MONITORING AT CHEMICAL AGENT DISPOSAL FACILITIES

Committee on Monitoring at Chemical Agent Disposal Facilities

Board on Army Science and Technology

Division on Engineering and Physical Sciences

NATIONAL RESEARCH COUNCIL OF THE NATIONAL ACADEMIES

THE NATIONAL ACADEMIES PRESS
Washington, D.C.
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Monitoring at Chemical Agent Disposal Facilities MONITORING AT CHEMICAL AGENT DISPOSAL FACILITIES Committee on Monitoring at Chemical Agent Disposal Facilities Board on Army Science and Technology Division on Engineering and Physical Sciences NATIONAL RESEARCH COUNCIL OF THE NATIONAL ACADEMIES THE NATIONAL ACADEMIES PRESS Washington, D.C. www.nap.edu

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Monitoring at Chemical Agent Disposal Facilities THE NATIONAL ACADEMIES PRESS 500 FIFTH STREET, N.W. Washington, DC 20001 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. International Standard Book Number 0-309-09732-0 (Book) International Standard Book Number 0-309-65280-4 (PDF) Cover: Images of decontaminated munitions and containers from a photograph courtesy of Colin Drury. Additional copies of this report are available from the National Academies Press, 500 Fifth Street, NW, Lockbox 285, Washington, DC 20001; (800) 624-6242 or (202) 334-3313 (in the Washington metropolitan area); Internet, http://www.nap.edu. Copyright 2005 by the National Academy of Sciences. All rights reserved. Printed in the United States of America

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Monitoring at Chemical Agent Disposal Facilities THE NATIONAL ACADEMIES Advisers to the Nation on Science, Engineering, and Medicine The National Academy of Sciences is a private, nonprofit, self-perpetuating society of distinguished scholars engaged in scientific and engineering research, dedicated to the furtherance of science and technology and to their use for the general welfare. Upon the authority of the charter granted to it by the Congress in 1863, the Academy has a mandate that requires it to advise the federal government on scientific and technical matters. Dr. Ralph J. Cicerone is president of the National Academy of Sciences. The National Academy of Engineering was established in 1964, under the charter of the National Academy of Sciences, as a parallel organization of outstanding engineers. It is autonomous in its administration and in the selection of its members, sharing with the National Academy of Sciences the responsibility for advising the federal government. The National Academy of Engineering also sponsors engineering programs aimed at meeting national needs, encourages education and research, and recognizes the superior achievements of engineers. Dr. Wm. A. Wulf is president of the National Academy of Engineering. The Institute of Medicine was established in 1970 by the National Academy of Sciences to secure the services of eminent members of appropriate professions in the examination of policy matters pertaining to the health of the public. The Institute acts under the responsibility given to the National Academy of Sciences by its congressional charter to be an adviser to the federal government and, upon its own initiative, to identify issues of medical care, research, and education. Dr. Harvey V. Fineberg is president of the Institute of Medicine. The National Research Council was organized by the National Academy of Sciences in 1916 to associate the broad community of science and technology with the Academy’s purposes of furthering knowledge and advising the federal government. Functioning in accordance with general policies determined by the Academy, the Council has become the principal operating agency of both the National Academy of Sciences and the National Academy of Engineering in providing services to the government, the public, and the scientific and engineering communities. The Council is administered jointly by both Academies and the Institute of Medicine. Dr. Ralph J. Cicerone and Dr. Wm. A. Wulf are chair and vice chair, respectively, of the National Research Council. www.national-academies.org

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Monitoring at Chemical Agent Disposal Facilities 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

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Monitoring at Chemical Agent Disposal Facilities 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

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Monitoring at Chemical Agent Disposal Facilities 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;1 Evaluation 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 1   NRC (National Research Council). 2001. Occupational Health and Workplace Monitoring at Chemical Agent Disposal Facilities. Washington, D.C.: National Academy Press. 2   NRC. 2002. Evaluation of Chemical Events at Army Chemical Agent Disposal Facilities. Washington, D.C.: The National Academies Press. 3   NRC. 2005. Impact of Revised Airborne Exposure Limits on Non-Stockpile Chemical Materiel Program Activities. Washington, D.C.: The National Academies Press.

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Monitoring at Chemical Agent Disposal Facilities 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

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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.

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Monitoring at Chemical Agent Disposal Facilities Contents     EXECUTIVE SUMMARY   1 1   INTRODUCTION   4      Report Genesis,   4      Chemical Demilitarization Challenge,   4      Committee Composition and Statement of Task,   5      Committee Activities,   6      Report Roadmap,   6      References,   6 2   CHEMICAL AGENT MONITORING CHALLENGES   7      Chemical Demilitarization and Storage Monitoring Requirements,   7      Chemical Agent Properties,   7      Chemical Agent Airborne Exposure Limits and Demilitarization Action Levels,   8      General Definitions,   8      Specific Limit Definitions,   9      References,   11 3   PROPERTIES OF MEASUREMENTS AND MEASUREMENT SYSTEMS FOR AIRBORNE AGENTS   12      Monitoring System Properties,   12      Methods of Detection,   12      Open-Path and Point Monitoring,   12      Sensitivity, Selectivity, and Time Response Trade-offs,   13      Limits of Detection and/or Quantification,   13      Selectivity,   14      False Negatives and False Positives (Confirmation),   15      Measurement Time and Measurement Trade-off,   15      Introduction to Sampling for GB, VX, and HD in Air,   15      Data Processing (Signal Processing, Display),   16      Reliability and Maintainability,   18      Operator and Operating Systems Interfaces,   18      References,   20

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Monitoring at Chemical Agent Disposal Facilities 4   CURRENT CHEMICAL AGENT MONITORING SYSTEMS   21      Overview of Current Air Monitoring Systems,   21      Description of the ACAMS and MINICAMS,   21      Description of the A/DAM System,   23      Description of the DAAMS,   23      Performance of ACAMS, MINICAMS, and DAAMS Monitors,   24      Assessment of Current Air Monitoring Systems,   28      Assessment of ACAMS and MINICAMS Monitors,   28      Assessment of the A/DAM System,   29      Assessment of the DAAMS Monitors,   30      Enhancements to Existing Technologies for Monitoring at the CDC’s 2003/2004 Airborne Exposure Limits,   31      Alarm Levels for Near-Real-Time Monitors,   33      Monitoring Data Acquisition Systems at Stockpile Disposal Sites,   36      References,   36 5   PROSPECTIVE INNOVATIVE CHEMICAL AGENT MONITORING TECHNOLOGIES   38      Overview of Optical Detection Technologies,   39      Basic Principles,   39      Long-Path Optical Measurements,   40      Surface-Enhanced Raman Scattering,   44      Overview of Ion Mobility and Mass Spectrometric Techniques,   44      Molecular-Level Chemical Sensors,   49      Electronic or Artificial Noses,   50      New Materials,   54      Lab-on-a-Chip Technology,   57      Summary of Chemical Sensor Technology,   58      Technical Maturity of Innovative Monitoring Technologies,   59      References,   60 6   OPPORTUNITIES FOR IMPROVED CHEMICAL AGENT MONITORING   64      Present Monitoring Needs and Capabilities,   64      Prospects for Improved Ambient Release Monitoring,   67      Fence-Line Monitoring for Community Protection,   67      Demilitarization Facility and/or Storage Area Monitoring,   67      Emergency Response to Major Events,   67      Potential Major Release Scenarios,   68      Scenario 1: Liquid Agent Spills,   68      Scenario 2: Explosive Dispersion of Agent,   69      Scenario 3: Major Releases in a Processing Facility,   70      Summary of Major-Release Scenario Analyses,   70      Applicability of Identified Advanced Monitoring Technologies for Agent Release Scenarios,   70      Technical and Commercial Maturity of Prospective Monitoring Technologies,   71      Open-Path Fourier Transform Infrared Spectroscopy,   71      Chemical Ionization Mass Spectrometry,   71      Ability to Meet Regulatory Requirements,   72      Summary of Opportunities for Improved Airborne Agent Monitoring,   72      References,   72

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Monitoring at Chemical Agent Disposal Facilities 7   FINDINGS AND RECOMMENDATIONS   74      General Airborne Chemical Agent Monitoring Challenges,   74      Airborne Chemical Agent Monitoring with Current Technology,   74      Airborne Chemical Agent Monitoring with Advanced Technology,   75      Summary of Airborne Chemical Agent Monitoring Findings and Recommendations,   76     APPENDIXES         A Biographical Sketches of Committee Members   79     B Committee Meetings and Other Activities   82     C Sense of the Senate on Airborne Chemical Agent Monitoring Systems at U.S. Chemical Stockpile Sites   84

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Monitoring at Chemical Agent Disposal Facilities Figures, Tables, and Boxes FIGURES 1-1   Location and original size (percentage of original chemical agent stockpile) of eight continental U.S. storage sites,   5 2-1   Chemical structures of the major components of the U.S. chemical weapons stockpile,   8 3-1   Random noise distribution using Gaussian peak,   14 3-2   Illustration of simple and complex automated measurements,   17 3-3   Depiction of pattern recognition applied to spectral detection of chemical agent,   17 4-1   Derivatization of VX,   22 4-2   ACAMS/MINICAMS and DAAMS operating ranges for the 1988/1997 GB AELs and required ranges for the CDC’s 2003 GB AELs,   25 4-3   ACAMS/MINICAMS and DAAMS operating ranges for the 1988/1997 VX AELs and required ranges for the CDC’s 2003 VX AELs,   26 4-4   ACAMS/MINICAMS and DAAMS operating ranges for the 1988 HD AELs and required ranges for the CDC’s 2004 HD AELs,   27 5-1   Infrared spectra of GB vapor and HD vapor in the 700 to 1400 cm−1 region,   41 5-2   Schematic depiction of open-path FT-IR spectroscopy,   42 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,   43 5-4   Schematic diagram of the system used to show the feasibility of SERS measurements of low-concentration explosives in the vapor phase,   45 5-5   SERS spectra of TNT, 2,4-DNT, and 1,3-DNB,   45 5-6   Electron impact and acetonitrile chemical ionization mass spectra of VX agent,   46 5-7   Schematic diagram of a generic chemical ionization mass spectrometry instrument,   47 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,   50 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,   52 5-10   Photograph of a “nose-chip,”   53 5-11   Microsphere sensors loaded onto the end of an optical fiber array,   53 5-12   The average fluorescence response patterns of 12 bead sensors,   53

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Monitoring at Chemical Agent Disposal Facilities 5-13   Color patterns obtained upon exposure to various chemical agents,   54 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,   55 5-15   A nanoscale optical biosensor,   56 5-16   Reflectivity spectra from a single-layer porous Si film and from a multilayered (rugate filter) porous Si film,   57 5-17   Metal ion catalysts containing a phosphorus-fluorine bond,   57 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,   58 5-19   Peaks exiting the CE chip: (a) methylphosphonic acid, (b) ethyl methylphosphonic acid, and (c) isopropyl methylphosphonic acid,   59 TABLES 2-1   Physical Properties of Chemical Warfare Agents,   8 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,   9 3-1   Minimum and Maximum AEL Concentrations for VX, GB, and HD,   15 4-1   False-Positive Alarm Rates in 2003 and 2004 for TOCDF ACAMS During VX Operations,   27 5-1   Summary of Potential Innovative Chemical Agent Monitoring Technologies,   60 6-1   Present Goals and Capabilities of Monitoring Systems,   64 6-2   QRA Public Risk Estimates for Three Sites,   68 6-3   Airborne Source Terms for Stockpile Sites from Design Basis Accident Scenarios,   68 6-4   Airborne Exposure Limits (2005 values) and Vapor Pressure of Agents,   68 6-5   One Percent Lethality Doses for the Agents and Exposure Times at IDLH Limit,   69 BOXES 2-1   Why Were the 1988 CDC AELs Changed?   10 4-1   Monitor Set Points and False Alarm Rates,   35 5-1   Detection-Limit Estimates for Open-Path FT-IR Spectroscopy,   42

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Monitoring at Chemical Agent Disposal Facilities 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

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Monitoring at Chemical Agent Disposal Facilities 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

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Monitoring at Chemical Agent Disposal Facilities 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.

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Monitoring at Chemical Agent Disposal Facilities 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).