and a reagent are reacted.
The reaction produces a color whose intensity is proportional to the concentration of the analyte.
The color is measured photometrically to provide a quantitative determination of the analyte in
the sample. The LaMotte SMART 2 uses LED light sources and filtered photodiode detectors.
To analyze cyanide with the LaMotte SMART 2, a 10.0-mL sample is measured into a sample
vial, and 1.0 mL of reagent is added to the sample with the disposable pipet. The sample is
shaken, two other granular reagents are added using the provided scoops, and the sample is
shaken again. If any cyanide is present in the water
sample, a reaction between cyanide and the reagents
added to the sample produces a color change. After a
20-minute color development period, the sample vial is
inserted into the LaMotte SMART 2; and the cyanide
concentration (in parts per million) is reported on the
digital display. For consistency with the results reported
by the reference laboratory, the data produced by the
LaMotte SMART 2 are reported in the equivalent units
of milligrams per liter (mg/L).
The range of the LaMotte SMART 2 is 0 to 0.50 parts
per million. It has automatic wavelength selection and is
supplied with four sample tubes, an AC adapter, and an
instruction manual including test procedures. The
dimensions of the LaMotte SMART 2 are 15 x 8 x 5.5
centimeters (6 x 3.25 x 2.5 inches), and it weighs 312
grams (11 ounces). The LaMotte SMART 2 operates at
120V/60Hz or 220V/50Hz. The list price for this unit is
$725.00 for the colorimeter and $64.00 for reagents
adequate for 50 water samples.
Figure 2-1. LaMotte SMART 2
Colorimeter
2
-------
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
0.200 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 LaMotte
SMART 2 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 LaMotte 1919 SMART 2 with the
3660-SC reagent system was verified by analyzing performance test (PT), surface, and drinking
water samples. A statistical comparison of the analytical results from the LaMotte SMART 2
and the reference method provided the basis for the quantitative performance evaluations.
The LaMotte SMART 2's performance was evaluated in terms of
¦ Accuracy
¦ Precision
¦ Linearity
¦ Method detection limit
¦ Inter-unit reproducibility
¦ Lethal or near-lethal dose response
3
-------
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 LaMotte SMART 2 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 LaMotte SMART 2s 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 1919 SMART 2 colorimeter and the 3660-SC reagent system. The
verification test involved challenging the LaMotte SMART 2 with a variety of test samples,
including sets of drinking and surface water samples representative of those likely to be
analyzed by the LaMotte SMART 2. The results from the LaMotte SMART 2 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 LaMotte SMART 2 and
the reference method.
The LaMotte SMART 2 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 LaMotte SMART 2s.
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 Battelle Verification
4
-------
Test Coordinator. The LaMotte SMART 2 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 concentration samples were prepared from
purchased standards. The PT and QC sample concentrations were targeted to the EPA maximum
contaminant 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 LaMotte SMART 2 also was
qualitatively evaluated with samples prepared in 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. In the case of the drinking
water samples, the spike solution used to prepare the LFM was prepared in the laboratory and
taken to the field site. 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 LaMotte SMART 2. The
QCSs for the LaMotte SMART 2 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.
5
-------
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 (also
listed below)
QCS
0.200 mg/L
10% of all
Performance Test
For the determination of
method detection limit
0.050 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
400
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
400
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 ma/L LFM
12
(a) Because the initial aliquot analyzed by the technical operator resulted in non-detectable concentrations of cyanide,
the technical operator did not analyze additional aliquots. However, the results for the initial aliquots analyzed by
the non-technical operator were other than a non-detectable concentration, so three additional aliquots were
analyzed.
6
-------
The LaMotte SMART 2 was factory calibrated, so no additional calibration was performed by
the operators. However, QCSs were analyzed (without defined performance expectations) by the
LaMotte SMART 2 to demonstrate their proper functioning to the operator. A QCS was
analyzed before and after each sample batch (typically consisting of 12 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 LaMotte SMART 2's accuracy, linearity, and
detection limit. Seven non-consecutive replicate analyses of a 0.050-mg/L solution were made to
obtain precision data with which to determine the method detection limit (MDL).(4) Five other
solutions were prepared to assess the linearity over a 0.030- to 0.800-mg/L range of cyanide con-
centrations. Four aliquots of each of these solutions were analyzed separately to assess the
precision of the LaMotte SMART 2. 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 LaMotte SMART 2 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 LaMotte SMART 2 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.
7
-------
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
Test for
Chlorine
Dechlorinate
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
Adjust pH
of four
aliquots
with HCI
to between
10.5 and 11
Analyze
aliquots
by portable
cyanide
analyzer
(background)
Analyze four
10-mL aliquots
by portable
cyanide
analyzer
(LFM)
Figure 3-1. Sampling through Analysis Process
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)
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
8
-------
cyanide to provide LFM aliquots, and the other subsample remained unspiked (background).
Four 10.0-mL aliquots were taken from each subsample and analyzed for cyanide by the
LaMotte SMART 2. 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, all four replicates of Columbus, OH,
city and well water samples were analyzed at the laboratory analysis site regardless of the
response of the first aliquot. Four LFM aliquots were prepared and analyzed for every drinking
and surface water source, regardless of the concentration of the initial aliquot. To avoid
replicating samples with non-detectable concentrations of cyanide, only one background aliquot
of each source of drinking water was analyzed if cyanide was not detectable in the first aliquot
analyzed by the LaMotte SMART 2. If cyanide was detectable in that initial aliquot, three
additional aliquots of that sample were analyzed in addition to four LFM aliquots.
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
LaMotte SMART 2. 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 was 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 to the results produced by the
LaMotte SMART 2 at the indoor and outdoor field locations and the laboratory location.
9
-------
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 LaMotte
SMART 2 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 of 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 LaMotte SMART 2s were tested independently. Each LaMotte SMART 2 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
10
-------
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 included records of the time required for sample analysis and operator observa-
tions concerning the use of the LaMotte SMART 2 (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
II ) and the analyte concentration for each sample.
11
-------
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 a 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)
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
12
-------
Table 4-1. Reference Method QCS Results
Known QCS Concentration
Date
Analysis Result
(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
13
-------
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.
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%
NAc)
(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 or 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 result 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.
14
-------
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
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:
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
Measured
Known
Concentration
Concentration
RPD
Sample
Date of Analysis
(mg/L)
(mg/L)
(%)
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.
15
-------
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.
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.
16
-------
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
-------
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 LaMotte SMART 2. 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 LaMotte SMART 2 and those
from the reference method, and is the average of the reference measurements. Accuracy was
assessed independently for each LaMotte SMART 2 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 LaMotte SMART 2 precision at each concentration.
(3)
1/2
7 n 0
s=^]^~c)
_n 1 k=i
(4)
18
-------
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 =
S_
c
x 100
(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 LaMotte SMART 2 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 LaMotte SMART 2 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=txS (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 LaMotte SMART 2 was reported separately.
5.5 Inter-Unit Reproducibility
The results obtained from two identical LaMotte SMART 2s were compiled independently for
each LaMotte SMART 2 and compared to assess inter-unit reproducibility. The results were
interpreted using a linear regression of one LaMotte SMART 2's results plotted against the
results produced by the other LaMotte SMART 2. If the LaMotte SMART 2s function alike, the
slope of such a regression should not differ significantly from unity.
5.6 Lethal or Near-Lethal Dose Response
The LaMotte SMART 2 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 its 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
-------
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 other
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 LaMotte SMART 2 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
-------
Chapter 6
Test Results
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 LaMotte SMART 2. Results
are shown for the technical and non-technical operators and for both LaMotte SMART 2s that
were tested (labeled as Unit #1 and #2). The 0.800-mg/L PT sample was outside the detectable
range of the LaMotte SMART 2. When these samples were inserted into the LaMotte SMART 2,
the result was reported as "over range."
All of the background drinking water samples and Alum Creek reservoir surface water samples
resulted in concentrations that were near or less than the LaMotte SMART 2's stated detection
limit of 0.010 mg/L. When analyzing the Olentangy River background water samples, the
technical operator's result on both LaMotte SMART 2 instruments was "BLANK?" for all eight
replicates (Table 6-lb). The non-technical operator's results on the same samples were reported
as below the detection limit of the LaMotte SMART 2. Both operators were analyzing surface
water aliquots from the same sample and using identical analysis techniques. There was no
visible color change in these samples, and they were not unusually turbid. The manufacturer
stated that the "BLANK?" display occurs when the detector recognizes that a sample contains
less color than the blank and is warning the user of such if the sample is a blank. When analyzing
an actual sample, a "BLANK?" result is the same as a result below the detection limit of the
LaMotte SMART 2 and is reported as such in Table 6-lb.
Tables 6-2a-d present the percent accuracy of the LaMotte SMART 2 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 LaMotte SMART 2, 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 2 to 31% for the PT samples; 11
to 30% for the surface water samples; 5 to 41% for the drinking water samples from around the
country; and 15 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.
21
-------
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
0.03
0.03
0.03
0.03
0.030
0.023
0.03
0.03
0.03
0.03
0.030
0.026
0.03
0.03
0.03
0.03
0.030
0.023
0.04
0.03
0.03
0.03
0.100
0.102
0.11
0.11
0.10
0.10
0.100
0.089
0.12
0.11
0.10
0.10
0.100
0.097
0.13
0.13
0.10
0.10
0.100
0.103
0.08
0.08
0.11
0.11
0.200
0.173
0.22
0.21
0.16
0.17
0.200
0.179
0.22
0.22
0.14
0.14
0.200
0.173
0.20
0.20
0.18
0.18
0.200
0.174
0.24
0.24
0.15
0.15
0.400
0.381
0.39
0.39
0.40
0.41
0.400
0.392
0.40
0.39
0.38
0.39
0.400
0.392
0.38
0.38
0.33
0.33
0.400
0.395
0.43
0.41
0.30
0.30
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 detectable range of LaMotte SMART 2.
22
-------
Table 6-lb. Cyanide Results from Surface Water
Non-Technical Operator Technical Operator
Sample Description
Cone.
(mg/L)
Unit #1
(mg/L)
Unit #2
(mg/L)
Unit #1
(mg/L)
Unit #2
(mg/L)
Alum Creek
Background
<0.005
<0.01
<0.01
<0.01
<0.01
Alum Creek
Background
<0.005
0.01
<0.01
<0.01
<0.01
Alum Creek
Background
<0.005
<0.01
<0.01
<0.01
<0.01
Alum Creek
Background
<0.005
<0.01
<0.01
<0.01
<0.01
Alum Creek LFM
0.166
0.21
0.21
0.17
0.17
Alum Creek LFM
0.183
0.13
0.13
0.16
0.16
Alum Creek LFM
0.173
0.22
0.21
0.14
0.14
Alum Creek LFM
0.151
0.09
0.09
0.14
0.14
Olentangy River
Background
<0.005
<0.01
<0.01
A
O
o
A
O
o
Olentangy River
Background
<0.005
<0.01
<0.01
A
O
o
A
O
o
Olentangy River
Background
<0.005
<0.01
<0.01
A
O
o
A
O
o
Olentangy River
Background
<0.005
<0.01
<0.01
A
O
o
A
O
o
M
Olentangy River
LFM
0.174
0.19
0.20
0.13
0.13
Olentangy River
LFM
0.178
0.21
0.22
0.16
0.17
Olentangy River
LFM
0.171
0.23
0.24
0.15
0.15
Olentangy River
LFM
0.176
0.17
0.18
0.09
0.09
(a) Result on the LaMotte SMART 2 digital display was
"BLANK?."
23
-------
Table 6-lc. Cyanide Results from U.S. Drinking Water
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,
<0.005
0.01
0.01
<0.01
<0.01
Background
Des Moines, IA, LFM
0.173
0.10
0.10
0.17
0.18
Des Moines, IA, LFM
0.173
0.23
0.23
0.17
0.17
Des Moines, IA, LFM
0.183
0.11
0.12
0.17
0.17
Des Moines, IA, LFM
0.181
0.13
0.13
0.16
0.17
Flagstaff, AZ,
<0.005
<0.01
<0.01
0.01
<0.01
Background
Flagstaff, AZ, LFM
0.157
0.10
0.10
0.14
0.15
Flagstaff, AZ, LFM
0.132
0.14
0.14
0.20
0.20
Flagstaff, AZ, LFM
SL(a)
0.15
0.15
0.16
0.16
Flagstaff, AZ, LFM
0.169
0.16
0.15
0.16
0.14
Montpelier, VT,
<0.005
0.03
0.01
<0.01
<0.01
Background
Montpelier, VT,
NR00
0.02
<0.01
NR
NR
Background
Montpelier, VT,
NR
<0.01
<0.01
NR
NR
Background
Montpelier, VT,
NR
0.01
0.01
NR
NR
Background
Montpelier, VT, LFM
0.167
0.14
0.14
0.14
0.14
Montpelier, VT, LFM
0.176
0.14
0.14
0.14
0.14
Montpelier, VT, LFM
0.168
0.15
0.15
0.13
0.13
Montpelier, VT, LFM
0.168
0.15
0.15
0.16
0.16
24
-------
Table 6-lc. Cyanide Results from U.S. Drinking Water (continued)
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)
Seattle, WA,
<0.005
0.01
0.01
<0.01
<0.01
Background
Seattle, WA,
NR
<0.01
<0.01
NR
NR
Background
Seattle, WA,
NR
0.01
<0.01
NR
NR
Background
Seattle, WA,
NR
0.03
0.01
NR
NR
Background
Seattle, WA, LFM
0.177
0.13
0.13
0.14
0.14
Seattle, WA, LFM
0.174
0.14
0.14
0.20
0.21
Seattle, WA, LFM
0.170
0.18
0.17
0.16
0.17
Seattle, WA, LFM
0.172
0.03
0.03
0.18
0.18
Tallahassee, FL,
<0.005
<0.01
<0.01
<0.01
<0.01
Background
Tallahassee, FL, LFM
0.157
0.11
0.11
0.08
0.08
Tallahassee, FL, LFM
0.161
0.13
0.13
0.11
0.11
Tallahassee, FL, LFM
0.165
0.13
0.14
0.11
0.11
Tallahassee, FL, LFM
0.159
0.09
0.09
0.08
0.08
(a) SL = reference sample lost due to a laboratory error.
(b) NR = sample not analyzed because initial aliquot analyzed by the technical operator resulted in a cyanide
concentration below 0.01 mg/L. The non-technical operator analyzed four background samples because of the
detectable concentration of cyanide in the initial aliquot.
25
-------
Table 6-Id. Cyanide Results from Columbus, OH, Drinking Water
Non-Technical Operator
Technical Operator
Sample Description
Ref. Conc.(a)
(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
<0.01
<0.01
<0.01
<0.01
City Water Background -
Indoor Field Site
<0.005
<0.01
<0.01
<0.01
<0.01
City Water Background -
Lab
<0.005
<0.01
<0.01
<0.01
<0.01
City Water Background -
Lab
<0.005
<0.01
<0.01
<0.01
<0.01
City Water Background -
Lab
<0.005
<0.01
<0.01
<0.01
<0.01
City Water Background -
Lab
<0.005
<0.01
0.01
<0.01
<0.01
City Water LFM - Outdoor
Field Site
0.176
0.02
0.02
0.03(b)
0.03(b)
City Water LFM - Outdoor
Field Site
0.167
0.02
0.02
0.03(b)
0.03(b)
City Water LFM - Outdoor
Field Site
0.165
0.02
0.02
0.02(b)
0.02(b)
City Water LFM - Outdoor
Field Site
0.178
0.01
0.01
0.03(b)
0.02(b)
City Water LFM - Indoor
Field Site
0.176
0.09
0.09
0.13
0.13
City Water LFM - Indoor
Field Site
0.167
0.06
0.06
0.11
0.11
City Water LFM - Indoor
Field Site
0.165
0.11
0.11
0.12
0.13
City Water LFM - Indoor
Field Site
0.178
0.10
0.11
0.13
0.13
City Water LFM - Lab
0.176
0.13
0.13
0.11
0.11
City Water LFM - Lab
0.167
0.15
0.15
0.13
0.13
City Water LFM - Lab
0.165
0.17
0.17
0.12
0.12
City Water LFM - Lab
0.178
0.14
0.14
0.16
0.16
26
-------
Table 6-Id. 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
<0.01
<0.01
<0.01
<0.01
Well Water Background -
Indoor Field Site
<0.005
<0.01
<0.01
<0.01
<0.01
Well Water Background -
Lab
<0.005
<0.01
<0.01
<0.01
<0.01
Well Water Background -
Lab
<0.005
<0.01
<0.01
<0.01
<0.01
Well Water Background -
Lab
<0.005
<0.01
<0.01
<0.01
<0.01
Well Water Background -
Lab
<0.005
<0.01
<0.01
<0.01
<0.01
Well Water LFM -
Outdoor Field Site
0.100
<0.01
<0.01
0.02
0.02
Well Water LFM -
Outdoor Field Site
0.121
<0.01
<0.01
<0.01
<0.01
Well Water LFM -
Outdoor Field Site
0.114
0.01
0.01
0.02
0.02
Well Water LFM -
Outdoor Field Site
0.091
<0.01
<0.01
0.01
0.01
Well Water LFM - Indoor
Field Site
0.100
0.14
0.14
0.13
0.13
Well Water LFM - Indoor
Field Site
0.121
0.16
0.16
0.13
0.14
Well Water LFM - Indoor
Field Site
0.114
0.15
0.13
0.13
0.15
Well Water LFM - Indoor
Field Site
0.091
0.11
0.11
0.14
0.15
Well Water LFM - Lab
0.100
<0.01
<0.01
<0.01
<0.01
Well Water LFM - Lab
0.121
<0.01
<0.01
<0.01
<0.01
Well Water LFM - Lab
0.114
0.01
0.01
<0.01
<0.01
Well Water LFM - Lab
0.091
<0.01
<0.01
<0.01
<0.01
(a) The same reference LFM samples are used for the outdoor, indoor, and laboratory analysis locations.
(b) Samples analyzed in pH range of 6.0 to 7.0.
27
-------
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
31%
21%
21%
21%
0.100
24%
22%
6%
6%
0.200
26%
24%
12%
10%
0.400
4%
2%
12%
12%
0.800
NA(a)
NA
NA
NA
(a) NA = Calculation of bias not appropriate when result was outside the detectable range of the LaMotte SMART 2.
Table 6-2b. Percent Accuracy of Surface Water Test Measurements
Non-Technical Operator
Technical Operator
Unit #1
Unit #2
Unit #1
Unit #2
Sample Description
(bias)
(bias)
(bias)
(bias)
Alum Creek LFM
30%
29%
11%
11%
Olentangy River LFM
16%
20%
24%
23%
Table 6-2c. Percent Accuracy of U.S. Drinking Water Measurements
Non-Technical Operator Technical Operator
Unit #1 Unit #2 Unit #1 Unit #2
Sample Description (bias) (bias) (bias) (bias)
Des Moines, IA, LFM 35% 34% 6% 5%
Flagstaff, AZ, LFM 13% 14% 17% 18%
Montpelier, VT, LFM 15% 15% 16% 16%
Seattle, WA, LFM 34% 32% 12% 12%
Tallahassee I L, LFM 28% 27% 41% 41%
28
-------
Table 6-2d. Percent Accuracy of Columbus, OH, Drinking Water Measurements
Non-Technical Operator Technical Operator
Unit #1 Unit #2 Unit #1 Unit #2
Sample Description (bias) (bias) (bias) (bias)
City Water LFM - Outdoor Field 90% 90% 84% 85%
Site
City Water LFM - Indoor Field 48% 46% 29% 27%
Site
City Water LFM - Lab 15% 15% 24% 24%
Well Water LFM - Outdoor Field 99% 99% 94% 94%
Site(a)
Well Water LFM - Indoor Field 30% 33% 34% 29%
Site(a)
Well Water LFM - Lab(a) 99% 99% 100%(b) 100%(b)
(a) 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.
^ 100% bias due to non-detect reading from LaMotte SMART 2.
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 LaMotte SMART 2 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 LaMotte SMART 2. 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 20% for the PT samples; 10 to 39% for the surface water
samples; 3 to 53% for the drinking water samples from around the country; and 4 to 77% for the
Columbus, OH, drinking water samples.
29
-------
Table 6-3a. Relative Standard Deviation of Performance Test Sample Measurements
Non-Technical Operator Technical Operator
Sample
Concentration Reference
Unit #1
Unit #2
Unit #1
Unit #2
(mg/L) Method (RSD)
(RSD)
(RSD)
(RSD)
(RSD)
0.030 8%
15%
0%
0%
0%
0.100 7%
20%
19%
5%
5%
0.200 2%
7%
8%
11%
11%
0.400 2%
5%
3%
13%
14%
0.800 1%
NA(a)
NA(a)
NA(a)
NA(a)
-------
Table 6-3d. Relative Standard Deviation of Columbus, OH, Drinking Water Measurements
Non-Technical Operator
Technical Operator
Sample Description
Reference
Method
(RSD)
Unit #1
(RSD)
Unit #2
(RSD)
Unit #1
(RSD)
Unit #2
(RSD)
City Water LFM -
Outdoor Field Site
4%
29%
29%
18%
23%
City Water LFM -
Indoor Field Site
4%
24%
26%
8%
8%
City Water LFM -
Lab
4%
12%
12%
17%
17%
Well Water LFM -
Outdoor Field Site
13%
NA
NA
11%
11%
Well Water LFM -
Indoor Field Site
13%
15%
15%
4%
1%
Well Water LFM -
Lab
13%
NA'a)
NA
NA
NA
Ul NA = calculation of precision was not appropriate when results were outside the detection range of the LaMotte
SMART 2.
6.3 Linearity
The linearity of the LaMotte SMART 2 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 an intercept of zero also is shown in
Figures 6-1 and 6-2.
y = 0.9952X + 0.0178
r2 = 0.9751
0.30 -
= O
o T 0.25 -
*7 15 E 0.20 -
0.15 -
0.10 -
0.05 -
0.00 -
0.1 0.15 0.2 0.25 0.3 0.35
Reference Method Results (mg/L)
0.45
Figure 6-1. Non-Technical Operator Linearity Results
31
-------
0.45
y = 0.8787X + 0.0106
r2 = 0.9585
0.40
0.35
0.30
0.25
0.20
0.15
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
A lineal- 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)=0.995 (± 0.059) x (reference result in mg/L)
+ 0.018 (± 0.013) mg/L with r=0.975 and N=32.
A lineal- regression of the data in Figure 6-2 for the technical operator gives the following
regression equation:
y (technical operator results in mg/L)=0.879 (± 0.068) x (reference result in mg/L)
+ 0.011 (± 0.015) mg/L with r=0.959 and N=32.
where the values in parentheses represent the 95% confidence interval of the slope and intercept.
Only the non-technical operator's intercept is significantly different from zero, and the r values
are both above 0.950. The non-technical operator's slope is not significantly different from unity
whereas, the technical operator's slope is significantly different from unity. However, at the 95%
confidence level, the uncertainty around both slopes is such that they are not significantly
different from one another.
6.4 Method Detection Limit
The manufacturer's estimated detection limit for the LaMotte SMART 2 is 0.01 mg/L cyanide.
The MDL(4) was determined by analyzing seven replicate samples at a concentration of
0.050 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 0.02 mg/L for the LaMotte SMART 2 when used by
either operator.
32
-------
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)
0.05
0.07
0.05
0.03
0.03
0.05
0.06
0.06
0.04
0.04
0.05
0.06
0.06
0.04
0.04
0.05
0.06
0.06
0.05
0.05
0.05
0.06
0.05
0.05
0.05
0.05
0.05
0.05
0.04
0.04
0.05
0.06
0.06
0.04
0.04
Std Dev
0.006
0.005
0.007
0.007
t (n=7)
3.140
3.140
3.140
3.140
MDL (mg/L)
0.02
0.02
0.02
0.02
6.5 Inter-Unit Reproducibility
The inter-unit reproducibility of the LaMotte SMART 2 was assessed by using a linear regression
of the results produced by one LaMotte SMART 2 plotted against the results produced by the
other LaMotte SMART 2. 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 LaMotte
SMART 2s.
0.5
0.5
y = 0.9963X - 0.0005
r2 = 0.9947
0.4
0.4
0.3
0.3
0.2
0.2
0.0
0 0.05 0.1 0.15 0.2 0.25 0.3 0.35 0.4 0.45
Unit #2 (mg/L)
Figure 6-3. Inter-Unit Reproducibility Results
33
-------
A linear 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)=0.996 (± 0.013) x (Unit #2 result in mg/L)
- 0.0005 (± 0.002) mg/L with r2=0.995 and N=120.
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 LaMotte SMART 2s functioned very 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 LaMotte
SMART 2. Upon the addition of the reagents to the water sample, the color of the sample
changed within five seconds to orange and, after approximately 35 more seconds, to dark red.
The change was much more rapid than for 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 20-minute
reaction time to reach its analysis color of a clear lavender. When the samples with lethal/near-
lethal concentrations were inserted into the LaMotte SMART 2 after the full reaction time, the
digital readout read "over range."
6.7 Operator Bias
The possible difference in results produced by the non-technical and technical operators 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.
A linear regression of the data in Figure 6-4 for the operator bias assessment gives the following
regression equation:
y (non-tech result in mg/L)=1.024 (± 0.113) x (tech result in mg/L) + 0.002
(± 0.018) mg/L with r2=0.732 and N=120.
where the values in parentheses represent the 95% confidence interval of the slope and intercept.
The slope of this regression is not significantly different from unity. However, the data between
0.100 and 0.200 mg/L, which represent data mostly from the surface and drinking water samples,
34
-------
0.5
0.45
v= 1.0236X +0.0021
¦C 3
8 8 0.25
if 0.2
o o
Z jjj 0.15
!. o.i
° 0.05
¦0) 0.4
n — 0.35
.2
_i
'Bi
E
0 1 1 1 1 1 1 1 1
0 0.05 0.1 0.15 0.2 0.25 0.3 0.35 0.4 0.45
Technical Operator Results (mg/L)
Figure 6-4. Non-Technical vs. Technical Operator Bias
Results
display a large amount of scatter about the regression line. The quantitative result of this scatter
was the large uncertainty around the slope (11%) and a low coefficient of variation (r=0.732).
Due to the scatter over a fairly small concentration range (0.1 mg/L), it is difficult to assess by
this plot alone the extensiveness of the differences in performance between the two operators; but
this can be further examined by referring to the two plots describing linearity in Section 6.3. The
non-technical operator's slope was closer to unity than the technical operator's slope, but Table
6-2a shows that the technical operator produced lower biases for all of the PT samples except for
the 0.400 mg/L PT sample. The difference in slope between operators apparently was the result of
the high degree of uncertainty in the technical operator's 0.400 mg/L results and general trend of
a positive bias by the non-technical operator, which is indicated by the regression line being
shifted above the dotted line with a slope of unity and a zero intercept. Based on a full evaluation
of the data, it seems that the performance of the LaMotte Smart 2 generally was not dependent on
which operator performed the analyses.
6.8 Field Portability
The LaMotte SMART 2 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 stand-
point, the LaMotte SMART 2 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 LaMotte
SMART 2 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 LaMotte SMART 2 reagents.
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 Columbus, OH, city
and well 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 to black. Such
35
-------
a color change would have indicated the presence of sulfides. Nonetheless, there was a 27 to 48%
bias in the indoor Columbus, OH, city water measurements and a 29 to 34% 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 29 to 34%
bias from initial fortification) because, by the time the well water LFM samples were analyzed by
the LaMotte SMART 2 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 (see Table 4-2). Because there was an apparent time-dependent matrix
interference, the data generated from the well water samples using the LaMotte SMART 2 in the
field setting cannot be meaningfully compared with the result produced from the identical
samples analyzed with the LaMotte SMART 2 in the laboratory or using the reference method.
The bias in the Columbus, OH, city water indoor LFM sample performed by the technical
operator (27 to 29%) was similar to the bias in the Columbus, OH, city water LFM sample
analyzed at the laboratory location (24%). The apparent matrix interference causing the
progressively larger (see Table 4-2) biases in the well water did not further mask the cyanide in
the city water LFM sample as evidenced by the similar biases at the field location and at the
laboratory two days later. Also, the reference LFM recoveries in the city water matrix were
similar when spiked just minutes before analysis or days before (see Table 4-2). These data
support the qualitative assessment that the LaMotte SMART 2 functions properly when operated
in field locations.
6.9 Ease of Use
The LaMotte SMART 2 and associated cyanide test reagents were easy to use. The instruction
manual was clear, and the sample and reagents were easily measured using a disposable pipet and
two 0.100-g scoops. While the sample handling and analysis were easy, the pH of each sample
did have to be adjusted to between 10.5 and 11.0 using NaOH and hydrochloric acid (HC1).
LaMotte provided dropper bottles of HC1 and NaOH, pH paper, and step-by-step instructions for
pH adjustment with each cyanide reagent kit. These provisions made a tedious task more
convenient for both operators. The sample jars containing the reacted sample had to be emptied
and rinsed between sample analyses.
36
-------
6.10 Sample Throughput
Sample preparation, including accurate volume measurement and the addition of reagents, took
one to two minutes per sample. After performing the sample preparation, a 20-minute period of
color development is required before sample analysis. Therefore, if only one sample is analyzed,
it would take approximately 22 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 40 to 45 minutes. Since the color development reaction takes place in
reusable reaction vials, additional vials would have to be purchased to conveniently analyze large
sample sets.
37
-------
Chapter 7
Performance Summary
Biases for the LaMotte SMART 2 ranged from 2 to 31% for the PT samples; 11 to 30% for the
surface water samples; 5 to 41% for the drinking water samples from around the country; and 15
to 100% for the Columbus, OH, drinking water samples.
The RSDs ranged from 0 to 20% for the PT samples, 10 to 39% for the surface water samples,
and 3 to 53% for the drinking water samples from around the country. For Columbus, OH,
drinking water samples, RSDs were 4 to 77%.
A linear regression of the linearity data for the non-technical operator gives the following
regression equation:
y (non-technical operator results in mg/L)=0.995 (± 0.059) x (reference result in mg/L)
+ 0.018 (± 0.013) mg/L with r2=0.975 and N=32.
A linear regression of the data for the technical operator gives the following regression equation:
y (technical operator results in mg/L)=0.879 (± 0.068) x (reference result in mg/L)
+ 0.011 (± 0.015) mg/L with r2=0.959 and N=32.
where the values in parentheses represent the 95% confidence interval of the slope and intercept.
Only the non-technical operator's intercept is significantly different from zero, and the r2 values
are both above 0.950. The non-technical operator's slope is not significantly different from unity;
whereas, the technical operator's slope is significantly different from unity. However, at the 95%
confidence level, the uncertainty around both slopes is such that they are not significantly
different from one another.
The MDL was determined to be 0.02 mg/L for the LaMotte SMART 2 when used by either
operator.
A linear regression of the data for the inter-unit reproducibility assessment gives the following
regression equation:
y (Unit #1 result in mg/L)=0.996 (± 0.013) x (Unit #2 result in mg/L)
- 0.0005 (± 0.002) mg/L with r2=0.995 and N=120.
38
-------
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 LaMotte SMART 2s functioned very similarly to one
another.
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 LaMotte
SMART 2. Upon the addition of the reagents to the water sample, the color of the sample
changed within five seconds to orange and, after approximately 35 more seconds, to dark red.
The change was much more rapid than for any of the PT samples. The PT samples took about
30 seconds to produce even a small change in the color of the sample and took the full 20-minute
reaction time to reach its analysis color of a clear lavender. When the samples with lethal/near-
lethal concentrations were inserted into the LaMotte SMART 2 after the full reaction time, the
digital readout read "over range." Even without using the LaMotte SMART 2, the reagent and
glass vial 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)=1.024 (± 0.113) x (tech result in mg/L) + 0.002
(± 0.018) mg/L with r2=0.732 and N=120.
where the values in parentheses represent the 95% confidence interval of the slope and intercept.
The slope of this regression is not significantly different from unity. However, the data repre-
senting mostly the surface and drinking water samples display a large amount of scatter about the
regression line. This scatter resulted in a 11 % uncertainty around the slope and a relatively low
coefficient of variation (r=0.732). However, after further analysis of the operator-specific
linearity data in Section 6.3, it seems that the performance of the LaMotte SMART 2 generally
was not dependent on which operator performed the analyses.
From an operational standpoint, the LaMotte SMART 2 was easily transported to the field
setting, and samples were analyzed in the same fashion in the field as they were in the laboratory.
No functional aspects of the LaMotte SMART 2 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 LaMotte SMART 2
reagents.
The operators found the LaMotte SMART 2 and associated cyanide test reagents easy to use. The
instruction manual was clear, and the sample and reagents were easily measured using a disposa-
ble pipet and two 0.100-g scoops. LaMotte provided dropper bottles of HC1 and NaOH, pH
paper, and step-by-step instructions for adjusting the pH of the water sample to between 10.5 and
11.0. The inclusion of these items made it convenient for both the non-technical and technical
operators to complete the pH adjustment step. The sample jars containing the reacted sample had
to be emptied and rinsed between sample analyses.
39
-------
Within one to two minutes, the sample volume could be accurately measured and the reagents
added to the sample, which after 20 minutes would produce a color change in the presence of
cyanide. If only one sample was analyzed, sample analysis would take approximately 22 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 40 to 45 minutes.
Since the color development reaction takes place in reusable reaction vials, additional vials would
have to be purchased to conveniently analyze large sample sets.
40
-------
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.
41
------- |