Assessment of Agent Monitoring Strategies for the
Blue Grass and Pueblo Chemical Agent Destruction
Pilot Plants
Committee on Assessment of Agent Monitoring Strategies for the Blue Grass and
Pueblo Chemical Agent Destruction Pilot Plants
Board on Army Science and Technology
Division on Engineering and Physical Sciences
NATIONAL RESEARCH COUNCIL
OF THE NATIONAL ACADEMIES
THE NATIONAL ACADEMIES PRESS
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This study was supported by Contract No. W911NF-11-C-0033 between the National Academy of Sciences and the U.S. Army. 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 ASSESSMENT OF AGENT MONITORING STRATEGIES
FOR THE BLUE GRASS AND PUEBLO CHEMICAL AGENT DESTRUCTION
PILOT PLANTS
CHARLES E. KOLB, Chair, Aerodyne Research, Inc., Billerica, Massachusetts
JESSE L. BEAUCHAMP (NAS), California Institute of Technology, Pasadena
ROBERT A. BEAUDET, University of Southern California, Pasadena
JOAN B. BERKOWITZ, Farkas Berkowitz and Company, Washington, D.C.
HAO CHEN, Ohio University, Athens
ADRIENNE T. COOPER, Florida Agricultural and Mechnical University, Tallahassee
FACUNDO M. FERNANDEZ, Georgia Institute of Technology, Atlanta
ROBERT D. GIBBONS (IOM), University of Chicago
JOHN A. MCLEAN, Vanderbilt University, Nashville, Tennessee
MAX D. MORRIS, Iowa State University, Ames
DONALD W. MURPHY (NAE), Bell Laboratories, Lucent Technologies (retired), Davis, California
C. SHANE REESE, Brigham Young University, Mapleton, Utah
LORENZ R. RHOMBERG, Gradient, Cambridge, Massachusetts
ALBERT A. VIGGIANO, Air Force Research Laboratory, Kirtland AFB, New Mexico
Staff
HARRISON T. PANNELLA, Study Director
NIA D. JOHNSON, Senior Research Associate
ANN F. LARROW, Research Assistant
BOARD ON ARMY SCIENCE AND TECHNOLOGY
ALAN H. EPSTEIN, Chair, Pratt & Whitney, East Hartford, Connecticut
DAVID M. MADDOX, Vice Chair, Independent Consultant, Arlington, Virginia
DUANE ADAMS, Independent Consultant, Carnegie Mellon University (retired), Arlington, Virginia
ILESANMI ADESIDA, University of Illinois at Urbana-Champaign
MARY E. BOYCE, Massachusetts Institute of Technology, Cambridge
EDWARD C. BRADY, Strategic Perspectives, Inc., Fort Lauderdale, Florida
W. PETER CHERRY, Independent Consultant, Ann Arbor, Michigan
EARL H. DOWELL, Duke University, Durham, North Carolina
JULIA D. ERDLEY, Pennsylvania State University, State College
LESTER A. FOSTER, Electronic Warfare Associates, Herndon, Virginia
JAMES A. FREEBERSYSER, BBN Technology, St. Louis Park, Minnesota
RONALD P. FUCHS, Independent Consultant, Seattle, Washington
W. HARVEY GRAY, Independent Consultant, Oak Ridge, Tennessee
JOHN J. HAMMOND, Lockheed Martin Corporation (retired), Fairfax, Virginia
RANDALL W. HILL, JR., University of Southern California Institute for Creative Technologies, Playa Vista
JOHN W. HUTCHINSON, Harvard University, Cambridge, Massachusetts
MARY JANE IRWIN, Pennsylvania State University, University Park
ROBIN L. KEESEE, Independent Consultant, Fairfax, Virginia
ELLIOT D. KIEFF, Channing Laboratory, Harvard University, Boston, Massachusetts
WILLIAM L. MELVIN, Georgia Tech Research Institute, Smyrna ROBIN MURPHY, Texas A&M University, College Station
SCOTT PARAZYNSKI, University of Texas Medical Branch, Galveston
RICHARD R. PAUL, Independent Consultant, Bellevue, Washington
JEAN D. REED, Independent Consultant, Arlington, Virginia
LEON E. SALOMON, Independent Consultant, Gulfport, Florida
JONATHAN M. SMITH, University of Pennsylvania, Philadelphia
MARK J.T. SMITH, Purdue University, West Lafayette, Indiana
MICHAEL A. STROSCIO, University of Illinois, Chicago
DAVID A. TIRRELL, California Institute of Technology, Pasadena
JOSEPH YAKOVAC, President, JVM LLC, Hampton, Virginia
Staff
BRUCE A. BRAUN, Director
CHRIS JONES, Financial Manager
DEANNA P. SPARGER, Program Administrative Coordinator
Preface
More than 25 years ago, in 1986, the U.S. Army began destruction of its nearly 30,000-ton legacy of stockpiled chemical agents, stored in approximately 3 million individual munitions as well as numerous bulk agent containers. The nation’s chemical weapons demilitarization effort has succeeded in destroying the chemical munitions and bulk agent stored at six of the eight chemical agent depots located in the continental United States. Chemical weapons that had been deployed abroad and relocated to a storage depot on Johnston Atoll, southwest of Hawaii, have also been successfully destroyed. To date, 90 percent of the original U.S. stockpile has been safely destroyed.
Six of the eight continental chemical stockpiles, as well as the Johnson Atoll site, contained large numbers of assembled chemical weapons as well as bulk agent containers, while the other two continental sites stored only bulk agent containers. The demilitarization facilities that successfully dealt with both assembled weapons and bulk agent at five storage sites used several types of specialized furnaces to incinerate chemical agent and energetic materials and decontaminate metal munitions casings, bulk agent containers, and many agent-contaminated secondary waste streams. The two demilitarization facilities dealing only with bulk agent used chemical neutralization (aqueous-based hydrolysis) reactions to fragment and detoxify the chemical agents and a combination of decontamination solutions and steam to clean the agent containers.
Demilitarization plants for the two remaining chemical weapons depots, which contain the remaining 10 percent of the nation’s chemical agent in assembled chemical projectiles and rockets, are currently under construction. These facilities are funded separately under the DOD’s Assembled Chemical Weapons Assessment (ACWA) program and implemented by a dedicated U.S. Army Element. Local concerns about incineration of chemical weapons forced the Army to design these facilities without the large furnaces used at other assembled chemical weapons demilitarization plants to destroy agent and energetics and to decontaminate many secondary waste materials. The lack of high-throughput furnaces to destroy or decontaminate secondary waste materials creates a need to easily and reliably determine which waste materials are contaminated with agent and if initial decontamination efforts have succeeded. Demilitarization facility closure activities might also be expedited if tools, equipment, and building surfaces could be monitored easily and reliably for agent contamination.
While the Army has developed and successfully used methods to detect chemical agent contamination of various materials, these tend to be indirect and time consuming. Recent advances in analytical instrumentation suggest that it may be feasible to deploy robust portable instruments that can detect and characterize chemical agent contamination
of a wide variety of materials in real time. Formed under the auspices of the Board on Army Science and Technology (BAST), the Committee on Assessment of Agent Monitoring Strategies for the Blue Grass and Pueblo Chemical Agent Destruction Pilot Plants (ACWA Monitoring Committee) was appointed by the National Research Council to survey the capabilities of newly available analytical instrumentation, and to assess how such capabilities might be deployed to better characterize chemical agent contamination of secondary waste materials during agent destruction operations and provide a real-time monitoring tool for contaminated equipment and construction materials during closure activities at the last two U.S. chemical weapons stockpile demilitarization facilities.
In the present report, the ACWA Monitoring Committee presents its findings and recommendations to the Program Manager for Assembled Chemical Weapons Alternatives (PMACWA), whose staff is responsible for the construction, operation, and closure of the last two U.S. chemical weapons stockpile demilitarization facilities. During its deliberations, the committee benefited from the insights and analyses of senior ACWA personnel and wishes to specifically acknowledge detailed inputs about anticipated ACWA operational procedures and requirements from C.J. Anderson and J.M. Kiley. The committee also benefited greatly from the efforts of BAST’s professional staff, including the study director, Harrison T. Pannella, senior research associate Nia D. Johnson, and research assistant and logistics expert Ann F. Larrow.
Charles E. Kolb, Chair
Committee on Assessment of Agent
Monitoring Strategies for the Blue Grass
and Pueblo Chemical Agent Destruction
Pilot Plants
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 (NRC’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:
Charles K. Bayne, Consultant;
John I. Brauman, NAS, Stanford University;
Robert B. Cody, JEOL USA, Inc.;
R. Graham Cooks, Purdue University;
Gary S. Groenewold, Idaho National Laboratory;
M. Douglas LeVan, Vanderbilt University;
Fred W. McLafferty, NAS, Cornell University;
W. Leigh Short, Consultant (retired); and
G. Geoffrey Vining, Virginia Tech.
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 Hyla S. Napadensky, Napadensky Energetics Inc. (retired). Appointed by the NRC, she 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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Contents
2 BGCAPP AND PCAPP DESIGNS AND RELEVANT PROCEDURES USED AT DESTRUCTION FACILITIES
Background on Safety Procedures and Requirements Used at Chemical Agent Destruction Facilities
Pueblo Chemical Agent Destruction Pilot Plant
Blue Grass Chemical Agent Destruction Pilot Plant
Description of the HVAC Systems Used at Both Facilities
3 AGENT MONITORING PRACTICES FOR WASTE GENERATED AT BGCAPP AND PCAPP
Waste Generation and Monitoring Overview
Monitoring Based on Vapor Measurements
Air Monitoring Instrumentation and Methods
Use of DPE Suits During Plant Operations
4 CURRENT STATUS OF SURFACE MEASUREMENT TECHNOLOGIES AND POTENTIAL ACWA SITE APPLICATIONS
Properties of the Target Molecules Relevant to Their Detection by Ambient Mass Spectrometry
Experimental Methods for Ambient Mass Spectrometry
Direct Analysis in Real Time (DART)
Desorption Electrospray Ionization (DESI)
Nonproximate Analysis by Ambient Mass Spectrometry
Potential Roles for Ambient Mass Spectrometry in the ACWA Program
5 STATISTICAL METHODS AND MEASUREMENT
Review of Existing Agent Measurement Approaches
Measurement Bias, Precision, and Detection Limits
Sampling Plans for Spatial Modeling
Sampling Plans for Hot Spot Detection
6 REPORT SUMMATION AND RECOMMENDATIONS
A Biographical Sketches of Committee Members
C Commercial Sources of Ambient Ionization Mass Spectrometry Instrumentation
Tables, Figures, and Boxes
TABLES
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Acronyms and Abbreviations
AAS | atomic absorption spectrometry | |
ACS | agent collection system | |
ACWA | Assembled Chemical Weapons Alternatives | |
AEGLS | acute exposure guideline levels | |
AEL | airborne exposure limit | |
AFAI | air flow assisted ionization | |
ALT | Acquisitions, Logistics & Technology | |
ANCDF | Anniston Chemical Agent Disposal Facility | |
ANR | agent neutralization reactor | |
ANS | agent neutralization system | |
APB | agent processing building | |
APCI | atmospheric pressure chemical ionization | |
BGAD | Blue Grass Army Depot | |
BGCAPP | Blue Grass Chemical Agent Destruction Pilot Plant | |
BRAC | base realignment and closure | |
CAM | cavity access machine | |
CDC | Centers for Disease Control and Prevention | |
CDPHE | Colorado Department of Public Health and the Environment | |
CLLE | continuous liquid-liquid extraction | |
CMA | Chemical Materials Agency (U.S. Army) | |
CWA | Chemical warfare agent | |
CWC | Chemical Weapons Convention | |
DAAMS | depot area air monitoring system(s) | |
DART | direct analysis in real time | |
DESI | desorption electrospray ionization | |
DL | detection limit | |
DMMP | dimethyl methylphosphonate | |
DPE | demilitarization protective ensemble | |
EBH | energetics batch hydrolyzer | |
ECR | explosive containment room | |
ECV | explosion containment vestibule |
EDT | explosive destruction technology | |
ENR | energetics neutralization reactor | |
EPA | Environmental Protection Agency | |
EQL | expected quantitation limit | |
ERB | enhanced reconfiguration building | |
ESI | electrospray ionization | |
ESSI | electrosonic spray ionization | |
FOAK | first-of-a-kind [equipment] | |
GB | a nerve agent (sarin) | |
GC-MS | gas chromatography-mass spectrometry | |
GPL | general population limit | |
H | mustard agent | |
HD | distilled mustard agent | |
HT | distilled mustard mixed with bis(2-chloroethylthioethyl) ether | |
HVAC | heating, ventilation, and air conditioning | |
ICB | immobilized cell bioreactor | |
ICP-MS | inductively coupled plasma mass spectrometry | |
IDLH | immediately dangerous to life or health | |
IP | ionization potential | |
JACADS | Johnston Atoll Chemical Agent Disposal System | |
LADESI | laser ablation/desorption electrospray ionization | |
LCL | lower confidence limit | |
LMQAP | laboratory monitoring quality assurance plan | |
LPMD | linear projectile/mortar disassembly | |
MCP | monitoring concept plan | |
MDB | munitions demilitarization building | |
MDL | method detection limit | |
MINICAMS | miniature continuous air monitoring system(s) | |
MPT | metal parts treater | |
MS | mass spectrometry; mass spectrometer | |
MSM | munitions storage magazine | |
MS/MS | tandem mass spectrometry | |
MTU | munitions treatment unit | |
MVUE | minimum variance unbiased estimate | |
MWS | munitions washout system | |
ND-EESI | neutral desorption-extractive electrospray ionization | |
NECDF | Newport Chemical Agent Disposal Facility |
NRC | National Research Council | |
OLS | ordinary least squares | |
OST | occluded space team | |
PCAPP | Pueblo Chemical Agent Destruction Pilot Plant | |
PCD | Pueblo Chemical Depot | |
PCE | protective clothing and equipment | |
PMACWA | Program Manager for Assembled Chemical Weapons Alternatives | |
PPE | personal protective equipment | |
PQL | practical quantitation limit | |
PVC | polyvinyl chloride | |
RASTIR | remote analyte sampling, transport, and ionization relay | |
RCM | rocket cutting machine | |
RCRA | Resource Conservation and Recovery Act | |
RD&D | research development and demonstration | |
SCWO | supercritical water oxidation | |
SFT | shipping and firing tube | |
SPME | solid phase microextraction | |
STEL | short term exposure limit Tchemical compound ((ClCH2CH2)2SCH2CH2)2O | |
TAP | toxological agent protective | |
TCLP | toxic characteristic leaching procedure | |
TOC | total organic carbon | |
TOF | time-of-flight | |
TSDF | treatment, storage and disposal facility | |
UCL | upper confidence limit | |
UPL | upper prediction limit | |
VOC | volatile organic compound | |
VSL | vapor screening level | |
VX | a nerve agent | |
WAP | waste analysis plan | |
WCL | waste control limit | |
WLS | weighted least squares |