THE ENVIRONMENTAL TECHNOLOGY VERIFICATION
&EPA
PROGRAM M
ETV
Batteiie
U.S. Environmental Protection Agency	puWng Tcchnology To Work
ETV Joint Verification Statement
TECHNOLOGY TYPE: PORTABLE CYANIDE ANALYZER
APPLICATION:	DETECTING CYANIDE IN WATER
TECHNOLOGY NAME: AQUAfast® IV AQ4000 with AQ4006 Cyanide Reagents
COMPANY:	Thermo Orion
ADDRESS:	500 Cummings Ctr.	PHONE: 1-800-225-1480
Beverly, MA 01915	FAX: 1-978-232-6038
WEB SITE:	http://www.thermo.com
E-MAIL:	xiaowen.wen@thermo.com
The U.S. Environmental Protection Agency (EPA) supports the Environmental Technology Verification (ETV)
Program to facilitate the deployment of innovative or improved environmental technologies 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 providing high-quality, peer-reviewed data on technology performance to those involved in the
design, distribution, financing, permitting, purchase, and use of environmental technologies.
ETV works in partnership with recognized standards and testing organizations, with stakeholder groups
(consisting of buyers, vendor organizations, and permitters), and with individual technology developers. The
program evaluates the performance of innovative technologies by developing test plans that are responsive to the
needs of stakeholders, conducting field or laboratory tests (as appropriate), collecting and analyzing data, and pre-
paring 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 Advanced Monitoring Systems (AMS) Center, one of seven technology areas under ETV, is operated by
Batteiie in cooperation with EPA's National Exposure Research Laboratory. The AMS Center has recently
evaluated the performance of portable cyanide analyzers used to detect cyanide in water. This verification state-
ment provides a summary of the test results for the Thermo Orion AQUAfast® IV AQ4000 colorimeter with
AQ4006 cyanide reagents.

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VERIFICATION TEST DESCRIPTION
The verification was based on comparing the cyanide concentrations of water samples determined by the Thermo
Orion AQ4000 with cyanide concentrations determined by a laboratory-based reference method (EPA Method
335.1, Cyanides Amenable to Chlorination). The Thermo Orion AQ4000 colorimeter was always used in
conjunction with the Thermo Orion AQ4006 cyanide reagents. Two Thermo Orion AQ4000s were tested
independently between January 13 and February 4, 2003; and the results were compared to assess inter-unit
reproducibility. Samples used in the verification test included quality control samples, performance test (PT)
samples, lethal/near-lethal concentration samples, drinking water samples, and surface water samples. The results
from the Thermo Orion AQ4000 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 both the Thermo
Orion AQ4000 and the reference method. To determine the detection limit, a solution with a concentration of
0.100 milligram per liter (mg/L) was used. Seven non-consecutive replicate analyses of this solution were made to
obtain precision data with which to determine the method detection limit (MDL). The Thermo Orion AQ4000 was
tested by a technical and a non-technical operator to assess operator bias. Sample throughput was estimated based
on the time required to analyze a sample. Ease of use was based on documented observations by the operators and
the Battelle Verification Test Coordinator. The Thermo Orion AQ4000 was used in a field environment as well as
in a laboratory setting to assess the impact of field conditions on performance.
QA oversight of verification testing was provided by Battelle. Battelle QA staff conducted a technical systems
audit, a performance evaluation audit, and a data quality audit of 10% of the test data.
TECHNOLOGY DESCRIPTION
The following description of the Thermo Orion AQ4000 was provided by the vendor and does not represent
verified information.
The Thermo Orion AQ4000 is a portable colorimeter in which a water sample and Thermo Orion AQ4006 cyanide
reagents are mixed and analyzed photometrically to provide a quantitative determination of cyanide in the sample.
The Thermo Orion AQ4006 cyanide reagents include Auto-Test™ cuvettes packaged in individual analyte
modules that contain 30 ampoules, a 25-milliliter (mL) graduated cylinder, and instructions. A coded blank cuvette
and an empty vial for background sample blanks are also included. The Thermo Orion AQ4000 automatically
identifies the species to be measured and selects the method, wavelength, and reaction time. The Thermo Orion
AQ4000's Auto-ID ensures that the pre-measured reagent is matched to the method. The Auto-Test™ cuvettes
containing the pre-measured reagent are broken open as the final step in sample preparation, assuring reagent
quality.
To measure cyanide with the Thermo Orion AQ4000, a prepared (dechlorinated and pH adjusted) 10-mL sample is
measured into the graduated cylinder, five drops of one reagent and 1.5 mL of another reagent are added to the
sample, the sample is stirred with the tip of an Auto-Test™ cuvette, and then the tip of an Auto-Test™ cuvette is
broken, allowing the sample to rush up into the vial. If any cyanide is present in the water sample, a reaction
between cyanide and the reagents added to the sample and those originally present in the Auto-Test™ cuvette
produces a color change. After a reaction time of 15 minutes, the Auto-Test™ cuvette is inserted into the Thermo
Orion AQ4000, and the cyanide concentration (in mg/L) is reported on the digital display. The Thermo Orion
AQ4000 is waterproof, operates on four AA batteries, has dimensions of 8 inches by 3 inches by 2 inches, and
weighs 16 ounces. The list prices are $989 for the colorimeter and $32 for AQ4006 refills. Display units include
concentration, absorbance, or percent transmittance. A time and date tag can be added to 100 data points in the
field and downloaded to a printer or computer in the laboratory.

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VERIFICATION OF PERFORMANCE
Accuracy: Biases for the Thermo Orion AQ4000 ranged from 4 to 23% for the PT samples with concentrations
ranging from 0.030 to 0.800 mg/L; 10 to 26% for the surface water samples; 6 to 51% for the drinking water
samples from around the country; and 27 to 100% for the Columbus, OH, drinking water samples. Since the latter
three types of water samples contained no detectable cyanide, they were fortified with 0.200 mg/L of cyanide to
test the performance of the Thermo Orion AQ4000 in water matrices.
Precision: The relative standard deviation ranged from 0 to 22% for the PT samples; 0 to 20% for the surface
water samples; 1 to 18% for the drinking water samples from around the country; 3 to 20% for the Columbus, OH,
drinking water samples analyzed at the indoor field site.
Linearity: The non-technical operator's results from the Thermo Orion AQ4000 for the PT samples (0.030 to
0.400 mg/L) plotted against the concentrations of the same samples as determined by the reference method gives
the following regression equation:
y (non-technical operator results in mg/L)=0.871 (± 0.020) x (reference result in mg/L)
+ 0.003 (± 0.004) mg/L with r2=0.996 and N=33.
The data for the technical operator gives the following regression equation:
y (technical operator results in mg/L)=0.829 (± 0.038) x (reference result in mg/L)
+ 0.012 (± 0.008) mg/L with r2=0.985 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 0.980. The
linearity of the Thermo Orion AQ4000 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 Thermo Orion AQ4000 compared with the results produced by
the reference method.
Method Detection Limit: The MDL was determined to be approximately 0.01 mg/L for the Thermo Orion
AQ4000 when used by the non-technical operator and approximately 0.02 mg/L for the Thermo Orion AQ4000
when used by the technical operator.
Inter-Unit Reproducibility: A linear regression of the data for the inter-unit reproducibility assessment gives the
following regression equation:
y (Unit #1 result in mg/L)=0.999 (± 0.015) x (Unit #2 result in mg/L) + 0.004
(± 0.002) mg/L with r2=0.994 and N=112.
where the values in parentheses represent the 95% confidence interval of the slope and intercept. The slope is not
significantly different from unity, while the intercept is significantly different from zero. These data indicate that
the two Thermo Orion AQ4000s functioned very similarly to one another.
Lethal/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 Thermo
Orion AQ4000. Upon breaking the Auto-Test™ cuvette in the lethal/near-lethal samples, the color of the sample
changed within five seconds to a 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 even
produce a small change in the color of the sample and took the full 15-minute reaction time to reach its analysis
color of a clear, light purple. When these samples with lethal/near-lethal concentrations were inserted into the

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Thermo Orion AQ4000 after the full reaction time, the digital readout read "over range." Even without using the
AQ4000 colorimeter, the reagents and Auto-Test™ cuvettes 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.
Operator Bias: A linear regression of the data for the operator bias assessment gives the following regression
equation:
y (non-tech result in mg/L)=1.000 (± 0.061) x (tech result in mg/L) - 0.013
(± 0.009) mg/L with r2=0.905 and N=112.
where the values in parentheses represent the 95% confidence interval of the slope and intercept. The slope is not
significantly different from unity, while the intercept is significantly different from zero. These data indicate that
there was very little difference in results generated by the non-technical operator compared with those of the
technical operator.
Field Portability: From an operational standpoint, the Thermo Orion AQ4000 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 Thermo Orion AQ4000 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 Thermo Orion AQ4006 cyanide reagents.
Ease of Use: The Thermo Orion AQ4000 and AQ4006 cyanide reagents and Auto-Test™ cuvettes were easy to
operate. The instructions were clear, and the sample and reagents were easily measured using a graduated cylinder,
syringe, and a dropper bottle. The Thermo Orion AQ4000 recognized the Auto-Test™ cuvettes when they were
inserted, and a 15-minute timer appeared on the digital readout. When analyzing large sample sets, this timer had
to be overridden before every sample analysis. While the sample handling and analysis were easy, the pH of each
sample had to be adjusted to between 10.5 and 11.0 using sodium hydroxide and hydrochloric acid. This step
required the availability of acid and base, pH paper or meter, and some knowledge of pH adjustment. The Auto-
Test™ cuvettes made waste disposal simple and mess free. Only the graduated cylinder used for measuring the
sample and adding reagents needed to be rinsed between samples.
Sample Throughput: Since the Thermo Orion AQ4000 did not require strict mixing/reaction time periods after
adding each reagent, and the Auto-Test™ cuvettes 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 throughput 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.
original signed by Gabor J. Kovacs 4/17/03
Gabor J. Kovacs	Date
Vice President
Environmental Sector
Battelle
original signed by Timothy E. Oppelt	4/29/03
Timothy E. Oppelt	Date
Director
National Homeland Security Research Center
U.S. Environmental Protection Agency

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NOTICE: ETV verifications are based on an evaluation of technology performance under specific, predetermined
criteria and the appropriate quality assurance procedures. EPA and Battelle make no expressed or implied
warranties as to the performance of the technology and do not certify that a technology will always operate as
verified. The end user is solely responsible for complying with any and all applicable federal, state, and local
requirements. Mention of commercial product names does not imply endorsement.

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