&EPA
EPA/600/R-08/034 I March 2008 I www.epa.gov/ord
United States
Environmental Protection
Agency
Testing of Screening Technologies
for Detection of Toxic Industrial
Chemicals in All Hazards
Receipt Facilities
TECHNOLOGY EVALUATION REPORT
Office of Research and Development
National Homeland Security Research Center
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EPA/600/R-08/034 I March 2008 I www.epa.gov/ord
Technology Evaluation Report
Testing of Screening Technologies for
Detection of Toxic Industrial Chemicals
in All Hazards Receipt Facilities
By
Thomas Kelly, Wesley Baxter, and Martha McCauley
Battelle
505 King Avenue
Columbus, OH 43201
Eric Koglin
Task Order Project Officer
National Homeland Security Research Center
Office of Research and Development
U.S. Environmental Protection Agency
944 East Harmon Ave.
Las Vegas, NV 89119
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Disclaimer
The U.S. Environmental Protection Agency through its not necessarily reflect the views of the Agency. No official
Office of Research and Development funded this research. endorsement should be inferred. EPA does not endorse the
It has been subject to an administrative review but does purchase or sale of any commercial products or services.
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Preface
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 (ORD) 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.
In September 2002, EPA announced the formation of the
National Homeland Security Research Center (NHSRC).
The NHSRC is part of the ORD; it manages, coordinates,
and supports a variety of research and technical assistance
efforts. These efforts are designed to provide appropriate,
affordable, effective, and validated technologies and methods
for addressing risks posed by chemical, biological, and
radiological terrorist attacks. Research focuses on enhancing
our ability to detect, contain, and clean up in the event of
such attacks.
NHSRC's team of world-renowned scientists and
engineers is dedicated to understanding the terrorist threat,
communicating the risks, and mitigating the results of
attacks. Guided by the roadmap set forth in EPA's Strategic
Plan for Homeland Security, the NHSRC ensures rapid
production and distribution of security-related products.
The NHSRC has created the Technology Testing and
Evaluation Program (TTEP) in an effort to provide reliable
information regarding the performance of homeland
security-related technologies. TTEP provides independent,
quality-assured performance information that is useful
to decision makers in purchasing or applying the tested
technologies. It provides potential users with unbiased,
third-party information that can supplement vendor-provided
information. Stakeholder involvement ensures that users'
needs and perspectives are incorporated into the test design
so that useful performance information is produced for each
of the tested technologies. The technology categories of
interest include detection and monitoring, water treatment, air
purification, decontamination, and computer modeling tools
for use by those responsible for protecting buildings, drinking
water supplies, and infrastructure and for decontaminating
structures and the outdoor environment.
The evaluation reported herein was conducted by Battelle as
part of the TTEP program. Information on NHSRC and TTEP
can be found at hltp://www.cpa.gov/ordnhsrc/indcx. him.
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Acknowledgments
The authors wish to acknowledge the support of all those and Brian Schumacher and Manisha Patel of the U.S.
who helped plan and conduct the evaluation, analyze the Environmental Protection Agency for their reviews of
data, and prepare this report. We also would like to thank this report.
Lance Brooks of the U.S. Department of Homeland Security
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Table of Contents
Disclaimer iv
Preface v
Acknowledgments vi
Table of Contents vii
List of Tables viii
List of Figures viii
Acronymns ix
Executive Summary x
1.0 Introduction 1
2.0 Technologies Tested 3
3.0 Testing Procedures 5
3.1 Performance Parameters 5
3.2 Test Procedures 5
3.3 Data Recording 8
4.0 Quality Assurance/Quality Control 9
4.1 Vapor-Phase Samples 9
4.2 Liquid-Phase Samples 10
4.3 QA/QC Reporting 10
4.4 Data Review 11
5.0 Test Results 13
5.1 Accuracy 13
5.2 False Positive/False Negatives 15
5.3 Analysis Time 16
5.4 Repeatability 17
5.5 Operational Factors 19
5.6 Screening Technology Costs 20
6.0 Performance Summary 23
7.0 References 25
Appendix A Results of Testing with Vapor-Phase Toxic Industrial Chemicals A-l
Appendix B Results of Testing with Toxic Industrial Chemicals in Liquid Samples B-l
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List of Tables
Table 2-1 Summary of TIC Screening Technologies Tested 4
Table 3-1 Challenge Concentrations for TIC Vapor Testing 7
Table 3-2 Test Conditions Used in TIC Vapor Testing 7
Table 3-3 Reference Methods for Vapor-Phase TICs 7
Table 3-4 TIC Concentrations Used in Liquid Testing 8
Table 4-1 Summary of Reference Results from TIC Vapor Testing 9
Table 4-2 Summary of TIC PE Audit Results 10
Table 5-1 Summary Results of TIC Vapor Testing 14
Table 5-2 Summary Results of TIC Liquid Testing 15
Table 5-3 Summary of False Negative Responses 16
Table 5-4 Summary of Sample Analysis Times 17
Table 5-5 Repeatability of Technology Readings 18
Table 5-6 Summary of Observations on Operational Factors of the Technologies 19
Table 5-7 Cost Information on TIC Screening Technologies 21
List of Figures
Figure 1-1 Summary of All Hazards Receipt Facility Sample Screening Process 2
Figure 3-1 Test System Schematic 6
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List of Acronyms
AC hydrogen cyanide (HCN)
ACS American Chemical Society
AEGL Acute Exposure Guideline Level
AHRF All Hazards Receipt Facilities
ATSDR U.S. Agency for Toxic Substances and Disease Registry
C celsius
CG phosgene (COC12)
CGI combustible gas indicator
CK cyanogen chloride (C1CN)
C12 chlorine
CN~ cyanide
CWA chemical warfare agent
DHS U.S. Department of Homeland Security
DIH2O deionized water
DoD U.S. Department of Defense
EPA U.S. Environmental Protection Agency
F~ fluoride
FBI Federal Bureau of Investigation
FID flame ionization detection
FSP flame spectrophotometer
G/V phosphorous compounds
GC gas chromatography
H2O2 hydrogen peroxide
H2S hydrogen sulfide
HD/HL sulfur compounds
HN/AC nitrogen compounds
IMS ion mobility spectrometer
Int interferent
L/SA arsenic compounds
LD50 lethal dose to half the population
m meter
MF mass flow meter
MFC mass flow controller
mg milligram
min minute
mL milliLiter
MSD mass selective detection
MV metering valve
MW molecular weight
NHSRC National Homeland Security Research Center
PE performance evaluation
PID photoionization detector
ppm parts per million
QA quality assurance
QC quality control
QMP Quality Management Plan
RH relative humidity
RSD relative standard deviation
SA arsine (AsH3)
sec second
St. Dev. standard deviation
TEEL Temporary Emergency Exposure Limit
T temperature
TIC toxic industrial chemicals
TSA technical systems audit
TTEP Technology Testing and Evaluation Program
UV ultraviolet
WMD weapons of mass destruction
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Executive Summary
This document is the final report on an evaluation of
commercially available screening technologies designed to
rapidly detect, and in some cases indicate the concentration
of, toxic industrial chemicals (TICs) in air or in water
samples. The technology evaluations described in this
report were performed by Battelle under the direction of the
U.S. Environmental Protection Agency's (EPA) National
Homeland Security Research Center (NHSRC) through the
Technology Testing and Evaluation Program (TTEP). The
technologies evaluated were identified as possible candidates
for use in EPA's All Hazards Receipt Facilities (AHRF).
The EPA, U.S. Department of Homeland Security (DHS),
and U.S. Department of Defense (DoD) have teamed
to develop, construct, and implement the AHRF for
prescreening unknown and potentially hazardous samples
collected during suspected terrorist events. The AHRF are
intended for screening of samples for chemical, explosive,
and radiological hazards to protect laboratory workers
from injury and facilities from contamination and to ensure
the integrity of collected samples. These facilities are not
intended to provide detailed or quantitative analytical results,
but instead to provide initial screening of samples prior to full
laboratory analysis, for the safety of laboratory personnel.
Screening technologies used in the AHRF are intended to be
rapid and qualitative, and may be "low tech" in design and of
relatively low cost, but must provide accurate identification
of hazardous samples.
The procedures and target TICs used in this evaluation were
chosen to represent likely conditions of use in the AHRF.
In performing this technology evaluation, Battelle followed
the procedures specified in a peer-reviewed test/QA plan
established prior to the start of the evaluation and complied
with all the quality requirements in the Quality Management
Plan for the TTEP program. The screening technologies
tested ranged from simple test papers, kits, and color-
indicating tubes to hand-held electronic detectors based
on photoionization detection (PID), electrochemical (EC)
sensors, and flame spectrophotometry (FSP). The screening
technologies were challenged with the TICs hydrogen
cyanide (designated AC), cyanogen chloride (CK), phosgene
(CG), arsine (SA), hydrogen sulfide (H2S), and chlorine (C12)
in air at concentrations that would be seriously hazardous to
personnel within a few minutes exposure. Those vapor-phase
challenges were delivered at room temperature and normal
(50%) relative humidity (RH), both with and without a
volatile exhaust hydrocarbon mixture added as an interferent,
and at relatively high (30 °C, 80% RH) and low (10 °C,
20% RH) temperature and humidity conditions without the
interferent. Water samples used in challenging the screening
technologies consisted of cyanide, hydrogen peroxide, or
fluoride, each made up in deionized water, and in tap water
and salt water as interferents. The water sample testing used
TIC concentrations that would be hazardous upon physical
contact with the water sample.
Most of the screening technologies showed 100% accuracy,
or nearly so, in detecting TICs in air. Several of those
technologies accurately detected TICs even though the TIC
vapor challenge concentrations were lower than the nominal
detection limits stated by the technology vendor. However,
none of the tested technologies was designed to detect all
six of the target TICs. The Sensidyne Gas Tubes and Draeger
Civil Defense Kit color tubes exhibited 100% detection
accuracy, or nearly so, for five TICs, and the Draeger CMS
Analyzer, an automated color tube sampler and reader,
showed 100% detection accuracy for four. The HazMat
Smart Strip was 100% accurate in detecting hydrogen
peroxide in water, as was the Truetech M272 Water Kit in
detecting cyanide.
For the three technologies that provided a quantitative
indication of the TIC vapor concentration during testing
(i.e., the Draeger CMS Analyzer, MultiRAE Plus PID [with
EC sensor for H2S], and Sensidyne Gas Tubes), the percent
relative standard deviation (%RSD) of triplicate responses
was within 15% in 32 of the 40 challenge sets with these
technologies and was within 10% in 22 of those 40 tests. Test
conditions had no apparent effect on the %RSD values. Thus,
close precision of responses can be obtained in screening
with these technologies but cannot be assumed in all tests.
None of the tested technologies produced any false positive
responses in testing with either vapor-phase TICs or water
samples. False negatives mainly occurred as the inability of
a technology to detect a TIC at the challenge concentration
even under the normal room conditions. The Anachemia
C2 color tubes, MultiRAE Plus PID, Proengin AP2C FSP
detector, Truetech M18A3 color tubes, and HazMat Smart
Strip all exhibited false negatives for one or more TICs
in vapor testing. The HazMat Smart Strip exhibited false
negatives for GST and F~, and the Proengin AP2C FSP for
GST, at the challenge concentrations in water sample testing.
No effect of interferents was seen in either vapor- or liquid-
phase testing. Temperature and RH effects in TIC vapor
testing were also minimal.
The speed and simplicity of the screening process varied
widely among the tested technologies. All of the color-
indicating tubes for vapor detection were simple to use in
principle but differed in the time and difficulty of obtaining
the sample. The number of manual pump strokes required
to draw the air sample ranged from 1 to 60, and the manual
effort needed for those technologies requiring 30 or more
pump strokes was excessive even when screening small
numbers of samples as in this test. Electric air sampling
pumps, whether internal to the technology (as in the
automated Draeger CMS Analyzer) or external (as in the
Nextteq Civil Defense Kit) greatly reduced the physical effort
needed but still required several minutes to draw the required
volume. Color-indicating tubes that require the minimum
volume would be preferable for use in the AHRF because
they enable rapid sample analysis and data generation. The
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use of an electrical sampling pump would be valuable if
large numbers of samples are to be screened. The two hand-
held analyzers tested (MultiRAE Plus PID with EC sensor
and Proengin AP2C FSP) provided easy and rapid sample
screening. However, although the MultiPvAE Plus was easy
to use, it was not effective, as only the electrochemical H2S
sensor in the MultiPvAE Plus provided a response in these
tests. The screening of water samples with the Proengin
AP2C FSP was also relatively rapid because of the simplicity
of wetting that detector's "scraper" attachment and desorbing
collected samples into the AP2C's inlet. The HazMat Smart
Strip was the simplest technology to use, requiring only
removal of a protective film to expose the indicating patches
on the card. However, this technology did not respond to
AC. For vapor detection in the AHRF, the HazMat Smart
Strip is best suited to be enclosed within a container or
attached to a surface, rather than used as a hand-held
sampling tool. The Anachemia CM256A1 multifunction card
was much more difficult to use, requiring hand manipulation
to heat and direct reagents to sections of the card but
provided accurate detection of the two TICs for which it was
designed (AC and CK).
In terms of the speed and simplicity of liquid sample
screening, the Truetech M272 Water Kit was found to be
deficient. The multiple detection tubes and reagent tablets
needed, and the requirement for 60 mL of water sample,
make it unlikely that this technology would be suitable
for the AHRF.
The applicability of a technology to screen for multiple
TICs at once is an important component of the speed of
analysis. Technologies using multiple color-indicating tubes
at once (e.g., the Draeger Civil Defense Kit and Nextteq
Civil Defense Kit) can provide this capability. Two other
technologies of widely different complexity also provide
multi-TIC capability: the simple HazMat Smart Strip card
and the Proengin AP2C FSP detector.
The initial cost of the tested technologies varied substantially,
with most technology purchase costs ranging from a few
hundred to a few thousand dollars. The Proengin AP2C FSP
detector was the exception at a discounted cost of nearly
$16,000. However, when considering long-term use of the
technologies in the AHRF, the per-sample screening costs
were generally similar across technologies, i.e., typically less
than $10 per sample.
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1.0
Introduction
This document is the final report on an evaluation of
commercially available screening technologies designed
to detect the presence, and in some cases indicate the
concentration, of toxic industrial chemicals (TICs) in air or
in liquid samples. The technology evaluations described in
this report were performed by Battelle under the direction
of the U.S. Environmental Protection Agency's (EPA)
National Homeland Security Research Center (NHSRC)
through the Technology Testing and Evaluation Program
(TTEP) (Contract GS-23F-0011L-3), and specifically under
Task Order 1119 of the TTEP program. The technologies
evaluated were identified as possible candidates for use in
EPA's All Hazards Receipt Facilities (AHRF), and the testing
was designed to evaluate their performance relative to the
needs of the AHRF as currently defined in the draft sample
screening protocol developed for the AHRF.1'2
The EPA, U.S. Department of Homeland Security (DHS), and
U.S. Department of Defense (DoD) have combined efforts
to develop, construct, and implement AHRF capabilities
for prescreening unknown and potentially hazardous
samples collected during suspected terrorist events. AHRF
development was initiated in response to requests from states
and federal agencies, particularly public health laboratories,
for standardized guidance on screening samples to protect
laboratory staff and ensure sample integrity and the validity
of analytical results. The AHRF are intended for in-process
screening of unknown samples for chemical, explosive,
and radiological hazards to protect laboratory workers and
facilities from contamination and injury. The AHRF are
intended to serve as a front-end assessment that can be used
on an "as needed" basis. These facilities are not intended to
provide detailed or quantitative analytical results, but instead
to provide initial screening of samples prior to full laboratory
analysis, for the safety of all laboratory personnel. Screening
technologies used in the AHRF are intended to be rapid and
qualitative, and may be "low tech" in design and of relatively
low cost, but must ensure meaningful qualitative results.
This report presents the results of the evaluation of
commercially available screening devices for rapid detection
of TICs in samples and on sample containers entering an
AHRF. A separate report3 presents the results of testing
such technologies for detection of chemical warfare agents
(CWAs). The procedures, target chemicals, and sample types
used in this evaluation were chosen to represent conditions
of use likely to be present in the AHRF.1'2 Figure 1-1 is
excerpted from the AHRF Draft Protocoll and illustrates
the sample screening process to be implemented through
the AHRF. As this figure shows, screening of an incoming
sample or sample container for chemical contamination
occurs in multiple steps of the process and may use multiple
screening technologies.
In performing this technology evaluation, Battelle followed
the procedures specified in a peer-reviewed test/quality
assurance (QA) plan established prior to the start of the
evaluation4 and complied with all the quality requirements in
the Quality Management Plan (QMP)5 for the TTEP program.
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Figure 1-1. Summary of All Hazards Receipt Facility Sample Screening Process
x- -
Sample Receipt and Transport Container Screen: Outside AHRF
Establish/Continue chain of custody
Review corresponding documentation and interview the delivery technician
Visual inspect transport container (Check for explosive device, radiation, and unusual liquid or powder.
If present, collect sample, mitigate hazard, and contact appropriate authorities.)
Document observations, complete Sample Receipt Forms, and assign tracking identification
Carry out a threat assessment and develop a screening plan
Primary Sample Container Screen: Inside Fume Hood
Screen headspace for CWAs with ion mobility spectrometer (IMS) or flame spectrophotometer (FSP)
Remove contents from transport container and secondary container (if necessary)
Visually inspect and screen primary sample container for radioactivity (surface screen), explosives
(colorimetric), and CWA (colorimetric)
If hazards are indicated, collect exterior wipe sample, mitigate hazards indicated via decontamination
of exterior surfaces or shielding, and contact appropriate authorities
Document observations and results on AHRF Screening Results Form
Assess need to continue screening process and ability to transfer to glove box
Primary Sample Screen: Inside Glove Box and Biosafety Cabinet
Transfer primary sample container to glove box
Open primary container and screen for VOCs (photoionization detector) and combustible gases
(combustible gas indicator)
Screen primary sample for radiation (surface scan)
If sufficient amount of sample is present, split sample and continue screening process
Remove small portion of the sample and transfer into the biosafety cabinet. Conduct the optional
screen using IMS and/or FSP. Conduct thermal susceptibility test to determine whether explosive
materials are present.
Perform water solubility and reactivity tests
Perform DB-3 dye test for alkylating agents (colorimetric)
Perform pH and starch iodide test (colorimetric)
Perform nerve agent test (colorimetric)
Perform the additional chemical screening as needed (colorimetric)
Document observation and results on AHRF Screening Results Form
Document Results
Complete and verify AHRF Screening Results Forms
Compile all forms into a single AHRF Screening Report
Contact sampling agency, appropriate local authorities, the local laboratory director, and the FBI
weapons of mass destruction (WMD) coordinator
Prepare subsample and primary sample for delivery to the designated laboratory and/or sampling
authority
Transfer to the biosafety cabinet to await transfer
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The screening technologies tested were identified based on
a review of commercially available detection devices for the
TICs and CWAs of interest. That review was wide ranging in
that information on detection devices was initially obtained
without concern about the applicability of each device to the
AHPJ7 sample screening process. Screening technologies
were then selected for testing based on criteria specific to the
intended use in the AHPJ7:
• Applicability to multiple target TICs and CWAs
• Applicability as a qualitative screening tool
• Applicability to multiple sample types (vapor, liquid,
surface)
• Speed and simplicity of use
• Cost of use and consumables
The technologies selected for testing were predominantly
relatively inexpensive, simple test kits, color tubes, and
test strips, but also included a few hand-held electronic
instruments employing various detection principles. The
reason for inclusion of the latter technologies was their
applicability to a wide range of TICs and/or CWAs, and
their rapid response, which made them attractive as potential
screening devices despite their relatively high initial cost.
Table 2-1 lists the vendor and name of each technology
selected for testing with TICs in this program, the detection
principle, and the TICs for which each technology was tested
in the vapor and liquid sample matrices. The target TICs
were all volatile compounds, so a surface sample matrix was
not applicable to this evaluation. As Table 2-1 shows, the
TICs hydrogen cyanide (HCN; designated AC), cyanogen
chloride (C1CN; CK), phosgene (COC12; CG), arsine (AsH3;
SA), chlorine (C12), and hydrogen sulfide (H2S) were used
in the vapor-phase, and cyanide (GST), hydrogen peroxide
(H2O2), and fluoride (F~) were used in the liquid phase. Brief
descriptions of each TIC screening technology are provided
below, along with Web addresses where pictures and more
information can be found.
Anachemia C2. This technology consists of color-indicating
tubes and a hand pump for drawing the required sample
volume through one tube at a time. With this technology
ten compressions of the pump provide the required sample
volume. liltp://wvvw.anachcmia.com/dcfcquip/pioduct.lilml
Anachemia CM256A1. This device is a multifunction card
that employs reagents placed in selected locations on the
card, with manual manipulation of portions of the card to
initiate reactions, produce heat, and observe color changes
in the reagents. Each card can indicate the presence of
TICs and CWAs by the performance of a series of about 15
sequential steps and manipulations. hllpj//www.anachcmia1
2.0
Technologies Tested
Draeger CMS Analyzer. This technology is based on
color-indicating tubes, but rather than using individual
tubes, the CMS Analyzer uses chips, or cards, on which
are mounted ten identical miniature color tubes. The card
is inserted into the CMS Analyzer and positioned so that
an internal pump draws sample air through one of the
tubes. Any resulting color change is read by an electronic
colorimeter and displayed as a quantitative indication of the
chemical concentration. The card may then be advanced to
position the next tube, readying the CMS Analyzer for the
next measurement. The cards are indexed so that tubes are
positioned accurately and cannot be reused by mistake.
^^
Dclcclion/ChipMcasurcmcntSystciTi/CMSAnaly/cr/pd_cms_
analy/cr.jsp
Draeger Civil Defense Kit. This technology uses a hand
pump to draw air through five different color-indicating
tubes simultaneously, with each tube providing an indication
of one TIC or CWA. All five tubes must be in place in the
five-port sampling holder for proper sampling to occur. Fifty
compressions of the hand pump provide the required sample
volumes to all five tubes.
^
pd_cds_sct.jsp
MSA Single CWA Sampler Kit. This device also uses
color-indicating tubes, with a hand pump to draw sample
air through a single indicating tube at a time. Thirty
compressions of the hand pump provide the required
sample volume. httpj//gwg^insanorthaunerica£om/cata]og/
prQduct679Jrtml
Nextteq Civil Defense Kit. This technology uses an electric
pump (or optional hand pump) to draw air through five
different color-indicating tubes simultaneously, with each
tube providing an indication of one TIC or CWA. All five
tubes must be in place in the five-port sampling holder for
proper sampling to occur. The electric pump is preset to draw
the required 3.5 L of air through the five sampling tubes
within a sampling period of 3.5 minutes. hllp://www.ncxttcq.
coin/Products.aspx?catcgory=3&subcat= 1 6
Proengin AP2C. The Proengin AP2C is a hand-held flame
spectrophotometer (FSP) that detects characteristic emissions
from hazardous chemicals as they are consumed in a flame.
The device burns hydrogen, supplied from a compact low-
pressure cylinder inside the instrument, with sample air
drawn continuously by an internal pump. Detection of a
target chemical triggers an alarm from the AP2C, and the
instrument provides identification and semi-quantitative
readings for the detected chemical. Such readings take the
form of a series of five bars that successively turn orange
depending on the intensity of response, with separate sets of
bars for sulfur compounds (HD/HL), nitrogen compounds
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Table 2-1. Summary of TIC Screening Technologies Tested
Screening Technology
Vendor
Anachemia
Draeger
MSA
Nextteq
Proengin
RAE
Systems
Safety
Solutions
Sensidyne
Truetech
Name
C2
CM256A1
CMS Analyzer
Civil Defense
Kit
Single CWA
Sampler Kit
Civil Defense
Kit
AP2C
MultiRae Plus
HazMat Smart
Strip
Gas Detection
Tubes
M272 Water
Kit
M18A3
Detection
Principle
color tubes
multifunction
card
multicolor
tubes on a chip
color tubes
color tubes
color tubes
flame
spectrometer
photoionization
detector
multifunction
card
color tubes
color tubes
color tubes
Vapor Samples
Hydrogen
cyanide
(AC)
X
X
X
X
X
X
X
X
X
X
X
Cyanogen
chloride
(CK)
X
X
X
X
X
X
X
X
Phosgene
(CG)
X
X
X
X
X
X
X
X
Areine
(SA)
X
X
X
X
Chlorine
ccy
X
X
X
X
X
Hydrogen
sulfide
(H2S)
X
X
X
X
X
Liquid Samples
Cyanide
(CN-)
X
X
X
Hydrogen
peroxide
("A)
X
Fluoride
(F)
X
(HN/AC), phosphorous compounds (G/V), and arsenic
compounds (L/SA). The AP2C also provides a general
indication of the presence of hydrocarbon compounds by
means of a single bar "CH" display. The S4PE accessories
set allows liquid samples to be picked up on disposable
"scraper" tips and vaporized into the inlet of the AP2C by
means of a heating circuit in the detachable scraper handle.
RAE Systems MultiRAE Plus. The MultiRAE Plus is a
hand-held photoionization detector (PID) for volatile organics
in air that also can incorporate electrochemical sensors for
oxygen, explosive gases, and selected TICs. In the PID,
an ultraviolet (UV) light source causes ionization of those
molecules in the sample air stream that have an ionization
potential less than the energy of the UV light. The MultiRAE
Plus unit tested was equipped with an electrochemical sensor
for H2S and was challenged separately with each of the six
target TICs. It should be noted that the PID principle of the
MultiRAE Plus is not necessarily expected to respond to the
TICs, but because the MultiRAE Plus is promoted for use as
a general toxic compound detector, it was tested with all six
TICs. hUp://www.racsy stcms.com/produc ts/mulli_gas
Safety Solutions HazMat Smart Strip. This device is a
card that may be attached to a surface, such as a person's
clothing, by means of its adhesive backing. The front surface
of the card has eight squares of colorimetric reagents that
produce qualitative indications of the presence of several
respective contaminants, including chlorine, acids or caustics
(pH indication), fluoride, nerve agents, oxidizers, arsenic,
hydrogen sulfide, and cyanide. Removal of a protective
film exposes the reagent squares and allows any indicating
reactions to take place. httpj//wjvw.smart^trip_.cQm/
Sensidyne Gas Detection Tubes. These are single-use glass
tubes containing reagents that change color when a suitable
volume of air containing the appropriate target chemical is
drawn through the tube. A hand pump is used to draw the
correct amount of air sample through one tube at a time.
One compression of the hand pump provides the 100-mL
volume of sample air required by the vendor's instructions.
The number of compressions may be increased if detection of
lower concentrations of the target chemical is needed.
hUp://www.scnsidync.com/prodcat.php?TD=l
Truetech M272 Water Kit. This kit for water analysis
includes two separate detection technologies, one for TICs
and one for CWAs. The TIC technology requires 60 mL of
sample and uses reagent tablets, color tubes, and heating
provided by lighted matches to obtain a qualitative indication
of the presence of chemicals in the sample. This technology
was tested with cyanide in aqueous samples.
^
Truetech M18A3. This technology uses color-indicating
tubes to detect the presence of TICs and CWAs in air. A hand
pump draws air through the tubes, with 60 compressions of
the pump providing the required sample volume.
http://www.tradewavsusa.com/eng/products/if detection. htm
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3.0
Testing Procedures
3.1 Performance Parameters
The key performance parameters evaluated for the TIC
screening technologies were:
• Accuracy of identifying hazardous samples
• False positive/false negative rates
• Analysis time
In addition, technologies providing more than a simple yes/
no response were evaluated for the following performance
parameter, using the responses displayed by these devices:
• Repeatability
These performance parameters are denned below, and
general test procedures are described in Section 3.2. The TIC
evaluation was performed according to the requirements of
the test/QA plan4 and the TTEP QMP.5
In addition to these key performance parameters, operational
characteristics of the screening technologies were evaluated
based on operator observations. These operational
characteristics included:
• Ease of use
• Data output
• Cost
3,1,1 Accuracy of Hazard Identification
Accuracy is the ability of a screening technology to identify
hazardous samples so that they can be properly handled
to minimize risk to laboratory personnel. Accuracy was
measured in terms of the percentage of prepared hazardous
samples that were correctly identified as hazardous by the
screening technology in question.
3.1.2 False Positive/False Negative Rates
A false positive screening result occurs when a technology
incorrectly identifies a safe sample as being hazardous. A
false negative screening result occurs when a technology
incorrectly identifies a hazardous sample as being safe.
Responses that identified samples as hazardous when they
contained none of the target TICs were denoted as false
positives. The absence of a hazard indication with a sample
containing a target TIC was denoted as a false negative.
3,1,3 Analysis Time
Analysis time is the time needed to screen a single sample
or group of samples with an individual technology. Analysis
time is driven by the response time of a technology in
indicating a hazard upon presentation of a sample and takes
different forms for different screening technologies. For
continuous monitors (e.g., the MultiRAE Plus orProengin
AP2C) analysis time is dependent on instrument response and
recovery time. For colorimetric papers the speed of analysis
is limited by the color development time after the start of
exposure, whereas for colorimetric gas sampling tubes, the
time required to draw the required volume of sample gas
through the tube is likely to be the limiting factor. For all
technologies tested, the appropriate response time was noted
to provide a consistent comparison of analysis times.
3.1.4 Repeatability
The responses provided by some sample screening
instruments include quantitative readings. Such readings
were recorded and the repeatability of such indications was
calculated in terms of a percent relative standard deviation
(% RSD) of the triplicate challenges at different test
conditions.
3.1.5 Operational Characteristics
Ease of use was assessed by operator observations, with
particular attention to the conditions of use during screening.
This assessment was done in the course of evaluating other
performance parameters with TICs, i.e., no additional test
procedures were designed specifically to address only the
operational characteristics.
For each screening technology, the type of indication or
data output was noted (e.g., color change, intensity of color
change, low/med/high indication, audio or visual alarm,
quantitative measure of concentration), and the clarity of the
indication was assessed.
Costs for each technology were assessed based on the
purchase and operational costs of the technologies as tested.
This technology evaluation was not of sufficient duration
to test long-term maintenance or operational costs of the
technologies. Estimates for key maintenance items were
requested from the vendors as necessary.
3.2 Test Procedures
3,2,1 Vapor-Phase Testing
Screening technologies were evaluated based on their ability
to respond to TICs in the vapor-phase, using a test apparatus
represented schematically in Figure 3-1. The test system
consists of a vapor generation system, a Nafion® humidifier,
two challenge plenums, a clean air plenum, metering valves
(MVs), RH sensors, thermocouples, and mass flow meters
(MFs) and controllers (MFCs). Only one of the two challenge
plenums was used in this evaluation. The challenge gas was
generated by diluting a commercially obtained compressed
gas standard of the target TIC.
-------
Figure 3-1. Test System Schematic
r=if
«¥^3 A M¥-3 B
^ « ~ '
Si«nwr
Temperature
C(?i»lnoW
-------
symptoms that could impair their abilities to take protective
action. Delivery of the vapor-phase challenges was deemed
acceptable if the TIC concentration determined by the
reference methods was within ± 20% of the respective target
value shown in Table 3-1.
For each screening technology, the test sequence of three
clean air blanks interspersed with three TIC challenges was
conducted with one TIC at a time at four different conditions:
at a base temperature and RH, at relatively high temperature
and RH, at relatively low temperature and RH, and at the
base temperature and RH with an interferent (a mixture of
hydrocarbons characteristic of polluted urban air) added to
both the blank and challenge mixtures. However, testing at
the base temperature and RH was conducted first, and if a
technology failed to respond in all three TIC challenges at
Table 3-1. Challenge Concentrations for TIC Vapor Testing
that test condition, then no tests were conducted at the other
three test conditions with that TIC. Table 3-2 summarizes
the TIC vapor-phase test conditions. The interferent
was a mixture of about 40 volatile organic compounds,
characteristic of gasoline engine emissions in urban air, in a
compressed gas standard in nitrogen. This mixture was added
to the blank or TIC challenge air flows at a ratio of 1:100
interferent mix to air flow.
Reference analysis methods were used to quantify the TIC
concentrations in the clean air and the challenge mixtures
to confirm that the concentrations delivered were within the
acceptable tolerance of ±20% from the target value. Table
3-3 lists the reference methods used for each of the TICs in
the vapor-phase testing. References to the methods used are
footnoted in Table 3-3.
TIC/CW Agent
Hydrogen cyanide (AC)
Cyanogen chloride (CK)
Phosgene (CG)
Chlorine (CI2)
Arsine (SA)
Hydrogen sulfide (H2S)
Concentration3
17 ppm (18.7 mg/m3)
0.4 ppm(1 mg/m3)
0.6 ppm (2.4 mg/m3)
2.8 ppm (8.4 mg/m3)
0.3 ppm (1 mg/m3)
41 ppm (57.4 mg/m3)
Basis for Concentration11
AEGL-2 value
TEEL-2 value
AEGL- 2 value
AEGL- 2 value
AEGL- 2 value
AEGL- 2 value
a At normal temperature and pressure, 1 ppm = (MW)(0.0409) milligrams per cubic meter (mg/m3),
where MW is the molecular weight of the compound
b AEGL = Acute Exposure Guideline Level; TEEL = Temporary Emergency Exposure Limit
Table 3-2. Test Conditions Used in TIC Vapor Testing
Condition
Base
High T/RH
Low T/RH
Interferent Test
Temperature (°C)
20
30
10
20
Relative Humidity (%)
50
80
20
50
Interferent"
None
None
None
hydrocarbon mix
See text for description.
Table 3-3. Reference Methods for Vapor-Phase TICs
TIC
Hydrogen cyanide (AC)
Cyanogen chloride (CK)
Phosgene (CG)
Chlorine (CI2)
Arsine (SA)
Hydrogen sulfide
Sampling Method
Air sample injected directly
into GC
Air sample injected directly
into GC
Continuous portable monitor
Continuous portable monitor
Collection in gas sampling
bag for GC injection and
Continuous portable monitor
Continuous electrochemical
detector
Analysis Method
GC/FID3
GC/FID"
Electrochemical detection0
Electrochemical detection0
GC/MSDd and
Electrochemical detection0
Electrochemical detection0
a Reference 8
b Reference 9
c Commercially available detectors used: Draeger MiniWarn for chlorine, Jerome Model 860 for
hydrogen sulfide, Draeger Pac III for phosgene and arsine
d Reference 10
-------
Table 3-4. TIC Concentrations Used in Liquid Testing
TIC
Cyanide
Fluoride
Hydrogen peroxide
Concentration
0.7 mg/mL
0.7 mg/mL
10% (100 mg/mL)
Solvent"
Water
Water
Water
Basis for Concentration
0.1 xOralLD50
0.1 x Acute Toxic Dose
ATSDR Guidelines
Solvents used for each TIC included Dl water, municipal tap water, and Dl water with 3% NaCI by
weight.
For the TICs hydrogen cyanide and cyanogen chloride, air
samples delivered from the test apparatus were injected
directly for detection by gas chromatography (GC)
with flame ionization detection (FID).8'9 Phosgene was
determined using a portable electrochemical detector,
the Draeger Pac III®. Chlorine was also determined by a
commercially available continuous electrochemical analyzer,
the Draeger MiniWarn. Arsine was determined initially by
a gas chromatographic method with a capillary column and
mass selective detection (MSD), using samples collected in
gas sampling bags from the test apparatus.10 Approximately
at the midway point of testing with arsine, a comparison was
made between arsine measurements made by the GC method
and simultaneous measurements from the Draeger Pac III
instrument. That comparison showed equivalent results from
the two methods, so for greater convenience the Pac III was
used for the remainder of the arsine testing. Hydrogen sulfide
was determined with the Jerome Model 860, a commercial
continuous electrochemical monitor.
3,2,2 Liquid Sample Testing
The testing with TICs in liquid samples used water as
the solvent because the target TICs (OST, F~, and H2O2)
are water-soluble species. However, to simulate potential
interfering sample matrices that might be encountered,
samples were prepared not only in deionized (Dl) water
(produced by a Labconco WaterPro PS water purification
system in Battelle's laboratory), but also in municipal tap
water and in Dl water containing 3.0% by weight NaCI.
Each of the TICs was prepared at a single concentration in
each of these three aqueous solvents, and each of these liquid
challenge samples contained a single TIC, i.e., no mixed
samples were prepared. Each screening technology was
tested with three blank samples of the aqueous matrix and
with three samples of the same matrix containing the TIC.
However, if a technology failed to detect a TIC in all three
challenge samples with the Dl water sample matrix, then
no tests were conducted with that TIC in the tap water or
salt water matrices. Table 3-4 lists the TICs tested in
liquid samples, the concentrations used in the evaluation
of liquid screening technologies, and the basis for the
concentrations used.
Because the purpose of the AHRF screening protocol is to
protect analytical personnel from toxic exposures in handling
and analyzing samples, the use of challenge concentrations
taken from drinking water standards was not appropriate,
i.e., it is unrealistic to assume that an analyst would
ever deliberately ingest a sample provided for analysis.
Furthermore, drinking water standards assume the ingestion
of several liters of water per day. As a result, the aqueous
challenge concentrations for cyanide, fluoride, and hydrogen
peroxide in Table 3-4 were based on reasonable assumptions
and/or the interpretation of information on toxic effects.
The concentration shown for cyanide was based on the
assumption that a water sample of 50-mL volume, containing
an amount of the target chemical equal to one-tenth of the
oral dose that would be lethal to half the population (LD50),
is spilled on the skin and that all of the chemical is then
absorbed into the body through the skin. For cyanide, with
an LD50 of 5 mg/kg of body weight, and an assumed body
weight of 70 kg, the total mass of cyanide would be 35 mg,
and the concentration in a 50-mL sample would be 0.7 mg/
mL, as shown in Table 3-4. Similarly, the acute toxic dose
of fluoride is generally reported as 3 to 5 mg/kg. Taking the
higher number, and making the same one-tenth adjustment
and assumptions as above for cyanide, results in the
0.7 mg/mL concentration shown in Table 3 4. For hydrogen
peroxide, the concentration of 10% (by weight) in Table 3-4
was identified by the U.S. Agency for Toxic Substances and
Disease Registry (ATSDR) as being strongly irritating and
potentially corrosive to skin.
The liquid challenge samples were made up gravimetrically
(for GST and F~) or volumetrically (for H2O2) from high-
purity (American Chemical Society [ACS] Reagent Grade or
better) chemicals. Laboratory volumetric glassware was used
for all dilutions, and the challenge samples were made up to
the required TIC concentration immediately before testing
took place. As a result, it was deemed unnecessary to conduct
reference analyses on the liquid challenge samples. This
choice to forego the reference analyses was documented by
preparation of a formal deviation from the test/QA plan.
3.3 Data Recording
Because of the qualitative nature of the technologies being
tested, the test observations were recorded manually by
the testing personnel on hard copy data sheets prepared for
this purpose. Upon completion of testing, the data sheets
were reviewed and signed by a Battelle staff member not
conducting the testing but familiar with the test procedures.
The data were then entered from the hard copy data sheets
into an Access® electronic database.
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4.0
Quality Assurance/Quality Control
Quality assurance/quality control (QA/QC) procedures
were performed in accordance with the QMP for the TTEP
programs and the test/QA plan for this verification test.4
QA/QC procedures and results are described below for the
vapor- and liquid-phase TIC testing. The only deviation from
the test/QA plan was the absence of reference analyses on the
liquid samples. As noted in Section 3.2.2, a deviation form
was prepared to document this difference.
4.1 Vapor-Phase Samples
4.1.1 Blank Challenges
As described in Section 3.2.1, challenges with TIC vapors
were interspersed with corresponding blank (i.e., clean
air) challenges. In all cases, blank challenges were at
the same temperature and of the same relative humidity
as the interspersed TIC challenge mixtures. In addition,
the reference methods described in Section 3.2.1 and
referred to in Section 4.1.2 were used to determine the TIC
concentrations in the blank challenges. At no time was a
detectable level of a target TIC found in any of the blank
challenges.
4.1.2 Reference Analyses
As described in Section 3.2.1, reference measurements were
made to document that the concentrations of vapor-phase
TICs in the challenge mixtures were within ± 20% of the
target concentrations listed in Table 3-1, as required in the
test/QA plan.4 At all times, those reference methods were
operated and calibrated according to the instructions provided
by the manufacturer or an applicable Battelle Standard
Operating Procedure. Table 4-1 summarizes the results of
the vapor-phase TIC reference measurements, showing the
target concentrations and acceptable ranges, and the mean,
standard deviation, and range of the reference results. All
reference results for AC, CK, CG, C12, and H2S were within
the required 20% tolerance. For S A, a few reference results
were slightly below the lower acceptable concentration
limit of 0.24 ppm. However, those reference results were
obtained at the end of a test in which the technology being
tested responded clearly and positively to the presence of the
TIC. As a result, it was concluded that the slightly low SA
concentration did not handicap the technology's performance,
so the test was not repeated, and the reference results were
nagged but kept in the data set.
4.1.3 TIC Vapor-Phase Testing Audits
Three types of audits were performed during the TIC testing:
a performance evaluation (PE) audit of the TIC vapor
delivery system using the reference analysis methods, a
technical systems audit (TSA) of the test procedures, and a
data quality audit of the recorded test data. Audit procedures
and results are described below.
4.1.3.1 Performance Evaluation Audit
PE audits of the TIC vapor delivery system were carried
out using a commercial gas standard of each TIC that was
independent of the TIC source gas used in testing. The PE
audit involved preparing two separate TIC challenge mixtures
by diluting the source gas that was used throughout testing
and by similarly diluting the independent gas standard. Both
TIC mixtures were then analyzed using the relevant reference
method, and the agreement of the reference results indicated
the overall agreement of the two TIC standards, as well
as the accuracy of the dilution system. The dilution of the
source gas and independent audit standards was done in such
a way that identical final TIC concentrations were targeted.
Agreement of the concentrations was required to be within
20% relative to the independent standard result.4 All TIC
mixtures for the PE audit were prepared at approximately
20 °C and 50% RH.
Table 4-1. Summary of Reference Results from TIC Vapor Testing
TIC
AC
CK
CG
CI2
SA
H2S
Target
Concentration
(ppm)
17
0.4
0.6
2.8
0.3
41
Acceptable
Range (ppm)
13.6 to 20.4
0.32 to 0.48
0.48 to 0.72
2.24 to 3.36
0.24 to 0.36
32.8 to 49.1
Reference Results
Mean (± St. Dev.)
(ppm)
17.5(0.9)
0.40 (0.03)
0.55(0.05)
2.78 (0.40)
0.28(0.05)
44.4 (2.9)
Range (ppm)
14.5 to 19.1
0.34 to 0.46
0.48 to 0.70
2.25 to 3.35
0.21ato0.36
39 to 49
SA reference results below the lower acceptable limit were observed in two tests in which the tested
technology responded clearly and positively to all challenges; test results retained.
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Table 4-2. Summary of TIC PE Audit Results
TIC
AC
CK
CG
SA
CI2
H2S
Audit Date
10/17/06
10/2/06
10/2/06
10/17/06
10/17/06
10/17/06
TIC Gas
Cylinder
Numbers3
XA3572
A0 16366
NA025680
NA025981
NA025205
NA025927
N1A013216
NA025688
A023136
1A1013
ALM022686
CLM010314
TIC Cylinder
Concentration,
ppm*
10,000
9,990
10,400
1,020
1,070
1,080
9,190
986
10,000
10,000
20,200
2,010
Reference
Method Results,
ppm*
23.0
20.9
0.38
0.44
0.64
0.61
0.84
0.88
15.1
14.5
30.0
34.0
Agreement %
10.0
13.6
4.9
4.5
4.1
11.8
First listing is source gas used in TIC testing, second gas listed is independent PE audit standard.
Table 4-2 summarizes the TIC PE audits, showing the target
TIC, the date of the PE audit, identification of the source and
independent standards used, the reference method results
for the delivered TIC concentration from each standard, and
the percent agreement. Table 4-2 shows that all the PE audit
results were well within the 20% target tolerance set in the
test/QAplan.4
4.1.3.2 Technical Systems A udit
A Battelle Quality Management representative conducted
a TSA of the TIC vapor testing on September 8, 2006, to
ensure that the test was being conducted in accordance with
the test/QA plan4 and the TTEP QMP.5 In the TSA, the test
procedures were compared to those specified in the test/QA
plan,4 and data acquisition and handling procedures, as well
as the reference standards and methods, were reviewed.
Observations and findings from the TSA were documented
and submitted to the Battelle Task Order Leader for response.
None of the findings of the TSA required corrective action.
Records from the TSA are permanently stored with the
Battelle Quality Manager.
4.1.3.3 Data Quality Audit
At least 10% of the data acquired during the TIC vapor
testing were audited. Battelle's Quality Manager traced the
data from the initial handwritten data record through to final
reporting, to ensure the integrity of the reported results.
All summaries and calculations performed on the data
undergoing the audit were checked.
4.2 Liquid-Phase Samples
4.2.1 Blank Challenges
As described in Section 3, the aqueous challenge samples
containing TICs were interspersed with corresponding blank
challenge samples. These blank samples consisted of the
same water used for the challenge samples. None of the
blank samples elicited any positive response from any of the
technologies being tested.
4.2.2 Reference Analyses
As noted in Section 3.2.2, the liquid challenge sample
solutions were made up gravimetrically or volumetrically
from high-purity chemicals and used immediately after
preparation. As a result, with the concurrence of the Battelle
Quality Manager, reference analyses were not conducted on
the liquid challenge samples.
4.2.3 TIC Liquid-Phase Testing Audits
Auditing of the liquid-phase testing was limited to a data
quality audit. No PE audit was performed on the liquid
samples because the high quality of the reagents and the
reliability of the preparation methods made reference
analyses unnecessary. No TSA was performed on the liquid
sample testing because of the short duration and simple
nature of that testing.
All of the data acquired during the TIC liquid sample testing
were audited. Battelle's Quality Manager traced the data from
the initial handwritten data record through to final reporting,
to ensure the integrity of the reported results. All summaries
and calculations performed on the data undergoing the audit
were checked.
4.3 QA/QC Reporting
Each audit was documented in accordance with the TTEP
QMP.5 Once the audit 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
submitted to EPA.
-------
4.4 Data Review a Battelle technical staff member involved in the verification
_. ... .,, . test. The person performing the review added his/her initials
Records generated in the verification test received a one- , ^ ,\ . . , , _, ,- „ ,, •
. , _ , , , and the date of review to a hard copy of the record being
over-one review before these records were used to calculate, . ,
evaluate, or report verification results. Data were reviewed by
-------
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5.0
Test Results
The primary results of this evaluation of potential AHRF
sample screening technologies consist of the observed
responses to the TIC challenges, which establish the accuracy
of each technology for sample screening. Those responses
were also reviewed to determine false positive and negative
rates for each technology and to establish the repeatability
of responses for those few technologies tested that provide
more than a qualitative (yes/no) response. Analysis time and
operational factors were also evaluated based on operator
observations and test records.
5.1 Accuracy
The test results for each technology were compiled into
databases that list the technology name, each target TIC and
its test concentration, reference method results confirming
the delivered TIC concentration, the test conditions (T,
RH, presence/absence of interferent), and the technology's
response to the triplicate blank and challenge runs. The
database of test results for the vapor-phase TICs is included
in this report as Appendix A, and the database of test results
for liquid-phase TICs is included as Appendix B. To make
these test results immediately understandable, a condensed
version of the database has been prepared, in which color
coding of the test results is used to provide a visual indication
of screening technology performance. In this format, a
technology that provides a positive response to all three
challenges in a single test condition with a TIC is indicated
with the color green; positive responses in only one or two
of the three challenges are shown by the color yellow; and
the absence of a positive response in all three challenges
is shown by the color red. This condensed summary of
screening technology performance is shown in Table 5-1 for
those technologies tested with vapor-phase TICs and in Table
5-2 for those technologies tested with TICs in liquid samples.
Table 5-1 shows that several of the technologies tested for
screening vapor-phase TICs correctly responded to the
presence of the TICs under all four test conditions, resulting
in an accuracy of 100%. The Anachemia CM256A1 card, the
two Draeger color tube technologies, the MSA and Nextteq
kits, and the Sensidyne color tubes all showed high accuracy
in detecting the target TICs with which they were challenged.
Among this group, only a single instance of failure to indicate
was noted, for the Draeger Civil Defense Kit in one of the
three trials with CK at the base condition. This technology
responded correctly to all other challenges with CK, at the
base condition and at all other test conditions, resulting in
92% accuracy (i.e., 11 out of 12 correct responses) for this
technology with CK. No single technology was applicable to
all six of the target TICs, but the the Draeger Civil Defense
Kit and Sensidyne tubes were the two technologies that had
high accuracy for five of the six TICs and between them can
detect all six.
Table 5-1 also shows that the Anachemia C2 tubes
were unable to detect the three TICs tested, at the target
concentrations used. The RAE MultiRAE Plus was
challenged with all six TICs and showed 100% accuracy
only to H2S and 0% accuracy for the other TICs. These
results show that the electrochemical sensor was effective
for H2S detection but that the PID is ineffective for detecting
the TICs. The Proengin AP2C and Truetech M18A3 tubes
did not show response to CK, and the HazMat Smart Strip
did not respond to AC. Also, an unusual response was seen
from the Proengin AP2C instrument in testing at low T and
low RH with AC. In all other tests with AC, the instrument
responded with a reading of one bar for HN/AC and with
a simultaneous reading of one bar for L/SA, suggesting an
arsenic compound. However, at the low T/low RH condition,
only the L/SA response was seen, i.e., the correct response
to hydrogen cyanide was not observed. Although the one-bar
reading for L/SA would provide some measure of protection
for laboratory staff, the Proengin readings at this test
condition were judged incorrect because of the absence of the
indication of cyanide observed at the other test conditions. An
overall accuracy of 75% resulted for the Proengin instrument
in detecting AC.
Table 5-2 shows that the Truetech M272 Water Kit correctly
indicated the presence of cyanide in all three water matrices,
and the Safety Solutions HazMat Smart Strip did the same
for hydrogen peroxide. No other positive responses were
found with the liquid samples.
-------
Table 5-1. Summary Results of TIC Vapor Testing
Technology
Anachemia C2 Tubes
TIC
AC
CG
CK
Test Condition3' b
Base
Base + Int
Low
High
Anachemia CM256A1
Draeger Civil Defense Kit
AC
CK
AC
CG
ci2
CK
SA
Draeger CMS Analyzer
AC
CG
CI2
H2S
MSA Single CWA Kit
AC
CG
CK
Nextteq Civil Defense Kit
AC
CG
CK
Proengin AP2C
AC
CK
H2S
SA
c
RAE MultiRAE Plus
AC
CG
CI2
CK
H2S
SA
S. S. HazMat Smart Strip
AC
ci2
H2S
-------
Table 5-1. (Continued)
Technology
Sensidyne Gas Tubes
TIC
AC
CG
CI2
H2S
SA
Test Condition3' b
Base
Base + Int
Low
High
Truetch M18A3 Tubes
AC
CG
CK
a Base = room land 50% RH; Base + Interferent (Int) = room T, 50% RH, and gas exhaust mixture at 1% of total flow; Low = 10 °C and 20%
RH; High = 30 °C and 80% RH.
b Green = proper response in all three challenges; Yellow = proper response in 1 or 2 of the 3 challenges; Red = no responses in the 3
challenges. Absence of color indicates test not conducted.
c The response of the instrument under these conditions is described on page 13.
Table 5-2. Summary Results of TIC Liquid Testing
Technology
Proengin AP2C
S. S. HazMat Smart Strip
Truetech M272 Water Kit
TIC
CN"
CN"
HA
F"
CN"
Test Solvent
DIH2O
Tap H2O
Dl + NaCI
* Green = proper response in all three challenges; Yellow = proper response in 1 or 2 of the 3 challenges; Red = no responses in the 3
challenges. Absence of color means test not conducted.
5.2 False Positive/False Negatives
5,2,1 False Positives
Testing for false positive responses was done through
challenges with a completely blank sample (i.e., clean air in
the TIC vapor testing or DI water in the liquid testing) and
through challenges with interferent in the absence of a target
TIC (i.e., the hydrocarbon mixture in the vapor testing or the
tap water and salt water matrices in the liquid testing). No
response was observed from any of the tested technologies
when challenged with blank samples or the interferent
matrices in either vapor or liquid testing. Thus, no false
positives were observed from any of the tested screening
technologies.
5.2.2 False Negatives
False negatives are shown by the red or yellow cells in Tables
5-1 and 5-2, which indicate the absence of a response in
all three challenges or the absence of a response in one or
two challenges, respectively. For clarity, Table 5-3 draws
information from Tables 5-1 and 5-2 to list the false negative
responses observed in the vapor and liquid TIC testing. None
of the false negatives was attributable to the hydrocarbon
mixture used as an interferent in the vapor testing or to the
tap water or salt water matrices used in the liquid testing. The
great majority of false negatives were simply the inability
of the technology to detect the target TIC at the challenge
concentration under the base test condition.
In vapor testing, for the Draeger Civil Defense Kit, a false
negative rate of 8% for CK (i.e., 1 out of 12 negative
responses) is calculated. False negative rates of 25% resulted
for the Proengin AP2C for AC and for the Truetech M18A3
tubes for CG. All other negative responses for both vapor
and liquid tests in Table 5-3 equated to false negative rates of
100%, as the target TIC was not detected even under the base
test conditions.
False negative responses are of great concern in the AHRF
sample screening process, so an assessment was made of
how the expected detection capabilities of the screening
technologies compare to the actual detection behavior
summarized in Tables 5-1 through 5-3. This assessment could
be done only for vapor-phase TIC detection, as summarized
-------
in Table 5-1, because no information was available from
the technology vendors on the likely detection limits of
their technologies for TICs in the liquid phase. Even for
vapor-phase TIC detection, stated detection limits were not
available from the vendors for all the technologies tested.
Regarding the detection of TIC vapors, this assessment
shows that in nearly all cases the screening technologies
were able to detect the TIC challenge concentrations, when
those concentrations were higher than the stated detection
limit of the technology. The inability of the Anachemia C2
tubes to detect AC, of the HazMat Smart Strip to detect AC,
and of the RAE MultiRAE Plus to detect AC and SA, are
the only examples of a technology failing to detect a TIC
present at or above the technology's stated detection limit.
On the other hand, there are many examples of technologies
accurately detecting the vapor-phase TICs, even though the
challenge concentrations were lower than the stated detection
limits of the technology. The Anachemia CM256A1, MSA
Single CWAKit, Nextteq Civil Defense Kit, Sensidyne Gas
Detection Tubes, and Truetech M18A3 tubes all showed
Table 5-3. Summary of False Negative Responses
accurate detection of one or more TICs, even when the
challenge concentrations were below their stated detection
limits. With this detection capability these technologies
offer greater protection in sample screening than would be
suggested by their stated detection limits.
5.3 Analysis Time
The time required to screen a sample with each of the
screening technologies was determined by the effort required
for sample collection (e.g., drawing of air sample with a hand
pump) or manipulation (e.g., mixing of reagents, breaking
of tubes), as well as by the inherent response time of the
detection principle of each technology. Table 5-4 summarizes
the analysis time observations for each technology, listing
the type of samples (vapor or liquid), the approximate typical
analysis time (seconds or minutes) characteristic of each
technology, and comments on the time response. It should be
noted that these results apply to the target TIC concentrations
used in this test. The presence of higher concentrations may
produce more rapid responses with some technologies.
Technology
Vapor
Anachemia C2 Tubes
Draeger Civil Defense Kit
Proengin AP2C
RAE MultiRAE Plus
S.S. HazMat Smart Strip
Truetech M18A3 Tubes
Liquid
Proengin AP2C
S.S. HazMat Smart Strip
TIC
AC, CG, CK
CK
AC
CK
AC, CG, CI2, CK, SA
AC
CG
CK
CN"
CN"
F"
Number of False Negatives
3 each
1
3a
3
3 each
3
3
3
3
3
3
Test Condition
Base
Base
Low T/Low RH
Base
Base
Base
High T/High RH
Base
Dl H2O
Dl H2O
Dl H2O
a At this test condition the Proengin AP2C indicated only L/SA (arsenic compound) and not HN/AC (cyanide compound), although both
indications were given with AC at the other three test conditions.
-------
Table 5-4. Summary of Sample Analysis Times
Technology
Anachemia C2 Tubes
Anachemia CM256A1
Draeger Civil Defense
Kit
Draeger CMS Analyzer
MSA Single CWA Kit
Nextteq Civil Defense
Kit
Proengin AP2C
RAE MultiRae Plus
S. S. HazMat Smart Strip
Sensidyne Gas Tubes
Truetech M18A3
Truetech M272 Water Kit
Sample
Type
Vapor
Vapor
Vapor
Vapor
Vapor
Vapor
Vapor
Liquid
Vapor
Vapor
Liquid
Vapor
Vapor
Liquid
Response Time*
min
sec
sec
min
min
min
sec
sec
sec
sec
sec
sec
min
min
Comments
Requires a few minutes to complete recommended ten pump strokes
Color occurs within several seconds after exposure; manipulation of
card takes up to one minute
Color change begins to occur in several seconds, however
recommended 50 pump strokes take a couple minutes to complete
Automated color tube sampler and reader, takes several minutes for
a reading
Time for noticeable color change depends on concentration of
analyte; recommended 30 pump strokes take a couple minutes to
complete
Time for noticeable color change depends on concentration of
analyte; required sample volume takes several minutes with electric
pump
Response typically occurs within a few seconds
Less than one minute to install scraper, wet scraper with sample,
desorb scraper into inlet, and obtain instrument response
Response within approximately 15 seconds
Color change within several seconds
Color change within a few seconds
Color change almost immediate (within a few seconds); one minute
needed per pump stroke; for test concentrations only one pump
stroke was needed
Recommended 60 pump strokes take several minutes to complete;
color change begins in a fraction of that time
Several minutes due to complexity of procedure required
Indication of whether typical time to response occurs in minutes (Min) or seconds (Sec).
5.4 Repeatability
For the three screening technologies that provided
quantitative readings (the Draeger CMS Analyzer, MultiRAE
Plus, and Sensidyne gas tubes), the repeatability of the
readings at each test condition was determined. Table
5-5 summarizes the responses obtained from these two
technologies, showing for each TIC and test condition the
nominal TIC concentration and the mean, standard deviation,
and %RSD of the screening technology readings.
-------
Table 5-5. Repeatability of Technology Readings
Technology
Draeger CMS
MultiRAE Plus
Sensidyne Tubes
TIC
AC
CG
C12
H2S
H2S
AC
CG
C12
H2S
SA
Condition
Base+Int
LowT/RH
High T/RH
Base
Base+Int
Low T/RH
High T/RH
Base
Base+Int
Low T/RH
High T/RH
Base
Base+Int
Low T/RH
High T/RH
Base
Base+Int
Low T/RH
High T/RH
Base
Base+Int
Low T/RH
High T/RH
Base
Base+Int
Low T/RH
High T/RH
Base
Base+Int
Low T/RH
High T/RH
Base
Base+Int
Low T/RH
High T/RH
Base
Base+Int
Low T/RH
High T/RH
Nominal TIC
Cone.
17 ppm
0.6 ppm
2.8 ppm
41 ppm
41 ppm
17 ppm
0.6 ppm
2.8 ppm
41pm
0.3 ppm
Readings
Mean
12.4
16.9
9.7
0.52
0.51
0.52
0.59
2.9
3.3
2.9
2.1
41.7
44.7
41.0
42.3
8.0
5.9
10.9
9.7
23.0
27.0
24.3
17.0
1.0
1.0
1.3
1.0
2.0
2.4
3.0
2.4
55.3
58.0
53.3
52.0
0.42
0.40
0.45
0.43
Std. Dev
2.8
4.0
1.4
0.06
0.07
0.06
0.05
0.8
0.2
0.5
0.5
2.1
1.5
1.0
2.1
0.7
0.8
1.0
1.4
1.4
1.7
3.2
0.0
0.0
0.0
0.3
0.0
0.0
0.4
0.2
0.5
1.2
2.0
1.2
2.0
0.03
0.0
0.05
0.06
%RSD
22.3
23.7
14.0
11.5
13.7
11.5
8.5
27.2
6.4
16.0
24.2
5.0
3.4
2.4
4.9
8.2
13.6
8.7
14.1
6.1
6.4
13.2
0
0
0
21.8
0
0
15.0
5.7
21.0
2.1
3.4
2.2
3.8
7.1
0
11.1
14.0
-------
Table 5-5 shows that most of the %RSD values (32 of 40
results) are less than 15% and over half (22 of 40) are less
than 10%, indicating that these screening technologies can
provide precise quantitative responses. However, several
%RSD values exceed 20%, most commonly with the Draeger
CMS for AC and C12. There does not appear to be any clear
dependence of the %RSD values on the test condition for
any of these three technologies. The overall result of this
evaluation is that close precision of readings can occur with
these quantitative screening technologies, but it cannot be
assumed under all circumstances.
5.5 Operational Factors
Operational factors were assessed based on the observations
of the test operator and are summarized in Table 5-6, which
for each TIC technology describes the general ease of use,
any problems noted in using the technology, and the physical
effort required for use. The latter issue was included because
several of the vapor sampling technologies rely on drawing
sample air through a colorimetric tube using a hand pump,
and such effort can become tedious if performed repetitively.
Table 5-6. Summary of Observations on Operational Factors of the Technologies
Technology
General Ease of Use
Problems with Use
Physical Effort Needed
Anachemia C2 Tubes
Relatively complex procedure
(with some analytes) of
breaking tube, inserting
into pump, drawing sample
through, then adding reagent
to tube
Sample tube packets say
not to use after September
10 with no specific year
indicated — distributor says
2010; pump difficult to use,
and could not tell if working
properly
Arm/hand strength needed for
pump
Anachemia CM256A1
Simple procedure of breaking
ampoules on a card to
wet/activate test patches and
exposing patches to sample;
easily distinguishable color
changes
Breakage of two green
ampoules at one time causes
rapid exothermic reaction
— creates fumes and sprays
green liquid
Minimal
Draeger Civil Defense Kit
Simple procedure of breaking
tubes, inserting into manifold,
and drawing sample through
tubes; easily distinguishable
color changes; five
compounds can be tested for
at one time
Prolonged use can cause
fatigue to hands; Draeger
sells five-tube sets to be
used with kit, which are
approximately five times more
expensive on a per-tube basis
compared to single tubes
purchased separately
Hand strength needed for
pump
Draeger CMS Analyzer
Simple procedure of sliding
chip back and forth inside
electronic device with a
slide switch; 10 sequential
analyses of a chemical per
chip; gives a digital reading
Gears for slide switch easily
become misaligned; if
misalignment occurs chip can
become unusable
Minimal effort needed to
move sliding switch back and
forth
MSA Single CWA Kit
Simple procedure of breaking
tube and inserting into pump;
most tubes test for more than
one compound
Some color changes not very
distinguishable; prolonged
use can cause hand fatigue;
squeeze counter on pump
broke after a couple uses
Hand strength needed for
pump operation
Nextteq Civil Defense Kit,
Simple procedure of breaking
tubes, inserting into manifold,
and drawing sample through
tubes; five compounds can be
tested for at one time
Impregnating adsorbent
layer by breaking liquid
ampoules sometimes difficult;
electric pump flow was easily
disrupted causing pump to
stop; some color changes
difficult to distinguish
Minimal effort with electric
pump; manual pump also
available
-------
Table 5-6. (Continued)
Technology
General Ease of Use
Problems with Use
Physical Effort Needed
Proengin AP2C
Simple procedure of starting
device and waiting for reading
(for vapors) or taking sample
with scraper tip, heating
scraper tip inline with device
and waiting for reading (for
liquids)
No significant problems; low-
pressure hydrogen supplies
will need replacement
periodically in regular use
(12-hour supply life easily
maximized by turning
instrument on and off)
None
RAE MultiRAE Plus
Simple procedure of starting
device and waiting for
electronic reading
Device uses PID for
general detection, with
electrochemical sensors for
specific compounds; PID
sensor nonresponsive to
TICs, only electrochemical
sensor for H2S gave
response
None
S. S. HazMat Smart Strip
Peel off protective cover for
immediate use
Some color changes almost
imperceptible; instructions
say mainly used for aerosols
making reliability of vapor and
liquid tests uncertain
None
Sensidyne Gas Tubes
Simple procedure of breaking
tube, inserting into pump,
and drawing sample through;
easily distinguishable color
changes; tubes graduated to
estimate concentration
Only one TIC can be tested
for at a time
Number of pump strokes
needed depends on
suspected concentration;
only one stroke required for
distinguishable color change
at tested concentrations
Truetech M18A3 Tubes
Relatively complex procedure
(with some analytes) of
breaking tube, inserting
into bulb, drawing sample
through, then adding reagent
to tube
Some tubes not scored
making breaking difficult;
repeated use causes ends
of tubes to shred bulb
orifice causing blockage
and potential leak problem;
some color changes not very
distinguishable; repetitive use
caused hand soreness
Hand strength needed
Truetech M272 Water Kit
Relatively complex procedure
involving wet chemistry and
adsorbent tubes
Requires 60 ml_ of sample
and multiple steps for
detection
Minimal effort but time
consuming
5.6 Screening Technology Costs
In choosing technologies for screening large numbers of
samples in an AHRF, both the initial cost of a TIC screening
technology and the cost per sample of the technology in
extended use are important. Table 5-7 summarizes the cost
information for each technology tested, showing the identity
of each technology, the purchase price of the technology as
tested, and the per-sample cost of consumable items.
Table 5-7 shows that the purchase costs of most of the
screening technologies were approximately $3,000 or less,
with the Proengin AP2C the exception at nearly $ 16,000.
(As noted in the table, the Proengin AP2C purchase price
was a discount from the vendor because of the nature of
this program; the normal purchase price is likely to be
approximately 30% higher.) However, comparison of the
purchase prices of different technologies can be misleading
because many of the technologies as purchased can screen
relatively few samples with the original materials. For
example, for most of the technologies in Table 5-7 that rely
on color-indicating tubes, the purchased technology typically
allows screening of only about 10 to 40 samples. Testing
larger numbers of samples requires obtaining additional
tubes, and indeed numerous purchases of additional
consumable items were needed to complete the testing
reported here. On the other hand, for the two Truetech
technologies in Table 5-7, the consumable sampling tubes
are not available except as part of the original kit, i.e.,
obtaining more screening capability means buying another
kit. The lowest extreme in terms of original purchase price is
the Safety Solutions HazMat Smart Strip at $20, however
this indicator card technology is purchased one at a time,
so only a single sample screening is obtained for that price.
At the other extreme, the relatively expensive MultiRAE
Plus and Proengin AP2C detectors are capable of screening
large numbers of samples without frequent replacement
of consumables.
-------
AHRF operations may call for screening of large numbers
of samples, and therefore the cost of extended use of each
technology is important. Table 5-7 shows that for most of
the TIC screening technologies tested, per-sample costs in
long-term use are typically $5 to $10, with some variation
depending on the TIC in question. Per-sample costs for
the HazMat Smart Strip and the Truetech Ml8A3 kit are
$20 and about $15, respectively. The purchase cost of each
Anachemia CM256A1 indicator card is about $17, but
because each card can detect three different TICs/CWAs,
the per-sample cost is estimated at about $5. Long-term
per-sample costs of the MultiRAE Plus and the Proengin
AP2C are lower but also less well defined. For the MultiRAE
Plus, the primary expendable cost will be replacement of
batteries; however, battery life was not assessed in this test.
This cost would probably equate to pennies per sample
in continuous use. The Proengin AP2C uses low-pressure
hydrogen supplies that are designed to last for 12 hours of
continuous use; supply life was not tested in this program but
Table 5-7. Cost Information on TIC Screening Technologies
this life seems reasonable based on the experience in testing
the instrument. The Proengin AP2C is designed to be turned
off whenever sample screening is not in progress, so the
12-hour supply life can equate to substantially longer periods
of use depending on the frequency of sample screening. An
indicator on the instrument shows the status of the hydrogen
supply. Two fully charged hydrogen supplies are provided in
the Proengin AP2C package. These supplies can be refilled
by Proengin at a cost of $25 each, plus a charge of $225 for
shipping of 1 to 10 supplies at a time to and from Proengin's
office in Fort Lauderdale, Florida. Purchase of single, new,
fully charged hydrogen supplies, separate from purchase of
the detector, costs $488 each. A refilling bench that allows the
user to recharge the supplies from a high pressure cylinder
of hydrogen is also available for approximately $65,000.
The Proengin AP2C also uses batteries; however, the cost of
battery replacement is likely trivial compared to the cost of
replacing the hydrogen supply.
Vendor
Anachemia
Draeger
MSA
Nextteq
Proengin
RAE Systems
Safety Solutions
Sensidyne
Truetech
Technology
C2
CM256A1
CMS Analyzer
Civil Defense Kit
Single CWA Sampler
Kit
Civil Defense Kit
AP2C
MultiRae Plus
HazMat Smart Strip
Gas Detection Tubes
M272 Water Kit
M18A3
Technology Cost
$684
$189
$1,922
$3,114
$1,295
$1,875
$15,708 (discount for
testing)
$3,290
$20
$532
$386
$1,189
Consumable Items
Tubes (boxes of 5)
Card
Chips (10 tubes per
chip)
Tubes (boxes of 10)
Tubes (boxes of 10)
Tubes (boxes of 10)
Hydrogen supplies;
batteries.
Scraper tips for liquid
sampling (packs of 10).
Batteries
Card
Tubes (boxes of 10)
Tubes (purchased as
part of kit)
Tubes (purchased as
part of kit)
Cost per Sample3
$7
~$5
AC: $5
CG:$7
CI2: $4
H2S$4
AC: $6
CK:$9
CG:: $8
SA:$8
CI2: $7
AC: $8
CK:$8
CG:$8
AC: $5
CK:$5
CG:$5
<$3b
$4 (for liquid sampling)
«$1
$20
AC: $6
CG:$6
SA:$6
CI2: $6
H2S: $6
~$5C
~$15C
Except as noted otherwise, approximate cost per sample analysis in extended use, based on cost of consumable items (excluding original
purchase price of the technology).
Per sample cost assumes 100 samples can be screened per hydrogen supply and that refill costs are worst-case $250 per supply (see text).
Cost per sample estimated based on original purchase price and number of analyses provided by original materials (consumables not available
except as part of kit).
-------
-------
6.0
Performance Summary
The ideal characteristics of a TIC screening technology
for use in the AHRF include accurate detection of TICs;
absence of false positive and negative responses; absence of
temperature, RH, or interferent effects; a rapid and simple
sample screening process; and low initial and operating costs.
As a secondary characteristic, for a technology that gives a
quantitative response, consistency of response is valuable
in that the technology may be able to distinguish heavily
contaminated from lightly contaminated samples.
The testing reported here was designed to evaluate the
screening technologies on each of the characteristics listed
above, and that purpose was accomplished. However,
the limitations of this evaluation relative to screening
samples in the AHRF should also be noted. This evaluation
addressed a wide variety of screening technologies and
focused on the relative performance of those technologies
for use in the AHRF, rather than on in-depth investigation
of any single technology. Similarly, testing of vendor
performance claims was not an objective of the evaluation.
For example, determination of the detection limits of the
screening technologies was specifically not a goal of this
evaluation. Rather, the challenge TIC concentrations were
chosen based on health risk information and the desire to
protect AHRF staff, and the ability to detect the presence
of TICs at those levels was assessed regardless of vendor
claims about detection limits. Also, test conditions in this
evaluation were intended to represent those under which the
screening technologies might actually be used in the AHRF,
but those actual conditions are not completely known at
this time. Thus, the sample matrices, temperature and RH
ranges, and interferences used may not fully address the
reality of AHRF operations. This evaluation also focused on
relatively inexpensive technologies suitable for screening
large numbers of samples. Other, far more expensive,
technologies exist that might prove useful in some aspects of
AHRF operations. On the other hand, this evaluation tested
each technology in realistic use by a skilled practitioner, in
a manner that closely represents how the technology would
be used under the AHRF screening protocol (Figure 1-1). As
a result, the results summarized below represent a valuable
assessment of the usefulness of each technology for AHRF
screening.
Regarding accuracy for vapor-phase TICs, most of the
tested technologies showed 100% accuracy, or nearly
so, in detecting the TICs to which they were applicable.
Notable exceptions were the Anachemia C2 tubes, which
did not detect any of the three TICs with which they were
challenged, and the PID sensor of the MultiRAE Plus
detector, which (consistent with the nature of the PID) did
not respond to several TICs. However, none of the tested
technologies was designed to detect all six of the target TICs;
the Sensidyne Gas Tubes and Draeger Civil Defense Kit
exhibited 100% accuracy, or nearly so, for five TICs, and
the Draeger CMS Analyzer for four. Regarding accuracy in
detecting TICs in water samples, the HazMat Smart Strip was
100% accurate in detecting hydrogen peroxide, as was the
Truetech M272 Water Kit in detecting cyanide.
For those technologies that provided a quantitative indication
of the TIC vapor concentration during testing (i.e., the
Draeger CMS Analyzer, MultiRAE Plus [for H2S only], and
Sensidyne Gas Tubes), the %RSD of triplicate responses
was within 15% in 32 of the 40 challenge sets with these
technologies and within 10% in 22 of those 40 tests. Test
conditions had no apparent effect on the %RSD values. Thus,
close precision of responses can be obtained in screening
with these technologies but cannot be assumed in all tests.
None of the tested technologies produced any false positive
responses in either vapor- or liquid-phase TIC testing. False
negatives mainly occurred as the inability of a technology
to detect a TIC even under the base test conditions. The
Anachemia C2 and MultiRAE Plus results noted above were
the prime examples, but false negatives under base conditions
also occurred with the Proengin AP2C and Truetech M18 A3
tubes for CK and the HazMat Smart Strip for AC in vapor
testing, and with the HazMat Smart Strip for GST and F~ and
Proengin AP2C for GST in liquid testing.
No effect of interferents was seen, in either vapor- or liquid-
phase testing, with those technologies challenged with the
interferents. Temperature and RH effects in vapor testing
were also minimal. In fact, results potentially attributable to
temperature and RH effects were seen in only two cases. The
Truetech M18A3 failed to respond to CG at the high T/high
RH condition, and the Proengin AP2C gave an incorrect
response to AC at the low T/low RH condition.
The speed and simplicity of the screening process varied
widely among the tested technologies. All of the vapor
detection technologies based on color-indicating tubes
are simple to use in principle but differed in the time and
difficulty of obtaining the sample. With such technologies,
the number of manual pump strokes required to draw the
sample ranged from 1 (Sensidyne Gas Tubes) to 60 (Truetech
M18A3), and the manual effort needed for those technologies
requiring 30 or more pump strokes was excessive even when
screening small numbers of samples as in this test. Electric
air sampling pumps, whether internal to the technology (as
in the automated Draeger CMS Analyzer) or external (as in
the Nextteq Civil Defense Kit) greatly reduce the physical
effort needed but still may require several minutes to draw
the required volume. Use of color-indicating tubes that
require the minimum volume would seem preferable for use
in the AHRF, and use of an electrical sampling pump might
be helpful even then, if large numbers of samples are to be
screened. The two real-time analyzers tested (MultiRAE
-------
Plus and Proengin AP2C) provided easy and rapid sample
screening, although only the electrochemical H2S sensor in
the MultiRAE Plus provided response from that instrument
in these tests. The speed of screening water samples with
the Proengin AP2C was also relatively rapid because of the
simplicity of wetting the "scraper" attachment and desorbing
into the instrument inlet. The HazMat Smart Strip was the
simplest technology to use, requiring only removal of a
protective film to expose the indicating patches on the card.
However, this technology did not respond to AC. For vapor
detection in the AHRF, the HazMat Smart Strip is best suited
to being enclosed within a container or attached to a surface,
rather than being used as a hand-held sampling tool. The
Anachemia CM256A1 multifunction card was considerably
more difficult to use, requiring hand manipulation to heat and
direct reagents to sections of the card, but provided accurate
detection of the only two TICs for which it was applicable
(AC and CK).
In terms of the speed and simplicity of liquid sample
screening, the Truetech M272 Water Kit was found to be
deficient. The multiple detection tubes and reagent tablets
needed, and the requirement for 60 mL of water sample,
make it unlikely that this technology would be suitable for
the AHRF.
-------
7.0
References
1 . Draft Interim All Hazards Receipt Facility Protocol, Standard Operating Procedures, (Guidance) - Working
Draft, U.S. Environmental Protection Agency, National Homeland Security Research Center, September 5, 2006.
2. Draft Interim All Hazards Receipt Facility (AHRF) Protocol, Quick Reference Guide - Working Draft, U.S.
Environmental Protection Agency, National Homeland Security Research Center, August 31, 2006.
3 . Testing of Screening Technologies for Detection of Chemical Warfare Agents in All Hazards Receipt Facilities,
final report for All Hazards Receipt Facility Monitoring and Detection Technology Testing and Evaluation,
Contract GS23F0011L-3, Task Order 1119, Battelle, Columbus, Ohio, April 2007.
4. Test/QA Plan for Evaluation of Sample Screening Technologies for the All Hazards Receipt Facility, Version 1,
Battelle, Columbus, Ohio, May 26, 2006.
5. Quality Management Plan for the Technology Testing and Evaluation Program, Version 2, Battelle, Columbus,
Ohio, January 2006.
6. Acute Exposure Guideline Levels published by the National Research Council, National Academy of Sciences,
and available from the U. S. Environmental Protection Agency at lilB;//WBy=CBajM/QH)t/acg]Ml
7. Temporary Emergency Exposure Limits established for the U.S. Department of Energy by the Subcommittee on
Consequence Assessment and Protective Actions (SCAPA), information and TEEL values available at
8. Battelle Chromatography Method for Hydrogen Cyanide (HCN), Method Designation, May 2003.
9. Battelle Gas Chromatography Method for Cyanogen Chloride (CK), Method Designation, May 2003.
10. Battelle Gas Chromatography Method for Arsine, Method Designation, May 2004.
-------
-------
Appendix A
Results of Testing with Vapor-Phase
Toxic Industrial Chemicals
Vapor Challenge Results Summary: results of all tests with vapor-phase TICs
Vapor Actual ppm vs Nominal ppm: results showing quantitative responses and %RSD values
for those technologies listed as providing a "concentration" response in the previous table
Vapor False Positives: results obtained from all technologies when challenged with exhaust gas
interferent in the absence of any TICs
-------
Technology
Anachemia €2
Humidity
Draeger CDS
AC
CG
CK
AC
AC
AC
AC
CK
CK
CK
CK
AC
AC
AC
AC
CG
CG
CG
CG
Chlorine
Chlorine
Chlorine
Chlorine
CK
CK
CK
CK
CK
SA
SA
Medium
Medium
Medium
Medium
Medium
Low
High
Medium
Medium
Low
High
Medium
Medium
Low
High
Medium
Medium
Low
High
Medium
Medium
Low
High
Medium
Medium
Medium
Low
High
Medium
Medium
Medium
Medium
Medium
Medium
Medium
Low
High
Medium
Medium
Low
High
Medium
Medium
Low
High
Medium
Medium
Low
High
Medium
Medium
Low
High
Medium
Medium
Medium
Low
High
Medium
High
None
None
None
None
Gas Exhaust (1%)
None
None
None
Gas Exhaust (1%)
None
None
None
Gas Exhaust (1%)
None
None
None
Gas Exhaust (1%)
None
None
None
Gas Exhaust (1%)
None
None
None
None
Gas Exhaust (1%)
None
None
None
Gas Exhaust (1%)
none
green (no CC
none
pink/blue
pink
pink
pink/blue
pink/blue
pink/blue
pink/blue
pink/blue
red
red
red
red
green
green
strong green
slight green
brown
brown
brown
brown stain
none
pink
pink
pink
pink
dark ring
purple stain
Count of Result
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
1
2
3
3
3
3
3
-------
Technology
CMS
SA
SA
AC
AC
AC
AC
CG
CG
CG
CG
Chlorine
Chlorine
Chlorine
Chlorine
H2S
H2S
H2S
H2S
AC
AC
AC
AC
CG
CG
CG
CG
CK
CK
CK
CK
Temperature
Low
High
Medium
Medium
Low
High
Medium
Medium
Low
High
Medium
Medium
Low
High
Medium
Medium
Low
High
Medium
Medium
Low
High
Medium
Medium
Low
High
Medium
Medium
Low
High
Low
High
Medium
Medium
Low
High
Medium
Medium
Low
High
Medium
Medium
Low
High
Medium
Medium
Low
High
Medium
Medium
Low
High
Medium
Medium
Low
High
Medium
Medium
Low
High
Interferent
None
None
None
Gas Exhaust (1%)
None
None
None
Gas Exhaust (1%)
None
None
None
Gas Exhaust (1%)
None
None
None
Gas Exhaust (1%)
None
None
None
Gas Exhaust (1%)
None
None
None
Gas Exhaust (1%)
None
None
None
Gas Exhaust (1%)
None
None
purple stain
purple ring
concentration8
concentration8
concentration8
concentration8
concentration8
concentration8
concentration8
concentration8
concentration8
concentration8
concentration8
concentration8
concentration8
concentration8
concentration8
concentration8
red spots
red spots
orange spots
yellow/orange
red
red
slight red
red
light pink
light pink
pink
slight pink
Count of Result
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
RAE Plus
AC
Medium
Medium
None
none
-------
Technology
Nextteq
Pmengin AP2C
CG
Chlorine
CK
H2S
H2S
H2S
H2S
SA
AC
AC
AC
AC
CG
CG
CG
CG
CK
CK
CK
CK
AC
AC
AC
AC
CK
H2S
H2S
H2S
H2S
H2S
SA
Temperature
Medium
Medium
Medium
Medium
Medium
Low
High
Medium
Medium
Medium
Low
High
Medium
Medium
Low
High
Medium
Medium
Low
High
Medium
Medium
Low
High
Medium
Medium
Medium
Medium
Low
High
Medium
Medium
Medium
Medium
Medium
Medium
Low
High
Medium
Medium
Medium
Low
High
Medium
Medium
Low
High
Medium
Medium
Low
High
Medium
Medium
Low
High
Medium
Medium
Medium
Medium
Low
High
Medium
Interferent
None
None
None
None
Gas Exhaust (1%)
None
None
None
None
Gas Exhaust (1%)
None
None
None
Gas Exhaust (1%)
None
None
None
Gas Exhaust (1%)
None
None
None
Gas Exhaust (1%)
None
None
None
None
Gas Exhaust (1%)
Gas Exhaust (1%)
None
None
None
none
none
none
concentration8
concentration3
concentration3
concentration3
none
dark pink
dark pink
red stain
red stain
red
red
red
red
pink
pink
pink
pink
HN.AC level 1; L,SA level 1
HN, AC level 1; L,SAIevel1
L,SA level 1 and 2
HN, AC level 1; L.SAIeveH
none
L,SA level 1 ; HD.HL level 1 , 2, and 3
L,SA level 1 ; HD.HL level 1 and 2
L,SA level 1 ; HD.HL level 1 , 2 and 3
L,SA level 1 ; HD.HL level 1 , 2 and 3
HD.HL level 1,2, 3, 4 and 5
L,SA level 1 and 2
Count of Result
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
O
Z
1
3
3
3
-------
Technology
Safely Solutions
Sens/dyne
Chemical
SA
SA
SA
SA
AC
Chlorine
Chlorine
Chlorine
Chlorine
H2S
H2S
H2S
H2S
AC
AC
AC
AC
CG
CG
CG
CG
Chlorine
Chlorine
Chlorine
Chlorine
H2S
H2S
H2S
H2S
Temperature
Medium
Low
High
High
Medium
Medium
Medium
Low
High
Medium
Medium
Low
High
Medium
Medium
Low
High
Medium
Medium
Low
High
Medium
Medium
Low
High
Medium
Medium
Low
High
Medium
Low
High
High
Medium
Medium
Medium
Low
High
Medium
Medium
Low
High
Medium
Medium
Low
High
Medium
Medium
Low
High
Medium
Medium
Low
High
Medium
Medium
Low
High
Interferent
Gas Exhaust (1%)
None
None
None
None
None
Gas Exhaust (1%)
None
None
None
Gas Exhaust (1%)
None
None
None
Gas Exhaust (1%)
None
None
None
GasExhaust(1%)
None
None
None
Gas Exhaust (1%)
None
None
None
Gas Exhaust (1%)
None
None
L,SA level 1 and 2
L,SA level 1 and 2
L,SA level 1 and 2
L,SA level 1,2, and 3
none
chlorine: grey; oxidizer: yellow
chlorine: grey; oxidizer: yellow
chlorine: grey; oxidizer: yellow
chlorine: grey; oxidizer: black
beige
beige
light beige
black
concentration3
concentration3
concentration3
concentration8
concentration3
concentration3
concentration3
concentration3
concentration3
concentration3
concentration3
concentration3
concentration3
concentration3
concentration3
concentration3
Count of Result
3
3
1
2
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
-------
Technology
Truetech
Chemical
SA
SA
SA
SA
AC
AC
AC
AC
CG
CG
CG
CG
CK
Temperature
Medium
Medium
Low
High
Medium
Medium
Low
High
Medium
Medium
Low
High
Medium
Humidity
Medium
Medium
Low
High
Medium
Medium
Low
High
Medium
Medium
Low
High
Medium
Interferent
None
Gas Exhaust (1%)
None
None
None
Gas Exhaust (1%)
None
None
None
Gas Exhaust (1%)
None
None
None
Result
concentration3
concentration3
concentration3
concentration3
blue stain
blue
blue
light blue
slight green
green
green
none
none
Count of Result
3
3
3
3
3
3
3
3
3
3
3
3
4
a: See table starting on page A-7 for summary of quantitative readings.
-------
¥S
Technology
AC
AC
AC
AC
CG
CG
CG
CG
Chlorine
Chlorine
Chlorine
Chlorine
H2S
H2S
H2S
H2S
RAE Plus
AC
CG
Chlorine
CK
H2S
H2S
H2S
H2S
Sens/dyne
AC
AC
AC
AC
CG
CG
Medium
Medium
Low
High
Medium
Medium
Low
High
Medium
Medium
Low
High
Medium
Medium
Low
High
Medium
Medium
Medium
Medium
Medium
Medium
Low
High
Medium
Medium
Low
High
Medium
Medium
RH
Medium
Medium
Low
High
Medium
Medium
Low
High
Medium
Medium
Low
High
Medium
Medium
Low
High
Medium
Medium
Medium
Medium
Medium
Medium
Low
High
Medium
Medium
Low
High
Medium
Medium
Interferenf
None
Gas Exhaust (1%)
None
None
None
Gas Exhaust (1%)
None
None
None
GasExhaust(1%)
None
None
None
Gas Exhaust (1%)
None
None
None
None
None
None
None
Gas Exhaust (1%)
None
None
None
Gas Exhaust (1%)
None
None
None
Gas Exhaust (1%)
14.77
12.37
16.93
9.67
0.52
0.51
0.52
0.59
2.87
3.29
2.88
2.07
41.67
44.67
41.00
42.33
0.00
0.00
0.00
0.00
7.97
5.90
10.90
9.70
23.00
27.00
24.33
17.00
1.00
1.00
Std Dew
7.31
2.76
4.01
1.35
0.06
0.07
0.06
0.05
0.78
0.21
0.46
0.50
2.08
1.53
1.00
2.08
0.00
0.00
0.00
0.00
0.65
0.80
0.95
1.37
1.41
1.73
3.21
0.00
0.00
0.00
AEGL-2 17ppm
AEGL-217ppm
AEGL-2 17ppm
AEGL-2 17ppm
AEGL-2 0.6 ppm
AEGL-2 0.6 ppm
AEGL-2 0.6ppm
AEGL-2 0.6ppm
AEGL-2 2.8ppm
AEGL-2 2.8ppm
AEGL-2 2.8ppm
AEGL-2 2.8ppm
AEGL-2 41 ppm
AEGL-2 41 ppm
AEGL-2 41 ppm
AEGL-2 41 ppm
AEGL-2 17ppm
AEGL-2 0.6ppm
AEGL-2 2.8ppm
TEEL-2 0.4 ppm
AEGL-2 41 ppm
AEGL-2 41 ppm
AEGL-2 41 ppm
AEGL-2 41 ppm
AEGL-2 17ppm
AEGL-2 17ppm
AEGL-2 17ppm
AEGL-2 17ppm
AEGL-2 0.6 ppm
AEGL-2 0.6 ppm
-------
Technology
Chemical
CG
CG
Chlorine
Chlorine
Chlorine
Chlorine
H2S
H2S
H2S
H2S
SA
SA
SA
SA
Temperature Range
Low
High
Medium
Medium
Low
High
Medium
Medium
Low
High
Medium
Medium
Low
High
RH Range
Low
High
Medium
Medium
Low
High
Medium
Medium
Low
High
Medium
Medium
Low
High
Interferent
None
None
None
Gas Exhaust (1%)
None
None
None
Gas Exhaust (1%)
None
None
None
Gas Exhaust (1%)
None
None
Average (ppm)
1.33
1.00
2.00
2.40
3.00
2.43
55.33
58.00
53.33
52.00
0.42
0.40
0.45
0.43
Std Dev
0.29
0.00
0.00
0.36
0.17
0.51
1.15
2.00
1.15
2.00
0.03
0.00
0.05
0.06
Nominal Concentration
AEGL-2 0.6 ppm
AEGL-2 0.6 ppm
AEGL-2 2.8ppm
AEGL-2 2.8ppm
AEGL-2 2.8ppm
AEGL-2 2.8ppm
AEGL-2 41 ppm
AEGL-2 41 ppm
AEGL-2 41 ppm
AEGL-2 41 ppm
AEGL-2 0.3 ppm
AEGL-2 O.Sppm
AEGL-2 0.3 ppm
AEGL-2 0.3 ppm
-------
Anachemia
Draeger CDS
Draeger CMS
AC or CK
AC, CK, CG, SA, or Chlorine
AC
CG
Chlorine
H2S
USA
AC, CK, orCG
Multi RAE Plus
AC, CK, CG, SA, Chlorine, or H2S
AC, CK, orCG
Proengin AP2C
AC, CK, SA, or H2S
Safety Solutions
AC, H2S, or Chlorine
AC
CG
Chlorine
H2S
Truetech
SA
AC
CG
Humidity
Medium
Medium
Medium
Medium
Medium
Medium
Medium
Medium
Medium
Medium
Medium
Medium
Medium
Medium
Medium
Medium
Medium
Medium
Medium
Medium
Medium
Medium
Medium
Medium
Medium
Medium
Medium
Medium
Medium
Medium
Medium
Medium
Medium
Medium
Medium
Medium
Gas Exhaust (1%)
Gas Exhaust (1%)
Gas Exhaust (1%)
Gas Exhaust (1%)
Gas Exhaust (1%)
Gas Exhaust (1%)
Gas Exhaust (1%)
Gas Exhaust (1%)
Gas Exhaust (1%)
Gas Exhaust (1%)
Gas Exhaust (1%)
Gas Exhaust (1%)
Gas Exhaust (1%)
Gas Exhaust (1%)
Gas Exhaust (1%)
Gas Exhaust (1%)
Gas Exhaust (1%)
Gas Exhaust (1%)
Challenge
Challenge
Challenge
Challenge
Challenge
Challenge
Challenge
Challenge
Challenge
Challenge
Challenge
Challenge
Challenge
Challenge
Challenge
Challenge
Challenge
Challenge
none
none
< 2.00 ppm
< 0.050 ppm
< 2.00 ppm
<2.00 ppm
none
0.0 ppm
none
none
none
none
none
none
none
none
none
none
none
none
<2.00 ppm
< 0.050 ppm
<2.00 ppm
<2.00 ppm
none
0.0 ppm
none
none
none
none
none
none
none
none
none
none
-------
-------
Appendix B
Results of Testing with Toxic Industrial
Chemicals in Liquid Samples
Liquid Challenge Results Grouped: results of all tests with liquid-phase TIC solutions
Liquid Challenge Results Grouped
Technology Chemical Interferent
Proengin AP2C
Safety Solutions
Truetech M272 Water Kit
CN7DI H2O
None
CN7DI H2O
F7DI H2O
H2O2/DI H2O
H2O2/DI H2O
H2O2/DI H2O
CN7DI H2O
CN7DI H2O
CN7DI H,O
None
None
None
Tap Water
3% NaCI
None
Tap Water
3% NaCI
Response
none
none
none
dark purple
dark purple
dark purple
Red tube: blue; blue tube: none
Red tube: blue; blue tube: none
Red tube: blue; blue tube: none
Count of Result
-------
&EPA
United States
Environmental Protection
Agency
Office of Research and Development
National Homeland Security Research Center
Cincinnati, OH 45268
Official Business
Penalty for Private Use
$300
Recycled/Recyclable
Printed with vegetable-based ink on
paper that contains a minimum of
50% post-consumer fiber content
processed chlorine free
PRESORTED STANDARD
POSTAGES FEES PAID
EPA
PERMIT NO. G-35
------- |