MONITORING AT CHEMICAL AGENT DISPOSAL FACILITIES
THE NATIONAL ACADEMIES PRESS
Washington, D.C.
www.nap.edu
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NOTICE: The project that is the subject of this report was approved by the Governing Board of the National Research Council, whose members are drawn from the councils of the National Academy of Sciences, the National Academy of Engineering, and the Institute of Medicine. The members of the committee responsible for the report were chosen for their special competences and with regard for appropriate balance.
This study was supported by Contract No. W911NF-04-C-0064 between the National Academy of Sciences and the Department of Defense. Any opinions, findings, conclusions, or recommendations expressed in this publication are those of the author(s) and do not necessarily reflect the views of the organizations or agencies that provided support for the project.
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COMMITTEE ON MONITORING AT CHEMICAL AGENT DISPOSAL FACILITIES
CHARLES E. KOLB, Chair,
Aerodyne Research, Inc., Billerica, Massachusetts
JEFFREY I. STEINFELD, Vice Chair,
Massachusetts Institute of Technology, Cambridge
ELISABETH M. DRAKE,
Massachusetts Institute of Technology, Cambridge
COLIN G. DRURY,
State University of New York at Buffalo
J. ROBERT GIBSON,
Gibson Consulting, LLC, Wilmington, Delaware
PETER R. GRIFFITHS,
University of Idaho, Moscow
JAMES R. KLUGH, U.S. Army (retired);
Dimensions International, Inc., Alexandria, Virginia
LOREN D. KOLLER,
Loren Koller & Associates, Corvallis, Oregon
GARY D. SIDES,
GTI Defense, Birmingham, Alabama (Until January 28, 2005)
ALBERT A. VIGGIANO,
Air Force Research Laboratory, Hanscom Air Force Base, Massachusetts
DAVID R. WALT,
Tufts University, Medford, Massachusetts
Staff
MARGARET N. NOVACK, Study Director
HARRISON T. PANNELLA, Program Officer
JAMES C. MYSKA, Research Associate
NIA D. JOHNSON, Research Associate
DETRA BODRICK-SHORTER, Senior Program Assistant
BOARD ON ARMY SCIENCE AND TECHNOLOGY
JOHN E. MILLER, Chair,
Oracle Corporation, Reston, Virginia
HENRY J. HATCH, Vice Chair,
U.S. Army Corps of Engineers (retired), Oakton, Virginia
SETH BONDER,
The Bonder Group, Ann Arbor, Michigan
JOSEPH V. BRADDOCK,
The Potomac Foundation, McLean, Virginia
NORVAL L. BROOME,
MITRE Corporation (retired), Suffolk, Virginia
ROBERT L. CATTOI,
Rockwell International (retired), Dallas, Texas
DARRELL W. COLLIER,
U.S. Army Space and Missile Defense Command (retired), Leander, Texas
ALAN H. EPSTEIN,
Massachusetts Institute of Technology, Cambridge
ROBERT R. EVERETT,
MITRE Corporation (retired), New Seabury, Massachusetts
PATRICK F. FLYNN,
Cummins Engine Company, Inc. (retired), Columbus, Indiana
WILLIAM R. GRAHAM,
National Security Research, Inc., Arlington, Virginia
PETER F. GREEN,
University of Texas, Austin
EDWARD J. HAUG,
University of Iowa, Iowa City
M. FREDERICK HAWTHORNE,
University of California, Los Angeles
CLARENCE W. KITCHENS,
Science Applications International Corporation, Vienna, Virginia
ROGER A. KRONE,
Boeing Integrated Defense Systems, Philadelphia, Pennsylvania
JOHN W. LYONS,
U.S. Army Research Laboratory (retired), Ellicott City, Maryland
MALCOLM R. O’NEILL,
Lockheed Martin Corporation, Bethesda, Maryland
EDWARD K. REEDY,
Georgia Tech Research Institute (retired), Atlanta, Georgia
DENNIS J. REIMER,
National Memorial Institute for the Prevention of Terrorism, Oklahoma City
WALTER D. SINCOSKIE,
Telcordia Technologies, Inc., Morristown, New Jersey
JUDITH L. SWAIN,
University of California, San Diego
WILLIAM R. SWARTOUT,
Institute for Creative Technologies, Marina del Rey, California
EDWIN L. THOMAS,
Massachusetts Institute of Technology, Cambridge
BARRY M. TROST,
Stanford University, Stanford, California
Staff
BRUCE A. BRAUN, Director
WILLIAM E. CAMPBELL, Manager, Program Operations
CHRIS JONES, Financial Associate
DEANNA P. SPARGER, Program Administrative Coordinator
Preface
The Committee on Monitoring at Chemical Agent Disposal Facilities was appointed by the National Research Council (NRC) in July 2004 to review the instrumentation systems and practices for monitoring airborne chemical agent levels associated with chemical weapons demilitarization and stockpile storage facilities operated by the U.S. Army’s Chemical Materials Agency (CMA). The committee was also charged with reviewing how the new chemical agent airborne exposure limits recommended by the Centers for Disease Control and Prevention (CDC) in 2003 and 2004 and implemented by the CMA in 2005 would impact the effectiveness of the Army’s current agent monitoring and whether new applicable monitoring technologies were available and could be effectively incorporated into the CMA’s overall airborne chemical agent monitoring strategies. The committee’s statement of task is presented in Chapter 1, along with an account of the committee’s activities. Biographies of the committee members’ professional activities are presented in Appendix A.
Airborne chemical agent monitoring systems at CMA weapons disposal and storage facilities serve multiple purposes: to warn workers of unexpected levels of agents within their workplaces, to ensure that workers are not exposed to persistent unhealthful concentrations of airborne agent, and to document any significant passage of airborne agent across facility boundaries that might harm the general population or the environment. The agent concentrations routinely monitored by the CMA are extremely low, with fence-line monitoring limits based on the new CDC recommendations ranging from 0.003 to 0.00005 parts per billion by volume, depending on the chemical agent. The detection of very low chemical agent concentrations within air masses containing much larger levels of other industrial and environmental contaminants that can interfere with chemical agent detection makes the CMA’s monitoring tasks very challenging.
Assessing the utility of both the current CMA monitoring technology and the future usefulness of potential advanced monitoring technology required the committee’s membership to understand a full range of modern analytical chemistry measurement techniques and instrumentation; the chemical, physical, and toxicological properties of the relevant chemical agents; and the operational characteristics of the CMA weapons disposal and storage facilities. In considering these topics, the committee reviewed the scientific literature, and it queried and was subsequently briefed by many capable scientists and engineers associated with the CMA, the CDC, and other relevant federal agencies. The committee also drew heavily on relevant recent NRC reports addressing chemical weapons demilitarization issues, including Occupational Health and Workplace Monitoring at Chemical Agent Disposal Facilities;1Evaluation of Chemical Events at Army Chemical Agent Disposal Facilities;2 and Impact of Revised Airborne Exposure Limits on Non-Stockpile Chemical Materiel Program Activities.3 The committee benefited from the experience and insights of members who participated in the preparation of each of these prior reports.
This study was conducted under the auspices of the NRC’s Board on Army Science and Technology (BAST). The chair acknowledges the strong support of the BAST
director, Bruce A. Braun, and the project’s study director, Margaret N. Novack. Valuable research and editorial assistance were provided by BAST staff members, Harrison Pannella, James Myska, and Nia Johnson. Detra Bodrick-Shorter provided outstanding logistical support. Finally, the committee’s vice chair, Jeffrey Steinfeld, and each of the committee members contributed critical content and innovative insights that inform this report, and they willingly shared the demanding writing and reviewing tasks in a highly professional and collegial manner.
Charles E. Kolb, Chair
Committee on Monitoring at Chemical Agent Disposal Facilities
Acknowledgment of Reviewers
This report has been reviewed in draft form by individuals chosen for their diverse perspectives and technical expertise, in accordance with procedures approved by the National Research Council’s Report Review Committee. The purpose of this independent review is to provide candid and critical comments that will assist the institution in making its published report as sound as possible and to ensure that the report meets institutional standards for objectivity, evidence, and responsiveness to the study charge. The review comments and draft manuscript remain confidential to protect the integrity of the deliberative process. We wish to thank the following individuals for their review of this report:
Gene H. Dyer, San Rafael, California
B. John Garrick, National Academy of Engineering, Laguna, California
Gary S. Groenewold, Idaho National Engineering and Environmental Laboratory, Idaho Falls
Eugene R. Kennedy, National Institute for Occupational Safety and Health, Cincinnati, Ohio
Sanford S. Leffingwell, HLM Consultants, Auburn, Georgia
Although the reviewers listed above have provided many constructive comments and suggestions, they were not asked to endorse the conclusions or recommendations, nor did they see the final draft of the report before its release. The review of this report was overseen by Royce W. Murray, University of North Carolina. Appointed by the National Research Council, he was responsible for making certain that an independent examination of this report was carried out in accordance with institutional procedures and that all review comments were carefully considered. Responsibility for the final content of this report rests entirely with the authoring committee and the institution.
Figures, Tables, and Boxes
FIGURES
1-1 |
Location and original size (percentage of original chemical agent stockpile) of eight continental U.S. storage sites, |
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2-1 |
Chemical structures of the major components of the U.S. chemical weapons stockpile, |
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3-1 |
Random noise distribution using Gaussian peak, |
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3-2 |
Illustration of simple and complex automated measurements, |
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3-3 |
Depiction of pattern recognition applied to spectral detection of chemical agent, |
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4-1 |
Derivatization of VX, |
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4-2 |
ACAMS/MINICAMS and DAAMS operating ranges for the 1988/1997 GB AELs and required ranges for the CDC’s 2003 GB AELs, |
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4-3 |
ACAMS/MINICAMS and DAAMS operating ranges for the 1988/1997 VX AELs and required ranges for the CDC’s 2003 VX AELs, |
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4-4 |
ACAMS/MINICAMS and DAAMS operating ranges for the 1988 HD AELs and required ranges for the CDC’s 2004 HD AELs, |
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5-1 |
Infrared spectra of GB vapor and HD vapor in the 700 to 1400 cm−1 region, |
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5-2 |
Schematic depiction of open-path FT-IR spectroscopy, |
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5-3 |
Single-beam spectra collected when the furnace from which exhaust was being sampled was operating and not operating but drawing ambient facility air, |
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5-4 |
Schematic diagram of the system used to show the feasibility of SERS measurements of low-concentration explosives in the vapor phase, |
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5-5 |
SERS spectra of TNT, 2,4-DNT, and 1,3-DNB, |
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5-6 |
Electron impact and acetonitrile chemical ionization mass spectra of VX agent, |
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5-7 |
Schematic diagram of a generic chemical ionization mass spectrometry instrument, |
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5-8 |
(A) Swelling occurs as an odorant partitions into the sorption phase. (B) A linear response of an individual sensor signal as a function of concentration is observed for a variety of analytes, |
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5-9 |
(A) Response patterns for three different solvents on a 17-element sensor array. (B) Data in principal component space from a 20-detector array, |
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5-10 |
Photograph of a “nose-chip,” |
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5-11 |
Microsphere sensors loaded onto the end of an optical fiber array, |
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5-12 |
The average fluorescence response patterns of 12 bead sensors, |
5-13 |
Color patterns obtained upon exposure to various chemical agents, |
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5-14 |
(A) Reaction of CWIC reporter with a nerve agent simulant produces a fluorescent reporter molecule. (B) Fluorescence spectrum of CWIC before and after exposure to a nerve agent simulant. (C) Nomadics, Inc.’s prototype handheld system for chemical detection using CWIC, |
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5-15 |
A nanoscale optical biosensor, |
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5-16 |
Reflectivity spectra from a single-layer porous Si film and from a multilayered (rugate filter) porous Si film, |
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5-17 |
Metal ion catalysts containing a phosphorus-fluorine bond, |
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5-18 |
(Left) Handheld nanosensor device for nerve agent developed for the Micro Unattended Ground Sensors program of the Defense Advanced Research Projects Agency. (Right) Testing run showing response to sarin at 10 ppm within 7 minutes of introduction, |
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5-19 |
Peaks exiting the CE chip: (a) methylphosphonic acid, (b) ethyl methylphosphonic acid, and (c) isopropyl methylphosphonic acid, |
TABLES
2-1 |
Physical Properties of Chemical Warfare Agents, |
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2-2 |
CDC’s 1988 and 2003/2004 Recommended Airborne Exposure Limits and U.S. EPA/NRC 2003 Acute Exposure Guideline Levels for GA, GB, VX, and HD, |
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3-1 |
Minimum and Maximum AEL Concentrations for VX, GB, and HD, |
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4-1 |
False-Positive Alarm Rates in 2003 and 2004 for TOCDF ACAMS During VX Operations, |
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5-1 |
Summary of Potential Innovative Chemical Agent Monitoring Technologies, |
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6-1 |
Present Goals and Capabilities of Monitoring Systems, |
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6-2 |
QRA Public Risk Estimates for Three Sites, |
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6-3 |
Airborne Source Terms for Stockpile Sites from Design Basis Accident Scenarios, |
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6-4 |
Airborne Exposure Limits (2005 values) and Vapor Pressure of Agents, |
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6-5 |
One Percent Lethality Doses for the Agents and Exposure Times at IDLH Limit, |
BOXES
Acronyms and Abbreviations
ABCDF
Aberdeen Chemical Agent Disposal Facility (Maryland)
ACAMS
Automatic Continuous Air Monitoring System
A/DAM
Agilent/Dynatherm agent monitor
AEGL
acute exposure guideline level
AEL
airborne exposure limit
AFRL
Air Force Research Laboratory
ANCDF
Anniston Chemical Agent Disposal Facility (Alabama)
ASC
allowable stack concentration
BAST
Board on Army Science and Technology
BMI
Bretby Maintainability Index
CAIS
chemical agent identification set(s)
CB
carbon black composite
CCD
charge-coupled device
CDC
Centers for Disease Control and Prevention
CE
capillary electrophoresis
CI
chemical ionization
CIMS
chemical ionization mass spectrometry
Cl
chlorine
CMA
(U.S. Army) Chemical Materials Agency
CRDS
cavity ringdown spectroscopy
cts
counts
CWA
chemical warfare agent
CWC
Chemical Weapons Convention
CWIC
Chemical Warfare Indicating Chromophore
1,3-DNB
dinitrobenzene
2,4-DNT
dinitrotoluene
DAAMS
Depot Area Air Monitoring System
DART
Direct Analysis in Real-Time
DCD
Deseret Chemical Depot (Utah)
DESI
desorption electrospray ionization
DIMP
diisopropylmethylphosphonate
DMMP
dimethyl methylphosphonate
DOAS
differential optical absorption spectroscopy
DPE
demilitarization protective ensemble
EI
electron impact
EPA
Environmental Protection Agency
FM
frequency modulation
FPD
flame photometric detector
FT-IR
Fourier transform infrared
GA
tabun (a nerve agent)
GB
sarin (a nerve agent)
GC
gas chromatography
GF
cyclosarin
GPL
general population limit
H
sulfur mustard
HD
sulfur mustard (distilled)
hr
hour
HS
sulfur mustard
HT
sulfur mustard, T-mustard mixture
HV
high volume
IDLH
immediately dangerous to life and health
IMS
ion mobility spectrometry
JACADS
Johnston Atoll Chemical Agent Disposal System
JCAD
Joint Chemical Agent Detector
LED
light-emitting diode
LOD
limit of detection
LOQ
limit of quantification
m3
cubic meter
MACT
maximum achievable control technology
MEMS
microelectromechanical systems
mg
milligram
mg/m3
milligram per cubic meter
MINICAMS
Miniature Chemical Agent Monitoring System
mm
millimeter
MPGC
multipass gas cell
MPI
Max Planck Institute
MSD
mass selective detector
ms/ms
mass spectrometry/mass spectrometry
mW
milliwatt
m/z
mass-to-charge ratio
4-NT
mononitroaromatics (incomplete nitration product in the production of TNT)
NaOH
sodium hydroxide
NCAR
National Center for Atmospheric Research
nm
nanometer
NO2
nitric oxide
NOAA
National Oceanic and Atmospheric Administration
NRC
National Research Council
NRT
near real time
OP/FT-IR
open-path Fourier transform infrared
OPH
organic phosphate hydrolase
O,S-DMP
O,S-diethyl methylphosphonothiolate (a by-product in the manufacture of VX)
OSHA
Occupational Safety and Health Administration
P&A
precision and accuracy
PAS
photoacoustic spectroscopy
PBCDF
Pine Bluff Chemical Agent Disposal Facility (Arkansas)
PDARS
process data acquisition and reporting system
PFPD
pulsed flame photometric detector
pg
picogram
PMT
photomultiplier tube
ppb
parts per billion
ppbv
parts per billion by volume
PPE
personal protective equipment
ppt
parts per trillion
QA/QC
quality assurance/quality control
QP
quality plant
QRA
quantitative risk assessment
RCRA
Resource Conservation and Recovery Act
RDX
cyclotrimethylenetrinitramine
RMSEC
root-mean-square error of calibration
RMSEP
root-mean-square error of prediction
s
second
S
sulfur
S/N
signal-to-noise ratio
SAIC
Science Applications International Corporation
SCD
sulfur chemiluminescence detector
SEL
source emission limit
SERS
surface-enhanced Raman scattering
Si
silicon
SMI
storage monitoring and inspection
SO
sulfur oxide
STEL
short-term exposure limit
THF
tetrahydrofolate
TNT
trinitrotoluene
TOCDF
Tooele Chemical Agent Disposal Facility (Utah)
TWA
time-weighted average
UMCDF
Umatilla Chemical Agent Disposal Facility (Oregon)
USACHPPM
U.S. Army Center for Health Promotion and Preventive Medicine
UV
ultraviolet
VLSI
very large scale integrated circuit
VX
a nerve agent
WPL
worker population limit
XSD
halogen-selective detector
Glossary
absorbance.
Log10 (transmitted light intensity/incident light intensity).
absorptivity.
Absorbance divided by path length times concentration.
adsorbent.
Material that causes a species in the supernatant vapor (e.g., air) or liquid phase to bind to its surface.
analyte.
The chemical species being measured; a substance whose identity or chemical composition is to be determined by chemical analysis.
array detector.
A photoelectric detector in which a large number of photosensitive elements are distributed, usually in regularly spaced lines over a rectangular area.
charge-coupled device (CCD).
Chip that stores information in the form of charge packets in an array of closely spaced capacitors. Many video recorders and digital cameras employ CCD chips.
chemical ionization.
The process of ionizing a molecule through a chemical or charge-transfer reaction.
electropherogram.
A record of the variation with time of the signal from a detector used in capillary electrophoresis.
electrospray source.
A dilute solution of an analyte in a solvent, forced through a capillary at high voltage. Charged particles are formed and the solvent evaporates, leaving a charged analyte.
library.
A collection, for example, of sensors (a sensor library), or a database of reference spectra.
Mie scattering.
Light scattering by particles with diameters that are greater than or similar to the wavelength of the scattered radiation, but are too small to yield specular or diffuse reflection.
multipass gas cell.
A cell in which light that has entered the cell is repeatedly reflected through a gaseous sample before it emerges to the detector.
near real time.
<15 minute response (see real time).
neural network.
A data-processing algorithm in which input data are multiplied by a series of weighting factors selected so that an association between the input pattern and a desired output pattern is “learned” by the software. From http://www.webopedia.com/: “A type of artificial intelligence that attempts to imitate the way a human brain works. Rather than using a digital model, in which all computations manipulate zeros and ones, a neural network works by creating connections between processing elements, the computer equivalent of neurons. The organization and weights of the connections determine the output.”
number density.
A measure of concentration, molecules per cubic centimeter.
partition.
The process in which an ensemble of molecules is distributed between two generally immiscible phases, e.g., oil and water. The partition coefficient is the ratio of the final concentrations in each of the two phases.
polarity.
The distribution of charge within a molecule.
preconcentration.
Collection of analyte, typically obtained by drawing air over an adsorbent so as to increase the amount of analyte available for a measurement.
proton affinity.
The negative of the enthalpy change resulting from adding a proton (H+ ion) to a molecule.
quantum efficiency (fluorescence yield).
The ratio of the amount of light reradiated by a molecule following absorption of light, generally on a photon-per-photon basis.
Raman scattering.
Scattering of light by a sample in which the optical frequency is changed by an amount corresponding to a vibrational transition of a molecule in the sample.
Rayleigh scattering.
Scattering of light from particles that are usually much smaller than the wavelength of the light. The incident and scattered light have the same optical frequency.
real time.
1 to 10 second response (see near real time).
retroreflector.
Precision mirror that reflects a beam of light exactly back to its source.
sensor surface functionality.
The chemical structure at the surface of a sensing material.
sensor training.
A type of calibration in which responses are collected from sensors exposed to a series of analytes and are used to create a pattern-recognition algorithm, also called a classifier.
solvatochromic fluorescence indicator.
A fluorescent dye that changes its intensity or color when placed in environments of different polarity.
transferable classifier.
A computer-based pattern-recognition algorithm that can be used on multiple sensor arrays (see sensor training).