oEPA
EPA/600/R-15/202 I October 2015 I www2.epa.gov/research
United States
Environmental Protection
Agency
Review of Thermal Destruction
Technologies for Chemical and
Biological Agents Bound on
Materials
Office of Research and Development
National Homeland Security Research Center
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Review of Thermal Destruction Technologies for
Chemical and Biological Agents
Bound on Materials
U.S. Environmental Protection Agency (EPA)
Office of Research and Development (ORD)
National Homeland Security Research Center (NHSRC)
109 T. W. Alexander Drive
RTP,NC 27711
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DISCLAIMER
The United States Environmental Protection Agency through its Office of Research and
Development managed the research described here under Contract No. EP-C-11-038, Task Order
Number 0020 to Battelle. It has been subjected to the Agency's review and has been approved
for publication. Note that approval does not signify that the contents necessarily reflect the
views of the Agency. Mention of trade names, products, or services does not convey official
EPA approval, endorsement, or recommendation.
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TABLE OF CONTENTS
LIST OF ACRONYMS 7
1 INTRODUCTION 14
1.1 Proj ect B ackground 14
1.2 Quality Assurance for Sources of Secondary Data 15
1.3 Background of Chemical and Biological Agents 16
2 THERMAL TECHNOLOGIES FOR THE DESTRUCTION OF CHEMICAL AND
BIOLOGICAL AGENTS BOUND ON MATERIAL SURFACES 20
2.1 Incineration/Combustion 20
2.2 Hazardous Waste Combustors 21
2.2.1 Municipal Waste Combustors 28
2.3 Medical Waste Incinerators 28
2.4 Chemical Weapon Demilitarization 30
2.4.1 Metal Parts Furnaces 30
2.4.2 Liquid Incineration 33
2.4.3 Plasma Pyrolysis 35
2.4.4 Pollution Abatement of Chemical Weapon Demilitarization 35
2.5 Emission and Aerosol Containment 36
2.6 Plasma Systems 41
2.6.1 Thermal Plasma 41
2.6.2 Cold Plasma 43
2.7 Mi crowave Irradi ati on 51
2.8 Autoclave 59
2.9 Landfill Flares 61
2.10 Bench-Scale Flame Mechanism Studies 62
2.11 Exothermic Intermetallic Interaction 63
2.12 Direct Heat Application 65
3 NEUTRALIZATION/HYDROLYSIS AND TREATMENT OF HYDROLYSATE 71
3.1 Neutralization/Hydrolysis 71
3.2 Treatment of Hydrolysate 72
3.2.1 Incineration of Hydrolysate 73
3.2.2 Supercritical Water Oxidation of Hydrolysate 73
3.2.3 Biological Treatment of Hydrolysate 76
3.2.4 Treatment of Hydrolysate Using Photoactivated Periodate 78
4 INCINERATOR MODELING RESULTS 80
4.1 COM Model 84
4.1.1 Gas Temperature 84
4.1.2 Minimum Piece Temperature 85
4.1.3 CB Agents Remaining 86
4.2 Stoker Model 87
4.2.1 Gas Temperature 87
4.2.2 Minimum Piece Temperature 88
4.3 MEDPATH Model 89
4.3.1 Gas Temperature 89
4.3.2 Minimum Piece Temperature 90
4.3.3 Agent Left 90
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5 CREMATION OF HUMAN REMAINS FOLLOWING CHEMICAL AND
BIOLOGICAL AGENT INCIDENTS 92
5.1 U.S. Military Protocols 92
5.2 UK Protocols 93
6 CONCLUSIONS 95
7 REFERENCES 96
LIST OF TABLES
Table 2-1. Chemical Agent Structure and Physical Properties 18
Figure 2-1. Ceiling Tile Bundle Spore Survival as a Function of Time in Kiln (Adapted with
permission from Wood et al., 2006) 23
Figure 2-2. The Effect of Heating Temperature and Time on Reduction of B. subtilis Spiked on
Ceiling Tile (Adapted with permission from Lemieux et al., 2005) 24
Figure 2-3. Log Reduction of G. stearothermophilus Bis in Ceiling Tile Bundles (Wet and Dry)
vs. Time in RKIS (Reprinted with permission from Wood et al., Copyright 2008 American
Chemical Society). 95% Confidence Interval (CI) 25
Figure 2-4. Histogram Showing Percent Survival of Both G. stearothermophilus and B.
atrophaeus Bis Versus the Maximum Temperature Inside the Bundle (Adapted with
permission from Wood et al., 2010) 26
Figure 2-5. Log Reduction with Time for B. subtilis on Wallboard at Various Initial
Temperatures (Adapted with permission from Denison et al., 2002 [Reaction Engineering
International]) 27
Figure 2-6. Comparison between Measured Data and Model Calculations of the Kiln Exit
Temperature for B. subtilis (Adapted with permission from Denison et al., 2005 [Reaction
Engineering International]) 27
Figure 2-7. Gas Temperature Distribution in the Afterburner of the Three-Zone MPF (Adapted
with permission from Denison et al., 2002 [Reaction Engineering International]) 31
Figure 2-8. Comparison of HD Destruction Kinetics with Experimental Data (Adapted with
permission from Denison et al., 2002 [Reaction Engineering International]) 32
Figure 2-9. Calculated Time Profiles for Zone 1 with 155 mm Projectiles with 5% Residual
Agent Added in a Three-Zone Furnace (Adapted with permission from Denison et al., 2002
[Reaction Engineering International]) 33
Figure 2-10. Calculated Destruction of VX, GB, HD, and H in a Plug Flow Reactor with Two-
Second Residence Time Versus Temperature (Adapted with permission from Denison et al.,
2004 [Reaction Engineering International]) 34
Figure 2-11. LIC Primary and Secondary Chambers with VX Agent Destruction Depicted by
Streamlines (Adapted with permission from Denison et al., 2004 [Reaction Engineering
International]) 34
Figure 2-12. Comparison of Total Furan and Dioxin Emissions for Burn Barrels and Municipal
Waste Incinerators (Adapted with permission from Lemieux et al., 2000) 41
Figure 2-13. Plot of Percent Kill Versus Target Velocity for G. stearothermophilus Spores on
Fiberglass with and without a Lens to Block Heat from the Steam-Plasma Torch (© 2000
IEEE. Reprinted, with permission from Farrar et al.) 43
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Figure 2-14. Atmospheric Pressure Plasma Jet (APPJ) (left); Destruction of the Anthrax
Surrogate Bg Using the APPJ Method Compared to the Dry Heat treatment (right) (Adapted
from Rosocha et al., 2003 with the permission of the Los Alamos National Laboratory)... 46
Figure 2-15. Destruction of Malathion using the APPJ Method as Compared to the Dry Heat
Treatment (Adapted from Rosocha et al., 2003 with the permission of the Los Alamos
National Laboratory) 46
Figure 2-16. Residual VX Remaining on Aluminum as a Function of Exposure Time (T = 70 °C,
d = 10 cm, Pressure = 30 torr, O2 or H2 at 10 % (Reproduced with permission from
Herrmann et al. Copyright 2000, AIP Publishing LLC.) 47
Figure 2-17. Residual HD Remaining on Aluminum (left) and Residual GD Remaining on
Aluminum (right) Versus Time. Test Conditions: T = 70 °C, d = 10 cm, Pressure = 30 torr,
O2 or H2 at 10 % (Reproduced with permission from Herrmann et al. Copyright 2000, AIP
Publishing LLC.) 47
Figure 2-18. Live Cells Versus Exposure Time for B. subtilis in Luria-Bertani Broth with
Applied Power of 42 W (left). SEM Photograph of E. coli on Plasma-Exposed Sample after
30 Seconds Exposure Time (right) (© 2000 IEEE. Reprinted, with permission from
Laroussi et al.) 49
Figure 2-19. Survivors of Bacterial Cells Inoculated on Polypropylene with Time with the
Application of OAUGDP (left). The Transmission Electron Micrograph of OAUGDP-
treated Cells: A) Initial E. coli, B) E. coli after 30 Seconds of Exposure, C) Initial S. aureus,
and D) S. aureus after 30 Seconds of Exposure (right) (© 2000 IEEE. Reprinted, with
permission from Montie et al.) 50
Figure 2-20. Airborne Exposure of B. subtilis var. niger, P. fluorescens and A. versicolor to
Microwave Irradiation at 700, 385, and 119 W for 1.5 Minutes (Adapted from Wu and Yao,
2010 with permission from Elsevier, Inc.) 52
Figure 2-21. Liquid-borne Exposure of B. subtilis var. niger to Microwave Irradiation at 700,
385, and 119 W (Adapted from Wu and Yao, 2010 with permission from Elsevier, Inc.).. 53
Figure 2-22. SEM Images of Liquid-borne Control and Exposed P. fluorescens, A. versicolor
and B. subtilis var. niger with 700 W and 90 Seconds Exposure Time (Reprinted from Wu
and Yao, Copyright 2010, with permission from Elsevier, Inc.) 53
Figure 2-23. Dynamic In-Flight On-Filter Disinfection of B. subtilis with Microwave
Application Time at 250, 500, and 750 W Power Levels (Reprinted from Zhang et al.,
Copyright 2010 with permission from Elsevier, Inc.) 55
Figure 2-24. SEM Images of (a) TiC>2 Nanofibers, (b) Millipore high efficiency particulate
arrestance (HEPA) filter, and (c) Military HEPA (Wu et al., 2009, Published by DTIC, No
Permission Required) 56
Figure 2-25. Percent Destruction of DMMP for Different V2O5 Catalysts (Cha et al., 2004,
Published by DTIC, No Permission Required) 57
Figure 2-26. Percent Destruction of DES for Different V2O5 Catalysts (Cha et al., 2004,
Published by DTIC, No Permission Required) 58
Figure 2-27. Parametric Test Output for the Destruction of DES Simulant (Cha et al., 2004,
Published by DTIC, No Permission Required) 58
Figure 2-28. Effect of Second Autoclave Cycle on Spore Survivability, Temperature with Time
(Adapted with permission from Lemieux et al., 2006a) 60
Figure 2-29. Effect of Packing Density for Wallboard, Temperature with Time (Adapted with
permission from Lemieux et al., 2006a) 61
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Figure 2-30. Dry Heat D-values and Z-values for Biological Indicators (Geobacillus
stearothermophilus [squares], B. cmthracis [circles], and B. atrophaeus [triangles])
(Adapted with permission from Wood et al., Copyright 2009 The Society for Applied
Microbiology) 66
Figure 2-31. Evaporation Profiles at Different Temperatures and Drop Size for HD at an Air
Flow of 175 SLPM (Reprinted from Jung and Lee, Copyright 2014 with permission from
Elsevier Inc.) 68
Figure 3-1. Time Course of Strain T09 with TDG at 30 °C Grown Aerobically, Closed Circles
(Residual TDG Concentrations) and Open Circles (Cellular Growth) (Reprinted from Bassi
et al., Copyright 2009 with permission from Elsevier, Inc.) 78
Figure 4-1. Modeling Concept 80
Table 4-1. Experimental Design Factors for CFS Model 82
Figure 4-2. CFS COM Model Bundle Input Parameters 83
Figure 4-3. COM Model, Gas Temperature 84
Figure 4-4. COM Model, Minimum Piece Temperature 85
Figure 4-5. COM Model, Agent Left 86
Figure 4-6. Stoker Model, Gas Temperature 87
Figure 4-7. Stoker Model, Minimum Piece Temperature 88
Figure 4-8. MEDPATH Model, Gas Temperature 89
Figure 4-9. MEDPATH Model, Minimum Piece Temperature 90
Figure 4-10. MEDPATH Model, Agent Left 91
Figure 5-1. Flow Diagram for Processing Contaminated Remains (Published by US Army, 2003,
No Permission Required) 93
APPENDICES
Appendix A: Summary Table of Thermal_Processes for CB Agent Destruction
Appendix B: Compiled References Worksheet
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LIST OF ACRONYMS
ACF
activated carbon fiber
ANOVA
analysis of variance
APD
atmospheric plasma decontamination
APPJ
Atmospheric Pressure Plasma Jet
Ba
Bacillus anthracis
BDR
building decontamination residue
Bg
Bacillus globigii
BI
biological indicator
bp
boiling point
BWA
biological warfare agent
BW
biological weapon
CAA
Clean Air Act
CARC
chemical agent resistant coating
CAM
chemical agent monitor
CB
chemical or biological
CB
chlorobenzene
CBR
chemical, biological or radiological
CBRNIAC
Chemical, Biological, Radiological and Nuclear Information Analysis Center
CFD
computational fluid dynamics
CFS
configured fireside simulator
CFU
colony forming unit(s)
CI
confidence interval
C02
carbon dioxide
COM
commercial hazardous waste burning rotary kiln
CP
chlorophenol
CWA
chemical warfare agent
CWC
Chemical Weapons Convention
DC
direct current
D/F
dioxin/furan
DES
diethyl sulfide
DFP
diisopropyl fluorophosphate
DFS
deactivation furnace system
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DEVEP diisopropyl methylphosphonate
DMMP dimethyl methylphosphonate
DMOR Disaster Mortuary Operational Response (Team)
DNA deoxyribonucleic acid
DoD Department of Defense
DTIC Defense Technical Information Center
DTP 3,3-dithiopropanol
DRE destruction and removal efficiency
DSA drop shape analysis
DST decision support tool
ECDAP enhanced corona discharge at atmospheric pressure
EPA U.S. Environmental Protection Agency
FTCMR flow-through catalytic membrane reactor
GA tabun
GB sarin
GC/MS gas chromatograph/mass spectrometry
GD soman
GDAP glow discharge at atmospheric pressure
GE ethyl sarin
GF cyclosarin
GH O-isopentyl sarin
GS S-butyl sarin
(is G. stearothermophilus
HAP hazardous air pollutant
HC1 hydrogen chloride
HCWA hydrolysates of chemical warfare agents
HD sulfur mustard
HDIAC Homeland Defense and Security Information Analysis Center
HEPA high efficiency particulate arrestance
HF hydrogen fluoride
HRT hydraulic retention time
HVAC heating, ventilating and air conditioning
HWC hazardous waste combustor
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HWI
hazardous waste incinerator
ICB
immobilized cell bioreactor
IPE
individual protective equipment
IZAYDAS
Izmit Hazardous and Clinical Waste Incinerator
JACADS
Johnson Atoll Chemical Agent Disposal System
kW
kilowatt
LANL
Los Alamos National Laboratory
LIC
liquid incinerator
LVOH
low volatility organohalogen (compound)
MACT
maximum achievable control technology
MEDPATH
medical/pathological waste incinerator
MOPP
mission-oriented protective posture
mp
melting point
MPA
methylphosphonic acid
MPF
metals parts furnace
MPT
microwave plasma torch
MW
megawatt
MWI
medical waste incinerator
MWC
municipal waste combustor
NHSRC
National Homeland Security Research Center
NIEHS
National Institutes of Environmental Health Sciences
NTIS
National Technical Information Service
OAUGDP
one atmosphere uniform glow discharge plasma
OPC
organophosphorus compound
PAN
polyacrylonitrile
PCAPP
Pueblo Chemical Agent-Destruction Pilot Plant
PCB
Polychlorinated biphenyl
PCDD
polychlorinated dibenzo-p-dioxin
PCDF
polychlorinated dibenzofuran
PIC
product of incomplete combustion
PNPDPP
para-nitrophenyl diphenylphosphate
POHC
principal organic hazardous constituent
ppm
part(s) per million
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PWC
plasma waste converter
QA
Quality Assurance
QAPP
Quality Assurance Project Plan
RF
radio frequency
RHELP
regenerative high efficiency low pressure
RKIS
rotary kiln incinerator simulator
rms
root mean square
RNA
ribonucleic acid
ROS
reactive oxygen species
see
secondary combustion chamber
SCWO
supercritical water oxidation
sew
supercritical water
SEM
scanning electron microscope
S02
sulfur dioxide
SRT
sludge retention time
STAATT
State Territorial Association Alternative Treatment Technologies
STO
stoker furnace
TD
thermal desorption
TDG
thiodiglycol
TEM
transmission electron micrography
TEQ
toxicity equivalent quantity
TOCDF
Tooele Chemical (Agent) Disposal Facility
TP AC
transduction-polymer and an acceptor-chromophore
TSDF
treatment, storage, or disposal facility
TTU
Texas Tech University
TX
1,4-thioxane
UK
United Kingdom
VOC
volatile organic compound
VR
Russian VX
VX
nerve agent
VXH
VX hydrolysate
W
watt
WMD
weapon of mass destruction
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ACKNOWLEDGMENTS
We would like to thank the following EPA staff members, outside organizations, and contractors
for their ongoing participation in this effort:
Ierardi, Mario
Lemieux, Paul
Oudejans, Lukas
Serre, Shannon
Wood, Joseph
EPA Office of Resource Conservation and Recovery (ORCR)
EPA National Homeland Security Research Center (NHSRC)
EPANHSRC
EPA Office of Emergency Management (OEM)
EPANHSRC
Outside Organizations
Reaction Engineering International (REI)
Contractors
Battelle Memorial Institute
Questions concerning this document or its application should be addressed to:
Paul Lemieux
National Homeland Security Research Center
Office of Research and Development
U.S. Environmental Protection Agency
Mail Code E343-06
Research Triangle Park, NC 27711
919-541-0962
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ABSTRACT
There is interest in identifying appropriate operating conditions to assure that thermal destruction
processes would result in complete destruction of any residual Chemical or Biological (CB)
agents bound on materials removed from contaminated sites. Compiling these operating
conditions, along with data on their efficacy, would greatly facilitate the management of waste
generated during cleanup following a CB contamination incident.
This review report gathered available information on the thermal destruction of CB agents bound
on solid materials. This review used information extracted from secondary data sources
including government reports, publications in the open literature, peer-reviewed journal articles,
and both published and non-published literature, including distribution limited reports. The
literature search included searches in the Dialog database, Google Scholar™, and active
identification of EPA research reports that were in varying stages of completion. Thermal
processes reviewed in this report include incineration, thermal plasma systems, microwave
irradiation, autoclaving, landfill flaring, exothermic intermetallic interaction, and direct heat
application. A description of the materials tested and operating conditions such as exposure
times, temperatures, and plasma flow rates and the corresponding CB reductions are included. A
summary table of the operating conditions and results from the thermal processes and
hydrolysate treatment discussed in this review are presented in Appendix A. In addition, a
review of the containment of aerosols and emissions from the incineration of CB material is also
discussed. The results of modeling of the designs of several incinerators burning CB materials
are also presented in this report.
The treatment of hydrolysate wastewater from neutralization of chemical agents with
supercritical water oxidation, incineration, and biological treatment are also discussed. The test
conditions, contact times, concentrations of chemicals and destruction efficiencies are included.
This review also discusses the available literature on the cremation of human remains after CB
contamination incidents. Specifically, literature protocols on the cremation of contaminated
human remains, including the required temperature and time, are discussed.
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This report reviewed literature on the destruction of CB agents and surrogates bound on various
materials such as ceiling tiles, wallboard, carpet, fiberglass, aluminum, concrete, pumice, stone,
wood, stainless steel, laminate, asphalt, brick, and others.
The studies showed that CB agents bound on porous materials such as ceiling tiles and carpet
bundles may require more exposure time to destroy CB agents than the CB agents bound on
nonporous materials. Furthermore, wet porous materials required more exposure time than dry
porous materials due to the large amount of water they can hold that must be boiled off prior to
heating the material beyond the boiling point of water. For example, Wood et al. (2006) reported
that at 800 °C, dry ceiling tiles achieved 6 logio reduction in spores after 12 minutes for an
anthrax surrogate, but up to 38 minutes was required for complete reduction with wet ceiling
tiles. Farrar et al. (2000) reported only partial destruction for the biological agent surrogate B.
stearothermophilus on a pumice block using a steam plasma torch (4,500 °F, up to 2 ft/s at a
distance of 1 inch from the exit plane) whereas 99.94% destruction was achieved on fiberglass
using the same test conditions.
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1 INTRODUCTION
This section discusses the project background, sources of secondary data used to compile this
report, the Quality Assurance (QA) of the references, and a background of Chemical or
Biological (CB) agents.
1.1 Project Background
EPA is designated as a coordinating Agency, under the National Response Framework, to
prepare for, respond to, and recover from a threat to public health, welfare, or the environment
caused by actual or potential oil and hazardous materials incidents. Hazardous materials include
chemical, biological, and radiological substances, whether accidentally or intentionally released.
Many items removed from contaminated areas either before or after contamination may be
treated using incineration or thermal destruction. Whether or not these items have undergone
decontamination operations, due to limitations in laboratory capacity, these items may or may
not be fully characterized with respect to the presence/absence of residual CB agents. Because
of this limitation, identifying packaging and incinerator or thermal destructor operating
conditions to assure that thermal destruction processes would result in complete destruction of
any residual CB agent bound on these items will greatly facilitate the management of the waste
generated during cleanup of a CB contamination incident.
This review report gathered available information on the thermal destruction of CB agents bound
on solid materials such as building materials. Results from this review will help address an
identified gap related to defining conditions under which effective thermal destruction can be
performed on solid materials resulting from cleanup following a CB contamination incident.
Thermal processes discussed include incineration, plasma systems, microwave irradiation,
autoclaving, landfill gas flaring, exothermic intermetallic interaction, and direct heat application.
The containment of aerosols and emissions from the incineration of CB material is also
discussed.
Neutralization and hydrolysis of chemical agents is discussed in this review. The treatment of
hydrolysate wastewater from neutralization of chemical agents by supercritical water oxidation,
incineration, and biological treatment is also discussed.
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This review also discusses the available literature on the cremation of human remains after CB
contamination incidents. Although the disposition of human remains is not part of EPA's
mission in the CB response area, the environmental consequences of the disposition of those
remains are part of EPA's mission to protect public health and the environment.
In addition, incineration models were conducted using EPA's Configured Fireside Simulator
(CFS) tool for four CB agents (Bacillus cmthrcicis [Ba], sarin [GB], VX, and mustard [HD]) and
three design types of furnaces (a commercial hazardous waste-burning rotary kiln, a
medical/pathological waste incinerator, and a stoker incinerator). The results from the incinerator
models are presented in this report.
Chemical (/®\) and biological (^/) icons are included in the headings of each section to
represent the type of contaminant discussed in the section.
1.2 Quality Assurance for Sources of Secondary Data
This review used information extracted from secondary data sources including government
reports, publications in the open literature, peer-reviewed journal articles, and both published and
non-published literature, including limited distribution reports. Secondary data are defined as
existing data (also termed non-direct measurements) that were not developed originally through
the project to which they are being applied. Applicable secondary data were sought from the
various sources of scientific literature. The literature search included searches in the Dialog
database, including Energy Science & Technology (formerly DOE ENERGY) and the National
Technical Information Service (NTIS), the Homeland Defense and Security Information
Analysis Center (HDIAC) managed by the Defense Technical Information Center (DTIC)
[formerly the Chemical, Biological, Radiological and Nuclear Information Analysis Center
(CBRNIAC)], Google Scholar™, and active identification of U.S. Environmental Protection
Agency (EPA) research reports that are in varying stages of completion. Battelle presented EPA
with the search criteria prior to embarking on the literature search.
The literature review not only identified but also assessed the secondary data for intended use(s).
After the literature searches were conducted and the results subsequently reviewed, the quality of
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the secondary data was examined against the overall needs of the Task Order (TO). The quality
of identified sources of secondary data was evaluated through a literature assessment factor
rating. Based on the numerical rating factor score of each source of secondary data, collected
information was deemed either appropriate or inappropriate for inclusion in the results. Results
are listed in the Excel® spreadsheet grouped by relevance (as determined by the rating factor) to
assist with the selection criteria for quality documents (presented in Appendix B). Articles and
reports were also assessed qualitatively according to document type and documented in the
Excel® spreadsheet. Each report or article referenced in the Excel® spreadsheet was identified
with the appropriate document type designation. Knowledge of the document type will help
EPA (or other readers/reviewers identified by EPA over the course of the TO) in understanding
the range of documents obtained.
All secondary data and source information compiled underwent an independent review (at least
10% of all secondary data mined from the literature) with regard to transcriptional accuracy in
the Excel® summary table (presented in Appendix B) by Battelle's Quality Assurance (QA)
Manager. This review was conducted for initial transcription of data from the secondary data
source and for each point of data transfer in process, including use of the data in the final
literature review report. This review confirmed that the populated literature search included
relevant information on thermal destruction of CB agents bound on different types of materials,
for which the sources of information are credible, and that proper information is included in the
correct categories. This review also ensured that the correct source of the data is maintained
throughout all processes using the data.
1.3 Background of Chemical and Biological Agents
Chemical warfare agents (CWAs) fall into three main classes: vesicants (e.g., sulfur mustards
(HD), nitrogen mustards (HN3)), blood agents (e.g., hydrogen cyanide), and organophosphorus
nerve agents (acetylcholinesterase inhibitors) of the G- type (tabun [GA], GB, soman [GD], ethyl
sarin [GE], cyclosarin [GF], S-butyl sarin [GS], O-isopentyl sarin [GH]) and V (VX, VE, VG,
VM). Biological warfare agents (BWAs) can be classified into at least five categories: viruses,
bacteria (spore-formers and vegetative bacteria), rickettsia, biological toxins, and genetically
engineered agents (Giletto et al., 2003). The physical properties of VX, mustard, and sarin are
presented in Table 2-1.
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Agents that are liquids at room temperature with high boiling points and low vapor pressures
such as HD and VX are classified as persistent agents that generally manifest themselves as
contact poisons. A persistent agent could pose long-term cutaneous and ingestion hazards, along
with an inhalation hazard upon slow evaporation. GB is not typically considered to be a
persistent agent, especially compared to HD and VX. HD would be difficult to remove through
water washing because of its insolubility, and VX may be difficult to remove with evaporation or
dispersion because of its high boiling point and low vapor pressure. All of these chemical agents
interact with materials that alter the fate and transport of the contaminant. An agent can be
absorbed into porous materials and drawn by capillary action into material seams and crevices.
Adsorption and infiltration of an agent may result in degradation of materials and can lead to
unexpected persistence of the agent, even after measures have been taken to decontaminate
(Hoette et al., 2010).
Bacterial endospores (e.g., B. anthracis) can survive in the environment for an extended period
of time and are resistant to a wide variety of treatments such as heat, desiccation, radiation,
pressure and chemicals. This resistance is the result of various factors such as the thick
proteinaceous spore coat, low water content in the spore core, and the a/b-type small, acid-
soluble spore proteins (Rogers, 2005).
Most CB agents can be destroyed or rendered harmless by suitable chemical treatments (Giletto
et al., 2003). There is no single technology that will be applicable in all situations and to all
types of contamination because the nature and extent of the contamination is different at different
places (Kumar et al., 2010). The optimal decontamination technology for a given application
generally depends on the material that is potentially contaminated. For instance, the optimal
technology for decontaminating wastewater may differ from the optimal technology for
decontaminating building materials (Wilhelmi et al., 2003).
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Table 2-1. Chemical Agent Structure and Physical Properties
Chemical Agent
Physical State
(at 25°C)
Vapor Pressure
mm Hg
(at 20 °C)
Water Solubility
(g/100 g Soln.)
Name
Code
Type
VX
VX
Nerve
liquid, mp: 39 °C,
bp: 298°C
0.0007
3.0 (at 25 °C)
Mustard
HD
Blister
liquid, mp: 14.5 °C,
bp: 218°C
0.0072
0.92 (at 22 °C),
limited
Sarin
GB
Nerve
liquid, mp: -56 °C,
bp: 158°C
2.1
miscible
ioette et al., 2010, Sandia Report); mp: melting point;
jp: boiling point.
The materials to be thermally treated may be primarily concrete or metal if CB agents are
released in urban areas, although there may be large quantities of other materials as well.
Concrete materials include walls, floors, ceilings, bio-shields, and fuel pools. Metallic materials
include structural steel, valves, pipes, glove boxes, reactors, and other equipment. Porous
materials such as concrete can be contaminated throughout their structure, although
contamination in concrete normally resides in the top quarter-inch below the surface. Metals are
normally only contaminated on the surface (Kumar et al., 2010). There may be varying amounts
of porous materials that make up a building's contents. Further, more porous materials like
ceiling tiles are much harder to decontaminate effectively than less porous materials (Wilhelmi et
al., 2003).
Non-thermal processes to destroy CB agents bound on materials are prevalent in literature, and
frequently the residuals resulting from application of these technologies may undergo thermal
treatment as part of the waste management process. Decontamination efficiency depends on
various factors: not only the characteristics of the agent, but also the weather conditions, the bio-
load on the material, and the type of material that is contaminated. Smooth surfaces painted with
chemical agent resistant coating (CARC) are relatively easy to clean with an effective
decontaminant, whereas the same decontaminant may not be able to clean more complex
structures with cracks or crevices or absorbing materials such as rubber sufficiently (Boone,
2007).
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The appropriate decontamination strategy also depends on the size of the contaminated area. If a
chemical or biological agent exists only in a small area (e.g., within one room), then spot
decontamination methods may be appropriate; however, spot decontamination is not feasible for
contamination over broad areas. The extent of the contaminated area may also affect the
decision on whether to conduct decontamination activities on site or at a remote location
(Wilhelmi et al., 2003).
Lemieux described I-WASTE, a web-based decision support tool (DST) developed by EPA to
assist decision makers through the process of planning the disposal of residual contaminated
materials. The web tool allows the user to create a decision scenario with the following input
parameters: incident location, type of waste material, waste quantity estimation,
contaminant/decontaminant selection, treatment specifications (including incinerators, landfills,
and wastewater treatment), and transportation plan (Lemieux et al., 2006b).
A universal formulation that can decontaminate all CB threats is not available. Existing
decontamination solutions are effective only against a certain class of agents. To be effective,
emergency response personnel would need several types of decontaminants available on hand.
For complicated treatment technologies, there will be less people available to operate them. Use
of existing decontaminants under inappropriate conditions can result in the formation of
dangerous by-products. The formation of these by-products may complicate a waste
management facility's willingness to accept the waste. Furthermore, some chemicals such as
sodium hydroxide dissolved in organic solvents are unsuitable for use under certain conditions
because they corrode, etch or erode materials (Giletto et al., 2003).
Current military decontamination techniques aimed at CW agents are corrosive and can cause
collateral damage to facilities and equipment. The military requires fast action (30 min or less),
whereas decontamination times on the order of several hours may be sufficient for the civilian
sector. Rather than speed, considerations that are more important in a civilian scenario include
availability of a reagent, low maintenance, ease of application, minimal training for application,
easy deployment by a variety of dispersal mechanisms and acceptable expense (Raber et al.,
2002).
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2 THERM AT, TECHNOLOGIES FOR THE DESTRUCTION OF
CHEMICAL AND BIOLOGICAL AGENTS BOUND ON MATERIAL
SURFACES^
This section presents a review of the following thermal processes for the destruction of CB
agents bound on material surfaces: incineration/combustion, plasma systems, microwave
irradiation, autoclave, landfill flare, flame mechanisms, exothermic intermetallic interactions,
and direct heat sterilization.
2.1 Incineration/Combustion
This sub-section reviews the literature on the incineration of CB agents, including processes such
as chemical weapons demilitarization including metals parts furnaces (MPFs), and liquid
incinerators (LICs) and processes using hazardous waste combustors (HWCs), municipal waste
combustors (MWCs), and medical waste incinerators (MWIs). In addition, the literature on
containment of emissions and aerosols from the incineration of CB agents is discussed.
Overall, there is a dearth of information in the literature on the destruction of CB agents at
MWCs and MWIs. The majority of the literature on the destruction of CB agents using
incineration involves the use of hazardous waste combustors in specially designed chemical
demilitarization facilities. Literature on the neutralization of stockpiled munitions and
subsequent secondary treatment by an HWC is also prevalent.
Incineration is an inherently attractive approach for destruction of organic compounds since the
carbon and hydrogen in the organic compound produce carbon dioxide and water when burned in
the presence of oxygen. Chemical warfare agents are combustible and therefore lend
themselves to destruction by incineration. The incineration products are far less toxic than the
original chemical warfare agents. In principle, incineration is an environmentally safe method of
toxic waste treatment provided that the temperature and residence time used are sufficient to
decompose the organic chemical to simple inorganic chemicals (Pearson and Magee, 2002) and
that the downstream flue gas cleaning equipment is sufficient to remove particulate matter and
acid gases and all other air pollutants from the stack gases that are emitted into the atmosphere.
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2.2 Hazardous Waste Combustors
Fixed hearth and rotary kiln incinerators are the most likely candidates to manage wastes
containing biological and chemical agents. Advantages of using these HWCs include the fact
that regulations already require these incinerators to have waste tracking mechanisms,
appropriate emission controls, and employee safety training programs. Possible disadvantages
include the location of most HWCs in relatively remote areas, the limited capacities of HWCs,
and size limitations. Some sizes of rotary kiln HWCs can process between 50 and 175 tons of
hazardous waste per day. Typically, the sizing for the feed stream to allow entry into the
combustor is the rough dimensions of a 55-gallon drum (Wilhelmi et al., 2003).
The afterburner is a critical part of the incineration system as it uses an auxiliary fuel such as
natural gas, propane, or fuel oil to ensure that temperatures in excess of 1,090 °C and gas-phase
residence times of 2 seconds or greater are achieved to ensure that any residual agent or products
of incomplete combustion are destroyed.
Spent decontamination fluids may also be injected into either the primary chamber or the
afterburner to destroy any residual agent in such fluids as well as to facilitate the evaporation and
discharge of the water vapor. This decontamination fluid also contains salts, which are deposited
in the bottom of the primary chamber or afterburner (Pearson and Magee, 2002).
Lemieux et al. (2010) reported on the potential difficulties that exist in thermally processing
waste building materials from a post-CWA event site remediation due to the refractory nature of
many materials found inside and outside buildings and the potential impact that waste packaging
at the site may have on the behavior of these materials and residual agent destruction in
combustion systems. Although CWAs are not particularly thermally stable and are readily
destroyed at typical incineration temperatures (greater than 800 °C), relatively short gas-phase
residence times (greater than 2 s) and solid-phase residence times (greater than 30 min) make it
possible for some of the residual agent to escape the incinerator due to bypassing the flame
zones, cold spots within the waste, and incomplete penetration of heat through the combustion
bed. Complete destruction of building material-bound CWAs can be achieved once the core
temperature of the building materials exceeds 300 °C. However, significant time may elapse
between the introduction of the material into the incinerator and the time at which the core of the
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material bundles approaches equilibrium with the gas temperatures (Lemieux et al., 2010). Due
to the refractory nature of some building materials such as ceiling tile, particularly if wetted, the
material will remain at the boiling point of water (100 °C) until all the water has been driven off.
Lemieux et al. (2010) conducted a study to examine the thermal decomposition of a surrogate
CWA (Malathion) in a laboratory reactor using heating rates similar to those found in a rotary
kiln incinerator processing building materials. The experiments were performed in small
constant-volume reactor vessels on the bench scale. The CWA simulant was carefully dispensed
into a stainless steel pipe through a Swagelok fitting using a syringe. The initial Malathion
concentration was 300,000 (J,g/L. The chamber was then placed into an oven, and the
temperature was ramped up to 400 °C at a set rate (5 or 10 °C/min), then maintained at that
temperature for 30 minutes. The Malathion concentration averaged 911 |ig/L after removal from
the reactor at the following test conditions, 175 °C after 30 minutes of exposure. The
experiments were performed using heating rates typical of the rates found inside bundles of
building materials in a pilot-scale hazardous waste incineration system and fit to a first-order
Arrhenius expression. An analysis of the results was done using reactor design theory.
Subsequently a scale-up of the results to a computer simulation of a full-scale commercial
hazardous waste incinerator processing Malathion-contaminated ceiling tile was performed
(Lemieux et al., 2010).
The decontamination of a building following release of a biological warfare agent (such as B.
anthracis) may result in a significant quantity of building decontamination residue (BDR)
consisting of non-structural components of the building (e.g., ceiling tile, carpet) and building
contents. Wood et al. (2006) described experiments that were performed in a pilot-scale rotary
kiln incinerator to evaluate the thermal destruction of B. anthracis surrogates (Geobacillus
stearothermophilus bacterial spores) present within bundles of carpeting and ceiling tile. No
spores were detected in the exhaust gas via any of the three sampling trains for the carpet burn
tests. For all of the tests, average kiln exit temperatures prior to the feeding of the carpet ranged
from approximately 804 to 827 °C (1,480 to 1,520 °F). For the dry ceiling tile bundles, a 1 to 2
logio reduction in the number of spores occurred sometime between 5 to 10 minutes, and
complete destruction (6 logio reduction) occurred after 12 minutes. The log reduction in the
number of spores is described by Equation 1.
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Page 23 of 103
Log Reduction = log(N/N') (Equation 1)
where N is the mean number of viable organisms recovered from the control and N' is the
number of viable organisms recovered from each test after decontamination (Rogers et al., 2005).
For the wet ceiling tile bundles, although the results were somewhat variable, reduction in spores
(from a 1-2 logio reduction up to complete destruction) occurred between 35 to 38 minutes.
Figure 2-1 shows the spore survival as a function of time for wet and dry bundles in the kiln
(Wood et al., 2006).
>
u.
Zi
L.
1000
10
10
30
40
Figure 2-1. Ceiling Tile Bundle Spore Survival as a Function of Time in Kiln (Adapted
with permission from Wood et al., 2006)
Lemieux et al. performed bench-scale tests on building materials. The building materials
included carpet, ceiling tile, and wallboard. The ceiling tiles were Class A, standard-white, fire-
retardant, texture-faced ceiling tiles composed of wood fiber (0 - 60%) and fibrous glass (0 -
13%). New drywall was used for these tests, which consisted of a gypsum core wrapped with a
paper lining. The carpet was nylon 6-6 carpeting acquired directly from the manufacturer. The
materials were cut into sample sizes measuring 7.62 x 3.81 cm, weighed, individually wrapped in
aluminum foil and steam-sterilized by autoclaving. The sterile samples were inoculated with
either 1.0 mL of a solution containing Bacillus subtilis spores for a final concentration of 108
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Page 24 of 103
spores/mL or 1.0 mL of a solution containing G. stearothermophilus spores for a final
concentration of 10 spores/m L. In the thermal destruction experiments, the BDR samples were
heated in a quartz reactor operating at 150, 200, 250, and 315 °C for various time intervals.
Total spore destruction was predicted by the EPA simulator model to occur between 4 and 5
minutes. The time was measured at the introduction of the samples into the reactor. Figure 2-2
shows a sample set of results illustrating the destruction of B. subtilis inoculated onto ceiling tile
(Lemieux et al., 2005).
* A
2W1
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Page 25 of 103
reduction of G. stearothermophilus in ceiling tiles with time. The high and low kiln
temperatures were 1,093 °C and less than 824 °C, respectively (Wood et al., 2008).
r ~ Dry. low kiln T
" ^ Dry. high kiln T
- ¦ wei lew mm T
¦ * Wei, high kiln T
_»
0
5
10
i$
W
40
Time Incinerator (minutes)
Figure 2-3. Log Reduction of G. stearothermophilus Bis in Ceiling Tile Bundles (Wet and
Dry) vs. Time in RKIS (Reprinted with permission from Wood et al., Copyright 2008
American Chemical Society). 95% Confidence Interval (CI).
Wood et al. conducted tests in a pilot-scale incinerator utilizing biological indicators comprised
of spores of G. stearothermophilus, Bacillus atrophaeus and B. anthracis (Sterne) embedded in
building material bundles (wallboard). In the pilot-scale incinerator tests, B. atrophaeus and G.
stearothermophilus demonstrated similar thermal sensitivity, but B. anthracis was less thermally
resistant than G. stearothermophilus. A histogram of an average of the percent survival of the
two species of spores is shown in Figure 2-4. The data provide evidence to support the use of
either G. stearothermophilus or B. atrophaeus as a surrogate microorganism for conducting
research to determine the dry thermal destruction requirements of B. anthracis-laden waste.
Wood et al. reported that data from this study may assist in the selection of surrogates or
indicator microorganisms to ensure that B. anthracis spores embedded in building materials are
completely inactivated in an incinerator (Wood et al., 2010).
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100
90-
if 80:
II 70f
1 2 |
60-
£ 00 f
I s 50"
II
30-
g ® 20-
10-
180 200 220 240 260 280 300 320
Maximum internal bundle (emperaiuefC)
Figure 2-4. Histogram Showing Percent Survival of Both G. stearothermophilus and B.
atrophaeus Bis Versus the Maximum Temperature Inside the Bundle (Adapted with
permission from Wood et al., 2010)
Denison et al. investigated a transient zonal model approach for use with a computational fluid
dynamics (CFD) model. Comparisons were made between the model and experimental data.
The model results were compared against pilot-scale data collected by EPA to characterize the
behavior. The typical gas residence times were 2 seconds in the kiln, 3 seconds in the transition
between the kiln and the secondary combustion chamber and 7 to 8 seconds in the secondary
combustion chamber. The bundles were fed approximately every 10.5 minutes. The bundles
were approximately 50% water. The typical residence time for the solid matrix material was 10
minutes. The 6 logio reduction for B. subtilis on wallboard occurred at 1,700 s at 600 °F, 2,700
s at 500 °F, and 4,500 s at 400 °F, as shown in Figure 2-5. The data showed that zonal and CFD
models of the laboratory scale kiln can be constructed and provide useful information on the
physical processes that affect furnace performance in terms of microbiological destruction
efficiency and operability. Figure 2-6 shows a comparison between the model calculations and
the measured data of the kiln exit temperature and the Secondary Combustion Chamber (SCC)
exit oxygen. The models predict complete destruction of the biological agent that remains in the
building material matrix when the incinerators and afterburners are operated as per standard
operating conditions (Denison et al., 2005).
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Page 27 of 103
9
8
~ 400 F Data
¦ 500 F Data
a 600 F Data
400 F z value
600 F Z value
400 F AiTftentus
500 F Antienius
600 F Arrfienios
500 F 2 value
0
0
1000
2000
4000
5000
Time (s)
Figure 2-5. Log Reduction with Time for B. subtilis on Wallboard at Various Initial
Temperatures (Adapted with permission from Denison et al., 2002 [Reaction Engineering
International])
Figure 2-6. Comparison between Measured Data and Model Calculations of the Kiln Exit
Temperature fori?, subtilis (Adapted with permission from Denison et al., 2005 [Reaction
Engineering International])
Fisher et al. investigated the destruction chemistry of organosulfur compounds under both
pyrolytic and oxidative conditions. The focus was on the destruction of alkyl sulfides that are
surrogates for chemical warfare agent related to sulfur mustard (11, 1 ID. and HT).
Thermochemistry, reaction pathways and kinetic parameters for multiple chemical subsystems
were developed using computational chemistry methods. A turbulent flow reactor with
2000
Measured Data
Model
1500
0 5 10 15 20
Time. min.
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Page 28 of 103
extractive sampling was used to examine the destruction of two mustard simulants under both
pyrolytic and oxidative conditions (Fisher et al., 2008).
2.2.1 Municipal Waste Combustors
Municipal (solid) waste combustors (MWCs), otherwise known as waste-to-energy facilities,
might be able to handle wastes containing chemical and biological agents. Several potential
advantages to these facilities when compared to HWCs are that waste-to-energy facilities tend to
be closer to urban centers where terrorist attacks on buildings would be most likely to occur,
MWCs generally have much larger processing capacities than HWCs, and MWCs are believed to
have more flexibility to implement specific engineering changes. Potential disadvantages
include public perception associated with incinerating special wastes near population centers and
permit restrictions for these facilities. Another limitation is the fact that, while waste-to-energy
facilities are designed to receive and process many thousands of tons of waste per week, they are
not particularly suited for large bulky items (Wilhelmi et al., 2003). In addition, those facilities
may have existing contracts to accept waste at or near their nominal capacity on a regular basis
and their ability to take large quantities of unplanned material (surge capacity) may be limited.
MWCs likely could handle, and would be allowed to process, certain types of wastes containing
chemical or biological agents, even though they are permitted to handle wastes primarily from
clinical and research settings. Regulators might need to issue permit modifications or
exemptions for MWCs to process these wastes. Watanabe et al. reported emission data during
the startup of two stoker-type MWCs (two lines, 150 x 2 metric tons/day [165 tons/day] and 450
x 2 metric tons/day [495 tons/day]) (Watanabe et al., 2010). Ash is a by-product of MWC and
further testing is required before disposal at an appropriate facility.
w
2.3 Medical Waste Incinerators V
The State and Territorial Association on Alternate Treatment Technologies (STAATT)
established a framework or guidelines that defined efficacy criteria for the destruction of
microorganisms for medical waste treatment technology and delineated the components required
to establish an effective state medical waste treatment technology approval process. The
guidelines recommended that all medical waste treatment technologies achieve 6 logs or greater
microbial inactivation of mycobacteria and 4 logs or greater reduction of spores (Lemieux et al.,
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Page 29 of 103
2006a). There are no federal standards related to the destruction of pathogens in incinerators and
STAATT is not a government entity.
Wood et al. (2004) summarized EPA test report data on G. stearothermophilus (Gs), a heat
resistant microorganism, as a worst-case surrogate bacterium for tests with medical waste
incinerators (MWIs). Similar to B. anthracis, the surrogate is a gram-positive, endospore-
forming, rod shaped bacterium. As B. anthracis spores are heat resistant and can survive for
long periods under harsh conditions, the potential exists for viable spores to escape detection and
decontamination or to survive multiple decontamination processes. The Gs bacterium was
spiked into the medical waste feed at certain intervals throughout an emissions test. The internal
pipe temperatures were above 816 °C in the small MWI. The results showed that for most of the
test runs, at least a five log reduction of the spores was achieved, although viable spores were
detected in 10 out of a total of 48 air emission test runs, and spores were detected in 10 out of 27
available ash samples MWIs may not completely destroy all of the spiked microorganisms
because of limitations including in-bed mass transfer limitations, incomplete bed mixing,
bypassing of hot zones due to poor gas phase mixing, dropping contaminated material through
the grate prior to destruction in the bed, or by coming into contact with cool zones within the
MWI. Coupled with complex fluid dynamics, these limitations would cause pockets within the
combustion chambers that are not exposed to sufficiently high temperatures and residence times.
The most notable limitation for MWCs is the size of the waste that can be processed where the
typical hopper size for most MWIs is 3 feet by 5 feet by 5 feet (Wilhelmi et al., 2003). Due to
the cost of complying with air emission standards and guidance developed in the 1990s, medical
waste treatment has shifted from small hospital MWIs to larger commercial MWIs with state-of-
the-art incinerator and air pollution control technology (Wood et al., 2004).
The Izmit Hazardous and Clinical Waste Incinerator (IZAYDAS) facility in Izmit, Turkey
incinerates medical and hazardous waste. Various types of wastes such as medical wastes, plastic
and lactic wastes (produced from food wastes), cosmetic wastes, used oil, petrochemical wastes
and oil wastes, solvent, and dyeing wastes are disposed by incineration at IZAYDAS. The
incinerator has a total area of 800,000 m2, 32,000 m2 of which is appropriated for incineration
facilities. The capacity of the plant is 35,000 tons/year. The plant consists of five major parts:
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Page 30 of 103
storage, combustion, energy production system, air pollution control system, fly ash and bottom
ash collection system (Cetin et al., 2003).
2.4 Chemical Weapon Demilitarization
The major portion of the literature on the destruction of CB agents using incineration involves
the use of hazardous waste combustors in specially designed chemical demilitarization facilities,
such as Johnson Atoll Chemical Agent Disposal System (JACADS) and Tooele Chemical Agent
Disposal Facility (TOCDF). The U.S and other counties agreed to destroy their stockpiles of
chemical weapons following the Chemical Weapons Convention (CWC) mainly using HWCs,
MPFs, and LICs.
During the past 40 years, more than 20,000 tonnes (22,000 tons) of chemical agent have been
destroyed in a number of countries and over 80 % of this material has been destroyed by
incineration. There are three principal categories of chemical warfare agents in the stockpiled
munitions and bulk agent storage: mustard, lewisite, and the nerve agents (GA, GB, GD, VR and
VX) (Pearson and Magee, 2002).
2.4.1 Metal Parts Furnaces
Pearson and Magee described the destruction of metal parts that had been drained of agent (such
as one-ton agent containers, bombs, spray tanks, artillery projectiles, and burster wells, which
were pulled to access the agent) in a Metal Parts Furnace (MPF). Metals parts are fed by
conveyor into a fuel-fired MPF and heated to 540 °C to produce metal suitable for release as
scrap after deformation to comply with CWC requirements. Residual or undrained (including
gelled) agent remaining in the metal parts is vaporized and burned within the furnace; the
residence time in the furnace is of the order of two hours. During this period, the residual agent
is vaporized (40 min), the metal parts are heated to 540 °C and maintained at that temperature for
at least 15 min (heated and maintained for 40 min), and then the metal parts are allowed to cool
in a cool-down zone (30 min) to minimize any fugitive emissions. This process takes additional
time and can limit the throughput of the system. Gases discharged from the metal parts furnace
are passed through an afterburner maintained at 1,090 °C before being treated in the pollution
abatement system. The decontaminated metal parts are discharged and shipped to an approved
disposal site or sold for scrap (Pearson and Magee, 2002).
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Denison reported on computer modeling tools playing an important role in reducing the time,
cost and technical risk of using incineration. A simulation workbench was developed to assist
the chemical demilitarization community. The workbench consisted of models for an MPF.
Both a transient zonal model and CFD models were prepared. In the MPF, metal parts pass
intermittently through the furnace at a set point gas temperature typically at 1,600 °F and with a
residence time sufficient to drive off and destroy the agent and bring the projectiles to at least
1,000 °F for at least 10 minutes. The models predict complete destruction of the chemical agent
when the incinerators and afterburners are operated as per standard operating conditions. In
Figure 2-7, the gas temperature distribution for the afterburner in the MPF is shown. The
workbench tool being developed included the ability to study the combustion process, agent
destruction and product species and concentrations for nerve agents (GB and VX) and HD. The
experimental data for HD destruction are compared with the kinetic data in Figure 2-8. The
calculated time profiles are shown in Figure 2-9 for the 5% of the agent remaining in the
projectile shells in the MPF. The models may also be useful in simulating incineration system
upset conditions and failures that could lead to an agent release, so that appropriate design and
operational modifications can be made to mitigate such occurrences (Denison et al., 2002).
¦ ,50°
Gas temperature. K
¦ 300
* ~ ~ Duct From MPF
Figure 2-7. Gas Temperature Distribution in the Afterburner of the Three-Zone MPF
(Adapted with permission from Denison et al., 2002 [Reaction Engineering International])
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Page 32 of 103
<* E^eriment
•— Fyolysis Kinetics
0 500 1000 1 500
T{K)
Figure 2-8. Comparison of HD Destruction Kinetics with Experimental Data (Adapted with
permission from Denison et al., 2002 [Reaction Engineering International])
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Page 33 of 103
~ lit
o i ;i
o f?
D 111
D 1Ji
D III
~ DIE
d as:
~ a:t
Tray Charged
\
d got
C U'.-
;
Figure 2-9. Calculated Time Profiles for Zone 1 with 155 mm Projectiles with 5% Residual
Agent Added in a Three-Zone Furnace (Adapted with permission from Denison et al., 2002
[Reaction Engineering International])
2.4.2 Liquid Incineration
For warfare agent destruction, liquid chemical agent drained from the munitions and storage
containers is collected in a storage tank from which it is fed into a high-temperature LIC where it
is burned at a temperature of 1,480 °C. The LIC is a two-stage refractory-lined incinerator
designed to destroy the nerve agents GA, GB, VX, and mustard (H, HD, and HT). The drained
agent is atomized by a nozzle and mixed with combustion air. Auxiliary fuel is used to maintain
combustion at or above 1,400 °C with the flue gases being passed to an afterburner maintained at
a minimum temperature of 1,090 °C before ducting to the pollution abatement system (Pearson
and Magee, 2002).
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Denison et al. developed models for analyzing the LIC for destroying liquid chemical weapon
agents (GB, HD, or VX) drained from munitions contained in the U.S. Army stockpile. The
destruction profiles with time are shown in Figure 2-10. The models predict complete
destruction of the chemical agents when the incinerators and afterburners are operated as per the
standard operating conditions. The agent is destroyed in the primary furnace chamber shown in
Figure 2-11. Both full CFD and streamlined calculations were performed for agent destruction
(Denison et al., 2004).
Figure 2-10. Calculated Destruction of VX, GB, HD, and H in a Plug Flow Reactor with
Two-Second Residence Time Versus Temperature (Adapted with permission from Denison
et al., 2004 [Reaction Engineering International])
100
90
80
70 H
60
50
40
30
20-1
10
0
600
Figure 2-11. LIC Primary and Secondary Chambers with VX Agent Destruction Depicted
by Streamlines (Adapted with permission from Denison et al., 2004 [Reaction Engineering
International |)
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Page 35 of 103
2.4.3 Plasma Pyrolysis
In plasma pyrolysis, components of chemical munitions, after disassembly, are introduced into a
plasma environment generated by an electric arc, at temperatures approaching 15,000 °C, in a
special furnace enclosure. Chemical agents are instantly decomposed, and metal parts are
melted. The gaseous decomposition products are passed through a pollution abatement system to
remove noxious constituents. Plasma pyrolysis can take several forms: plasma plants in which
the plasma torch treats material fed into the plasma oven, and plasma waste converters (PWCs)
in which a plasma torch is inserted into a chamber into which the material to be destroyed is
introduced. Alternatively, plasmas can be created using two electrodes where the plasma is one
electrode, and the material to be treated is at the bottom of the oven as an anode. Significantly
lower temperatures are measured at the surface of the treated material (slag) depending on the
melting temperature of the slag. By-products will have to be tested and disposed at an
appropriate facility. Plasma pyrolysis reactors can be designed to treat all components of
chemical munitions (i.e., chemical agent, fuses, bursters, propellant, metal casings, and packing
materials). An explosion chamber can be used to deactivate explosive components by energetic
initiation (detonation or deflagration), and the resulting debris and gas from the chamber are then
treated in a high-temperature plasma (Pearson and Magee, 2002).
Of the research initiatives by the U.S. Department of Energy and the DoD over the past 10 years
on plasma treatment of hazardous waste, two have reached the implementation stage: a U.S.
Navy project to destroy hazardous materials on shore; and an asbestos destruction project at Port
Clinton, Ohio. Other projects are still in the research phase (Pearson and Magee, 2002).
2.4.4 Pollution Abatement of Chemical Weapon Demilitarization
The liquid incinerator, the energetics deactivation furnace, and the metal parts furnace all have
identical, separate, dedicated pollution abatement systems. Gases leaving the secondary chamber
of the liquid incinerator or the metal parts furnace flow to these pollution abatement systems for
removal of gaseous pollutants and particles to meet emission standards. Hot gases leaving the
energetics deactivation furnace system kiln flow to a refractory lined cyclone separator, where
large particles such as glass fibers from rocket launch tubes are removed. The gases then enter
the afterburner and subsequently flow into a similar pollution abatement system (Pearson and
Magee, 2002).
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Page 36 of 103
The exhaust gas stream enters the quench tower near the bottom, where it is cooled by contact
with a countercurrent spray of brine pumped from the packed-bed scrubber sump. Acidic or
acid-forming gases [such as hydrogen chloride (HC1), hydrogen fluoride (HF), nitrogen oxides
(NOx), and sulfur dioxide (SO2)] react with the caustic brine to form salts, which remain in
solution in the brine. The cooled gas stream exits from the top of the quench tower and enters a
variable throat venturi where it is scrubbed to remove particulates. The venturi has a variable
throat to maintain a constant pressure drop independent of the flow of exhaust gases. The brine
streams from the quench and venturi scrubber are then returned to the scrubber tower sump
(Pearson and Magee, 2002).
The scrubbed gases enter a candle mist-eliminator vessel. Mist-eliminator candles remove very
fine mist and submicron particulate matter that were not removed in the venturi scrubber. The
cooled and cleaned exhaust gases are pulled through an induced draft blower located upstream of
the stack shared by the three pollution abatement systems (Pearson and Magee, 2002).
Emissions testing at JACADS and TOCDF has demonstrated the ability of these incineration
systems to consistently meet all emissions standards for particulates, organic compound
destruction, and emissions of dioxins/furans. Examples of recorded data were as follows:
particulate emissions were on average 14.7 grains per dry standard cubic meter (gr/dsm3) (103
runs), agent destruction was complete (40 runs) in the stack gases, and dioxins and furans (36
runs) were near detectable levels (average) of 0.037 ng/dsm3. Finally, polychlorinated biphenyl
(PCB) destruction in the Deactivation Furnace System (DFS) exceeded the 99.9999 % regulatory
requirement (Pearson and Magee, 2002).
2.5 Emission and Aerosol Containment
Werner and Cool reported that in the highly non-uniform combustion mixtures present in
furnaces, large gradients in temperatures and composition exist, which may result in incomplete
chemical agent destruction. Under differing flame conditions, the presence of organophosphorus
compounds may either inhibit or promote combustion. Localized pockets of the reacting mixture
may exist where combustion is inhibited or incomplete; if such pyrolysis pockets escape the
primary flame zone, then traces of the chemical agent may survive the primary incineration
furnace. Because of this possibility, current thermal processing facilities employ an afterburner
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to ensure adequate destruction and removal efficiencies for CWAs (Werner and Cool, 1999).
Furthermore, modern refuse combustors have tall stacks, specially designed combustion
chambers, and high-efficiency flue gas cleaning systems that serve to minimize the impact of
emissions associated with waste combustion (Lemieux et al., 2000).
Emissions from all incinerators are subject to regulations promulgated through the 1990 Clean
Air Act (CAA). Regulations developed under the CAA are intended to limit atmospheric
concentrations of six criteria pollutants as well as the 188 hazardous air pollutants (HAPs). EPA
has defined maximum-achievable-control-technology (MACT) standards for incinerators and
other HAP sources. MACT standards require all pollutant sources within a category (such as
incinerator sources) to attain a level of control that reflects the average of the best-performing
facilities (top 12%) in that category. There are three by-product streams from an incinerator: the
stack emissions, the ash residue, and the residues from the pollution control equipment. The
largest volume of material released from an incinerator is the stack-gas stream, which contains
mostly carbon dioxide and water vapor with small amounts of particulate matter and pollutant
vapors. Many of the organic compounds in the stack and waste residue are products of
incomplete combustion (PICs) whose rate of production is controlled by combustion conditions.
Ideal combustion conditions are needed to maximize the destruction of PICs and minimize the
partitioning of heavy metals in the vapor and particle-phase emissions that go out the stack.
During startup and during transient events, ideal conditions are unattainable and pollution
emissions can increase significantly (McKone, 2000). However, startup is typically performed
using conventional fuels and not wastes. Minimization of transients due to feeding containerized
waste can be achieved by closely monitoring the volumetric heat release by timing the
introduction of containers into the combustor.
The performance standards for hazardous waste incinerators consist of the following: (1) a
destruction and removal efficiency (DRE) of principal organic hazardous constituents (POHCs)
of 99.99%, or 99.9999% for dioxin-listed wastes; (2) particulate matter emissions not to exceed
180 milligrams per dry standard cubic meter (mg/dscm) or 0.08 grains per dry standard cubic
foot (grains/dscf), corrected to 7% oxygen; and (3) gaseous hydrochloric acid (HC1) emissions
not to exceed 1.8 kilograms per hour or a removal efficiency of 99%. Compliance with these
performance standards is generally established through a carefully designed trial burn (40 CFR §
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270.62) (EPA, 2001). These DRE standards are based upon the demonstrated capabilities of
proper regulatory agencies as well as a review of organic PICs and inorganic metals emissions
measured during the trial burns. Through the use of air dispersion models, the maximum likely
air concentrations of these substances in surrounding communities can be predicted. Based upon
the predicted level and duration of exposure at these concentrations, the degree of risk that the
emission of these substances poses to the public's health can be estimated. Trial burns are
typically conducted under extreme operating conditions of the unit to define the maximum
operating range (or operating envelope) that assures compliance. As long as the incinerator
continues to operate within the operating envelope demonstrated during a successful trial burn,
the incinerator is presumed to be in compliance with the regulatory performance standards.
When a risk burn involves multiple test conditions, the permit writer and facility will need to
decide whether the data from each test condition should be evaluated separately, or whether the
data will be combined. In addition, decisions will be needed regarding evaluation of emissions
beyond those measured during the risk burn. For example, a facility may prefer to evaluate risks
associated with emissions at a regulatory standard or with an emissions estimate (EPA, 2001).
The storage and treatment of bulk and chemical agents and weapons involve unique hazards of
handling extremely toxic materials. Harper described the methods that have been developed to
detect the presence of chemical agents in the air, and these are used to help assure worker
protection and the safety of the local population. Exposure limits for all chemical agents are low,
sometimes nanograms per cubic meter for worker control limits and picograms per cubic meter
for general population limits. The most common detector is the flame photometric detector, in
sulfur or phosphorous mode, although others, such as mass-selective detectors, also have been
used. Monitoring is made more difficult by interferences from chemicals applied in pesticide
spraying, busy roadways or military firing ranges (Harper, 2002).
Incineration of organic chemicals containing carbon, hydrogen, and oxygen leads to the
formation of carbon dioxide and water. As chemical warfare agents also can contain fluorine,
chlorine, nitrogen, phosphorus, and sulfur, incineration will produce hydrogen fluoride (from
GB), hydrogen chloride (from H, HD, and HT), nitrogen dioxide (from GA, VR, and VX),
phosphorus pentoxide (from GA, GB, VR, and VX), and sulfur dioxide (from H, HD, and HT).
All of these can be removed by scrubbing (Pearson and Magee, 2002).
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The incineration of lewisite, a blister agent which contains arsenic, requires that the arsenic
products be collected and not released to the environment. The exhaust gases are typically
scrubbed by passing them through countercurrent liquid absorption beds to reduce the level of
pollution in the gases released to the atmosphere to an acceptable level that protects public health
and the environment (Pearson and Magee, 2002).
Watanabe et al. (2010) reported that dioxins and their surrogates were continuously monitored
during the startup of two stoker-type MWCs (two lines 150 x2 metric tons/day [165 tons/day]
and 450 x 2 metric tons/day [495 tons/day]). The surrogates studied included low-volatility
organohalogen (LVOH) compounds sampled by online systems, as well as chlorobenzenes (CBs)
and chlorophenols (CPs). The changes in levels of LVOH compounds, CBs, and CPs
corresponded well with the trend of the toxicity equivalent quantity (TEQ). Sampling of dioxins,
CBs, and CPs began immediately after the furnace temperature reached a steady state of 900 °C.
Sampling occurred at 2 h, 4 h, and 20 h intervals. An LVOH monitor operated continuously.
Manual sampling was also done. The isomer analysis of the dioxins present under startup
conditions showed evidence of the memory effect (where highly chlorinated isomers were
emitted slowly), whereas low-chlorinated isomers and LVOH decreased rapidly as the
temperature rose (Watanabe et al., 2010).
IZAYDAS is located 15 km east of Kocaeli, Turkey. Various types of wastes such as medical
wastes, plastic and lactic wastes, cosmetic wastes, used oil, petrochemical wastes and oil wastes,
solvents, and dyeing wastes are disposed by incineration at IZAYDAS. Mercury and its
components, explosives and radioactive materials, slaughter house wastes, feces and corpses are
not accepted. The waste feed rate for the incinerator is 4,100 kg/h. To start the removal process,
the rotary kiln temperature is raised to 850-875 °C by fuel oil. When the rotary kiln temperature
reaches 425 to 450 °C, the rotating process automatically starts and during the combustion
process, the rotation speed is controlled by the control chamber operations, depending on the
waste amount and properties. Removal of bottom ash occurs in 100 to 150 minute periods
during the combustion of wastes at 900 to 1,100 °C. To achieve complete combustion and a
good air mixture, secondary air is transferred from the bunker to the rotary kiln by using the
sucking fans. Oxygen (8 %) is obtained automatically at the rotating kiln. The waste gas
treatment system, consists of an electrostatic filter, a venturi scrubber, a lime scrubber, a
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physical/chemical treatment plant, a flue gas on-line analysis room and a stack unit (Cetin et al.,
2003).
The formation of dioxins/furans (D/Fs) in hazardous waste combustion units is highly dependent
on post-combustion temperature, time, and the presence of flyash to provide a reactive surface.
Even in systems achieving good combustion (with low carbon monoxide concentrations), D/F
formation may occur in cooler zones downstream from the combustion chamber. Almost any
combination of carbon, hydrogen, oxygen, and chlorine can yield some D/Fs, given the proper
time and temperature. There could be substantial increases in D/F emissions under conditions of
poor combustion and carbon monoxide levels greater than 2,000 parts per million (ppm). Some
waste combustors that burn wastes containing D/F precursors, including chlorobenzenes,
chlorophenols, and PCBs, have been shown to have high D/F emissions. D/F emissions could be
a concern with the incineration of materials bound with CB agents if the material also contains
D/F precursors. For most incineration and boiler systems, the generation of organic products of
incomplete combustion is typically associated with poor combustion situations (organic
emissions from cement kilns and lightweight aggregate kilns are typically dominated by organics
that are volatilized from the raw materials). These conditions lead to incomplete combustion and
subsequent increases in fly ash and carbon monoxide and total hydrocarbon concentrations
(EPA, 2001).
Lemieux et al. (2000) conducted field studies on MWCs have shown that the amount of fly ash
(and its accompanying metallic catalysts) and organic precursors that pass through the
temperature window between 250 and 700 °C as well as the amount of time spent in that optimal
temperature window are the primary variables affecting polychlorinated dibenzodioxins and
polychlorinated dibenzofurans (PCDD/PCDF) emissions. Estimated emissions of PCDDs/
PCDFs per unit mass consumed by combustion were calculated by assuming thorough mixing of
air inside the burn hut and using:
/ma\ Concentration Pollutant ( — )xFlow rate of Air )xRun Time (min.)
Emissions (^) = ^, mm (Equation 2)
\kg / Mass of Waste Burned (kg) v 1 y
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A comparison of total dioxin and furan emissions for various combustion sources is presented in
Figure 2-12 (Lemieux et al., 2000).
: 1-06*0
1 OE-l
1.0E-3
1 OE-3
t.oe-4
VOE-5
3 3
Abbreviation
BS»6um Bftfftl
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ME.Mofetf Ei«us A*
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FF=Faboc F*w
(I) Un«nHJtt»ck£rr«»^rtl
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Figure 2-12. Comparison of Total Furan and Dioxin Emissions for Burn Barrels and
Municipal Waste Incinerators (Adapted with permission from Lemieux et al., 2000)
2.6 Plasma Systems
This section reviews the literature on thermal plasma and cold plasma systems for the destruction
of CB agents.
Plasma is defined as an energetic collection of ionized particles (electrons, ions, and radicals)
that exhibit a collective behavior due to electromagnetic forces (Boone, 2007). Thermal plasma
is the term used when a substantially larger fraction of the bulk gas is ionized, and can achieve
bulk gas temperatures of 2,000 °C to 10,000 °C or higher (Konesky, 2008). The temperature of
the gas discharge for cold plasma typically ranges from 50 °C to 300 °C, which allows for
plasma processing of sensitive materials and equipment at low temperatures and accelerated
processing of more robust surfaces at higher temperatures (Rosocha et al., 2003).
w
2.6.1 Thermal Plasma V
Farrar et al. (2000) evaluated two technologies, a steam plasma torch at Montec and an arcjet
thruster at Texas Tech University (TTU) to determine their efficacy to destroy biological agent
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surrogates on materials. In these experiments, the post-test evaluation showed residual spore
counts of a few hundred down to ten or less. The majority of the experiments were conducted
using G. stearothermophilus spores as a simulant for anthrax spores. The G. stearothermophilus
spores were deposited on thin 1-cm square wafers (coupons) of G-10 fiberglass, stone, and
pumice. The specific types of areas investigated are representative of runways and roads, but the
technologies could also be used on buildings, vehicles, and equipment (Farrar et al., 2000).
For the arcjet system, the temperature at the nozzle was estimated at 7,200 °F to 9,000 °F. At a
velocity of 0.67 ft/s and at 1 inch from the exit plane, the peak for the nitrogen arc temperature
was 2,300 °F. During these tests, the arcjet was operated for five to ten seconds duration. The
selected bounds were 0.5 and 3.5 ft/s. Only a couple of flow rates and power settings were used
for the devices, the distances between the nozzle and surface were limited to 1 to 3 inches (Farrar
et al., 2000).
Montec's steam plasma torch was operated at two power levels, 60 and 90 kilowatts (kW), and
produced a plume with a diameter of 4-6 inches at the sampling point. The steam-plasma
temperature was calculated to be between 4,500 °F and 5,400 °F for steam-plasma torch electric
input power levels of 60-90 kW. The Montec results showed that at 90-kW power, the steam
plasma produced a 99.94 % or greater kill rate at velocities up to 2 ft/s at a distance of linch
from the exit plane. At this same power level and at a distance of 3 inches, the percent kill
ranged from 97 % to 85 % as the speed increased from 0.5 to 2 ft/s. At the lower power level of
60 kW, the maximum speed that would produce 99.94 % kill at 1 inch was 1.5 ft/s. A third
substrate, pumice block (a highly porous material), was also contaminated with biological agent.
Only partial destruction of the biological agent was achieved over the range of operating
conditions tested. These tests showed that when the agent was absorbed deeply into a very
porous material, the effectiveness of the plasma was limited. UV radiation alone (when the
quartz plate was placed between the plume and the target) did an impressive job of killing a large
number of the spores as shown in Figure 2-13. The quartz lens allowed passage of UV from 190
to 400 nm. However, UV radiation alone did not result in a 100 % kill, except at longer
exposure times. The peak temperature measured with the quartz lens in place was 270 °F. The
steam torch indicated a higher value of radiation around 280 nm than did the arcjet. The
percentage of kill at a given speed was slightly higher for the arcjet (Farrar et al., 2000).
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100
80
X*
¥
c
Si
p
+ No Lens
xLens Blocking Heat
o
Q.
0
-»x—XX
o.oo
1.00 2.00 3.00
Target Velocity (ft/sec)
4.00
Figure 2-13. Plot of Percent Kill Versus Target Velocity for G. stearothermophilus Spores
on Fiberglass with and without a Lens to Block Heat from the Steam-Plasma Torch (©
2000 IEEE. Reprinted, with permission from Farrar et al.)
The emission spectroscopy of an arc-seed microwave plasma torch (MPT) was examined, and
the spectral line of 777.194 nm indicated relatively high atomic oxygen content in the torch. In
the decontamination experiments reported by Kuo et al., Bacillus cereus was chosen as a
simulant for B. cmthrcicis spores and the airflow rate was fixed at 0.393 L/s. The results of
experiments using dry samples showed that all spores were killed in less than 8 seconds at 3 cm
distance, 12 seconds at 4 cm distance, and 16 seconds at 5 cm distance away from the nozzle of
the torch (Kuo et al., 2005).
Cold plasma is a partially ionized gas where only typically 10"3 to 10"6 of the gas molecules are
ionized. This range would represent strong and weak cold plasma, respectively. The term cold is
a relative one, and the bulk gas can reach temperatures of 100 °C or more in a strong beam
(Konesky, 2008). Cold plasmas can be generated by microwave power, direct current (DC),
radio-frequency (RF), or pulsed power supplies. Among the attractive features of nonthermal
discharges is the ability to control their characteristics, allowing the plasma to be tailored for
each specific application (Laroussi et al., 2000).
2.6.2
Cold Plasma
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When partially ionized, the carrier gas acts as a gaseous wire and directs the plasma to the target
application area with great precision and stability. This form of cold plasma applicator, often
referred to as a plasma jet, consists essentially of a carrier gas flowing over a conductor with a
sharp point that is held at high voltage and high frequency. The conductor is typically made of
either stainless steel or tungsten. Voltages typically range from a few kilovolts to over 10 kV,
and frequencies can range from a few kilohertz to over a megahertz. Electrical currents in the
plasma jet may be as low as several tens of microamperes (a weak beam) to over 100
milliamperes (a very intense beam) (Konesky, 2008).
The plasma jet configuration has many advantages over previous cold plasma applicators. Now
there are two independently controllable variables, electrical power input and gas flow rate, that
give the plasma jet a wide range of effects. Helium is preferred as an ionized gas for plasma
applications because its high thermal conductivity helps carry away heat, and its rich UV spectral
components enhance its sterilization capability (Konesky, 2008).
The overall effect of a plasma jet results from a combination of ion bombardment, electron
bombardment, thermal effects, localized UV exposure, and the production of free radicals and
some ozone. The production of free radicals and ozone is possible because an oscillating electric
field heats mainly the electrons rather than the heavier ions, which respond much more slowly.
However, these energetic electrons can transfer their energy effectively to excite and dissociate
molecules, yielding reactive radicals such as oxygen atoms (Konesky, 2008). Reactive oxygen
species (ROS) such as metastable oxygen, ozone, and oxygen ions can destroy just about all
kinds of organic contaminants more effectively than the thermal method (Herrmann et al., 1999).
This athermal destruction mechanism primarily involves the chemical reactions of ROS with
nucleic acids, lipids, proteins and sugars in biological organisms. These chemical modifications
result in protein cleavage, with aggregation and loss of catalytic and structural function by
distorting secondary and tertiary protein structures. These oxidative proteins are irreversibly
modified and cannot be repaired. This occurrence is known as protein degradation (Kuo, 2005).
The plasma also generates ultraviolet radiation that can destroy many biological agents as well as
enhance chemical-reaction rates (Herrmann et al., 1999).
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Atmospheric plasma decontamination (APD) can be applied to the destruction of biological
organisms by passing energy through air. The molecules are ionized, generating both positively
and negatively charged reactive species. The interaction of these ions, along with the associated
ultraviolet light, kills the microorganisms. APD is applicable to the cleaning, and perhaps the
disinfection, of small areas and electronic equipment (Boone, 2007).
Rosocha et al. presented the results for decontamination of Bacillus globigii (Bg), a surrogate for
anthrax spores, using both plasma and dry heat treatments. The dry heat treatment flowed hot
air, or some other gas, onto the biological agent. Results indicate a seven-log kill (a factor of 10
million removal or decrease of the contaminant) of Bg spores in 30 s with an Atmospheric
Pressure Plasma Jet (APPJ) effluent temperature of 175 °C, which was ten times faster than dry
heat at the same temperature, as shown in Figure 2-14. In Figure 2-15, the destruction of
Malathion is shown for APPJ and compared to the dry heat treatment (Rosocha et al., 2003).
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Plasma
30 60 90
Exposure time {$)
Temperature - 175DC
Distance = S mm
Figure 2-14. Atmospheric Pressure Plasma Jet (APPJ) (left); Destruction of the Anthrax
Surrogate Bg Using the APPJ Method Compared to the Dry Heat treatment (right)
(Adapted from Rosocha et al., 2003 with the permission of the Los Alamos National
Laboratory)
1.0
_ 0.8
©
i
£ 0 j6
|
% m
£
°o v> too iso m
Temperature (C)
Figure 2-15. Destruction of Malathion using the APPJ Method as Compared to the Dry
Heat Treatment (Adapted from Rosocha et al., 2003 with the permission of the Los Alamos
National Laboratory)
Hoi-gas
evaporation
Plasma
conversion
BoHlng point •
Herrmann et al. reported on a plasma decontamination chamber that has been developed at Los
Alamos National Laboratory (LANL), Albuquerque, NM, to study the decontamination of
chemical and biological warfare agents. This technology was targeted at sensitive electronic
equipment for which there is currently no acceptable nondestructive means of decontamination.
Sensitive equipment is defined as equipment that cannot be exposed to aqueous decontaminants
and strong oxidizing or caustic solutions without destruction, degradation in performance, or
significant disruption in use. To the military, this means electronic equipment such as avionics,
communications, fire control and navigational equipment and electro-optics such as range finders
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and night-vision goggles. Exposures were conducted at a system pressure of 30 torr, exposure
temperature of 70 °C, plasma-to-sample standoff distance of 10 cm, and 10 % addition of oxygen
or hydrogen to a helium balance. The agents studied were VX and GD nerve agents and HD
blister agent, as well as a thickened simulant. All agents were decontaminated off aluminum
substrates to below the detection limit of 0.1 % of the initial contamination level of
approximately 1 mg/cm2, as shown in Figures 2-16 and 2-17. For VX, this level of
decontamination was achieved in 8 to 16 min of exposure, while only 2 min were required for
the more volatile HD and GD. Decontamination levels of 99.9 % were achieved in under 2 min
for chemical agents HD and GD, and under 16 min for VX. Evaporation and subsequent
chemical breakdown during recirculation through the plasma was believed to be the dominant
decontamination process for these agents (Herrmann et al., 1999).
1
0.1
X
>
§ 0.01
¦u
"m
4>
c 0.001
0.0001
0 2 4 6 6 10 12 14 16 18
time {min)
Figure 2-16. Residual VX Remaining on Aluminum as a Function of Exposure Time. Test
Conditions: T = 70 °C, d = 10 cm, Pressure = 30 torr, O2 or Fh at 10 % (Reproduced with
permission from Herrmann et al. Copyright 2000, ATP Publishing LLC.)
Min Detectable
0 0-1
X
¦5
3
1 001
o
EE
0001
Mm Detectable
0
iD
1
3
yi
f
DC
1 E-CO
1 E-01
1.E-0S j
IE-03
I.E-Ofl !
1.E-05 | ¦-
Min Detectable
1.E-W *
0 0001
0
1
I (min)
1
lime (min)
Figure 2-17. Residual HD Remaining on Aluminum (left) and Residual GD Remaining on
Aluminum (right) Versus Time. Test Conditions: T = 70 °C, d = 10 cm, Pressure = 30 torr,
O2 or H2 at 10 % (Reproduced with permission from Herrmann et al. Copyright 2000, ATP
Publishing LLC.)
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Laroussi et al. presented two studies on bacteria inactivation obtained by two different
discharges: a glow discharge at atmospheric pressure (GDAP) and an enhanced corona discharge
at atmospheric pressure (ECDAP). The plasma generated by the GDAP is a source of charged
particles, free radicals (O and OH ), and radiation (infrared, visible, and ultraviolet). This
environment was found to be lethal to various microorganisms. The root mean square (rms)
voltage was 5 kiloVolts, the frequency was 17 kiloHertz, the gap distance was 3 cm, the gas was
a mixture of helium and air, the bacteria were Escherichia coli (pbr 322) and Pseudomonas
aeruginosa (frdl) (Laroussi et al., 2000).
Pseudomonas aeruginosa on a nitrocellulose filter membrane was tested. These bacteria were
harder to kill since it took approximately 15 min to sterilize a sample seeded with a cell density
in the 105/mL range. Pseudomonas was even harder to kill when it was in a liquid broth since for
similar experimental conditions, only half of the initial cells were killed in 15 minutes.
Therefore, the kill rate of microorganisms by the GDAP is strongly dependent on the type of
microorganism, the type of medium supporting the microorganism, and the type of sterilization
(surface versus volume). To understand what happens to the microorganisms after they were
treated by the plasma discharge, scanning electron microscope (SEM) micrographs of the cells
were taken showing the appearance of non-treated cells and cells treated for 30 s in the GDAP.
The treated cells appeared to be in the process of leaking internal matter. The outer membranes
of the cells appeared to have been punctured by the plasma. With a damaged outer membrane,
the microorganisms became very vulnerable to the reactive environment of the discharge
(Laroussi et al., 2000).
Like the glow discharge at atmospheric pressure, the ECDAP is a source of active species that
can react adversely with the cells of microorganisms. For ECDAP, the power dependence on the
kill rate was paramount. The power was tripled from 20 Watts (W) to 60 W, and the kill rate
increased by approximately two orders of magnitude. B. subtilis bacteria in Luria-Bertani broth
were a little harder to kill than E. coli since for a power of 42 W and after a 12-min exposure
time, approximately 100 cells were still alive (as compared to complete kill in 8 min for E. coli),
as shown in Figure 2-18 (Laroussi et al., 2000).
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T«*T0O
M 1 ,-o-42W*ts
*0*4 r|
f !
I 1»»7 A
J ~ 1
y 1HS f I
- ! I
if*5 Cl
ic*4 t \
'**2 0 2 4 6 ft 10 t2 U
Exposure Tim® (mmutes)
Figure 2-18. Live Cells Versus Exposure Time for B. subtilis in Luria-Bertani Broth with
Applied Power of 42 W (left). SEM Photograph of E. coli on Plasma-Exposed Sample after
30 Seconds Exposure Time (right) (© 2000 IEEE. Reprinted, with permission from
Laroussi et al.)
Montie et al. reported the results of a plasma source, the One Atmosphere Uniform Glow
Discharge Plasma (OAUGDP), which operates at atmospheric pressure in air and produces
antimicrobially active species at room temperature. The OAUGDP reactor is composed of a
radio frequency (RF) power supply and a pair of water-cooled parallel plane plate electrodes,
between which an atmospheric glow discharge plasma is generated, producing antimicrobially
active species. These antimicrobially active species include ozone, monatomic oxygen, free
radicals such as superoxide, hydroxyl, and nitric oxide, and ultraviolet photons. The nature of
the surface influences the degree of lethality, with microorganisms on polypropylene being most
sensitive, followed by microorganisms on glass, and cells embedded in agar. Experimental
results showed at least a 5 logio colony forming unit (CFU) reduction in bacteria within a range
of 50 to 90 s of exposure. After 10 to 25 s of exposure, macromolecular leakage and bacterial
fragmentation were observed. li. coli and Pseudomonas aeruginosa were as susceptible to the
plasma as Staphylococcus aureus, B. subtilis, and Deinococcus radiodurans. The latter organism
is unusually resistant to drying, irradiation and ultraviolet light. Spores were more resistant, with
values in the range of 1.8 to 5.5 min instead of seconds. Bacillus stearothermophilus spores,
normally a very resistant organism, were killed to the same extent (five logs in 5.5 min) as B.
subtilis var. niger spores, while only 2.5 min was required to inactivate approximately the same
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Page 50 of 103
number of B. pumihis spores. Data from Montie et al. suggest that membrane lipids may be the
most vulnerable macromolecule of the cell, probably because of their location near the cell
surface and their sensitivity to ROS. Gram-negative bacteria as a group would be most
vulnerable because they possess a unique outer membrane in their cell envelope. By contrast,
leakage from the Gram-positive S. aureus was delayed, and no evident fragmentation occurred,
suggesting that the thick polysaccharide on the outside of the cell of S. aureus is resistant to
chemical change but allows diffusion of ROS to the cytoplasmic membrane, which is again
vulnerable to attack. When the cytoplasmic membrane lipids are altered in both groups of
bacteria, this alteration results in a massive release of macromolecules. In Figure 2-19, the
bacterial survivors inoculated on polypropylene are plotted with time, and the Transmission
Electron Micrographs (TEM) of E. coli and S. aureus initially and after 30 seconds of exposure
are presented (Montie et al., 2000).
5. aureus, MOI> V
E. coJi, MOD V
Time (sec)
n
Figure 2-19. Survivors of Bacterial Ceils Inoculated on Polypropylene with Time with the
Application of OAUGDP (left). The Transmission Electron Micrograph of OAUGDP-
treated Cells: A) Initial E. coli, B )E coli after 30 Seconds of Exposure, C) Initial S. aureus,
and D) S. aureus after 30 Seconds of Exposure (right) (© 2000 IEEE. Reprinted, with
permission from Montie et al.)
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2.7 Microwave Irradiation
Microwave energy is a form of electromagnetic energy that penetrates deeply into many
materials, transforming energy directly into heat by exciting absorbing molecules into rapid
oscillatory motion. With such unique attributes, microwave offers several practical advantages,
including reduced thermal gradients, selective heating, rapid energy decomposition, and
acceleration of certain chemical reactions (Cha et al., 2004).
Microwave scabbling is a new method of removing the surface of concrete which uses
microwave energy to heat the moisture present in the concrete matrix. Continued heating
produces steam under pressure that generates internal mechanical and thermal stresses, bursting
the surface layer of the concrete. The analysis showed that the main factors affecting
scarification are the pore dimensions and the evaporable water content of the cement (Kumar et
al., 2010).
Wu and Yao investigated the survival of both laboratory-generated and environmental
bioaerosols when these bioaerosols were exposed to microwave irradiation (2,450 MHz) for 2
min at different output power (700, 385, and 119 W), as shown in Figures 2-20 and 2-21. Three
different microbial species (B. subtilis var. niger (hardy species, Gram-positive), P. fluorescens
(sensitive species, Gram-negative) and fungus A. versicolor (hardy species) were studied as
surrogates for harmful agents. The survival rates of airborne B. subtilis var. niger spores were
shown to be approximately 35%, 44% and 35% when exposed to the microwave irradiation for
1.5 min with high, medium and low power applied. The airborne Pseudomonas fluorescens was
shown to have lower survival rates of 5.8%, 12.2% and 21% (p-value = 0.0045). Similar
patterns but higher survival rates at respective powers were observed for airborne Aspergillus
versicolor exposure (p-value 0.0001). SEM and TEM images showed visible damage to both
membrane and intracellular components of the microwave-treated microbes (Figure 2-22). In a
previous study, several dark spots were also observed in the cytoplasm of both B. subtilis and E.
coli through examining their TEM images, and the protein aggregation was suggested to play a
role in the inactivation (Wu and Yao, 2010).
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Thermal effects could result from the denaturation of enzymes, proteins and nucleic acids, as
well as the disruption of membranes when the temperature reaches 50-60 °C. The athermal
effect by microwave application could arise from the interference of cell metabolic activities and
energy absorption and deoxyribonucleic acid/ ribonucleic acid (DNA/RNA) molecule rotation in
response to microwave irradiation. The results obtained by Wu and Yao can be used to develop
microwave-based air sterilization technologies especially targeted for biological aerosols.
Microorganisms in wet form sustained substantial inactivation upon microwave irradiation,
while those in dry or lyophilized form were not affected even by extended exposure, suggesting
that the thermal effects may be responsible for the microwave inactivation. The presence of
water may be necessary for the athermal effects to occur (Wu and Yao, 2010).
Airborne exposure of 1,5 min to microwave irradiation
50
¦M High power
'•¦¦NNM Medium power
¦¦ Lower power
p-value=0 37
p-value=0.00<»5 p-varue<0,0001
Bacfcs subbis Pseudomonas AspBtgius versicolor
IVs
Figure 2-20. Airborne Exposure of B. subtilis var. niger, P. fluorescens and A. versicolor to
Microwave Irradiation at 700, 385, and 119 W for 1.5 Minutes (Adapted from Wu and
Yao, 2010 with permission from Elsevier, Inc.)
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Liquid-borne exposure to microwave irradiator!
120 1
High Power
LrssA Medium Power
¦¦¦ Low Power
6. subtilis
1 2 3
Exposure Time.min
Figure 2-21. Liquid-borne Exposure of B. subtilis var. niger to Microwave Irradiation at
700, 385, and 119 W (Adapted from Wu and Yao, 2010 with permission from Elsevier, Inc.)
Bacillus subtilis
5 urn
1 1
control exposed
a b
Pseudomonas fluorescent
• V #
%
%
%
\
0
1 2 pm |
control exposed
Figure 2-22. SEM Images of Liquid-borne Control and Exposed P. fluorescens, A.
versicolor and B. subtilis var. niger with 700 W and 90 Seconds Exposure Time (Reprinted
from Wu and Yao, Copyright 2010, with permission from Elsevier, Inc.)
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Zhang et al. developed a microwave-assisted nanofibrous air filtration system (a microwave
device to disinfect airborne pathogens collected on nanofibers) to disinfect air containing
airborne pathogens. Aerosolized E. coli vegetative cells and B. subtilis endospores were tested
as benign surrogates of pathogens and were collected on nanofibrous filters and treated by
microwave irradiation. As a Gram-positive bacterium, B. subtilis has the ability to sporulate and
has been used extensively as a benign surrogate for B. anthracis spores. B. subtilis endospores
are ellipsoidal in shape, approximately 0.8-1.2 mm in length, and have an aerodynamic diameter
of 0.9 mm. Both static on-filter and dynamic in-flight tests were carried out. Results showed
that E. coli cells were efficiently disinfected in both static and in-flight tests, whereas B. subtilis
endospores were more resistant to this treatment. The microwave power level was found to be
the major factor determining the effectiveness of disinfection. Both thermal and athermal effects
of microwave irradiation contributed to the disinfection. Reducing flow velocity to decrease heat
loss yielded higher disinfection efficiency (Zhang et al., 2010).
Zhang et al. prepared electrospun polyacrylonitrile (PAN) nanofibers that were sandwiched
between two activated carbon fiber (ACF) mats for testing. B. subtilis endospores were tested
because of their relatively high heat resistivity compared to E. coli. B. subtilis spore tests show a
similar trend in log disinfection. As shown in Figure 2-23, after irradiation at 750 W for 90 s,
2.7 logs disinfection of the spores was observed. Less powerful microwave power applications
proved less effective. For 250 W, 45 s of application time was required to achieve any
disinfection at all. Compared with E. coli tests, B. subtilis spores were more difficult to destroy,
requiring irradiation at 750 W for 90s for 3 logs disinfection. This apparent difficulty in
destroying the spores would also be observed during in-flight testing. This result is likely
attributed to the heat resistivity of the endospores. Analysis of variance (ANOVA) statistical
analysis indicated that microwave power, rather than application time, was the most significant
factor in the reduction of viable B. subtilis spores on the filter (p-value 0.05) (Zhang et al., 2010).
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O250 W D500 W "750 W
10 mins/cyclc
5 mins'cyclc
Microwave Application Time
1.25 mins/cyclc
Figure 2-23. Dynamic In-Flight On-Filter Disinfection of B. subtilis with Microwave
Application Time at 250, 500, and 750 W Power Levels (Reprinted from Zhang et al.,
Copyright 2010 with permission from Elsevier, Inc.)
McFarland et al. treated biological warfare agents with the transduction-polymer and an
acceptor-chromophore (TPAC) compound and then exposed the treated agents to microwaves.
Using this approach, significant kill of the BWAs was achieved using standard microwave
equipment at moderate power. A 5.5 out of a total of 6 log kill was achieved on surrogate B.
anthracis spores, the hardest BWA to defeat. The AC molecule is designed so that it easily
penetrates the wall of the BWA and binds to surface matrix targets. Upon microwave exposure,
the TP emits a blue photon that activates the AC producing saturated levels of chemical radicals
that are irreversibly bound to the target spore wall, resulting in lethal failure of the spore upon
germination. The TP molecule is resonant and thus responds to a given microwave frequency
better than others (McFarland et al., 2001).
Microwave irradiation can be used for decontamination and regeneration with very little warmup
time while generating almost none of the problematic byproducts. Wu et al. developed the
RHELP (Regenerative High Efficiency Low Pressure) air purification system using a novel
ceramic nanofiber on silicon carbide in a microwave oxidizer to effectively decontaminate air
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containing aerosolized CB agents. Nanofiber mats of several materials (shown in Figure 2-24)
were designed and fabricated: I) (PAN nanofibers on ACF mat; II) titania nanofibers; III) silicon
carbide nanofibers; IV) titania carbon nanotube reinforced nanocomposite nanofibers; and V)
titania silica nanocomposite nanofibers. Three microorganisms, Escherichia coli, MS2
bacteriophage, and B. subtilis endospores were tested as benign surrogates for more dangerous
microbes. For static on-filter tests, all biological agents were able to be completely destroyed by
microwave irradiation within two minutes, with E. coli being the most sensitive and B. subtilis
endospores being the least sensitive. For the dynamic system in-flight filtration tests that
coupled PAN nanofiber filtration, at 500 W of continuous microwave application, the system
was able to remove over 95% of viable MS2 virus and B. subtilis endospores (Wu et al., 2009).
Figure 2-24. SEM Images of (a) TiCh Nanofibers, (b) Millipore high efficiency particulate
arrestance (HEPA) filter, and (c) Military H E PA (Wu et al., 2009, Published by DTIC, No
Permission Required)
Cha et al. used catalysts and microwave energy to test the destruction of simulated chemical
agents including the monofunctional derivatives of mustard gas and a series of
organophosphorus esters used to simulate G agents including dimethylmethyl phosphate
(DMMP), diisopropyl methylphosphonate (DIMP), diisopropyl fluorophosphates (DFP), and 4-
nitrophenyl diphenyl phosphate (PNPDPP). Outlet temperature and concentration measurements
were taken at regular intervals from 1 to 80 minutes after flow into the reactor. During the test,
the outlet simulant concentration was monitored by a Total Flydrocarbon Analyzer (accurate
within 0.1 ppm) (Cha et al., 2004).
The catalyst absorbed microwave energy to perform the microwave-induced chemical reactions.
Most catalyst substrates such as aluminum oxide (AI2O3) do not absorb microwave energy.
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Since silicon carbide (SiC) is an excellent microwave absorber, commercially available catalysts
were mixed with SiC to carry out microwave-induced chemical reactions. Three different
substrates were used to prepare the vanadium pentoxide (V2O5) catalyst for a series of tests to
evaluate the performance in the oxidation reactions. The first V2O5 catalyst was V2O5 on silicon
carbide, and the second was V2O5 on 50% SiC/AhCb support. An air stream containing either
300 ppm DMMP or 600 ppm diethyl sulfide (DES) was used to evaluate these substrates for the
V2O5 catalyst. Air flow rates of 35 bed volume per minute and 300 W microwave power were
used for these experiments (Cha et al., 2004).
In Figure 2-25, for DMMP the best DRE (>99.5%) was obtained from tests using the alumina-
based vanadium catalyst. The higher catalyst surface area appears to yield greater DRE.
Alumina alone does not absorb microwave energy. However, alumina impregnated with the
V2O5 absorbs enough microwave energy to induce the oxidation reaction. Mixing a small
amount of SiC with the catalyst was sufficient to initiate microwave-induced catalytic oxidation
(Cha et al., 2004).
35 Bed Volumes p«r Minute - DMMP • 300W
Foed Concentration about 300 ppm
100
-
Q 97
96 *
0 20 40
Time, minute
Figure 2-25. Percent Destruction of DMMP for Different V2O5 Catalysts (Cha et al., 2004,
Published by DTIC, No Permission Required)
In Figure 2-26, the DES outlet concentration reached a steady-state concentration within 10
minutes after the experiment started. All the tests were performed using DES as the CWA
simulant and using a 10% by mass V2O5 catalyst impregnated on alumina beads (Cha et al.,
2004).
• iooxsc
Subural*
¦SCrw *iC VJS
¦ 1D\Aunm
SuMnk
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35 Bed Volumes per Minute - DES -
30QW
Feed Concentration about 600 ppm
100
* "
—100XSC
SMtMMto
uj 9fl _ -m-M
0C Jh#L
—40 40%
SubUr*)*
—*—100% MumMe
0 20 40
buMeate
Time, minute
Figure 2-26. Percent Destruction of DES for Different V2O5 Catalysts (Cha et al., 2004,
Published by DTIC, No Permission Required)
In Figure 2-27, the DRE and temperature (secondary axis) for DES are plotted versus time. The
experimental results positively demonstrate that microwave catalytic oxidation is a strong
candidate for the destruction of CWAs in air at low temperatures. The microwave power and
inlet air flow rate are major parameters controlling the destruction and removal efficiency. The
DRE is closely correlated to the combined parameter, microwave power/inlet flow rate (kJ/bed
volume). For the V2O5 catalyst, DREs greater than 90% were obtained with the ratio of
microwave power to inlet flow rate greater than approximately 0.3 kg/bed volume (ft3) (Cha et
al., 2004).
ORE(%) T»»t 44
\
100
1»
•5 / / O
S Temperature (C) w =
8 90 * Temperature (C) J
Rewrite 65 Bed Volumet min
Forward Power: 1000 W 40
Chemical Simulant DES
Chemical Concentration: 671 ppm
as
80
10 2S 40 SS
Time, mm
Figure 2-27. Parametric Test Output for the Destruction of DES Simulant (Cha et al.,
2004, Published by DTIC, No Permission Required)
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w
2.8 Autoclave V
Autoclaves are commonly used to sterilize medical wastes using steam, heat, and pressure.
Autoclaves range in size from bench-top devices to large commercial operations. These large
commercial facilities can process up to 96 tons of waste per day, and some have waste inlet
openings up to 8 feet in diameter. Potential advantages of using commercial autoclaves to
sterilize waste include the ease with which processing conditions can be altered for specific
waste streams, the ability to process large waste items, and the fact that these facilities often have
testing requirements for spore destruction. Potential disadvantages include worker safety issues,
packaging requirements, and the issue of disposing of decontaminated wastes (Wilhelmi et al.,
2003).
The EPA conducted an experiment to evaluate the effectiveness of a commercial autoclave for
treating simulated BDR. Tests were conducted at the Healthcare Environmental, Inc., facility
located in Oneonta, NY. This facility can treat up to 84 tons of medical waste per day using two
identical autoclaves that are 8 ft in diameter and 32 ft long, which accept large metal bins (80 in
by 54 in by 69 in) on rollers. The nominal autoclave operating cycle time was 40 min plus cool
down time to prepare for subsequent loads. The nominal operating conditions during the cycles
are 31.5 lb/in2 and 275 °F (Lemieux et al., 2006a).
The BDR (carpet, wallboard, and ceiling tile) was intended to simulate porous materials removed
from a building deliberately contaminated with biological agents such as B. cmthrcicis (anthrax)
in a terrorist attack. The test team created simulated BDR from wallboard, ceiling tiles, carpet,
and upholstered furniture, and embedded in the BDR were G. stearothermophilus BI strips. The
purpose of the tests was to assess whether the standard operating procedure for a commercial
autoclave provided sufficiently robust conditions to adequately destroy bacterial spores bound to
the BDR (Lemieux et al., 2006a).
Lemieux et al. (2006a) investigated the effects of several variables related to autoclaving BDR,
including time, temperature, pressure, item type, moisture content, packing density, packing
orientation, autoclave bag integrity, and autoclave process sequence. The effect of a second
autoclave cycle on spore survivability is shown in Figure 2-28. The results indicated that a
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single standard autoclave cycle did not effectively decontaminate the BDR. Autoclave cycles
consisting of 120 min at 31.5 lb/in2 and 275 °F and 75 min at 45 lb/in2 and 292 °F effectively
decontaminated the BDR material. Two sequential standard autoclave cycles consisting of 40
min at 31.5 lb/in2 and 275 °F proved to be particularly effective, probably because the evacuation
step in the second cycle pulled the condensed water out of the pores of the materials, allowing
better steam penetration. The results also indicated that the packing density and material type of
the BDR in the autoclave could have a significant impact on the effectiveness of the
decontamination process. In Figure 2-29, the effect of packing density for wallboard is
presented. The most effective spore destruction was obtained with a loose packing arrangement,
dry BDR material, a higher autoclave operating pressure and higher temperature, multiple
autoclave cycles performed in sequence, and bags cut open prior to loading (Lemieux et al.,
2006a).
350 -i
Carpet
Ceiling Tile
Walboard
Initiation of 2nd Autoclave Cycle
Wet Walboard (3 points)
Dry Wallboard (3 points)
Wet Carpet (3 points)
Run5
Multiple BDR Types
Vertical Orientation
Two Autoclave Cycles
31.5 psig/275 °F
Dry Ceiling Tiles {3 points)
50 -i
0
20
40
60
80
Time (min)
Figure 2-28. Effect of Second Autoclave Cycle on Spore Survivability, Temperature with
Time (Adapted with permission from Lemieux et al., 2006a)
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350 -i
Reference and Control TC
Carpet
Ceiling Tile
Walboard
300 -
Run 6
Multiple BDR Types
Vertical Orientation
Two Autoclave Cycles
31 psig/275 °F
50
0
20
40
60
Time (min)
Figure 2-29. Effect of Packing Density for Wallboard, Temperature with Time (Adapted
with permission from Lemieux et al., 2006a)
2.9 Landfill Flares
As organic waste decomposes inside a landfill, the decomposing waste releases a combustible
gas called "landfill gas" that has a heating value on the order of half of the heating value of
natural gas (EPA, 2009). This gas is commonly burned either in a boiler or engine (for energy
recovery) or a flare.
Although incineration may be a preferred method to treat biologically contaminated materials,
other management options would likely be required in a large-scale incident because the high
volume of waste might overwhelm incineration facilities. One management option is the use of
municipal solid waste (MSW) landfills. As the landfill reaches final grade, it is capped with clay
and plastic to prevent water infiltration. Bacteria break down the organic wastes within each cell
to produce landfill gas. Landfill gas generally consists of about half methane (CFL), half carbon
dioxide (CO2), and <1% non-methane organic compounds as well as hydrogen sulfide and other
sulfur compounds. These gases, including methane, are collected through a series of pipes and
are routed by blowers to landfill flares, gas turbines, internal combustion engines, or other
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devices that combust the gases and prevent the escape of methane into the atmosphere (Tufts and
Rosati, 2012).
A bench-scale landfill flare system was designed by Tufts and Rosati and built to test the
potential for landfilled biological spores that migrate from the waste into the landfill gas to pass
through the flare and exit into the environment as viable. For the bench tests, N2 and CH4 were
used to simulate landfill gas with combustion air. Flows were corrected to a temperature of
1,000 °C, the maximum average temperature of the flare measured at its widest point which was
within the 870 to 1,037 °C operating range for an enclosed flare. G. stearothermophilus and B.
atrophaeus are nonpathogenic spores that serve as surrogates for B. cmthracis. They were
investigated to determine whether these organisms would be inactivated or remain viable after
passing through a simulated landfill flare (Tufts and Rosati, 2012).
High concentration spore solutions were aerosolized, dried, and sent through a bench-scale
system to simulate the fate of biological weapon (BW) grade spores in a landfill gas flare.
Spores were collected from the stack exhaust using a sterile BioSampler. The flare and stack
residence times were estimated to be 0.2 and 0.6 sec, respectively. A comparison of the basic
operating attributes (e.g., temperatures, gas-phase residence time) showed that the bench-scale
system exhibited good similarity to the real-world conditions of an enclosed standard combustor
flare stack with a single orifice, forced-draft diffusion burner. All spores of G.
stearothermophilus and B. atrophaeus were inactivated in the flare, indicating that spores that
become re-entrained in landfill gas may not escape the landfill as viable, apparently becoming
completely inactivated as they exit through a landfill flare (Tufts and Rosati, 2012).
2.10 Bench-Scale Flame Mechanism Studies
Nogueira and Fisher studied the flame inhibition impact of DMMP in a premixed
methane/oxygen/N2-Ar flame in a flat flame burner slightly under atmospheric pressure at two
different equivalence ratios: rich and slightly lean. Interest in the combustion chemistry of
organophosphorus compounds was motivated by two applications: incineration of chemical
warfare agents and fire suppression. DMMP addition caused all profiles except that of CH3OH
to move farther away from the burner surface, which can be interpreted as a consequence of a
reduction in the adiabatic flame speed. This shift is a consequence of the flame inhibition
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properties of the DMMP additive. Decreases in the overall reaction rate with doping led to flame
stabilization farther from the burner surface. Experimentally, the magnitude of the shift was
50% greater for the near-stoichiometric flame than for the rich flame. Experimental CH3OH
profiles were four to seven times higher in the doped flames than in the undoped flames
(Nogueira and Fisher, 2003).
Korobeinichev et al. studied the possible mechanisms for the destruction of sarin in flames. The
structure of a premixed Th/Ch/Ar (0.26/0.13/0.61 by volume) flame doped with DMMP
stabilized on a flat burner at 47 torr has been studied by molecular beam mass spectrometry and
modeling. A study of the combustion of organophosphorus compounds (OPCs), including sarin
and its simulants (phosphates and phosphonates) such as DMMP, trimethyl phosphate (TMP),
and tributyl phosphate was of great interest for understanding and improving the incineration of
CWAs. The hallmark of the mechanisms for the destruction of DMMP and TMP is that
bimolecular reactions of either the hydroxyl radical or the free hydrogen atom are more
important than unimolecular decomposition. Some conclusions on possible mechanisms for the
destruction of sarin in flames can now be made. Unimolecular decomposition of sarin is likely
to be less important than the substitution of C3H7O or C3H7 groups by OH or H as the rate-
controlling stage for the destruction of sarin in a flame (Korobeinichev et al., 2000).
Werner and Cool developed a kinetic model of the combustion chemistry of a hydrogen/oxygen-
based flame, doped with dimethyl methylphosphonate, a useful simulant for nerve agents VX
and GB, to assist in the controlled thermal destruction of CWA stockpiles. The kinetic model
incorporated several key reaction intermediates, which included methyl metaphosphate
(CH3OPO2), methyl dioxophosphorane (CH3PO2), and monomethyl methylphosphonate
(PO(OH)(CH3)(OCH3)) (Werner and Cool, 1999).
2.11 Exothermic Intermetallic Interaction
Zavitsanos et al. developed a thermobaric self-sustaining reactive composition method and
device for destroying chemical or biological agents. The invention incorporates self-
propagating high temperature reactive materials capable of self-sustaining reactions with the
evolution of large quantities of thermal energy, creating an area of high temperatures (in excess
of 800 °C). The method involves the interaction of metals, typically of Groups IV and V of the
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periodic table, with aluminum, boron, carbon, nitrogen and silicon. Such intermetallic reactions
occur pyrotechnically without requiring an outside oxidizer source (such as atmospheric
oxygen). Energy levels released by these types of reactions can reach 17.6 kJ/cm3 (Zavitsanos
etal.,2012).
Wei et al. investigated electrically conducting polymers such as polyaniline to be used as
coatings or fabrics on military equipment (e.g., tanks, personnel carriers, artillery pieces, etc.)
and installations (e.g., buildings and other structures). These conducting polymers function as
heating elements to convert applied electric energy to thermal energy, which would raise the
surface temperature of the coatings and fabrics high enough to thermally decompose the
chemical or biological warfare agents on the equipment or installations. Through embedded
metallic (e.g., copper) wire or carbon fiber electrodes, household alternating current can be
applied to the polyaniline-coated panels leading to a rapid increase in the surface temperature
from 120 to 180 °C within a few minutes to degrade CB agents (Wei et al., 2004).
A new technique uses the flameless burning of powders containing aluminum, magnesium,
sodium nitrate (NaNCb), and oil. The powder is applied as a flat layer, approximately 10 mm
thick, and is used to remove surface coatings from the concrete, e.g., asphalt (Kumar et al.,
2010).
Motamedhashemi et al. applied the flow-through catalytic membrane reactor (FTCMR) concept
to the thermal oxidation of a chemical warfare simulant (DMMP) in air. Preliminary
experiments under different DMMP feed concentrations and reactor temperatures (373 to 573 K)
have demonstrated the potential advantage of the FTCMR concept in the catalytic oxidation of
DMMP. Complete destruction of various concentrations of DMMP in air was achieved at lower
temperatures, with the FTCMR showing superior performance when compared to a wall-coated,
plug-flow reactor (monolith) containing the same amount of catalytic metal. A mathematical
model was also developed to provide a better understanding of the fundamental transport
phenomena underpinning the FTCMR operation. The model was used for identifying the
advantages of the FTCMR concept in comparison with the wall-coated catalytic monolith and
also for investigating some of the limitations, which may exist in applying this concept for the
complete oxidation of chemical warfare simulants. The results of the model support the
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superiority of the FTCMR concept over the more conventional plug-flow monolith reactor
(Motamedhashemi et al., 2011).
2.12 Direct Heat Application
This section discusses direct heat sterilization processes for spores and evaporation rates for
chemical weapons on various surfaces.
The F-value is the minimum time that an organism present in or on an item has to be exposed at
a certain temperature to assure sterility of that item. Sterility of medical devices is defined as
finding 1 remaining viable organism in or on an item out of 106 present before sterilization (6
logio reduction). F-values are used to optimize sterilization processes to save time, energy,
money, or to reduce the exposure time of thermo-liable products to high temperatures. For a
given temperature and time, the F-value for a process can be calculated. To calculate the F-value
for temperatures other than those reported in the literature, empirical models are used with the
decimal reduction time (D) and the temperature resistance coefficient (Z) as parameters. The D-
value (min) is the time required to reduce the number of organisms by a factor of 10. The Z-
value (°C) is the temperature required for one logio reduction in the D-value. The Z-value can be
found by making a thermal resistance curve by plotting the logarithm of the D-value versus the
temperature. The Z-value can be found by taking the reciprocal of the slope from the plot
(Doornmalen and Kopinga, 2009).
The dry heat F-value, the time (in minutes) that causes the complete destruction of
microorganisms at 200 °C for G. stearothermophilus and B. atrophaeus is 1.3 and 1.1 min,
respectively. These times are similar to the F-value of 1.2 min for B. cmthracis at the same
temperature (Wood et al., 2010). Wood et al. conducted tests in a dry heat oven to determine the
destruction kinetics for B. atrophaeus, B. anthracis (Sterne) and G. stearothermophilus. The dry
heat oven tests were conducted at 175 °C, and the D-values were 0.4, 0.2 and 0.3 min for B.
atrophaeus, B. anthracis (Sterne), and G. stearothermophilus, respectively (Wood et al., 2010).
The dry heat D values and Z values are shown in Figure 2-30.
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r-valxje = 35-7 C
R--0-99
z-value = 56-8 C
R=-0-99
0-1
150
175
200
Temperature (°C)
Figure 2-30. Dry Heat D-values and Z-values for Biological Indicators (Geobacillus
stearothermophilus [squares], B. anthracis [circles], and B. atrophaeus [triangles]) (Adapted
with permission from Wood et al., Copyright 2009 The Society for Applied Microbiology)
Denison et al. determined the sterilization values of B. subtilis spiked on ceiling tile and
wallboard. The bundles were approximately 50% water. Testing was performed at the EPA's
RKIS facility. The Z values were 159 and 281 K for ceiling tile and wall board, respectively
(Denison et al., 2005).
Jung et al. investigated the thermal effects on bacterial bioaerosols of Escherichia coli and B.
subtilis by using a thermal electric heating system in continuous air flow. The bacterial
bioaerosols were exposed to a surrounding temperature that ranged from 20 °C to 700 °C for
approximately 0.3 s. Both E. coli and B. subtilis vegetative cells were rendered more than 99.9%
inactive at 160 °C and 350 °C of wall temperature of the quartz tube, respectively. Although the
data on bacterial injury showed that the bacteria tended to sustain greater damage as the
surrounding temperature increased, Gram-negative E. coli was highly sensitive to structural
injury but Gram-positive B. subtilis was slightly more sensitive to metabolic injury. In addition,
the inactivation of E. coli endotoxins was found to range from 9.2% (at 200 °C) to 82.0% (at 700
°C). However, the particle size distribution and morphology of both bacterial bioaerosols were
maintained, despite exposure to a surrounding temperature of 700 °C. The results show that
thermal heating in a continuous air flow can be used with short exposure time to control bacterial
bioaerosols by rendering the bacteria and endotoxins to a large extent inactive (Jung et al., 2009).
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Geyer et al. described a concept of applying heat to a structure to sterilize biological agents. Dry
heat of 150 °C for 10 minutes effectively sterilizes most items contaminated with active
biological agents, e.g., bacteria, fungi, etc. While 150 °C may be difficult to achieve when
heating an entire structure, at least not without adversely affecting some architectural elements,
heating a structure and its contents to 80 °C has its merits and is possible with today's
technology. Moreover, holding a structure at 80 °C for 60 minutes not only kills most active
biological agents, it accelerates the neutralization of many harmful toxins, accelerates
vaporization of water vapor and chemicals, and oxidizes odors. If an anthrax-contaminated
structure is heated so that the architectural components are 150 °C for 480 minutes, the structure
should not only be free of viable anthrax spores, but some of the components may be damaged
from the high temperature (Geyer et al., 2002).
Heat can be generated using thermal solar radiation, the heating ventilation and air conditioning
(HVAC) system of a building, portable electric-inductive heaters, lamps, etc. Portable fuel-fired
heaters (burning natural gas, propane, or kerosene) can also generate heat. The type of
contamination helps to determine the degree of necessary heat penetration. If contamination
occurs from airborne spores, the spores may be surficial and not deep within walls, dimensional
timber, or masonry units. The heating process can therefore be surficial in design. Where
materials have become moist and promote fungal growth and amplification, heating should be of
sufficient duration to achieve the saturation temperature required to kill organisms deep within
affected materials. Thermal desorption of CWAs can be achieved by the use of heated air that
results in evaporation of the contaminant. With this method, the toxic agent is released into the
atmosphere and may present an increased vapor hazard (Boone, 2007). Depending on the site,
HEPA units could be used to filter and circulate air within the heated area, assisting in heat
distribution; it may also be necessary to place HEPA units outside of the heated area and duct the
air to the unit. Propane-fired burner-fan units have been demonstrated to be the most flexible,
scalable, and cost-effective heat generators. Heating contaminated materials will not take the
place of removing gross levels of contamination. This technology complements traditional
remediation methods after gross removal is complete and reduces most labor-intensive detailed
cleaning efforts currently performed to achieve clearance criteria (Geyer et al., 2002).
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The evaporation rates and reaction mechanism for a droplet of distilled sulfur mustard agent
from stainless steel and aluminum substrates are reported by Jung and Lee. For systematic
analysis, we used a laboratory-sized wind tunnel, thermal desorption (TD) connected to a gas
chromatograph/mass spectrometer (GC/MS) and droplet shape analysis (DSA). Jung and Lee
found that the evaporation rates (mg/'m3) of HD from stainless steel and aluminum increased with
temperature as shown in Figure 2-3 1. The rates were also linearly proportional to droplet size.
The time-dependent contact angle measurement showed that the evaporation of the droplet of
HD proceeded only by a constant contact area mechanism from stainless steel surface. The
evaporation of HD from aluminum proceeded by a combined mechanism of constant contact
area mode and constant contact angle mode. The experimental data sets and analysis could be
used to predict vapor and contact hazard persistence of CWAs in the air and on exterior surfaces
with chemical releases, which assists the military decision influencing personnel safety and
decontamination of the site upon a chemical attack event (Jung and Lee, 2014).
M
^ 0»
If*"
#«
DM
Stainless steel
•
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Page 69 of 103
Rowland et al. developed methods for testing off-gassing from selected military-relevant
surfaces and to establish a model for predicting off-gassing from a broad range of such surfaces.
Vapor-contaminated surfaces were investigated by exposing representative field materials to
CWA simulants and then monitoring the off-gassing concentration as a function of time.
Concrete, plastic, wood, steel and latex paint surfaces were contaminated with triethyl phosphate,
4-chlorobutyl acetate, 3-hepten-2-one, trimethyl phosphate, and 2-isobutyl-3-methoxypyrazine.
The testing process and simple analysis model provided test and analysis methods that were used
to test agent off-gassing and served as a standard for vapor hazard testing following vapor
exposure. Use of the simple model was justified, based on analyses of the measured off-gassing
trends and the predicted trends of interaction between each compound and each surface
(Rowland et al., 2010).
A model for evaporation of chemical warfare agents on the ground was developed by Westin et
al. The process of evaporation is described in three steps: 1) the immediate drop enlargement
due to impact momentum is modeled using an empirical correlation from the technical literature;
2) further enlargement caused by capillary spreading upon the surface and the simultaneous
sorption into the substrate, modeled in three dimensions; and 3) subsequent drying and
redistribution of the sorbed material is described as a one-dimensional vertical process. The
formulation of the flux in the soil takes into account vapor, liquid, solute, and adsorbed phases.
The evaporation from the surface was determined by the vapor concentration at the surface and
the conditions in the atmospheric viscous sub-layer close to the droplet spots on the surface.
Model results agreed with the limited experimental data found in the literature. The model
showed a very rapid sorption and redistribution of chemical warfare droplets on sand. This
effect gives a rapid decrease of the evaporation, except for a shorter initial period. However, a
small residual evaporation from liquid exists for a rather long time when the liquid has
penetrated down into the soil (Westin et al., 1998).
Steam cleaning, which combines the solvent action of hot water with the kinetic energy effect of
blasting, is recommended for removing contamination from complex shapes and large surfaces,
even if grease or similar substances are present, and for removing contaminated soil particles
from earth moving and drilling equipment. Secondary waste volumes produced by the process
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Page 70 of 103
are relatively low as the steam can be collected by vacuum extraction or similar means and
condensed (Kumar et al., 2010).
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3 NEUTRALIZATION/HYDROLYSIS AND TREATMENT OF
HYDROLYSATE
This section reviews neutralization/hydrolysis of chemical agents and treatment of hydrolysate.
3.1 Neutralization/Hydrolysis
Neutralization employs process conditions that are specific for each type of agent. Thus, a
neutralization process for destroying a specific agent or class of agents would not be suitable for
treating a wide range of other wastes (e.g., commercial hazardous wastes). Variations in the
process may be needed when treating different types of the same agent such as H, HD, and HT.
A particular benefit from neutralization is that it detoxifies the mustard agent rapidly at low
temperature and low pressure. Batch or semi-batch processing allows retention of the products
from neutralization until testing can verify destruction of the chemical agent (Pearson and
Magee, 2002).
Two methods of neutralization of mustard through hydrolysis have been demonstrated: hot water
at 90 °C and a caustic solution. The Pueblo Chemical Agent-Destruction Pilot Plant (PCAPP)
used hot water hydrolysis to neutralize the mustard agent. However, because sulfonium ions
(SR3+) present after water hydrolysis can cause a false positive in the analytical gas
chromatographic method for testing the hydrolysate to establish that the hydrolysate is clear of
mustard agent, a heated caustic hydrolysis step (using sodium hydroxide (caustic) at pH > 10)
follows the hot water hydrolysis reaction. The caustic hydrolysis removes the interference due to
SR3+ where R is an organic substitute such as methyl (CH3) attached to sulfur (Nurdogan et al.,
2012).
The hydrolysis process results in an irreversible chemical reaction in which the mustard agents
are destroyed and a byproduct called hydrolysate is formed. In the hot water reaction, HD is
converted to TDG (HOCH2CH2SCH2CH2OH), a readily biodegradable compound, and HC1.
The reaction proceeds to completion with no detectable agent (< 4 ppb) remaining in the product
(Nurdogan et al., 2012).
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Many kinetic and mechanistic studies have been done on the hydrolysis of G-type chemical
agents, which include tabun (GA), GB, and GD. Hydrolysis in basic media works well for these
agents but less well with sulfur mustard (H or HD). Direct base hydrolysis is not effective for V
agents, an example of which is VX. However, oxidation of the sulfur in VX in an aqueous acid
medium is rapidly followed by hydrolysis to non-toxic products. An acidic medium also causes
protonation of the amine nitrogen, both increasing the solubility of VX and enhancing the
oxidation of sulfur (Raber and McGuire, 2002).
3.2 Treatment of Hydrolysate
Chemical agents can be disposed of with technologies based on chemical neutralization. This
destruction process results in the production of a solution called hydrolysate that retains some
undesirable characteristics and requires further treatment to comply fully with the requirements
of the CWC (Pearson and Magee, 2002).
Although neutralization of HD detoxifies the agent, the resulting hydrolysate needs further
treatment prior to final disposal. Treatment of the hydrolysate has to destroy both thiodiglycol,
which is the major residual in the hydrolysate, and any chlorinated volatile organic compounds
(VOCs) that result from impurities in the HD. Management of hydrolysate from HD
neutralization may be either on site, through additional treatment following the neutralization
process, or off site, by shipping the hydrolysate to a permitted waste-management facility
(Pearson and Magee, 2002).
On-site treatment of the hydrolysate requires substantially more complex processing than does
the neutralization process alone. The primary process considered for on-site treatment of
mustard agent hydrolysate is biodegradation. Aqueous effluent from an on-site biodegradation
process could potentially be discharged to the existing publicly or federally owned treatment
works or, alternatively, the water could be recycled if zero liquid effluent discharge is desired
(Pearson and Magee, 2002).
The hydrolysate produced by the neutralization of mustard is a turbid amber liquid that is
approximately 90% water and salts (mainly sodium chloride and iron salts). HD mustard is
hydrolyzed to an organic chemical called thiodiglycol (TDG), while HT mustard is hydrolyzed to
TDG and a similar compound, T-alcohol (an ethyl ether compound) (Nurdogan et al., 2012).
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3.2.1 Incineration of Hydrolysate
Ember reported on the incineration of VX hydrolysate (VXH) from the destruction of VX
chemical weapons in Newport, Indiana. The VXH was transported to the Veolia Environmental
Services incineration facility in Port Arthur, Texas. By March of 2008, 84% of the VHX was
incinerated (Ember, 2008).
Notman reported that following pressure from the international community, the Syrian
government joined the Chemical Weapons Convention (CWC) and in doing so, agreed to destroy
their chemical weapon stockpiles. In September 2014, the Syrian government declared
approximately 1,000 tonnes (1,100 tons) of chemical weapons, mostly precursors, and
approximately 290 tonnes (319 tons) of raw materials. The blister agent sulfur mustard was the
only complete chemical weapon declared. The plan was to chemically neutralize approximately
560 tonnes (616 tons) of sulfur mustard at sea aboard the US Navy ship Cape Ray. The effluent
from the Cape Ray hydrolysis operation was incinerated in Germany. The mustard would be
hydrolyzed using a batch process facilitated by the titanium reactor at a ratio of approximately
13.5 parts 95 °C water to one part ambient mustard. The mustard breaks down in hot water to
hydrochloric acid and thiodiglycol. The second step was to adjust the pH of the effluent to
neutral using sodium hydroxide. The neutralization process generates hazardous waste effluent
in volumes of five to 13.5 times the volume of the chemical warfare material being treated
(Notman, 2014).
3.2.2 Supercritical Water Oxidation of Hydrolysate
A one-component fluid is loosely defined to be supercritical when its temperature and pressure
exceed its critical temperature and pressure, respectively, while it is not far from its critical state.
Supercritical water oxidation (SCWO) is the oxidation of organics with air or oxygen, in the
presence of a high concentration of water, under temperatures and pressures above the critical
point values of water, 374 °C and 22 MPa (218 atmospheres) (Yesodharan, 2002).
As a waste destruction process, SCWO has several advantages over conventional processes and
even some of the relatively modern processes such as wet-air oxidation and incineration. These
advantages arise mainly from the properties of supercritical water (SCW) itself. The gas-like
low viscosity promotes mass transfer. The liquid-like density promotes solvation. The low
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dielectric constant promotes dissolution of nonpolar organic materials. The high temperature
increases thermal reaction rates. These properties provide a reactor medium in which mixing is
fast, organic materials dissolve well and react quickly with oxygen, and the salts precipitate
(Yesodharan, 2002).
The oxidation reaction is complete when carbon goes to carbon dioxide, hydrogen to water,
nitrogen compounds to nitrogen or nitrous oxide. Heteroatoms form the corresponding oxyacids
or salts if cations are present in the waste or added to the feed. Under supercritical conditions,
the salt may remain dissolved in the SCW medium or condense as a concentrated brine solution
or as a solid particulate. Heavy metals may form oxides or carbonates, which may or may not
precipitate, depending on their volatility. Inert solids will largely be unaffected by the medium
and remain as solids. Time required to complete the reactions is short. Reactor residence time
ranging from a few seconds to a few minutes is sufficient for complete decomposition of most
waste materials. Shorter reactor residence time means higher waste throughput (Yesodharan,
2002).
SCWO was originally selected for the treatment of the hydrolysate from the nerve agent VX
stored at the Newport, Indiana, storage site. The SCWO system is a hydrothermal process for
the oxidation of hydrolysate that yields a wastewater stream and salts. In a typical chemical
agent destruction process, agent would be drained from the weapon or container, hydrolyzed in a
well-stirred reactor, tested to verify agent destruction, and then released to the SCWO process
unit. The hydrolysate is heated and pumped into an SCWO reactor along with an oxidizing
agent (air or oxygen), and the heat of reaction increases the temperature to 600 to 650 °C under
about 275 bar pressure. In the course of approximately 30 s, the organic components are largely
(approximately 99.99 %) oxidized to water and sodium salts, as well as gaseous nitrogen
containing products (e.g., N2 and NOx). This mixture of materials is cooled by adding quench
water and through heat exchange and then released from the SCWO reactor through a pressure
reduction system. The resulting effluent is a mixture of gases (O2, N2, CO2), a concentrated
aqueous salt solution, and entrained solid salts. Trace concentrations of partially oxidized
organic constituents may also be present. The aqueous products from the SCWO reactor,
including entrained solids, are then fed to the evaporation unit, where the mixture is heated to
distill excess water. At this point, the salts that have crystallized from solution are filtered and
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Page 75 of 103
packaged for disposal in a secure landfill. A large portion of the water distilled from the SCWO
effluent is recycled back to the process. All gases reduced during the SCWO treatment step are
filtered prior to release (Pearson and Magee, 2002). The Newport site decided to use
incineration for hydrolysate treatment at Veolia in Port Arthur, TX (hydrolysate was shipped
there).
DMMP is a simulant for VX. DMMP can readily be hydrolyzed to methylphosphonic acid
(MP A) during the preheating stage of the SCWO process. Laboratory-scale, continuous-flow
reactor tests were conducted to confirm the destruction efficiency of MP A and the effect of
sodium hydroxide on MPA destruction efficiency under SCWO conditions. The reaction
temperatures ranged from 400 to 594 °C; the reactor residence times varied from 3 to 83 s; and
the oxygen concentrations varied from 110 to 200% of stoichiometric requirements. Fixed
parameters included: (1) a nominal pressure of 27.6 MPa (4,000 psi); (2) a MPA feed
concentration of 1,000 mg/L; (3) a feed flow rate of 25 g/min; and (4) a NaOH to MPA molar
ratio of 2:1. MPA was effectively destroyed, as indicated by the C-P bond cleavage, within the
selected SCWO conditions. Specifically, greater than 99% DE of MPA was achieved at a
temperature of 550 °C, pressure of 27.6 MPa, oxygen concentration of 200% of stoichiometric
requirements, and reactor residence times of less than 20 s. In addition to the oxidation end
product of CO2, CO and CH4 were major gaseous byproducts. Methanol was the only liquid
organic byproduct detected. Data derived from these limited MPA/NaOH experiments indicated
that the formation of salts did not affect the overall effectiveness of SCWO for destroying MPA.
Eventually, means to remove precipitated salts from the reactor should be incorporated into the
overall design of an SCWO facility for treating the VX/NaOH hydrolysate (Bianchetta et al.,
1999).
Kim et al. reported that in 2003, neutralization followed by SCWO was selected as the
technology to destroy the chemical weapons stockpile at the Blue Grass Army Depot. After
neutralization and chemical analysis, the hydrolysate was transferred with oxidizing agent (air or
oxygen) to the SCWO. The SCWO reaction mechanism generally follows free radical chain
pathways that involve important oxidative radicals such as *OH and •OOH, Within
approximately 30 s, the organic components were largely oxidized to water and sodium
carbonate, phosphate, and sulfate, as well as gaseous nitrogen-containing products (e.g., N2 and
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Page 76 of 103
N2O). After cooling with quench water, the mixture from the SCWO reactor was released
through a pressure reduction system. The resulting effluent was a mixture of gases (O2, N2, and
CO2), a concentrated aqueous salt solution, and entrained solid salts. The aqueous salts
underwent distillation to remove water in the evaporating section. Salts crystallized from this
solution were filtered and packaged for landfill disposal. The disadvantage of second-stage
technology is the corrosion of heating and cooling elements on either side of the supercritical
water reactor. Frequent replacement of the reactor liner was planned for the SCWO units at the
Blue Grass Chemical Agent Destruction Plant (Kim et al., 2011).
3.2.3 Biological Treatment of Hydrolysate
Biodegradation exploits the ability of certain microorganisms—bacteria or fungi—to degrade
hazardous organic materials to innocuous materials such as carbon dioxide, methane, water,
inorganic salts, and biomass. Microorganisms can derive the carbon and energy required for
growth through biodegradation of organic contaminants. The biodegradation of organic
constituents in agent destruction process streams can be carried out either on site in coordination
with the agent destruction process or off site at a permitted commercial TSDF (treatment,
storage, or disposal facility) (Pearson and Magee, 2002).
The bioreactor design for aerobic treatment needs to solve two problems. First, the bacteria must
be in contact with the contaminants for extended periods of time to complete the biochemical
reactions. Secondly, the design needs to ensure oxygen transfer to the bacteria. Energy
requirements for oxygen transfer usually constitute the main operating cost of a bioreactor, other
than manpower costs. Designs for biological treatment of hydrolysate are based on systems
designed to treat wastewater. Bioreactors for treating contaminated water can be separated into
several main types:
• Suspended-growth reactors. The bacteria are grown in the water and mixed with the
organic contaminants in the water. Oxygen is supplied through a surface aerator or air
diffusers.
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Page 77 of 103
• Fixed-film reactors. The bacteria are grown on an inert support medium within the
reactor. The contaminated water passes over the attached bacteria and forms a thin water
film into which the contaminants and oxygen diffuse.
• Submergedfixed-film reactors. In this version of the fixed-film reactor, the water is in
constant contact with the bacterial film, as opposed to passing through in thin water films.
• Reactors based on activated carbon. The combination of powdered activated carbon
adsorbs organic contaminants and acts as an attachment site for bacteria (Pearson and
Magee, 2002).
In an aqueous solution, sulfur mustard spontaneously hydrolyzes and generates TDG. Thus,
TDG as a hydrolyzate of sulfur mustard will accumulate in soil and remain in nature for long
periods. Nocardioforms of bacterium such as Rhodococcus and Gordonia are frequently isolated
from soil and have been shown to exhibit a wide range of degradative and/or oxidative functions,
including hydroxylation, sulfoxidation, or dehalogenation. Cultivation and resting cell reactions
are carried out aerobically at 30 °C. The reaction was started by adding the substrate TDG
aqueous solution to the cell suspension. Among the tested strains, strain T09 showed the highest
degradation activity as shown in Figure 3-1 where cell growth increased with time and TDG
concentration decreased (Bassi et al., 2009).
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Page 78 of 103
d.oi P
o
4
-------
Page 79 of 103
(DTP), and 1,4-thioxane (TX). These hydrolysates were investigated at pH 3, pH 7, and pH 10
under dark and monochromatic UV light irradiation. The presence of monochromatic UV light
at 220 nm, 240 nm, or 254 nm made insignificant improvements in hydrolysates of chemical
warfare agents HCWA degradation at low pH (Tang and Weavers, 2007).
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INCINERATOR MODELING RESULTS
Systematic evaluation of the effectiveness of incineration of CB agents bound on building
materials in a full-scale incineration system is not practical. The chemical demilitarization
incinerators that process CWAs on a routine basis are tightly regulated facilities that have strict
operating permits, in addition to the international agreements that define their operations. These
facilities would not be amenable to a performance test where there may be suboptimal operating
conditions as part of the test matrix. Testing CB agents on conventional incinerators would be
difficult at best, due to community relations and shareholder issues with the facility that would
likely arise, even if the permitting hurdles could be overcome. In addition, performing such a
test on a full-scale facility that potentially would require tens to hundreds of tons of feed material
per day would be prohibitively expensive.
Rather, an approach has been taken to perform bench- and pilot- scale testing using surrogates,
combined with computer simulations of full-scale incineration facilities that use the data derived
through the sub-scale experiments and other sources to provide the required kinetic mechanistic
information. Figure 4-1 illustrates this concept.
Bench-Scale
Experiments
Develop
Destruction
"Kinetics"
Modeling of
Pilot-Scale
ncinerator
Pilot-Scale
Experiments
Model
Calibration
Modeling of
Full-Scale
Incinerator
Figure 4-1. Modeling Concept
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Page 81 of 103
To achieve this goal, a computer simulation was developed that was based on a simulation
developed for the U.S. Department of Defense (DoD) to predict the behavior of CWA-containing
munitions in the various furnaces used in the chemical demilitarization program (Denison et al.,
2004). This simulation was adapted to model conventional full-scale incinerators feeding solid
fuel mixed with arbitrary solid materials with user-defined amounts of chemical and biological
agents bound on the solid materials. This simulator was called "The Configured Fireside
Simulator" or CFS. The kinetic data for CWA destruction were the same mechanisms used in
the previous work for the DoD (Denison et al., 2004). The kinetic data for the BWA destruction
was derived from the bench- scale experiments described earlier (Lemieux et al., 2005).
This section discusses the results from the incinerator models using EPA's CFS tool to model the
destruction of three chemical agents (GB, VX, and HD) and one f (Ba) with three types of
furnaces: a commercial hazardous waste burning rotary kiln (COM), a medical/pathological
waste incinerator (MEDPATH), and a stoker furnace (STO).
In 2005, Lemieux evaluated thermal processing of BDR material in commercial incinerators by
using an incinerator modeling tool developed by EPA. The simulator included a range of
models, from time-dependent process models to detailed Computational Fluid Dynamics (CFD)
models. Using computational chemistry methods, detailed chemical kinetic mechanisms were
developed that describe the incineration of mustard blister agent and the nerve agents GB and
VX. The first unit, the EPA RKIS facility, is a simulated pilot-scale rotary kiln incinerator
located at the EPA research facilities in RTP, NC. The EPA RKIS facility has a primary and
secondary burner, each rated at 73 kW. The second combustion unit is a commercial dual-
chamber starved-air modular medical/pathological waste incinerator that is currently being
operated jointly by the EPA and National Institutes of Environmental Health Sciences (NIEHS)
on their RTP, NC campus. This facility has a nominal firing rate of 1 megawatt MW and is
capable of processing approximately 400 kg/h of wastes, which consist mostly of animal
bedding. The third combustion unit is a commercial hazardous waste-burning rotary kiln system
currently in operation in East Liverpool, OH. This unit has a nominal firing rate of 35 MW and
processes approximately 8,100 kg/h of hazardous waste from various sources. Data available for
interrogation from the CFD model include gas temperature, velocity, agent concentration,
combustion products (major and minor species), pressure as well as wall and equipment surface
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temperatures and incident heat fluxes. Pilot-scale experiments were used to calibrate the models
(Lemieux et al., 2005).
In 2015, EPA ran incinerator models following the design factors in Table 4-1 with three furnace
types, four CB agents, and three bundle bed locations in the furnace. The bed location was the
percent of the bundle exposed to hot gas in the furnace. The high bed location corresponds to
70% of the bundle exposed to the hot gas. For the mid and low conditions, 45% and 20% of the
bundle was exposed to the hot gas in the furnace, respectively. Therefore, the low bed condition
simulated bundles buried in the furnace. In Table 4-2, the simulator model test parameters are
presented.
Table 4-1. Experimental Design Factors for CFS Model
Factor
Level
A
B
C
Furnace
Agent
Bed Location
1
Stoker
GB
low
0
Med/Path
VX
mid
-1
Rotary Kiln
HD
high
0.5
Ba
Nine net files were created for each furnace model with inputs for the type of agent, bundle
moisture content, and bed location. A total of 36 net files were created. After the net files were
created, the net files were entered into the CFS simulator and executed in transient mode. The
bundle parameters (density, conductivity, specific heat, moisture mass fraction, surface
emissivity, dimensions, and Z value [for biological agents]) in the CFS simulator are shown in
Figure 4-2. Group A is for the furnace type, group B for the agent, and group C for the bed
location.
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Table 4-2. Simulator Model Table of Test Parameters
Test ID
Furnace
Agent
Bed
Location
1
A-i
Bi
C-i
2
A-i
Bi
Ci
3
Ai;i
Bi
Co
4
Ai
Bi
C-i
5
Ai
Bi
Ci
6
A-i
Bo
Co
7
Ai;i
Bo
C-1
8
Ai;i
Bo
Co
9
Ai;i
Bo
Ci
10
Ai
Bo
Co
11
A-i
B-i
C-1
12
A-i
B-i
Ci
13
Ai;i
B-i
Co
14
Ai
B-i
C-1
15
Ai
B-i
Ci
16
Ai;i
Bo. 5
C-1
17
A-i
Bo. 5
Co
18
Ai;i
Bo. 5
Co
19
Ai
Bo. 5
Co
20
Ai;i
Bo. 5
Ci
<7k transientComJD
I b U J
Zones ^ Natural Gas ^ Bundle \ Bundle (cont) \
|0.0001
1534.0
—General Properties
Agent Mass Fraction
Density (kg/m"3)
Conductivity (W/rnK)
Specific Heat (J/kg-K) |835
Furnace view factor'bundle surface emissivity 10.2
Critical moisture mass fraction
|0.6
10.08
X Dimension 0.3
Y Dimension 0.075
2 Dimension 0.075
Number of Nodes
X Dimension [3
Y Dimension [3
Z Dimension |3
Bio Destruction
AorC,1/sf3O0i
E/R or2,K 13568.3
(* Arrhenius
C Z Value
Only apply when agent is BIO
Figure 4-2. CFS COM Model Bundle Input Parameters
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4.1 COM Model
This section discusses the CFS COM model results. The CFS simulator allows the user to plot
furnace parameters against time. The gas temperature, the minimum temperature of pieces of
bundle, and fraction of agent remaining were plotted against time in the furnace.
4.1.1 Gas Temperature
In Figure 4-3, the gas temperature for Ba, GB, HD, and VX are plotted versus time for the COM
model. The gas temperature is the highest (approximately 1,200 °C) for the low bed condition
for all the agents, which is expected as the bundle is buried in the furnace. The gas temperature
is the lowest (approximately 1,125 °C) for the high bed location condition (bundles are not
buried in the furnace and are exposed to hot gas) for GB, FID, and VX. For GB, HD, and VX the
gas temperatures are fairly stable for all bed conditions.
COM Model Gas Temperature, Ba
1,400
1.200
u- 1,000
t
= 800
E
o
5 600
£
O 400
200
0
—zone temp-com-BA-low
—zone temp-com-BA-mid
—zone temp-com-Ba-high
50 100 150 200 250 300 350 400 450 500
Time (min)
COM Model Gas Temperature, GB
1,400
1,200
1,000
800
600
400
200
0
—zone temp-com-GB-low
—zone temp-com-GB-mid
—zone temp-com-GB-high
50 100
150 200 250 300
Time (min)
350 400 450 500
1,400
1,200
g
E 600
O 400
200
0
COM Model Gas Temperature, HD
COM Model Gas Temperature, VX
—zone temp-com-HD-low
—zone temp-com-HD-mid
zone temp-com-HD-high
200 250 300
Time (min)
350 400 450
1,400
1,200
1,000
800
600
400
200
0
—zone temp-com-VX-low
—zone temp-com-VX-mid
— -zone temp-com-VX-high
200 250 300
Time (min)
350 400 450
Figure 4-3. COM Model, Gas Temperature
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Page 85 of 103
4.1.2 Minimum Piece Temperature
In Figure 4-4, the minimum piece temperatures for Ba, GB, HD, and VX are plotted versus time
for the COM model. In the plots, the temperature remains at 100 °C for approximately 50
minutes as the water in the bundles vaporizes. Then, the bundle temperature starts to increase
again. The high and medium bed locations reach 100 °C before the buried bundles in the low
condition. For all the agents, the temperature in the bundle for the low bed condition does not
increase above 450 °C at the end of the heating cycle, whereas for the high and medium bed
conditions, temperatures climb to approximately 600 °C. For Ba, the temperature reaches 450
°C after 475 minutes at the low bed condition, but it takes approximately 300 minutes to reach
the same temperature for GB, HD, and VX.
COM Model Piece Tmin, Ba
COM Model Piece Tmin, GB
700
700
—piece tmin-com-BA-low
—piece tmin-com-BA-mid
—piece tmin-com-Ba-high
—piece tmin-com-GB-low
—piece tmin-com-GB-mid
— piece tmin-com-GB-high
600
600
500
500
400
400
« 300
g 300
200
200
100
100
0
0
0
100 150 200 250 300 350 400 450 500
Time (min)
150 200 250 300 350 400 450 500
Time (min)
0
100
COM Model Piece Tmin, HD
COM Model Piece Tmin, VX
700
700
600
500
—piece tmin-com-HD-Iow
—Piece tmin-com-HD-mid
—piece tmin-com-HD-high
600
500
—piece tmin-com-VX-low
—piece tmin-com-VX-mid
—piece tmin-com-VX-high
g
~400
1
H
g 300
£
JZL //
U
~ 400
E
H
S 300
-
£
1±h01+F
200
//
200
///
100
/ /
100
///
^
0
0
0 50 100 150 200 250 300 350 400 450 500
0 50 100 150 200 250 300 350 400 450 500
Time (min)
Time (min)
Figure 4-4. COM Model, Minimum Piece Temperature
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Page 86 of 103
4. /. 3 CB Agents Remaining
In Figure 4-5, the fraction of agent left for Ba, GB, HD. and VX is plotted versus time for the
COM model. For all the agents, the low bed condition requires the most time for all of the agent
to be destroyed. For Ba, no agent remains after 45 minutes for the high bed condition, but
approximately 350 and 400 minutes, respectively, are required for all the agent to be destroyed
for the medium and low bed conditions. For GB, FID, and VX, no agent remains for the high
bed condition after 175, 180, and 220 minutes, respectively. VX required the most time to
destroy all the agent as it has a higher boiling point (298 °C) than FDD (218 °C) and GB (158 °C).
•c q ^ —agent left-com-HD-low
Jj | —agent left-com-HD-mid
\ -X —agent left-com-HD-high
200 250 300 350 400 450
Time (min)
1.0
0.9
« 08
| 0.7
I 0.6
I 0.5
0.4 ,
¦s ^ ^ -w —agent left-com-VX-low
S ~\ \ \ —agent left-com-VX-mid
0.2 1 \ \ —agent left-com-VX-high
0.1
150 200 250 300 350 400 450
Time (min)
1.0
0.9
0.8
on
c
1 0.7
cs
E
£ 0.6
S n c
51
•<
® 04
—agent left-com-GB-low
g ' —agent left-com-GB-mid
0.2 *• —agent left-com-GB-high
0.1
200 250 300 350 400 450
Time (min)
200 250 300 350 400 450
Time (min)
COM Model Agent Remaining, Ba
COM Model Agent Remaining, GB
COM Model Agent Remaining, HD
COM Model Agent Remaining, VX
Figure 4-5. COM Model, Agent Left
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4.2 Stoker Model
This section discusses the stoker model results. The gas temperature and the minimum piece
temperature are plotted with time for Ba, GB, HD, and VX.
4.2.1 Gas Temperature
In Figure 4-6, the gas temperature for Ba, GB, HD, and VX is plotted with time. For all the CB
agents and bed conditions, the gas temperature profiles are similar. The gas temperature rises
quickly to 200 °C, then climbs to 1,200 °C after approximately 360 minutes.
Stoker Model, Gas Temperature, Ba
Stoker Model, Gas Temperature, GB
1,400
1,400
—zone temp-stoker-Ba-low
—zone temp-stoker-Ba-mid
—zone tenip-stoker-Ba-high
—zone temp-stoker-GB-low
—zone tcmp-stoker-GB-mid
—zone temp-stoker-GB-high
1,200
1,200
1,000
« 400
W 400
200
200
100
150
200
Time (min)
250
300
400
100
150
200
Time (min)
250
300
350
400
Stoker Model, Gas Temperature, HD
Stoker Model, Gas Temperature, VX
150
250
350
100
200
Time (min)
300
400
100
150
200
Time (min)
250
300
350
400
Figure 4-6. Stoker Model, Gas Temperature
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4.2.2 Minimum Piece Temperature
In Figure 4-7, the minimum piece temperature for Ba, GB, HD, and VX is plotted with time for
the stoker model. For all the CB agents, the minimum temperature for the low bed condition
does not raise above 100 °C. The high bed condition reaches 100 °C before the other bed
conditions. The medium and high bed conditions remain at 100 °C for approximately 70 minutes
for all the agents. The minimum temperature for the medium bed location rises to approximately
300 °C for all the agents. For all the agents, the minimum piece temperature reaches
approximately 400 °C for the high bed condition.
Stoker Model, Piece Tmin, GB
Stoker Model, Piece Tmin, HD
450
—piece tmin-stoker-HD-low
—piece tmin-stoker-HD-niid
—piece tmin-stoker-HD-high
—piece tmin-stoker-GB-low
—piece tmin-stokcr-GB-mid
piece Imin-stoker-GB-high
400
400
350
350
300
300
U
u
B 250
1
t 200
5
h-
200
150
150
100
100
50
50
0
0
200
Time (min)
250
300
350
400
0
100
150
0
100
150
200
Time (min)
250
300
350
400
Stoker Model, Piece Tmin, VX
Stoker Model, Piece Tmin, Ba
450
450
—piece tmin-stoker-Ba-low
—piece tmin-stoker-Ba-mid
—piece tniin-stoker-Ba-high
—piece tmin-stoker-VX-low
—piece tmin-stoker-VX-mid
—piece tmin-stoker-VX-high
400
400
350
350
^300
U
= 250
1
« 200
«
150
300
250
200
150
100
100
50
0
0
0
50
100
150
200
Time (min)
250
300
350
400
0
100
150
200
Time (min)
250
300
350
400
Figure 4-7. Stoker Model, Minimum Piece Temperature
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4.3 MEDPATH Model
This section discusses MEDPATH model results. The gas temperature, the minimum
temperature of a piece of bundle, and the fraction of agent remaining are plotted against time for
Ba, GB, ITD, and VX.
4.3.1 Gas Temperature
In Figure 4-8, the temperatures rise quickly to 850 °C for the first cycle and peak at
approximately 1,100 °C before dropping. The peak temperatures for the subsequent cycles are
lower, approximately 1,025 °C for all the agents. For the third cycle in the plots, the temperature
of the lower bed condition rises before the other bed conditions.
MEDPATH Model Gas Temperature, Ba
MEDPATH Model Gas Temperature, GB
1,200
1,200
1,000
,000
600
600
—zone temp-medpath-GB-low
—zone temp-medpath-GB-mid
zone temp-med path-GB-high
400
—zone temp-med path-Ba-lon
—zone temp-med path-Ba-niid
—zone temp-med path-Ba-high
200
200
100
Time (min)
Time (min)
MEDPATH Model Gas Temperature, HD
MEDPATH Model Gas Temperature, VX
1,200
1,000
800
800
600
400
400
—zone temp-medpath-VX-low
—zone temp-medpath-VX-mid
—zone temp-niedpath-VX-high
—zone temp-medpath-HD-low
—zone temp-medpath-HD-mid
zone temp-niedpatli-HD-high
200
200
Time (min)
Time (min)
Figure 4-8. MEDPATH Model, Gas Temperature
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4.3.2 Minimum Piece Temperature
In Figure 4-9, the minimum piece temperature is plotted for Ba, GB, HD, and VX with time. For
all the agents the high bed condition reaches 100 °C before the other bed conditions and climbs
to approximately 725 °C after approximately 500 minutes. Approximately 60 minutes is
required to boil off the water in the bundles. For all the agents, the low bed condition reaches a
maximum temperature of 650 °C.
MEDPATH Model Piece Tmin, Ba
MEDPATH Model Piece Tmin, GB
800
800
—piece tmin-medpath-GB-low
apiece tmin-medpath-GB-mid
piece tmin-med path-GB-high
—piece tmin-med path-Ba-low
—piece tmin-medpath-Ba-mid
—piece tmin-med path-Ba-high
700
700
600
600
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MEDPATH Model Agent Remaining, GB
MEDPATH Model Agent Remaining, Ba
1.0
—agent left-medpath-GB-lo\v
—agent left-medpath-GB-mid
—agent left-med path-GB-high
0.9
0.9
— agent left-med path-Ba-low
—agent left-med path-Ba-mid
- - agent left-med path-Ba-high
0.8
0.8
1 0-7
as 0.6
£ 0.6
0.5
® 0.4
o 0.4
Z 0.3
0.3
0.2
0.2
0.0
0.0
Time (min)
Time (min)
MEDPATH Model Agent Remaining, HI)
MEDPATH Model Agent Remaining, VX
0.9
0.9
—agent left-medpath-1 ID-low
—agent left-medpath-1ID-mid
agent left-medpath-HD-high
—agent left-medpath-VX-low
—agent 1 eft-medpath-VX-m id
agent left-medpath-VX-high
0.8
0.7
1 0.7
£
X 0.6
£ 0.6
0.5
0.5
® 0.4
® 0.4
ti 0.3
0.3
0.2
0.2
0.0
0.0
Time (min)
Time (min)
Figure 4-10. MEDPATH Model, Agent Left
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5 CREMATION OF HUMAN REMAINS FOLLOWING
CHEMICAL AND BIOLOGICAL AGENT INCIDENTS
This section describes the US and UK protocols for cremation of human remains contaminated
with CB agents.
5.1 U.S. Military Protocols
Ryder described the decontamination process for remains of military personnel contaminated
with CB agents. Mortuary Affairs defines contaminated remains as 'remains of personnel which
have absorbed or upon which have been deposited radioactive material, or biological, or
chemical agents'. Mortuary doctrine for decontamination remains much the same as it has been
for the last 20 years and depends upon sodium hypochlorite (5% solution) and water in sufficient
amounts to wash away and/or dilute the presence of chemicals. The decontamination efforts are
carried out in full individual protective equipment (IPE), most likely worn at the highest mission-
oriented protective posture (MOPP) levels. Decontamination of remains is done using nearly the
same methods used in decontaminating equipment. Therefore, the decontamination process just
cleans the exterior surface. Men and women killed by biological or chemical weapons will most
likely have ingested or absorbed the agents in some way, making their remains contaminated on
the inside. The outside and inside levels of contamination will vary. In 2002, Mortuary Affairs
ordered a re-evaluation of existing mortuary policy to assess the policy that cremation is not an
option for contaminated remains (Ryder, 2003).
The U.S. Army prepared a report to assist emergency managers, medical examiners, and
coroners to better prepare for and determine the best course of action for responding to a mass
fatality situation following a chemical weapon of mass destruction (WMD) incident. At the
federal level, the Disaster Mortuary Operational Response Team (DMORT) is the only response
organization prepared to handle large numbers of fatalities. Time, effort, and resources may
dictate a blanket policy to mass incinerate all animal remains resulting from a chemical WMD
incident. To ensure that human remains are free from contamination, the medical examiner
should monitor human remains before releasing them to the community for final disposition.
Two main types of chemical agent monitors exist. The Chemical Agent Monitor (CAM)
provides high level monitoring capability, which technicians use to monitor levels of agent. The
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second type of monitoring is mass spectrometer monitoring. This type of monitor is used for low
level monitoring. Army Regulations (AR 385-61) state that all chemical warfare agents are
nullified when exposed to temperatures of 1,000 °F for fifteen minutes. United States crematoria
set their cremation temperature higher than 1,000 °F, so cremation will nullify all chemical
agents. Cremation of human remains requires temperatures approximately 650 °C for sufficient
lengths of time (usually 2.5-3 hours) for complete burning (Morgan, 2004). When
contamination cannot be mitigated with decontamination efforts, involuntary individual
cremation may be the only remaining option. The emergency plan of a jurisdiction should reflect
the location and capability of area crematoria. Medical examiners should consider preparing
remains for cremation even if authorities have not determined their final disposition. The
appropriate time to prepare remains for possible cremation is before they are embalmed.
Personnel should scan and remove all internal devices such as automatic defibrillators and
internal pacemakers before embalming, and personnel should be wearing PPE. A flow diagram
for processing contaminated remains is shown in Figure 5-1 (US Army, 2003).
Reman
Reooveiy
Figure 5-1. Flow Diagram for Processing Contaminated Remains (Published by US Army,
2003, No Permission Required)
5.2 UK Protocols
The UK Home Office recommended that if cremation were chosen as the disposition option for
victims contaminated with CB agents, the victim must first be placed in a chemical resistant
body bag. The crematorium should be located in a remote area to reduce the number of potential
human receptors. The crematorium should be fitted with regulation air filters to reduce
emissions. Ashes should be collected and sealed in an air tight container. All personnel
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involved with the disposal should wear the correct PPE. Decontamination of the crematorium
may also be necessary after cremation (Home Office and Cabinet Office, 2004).
Baker et al. reported that crematoria are carefully regulated to prevent environmental hazards
from emissions. Current UK regulations state that crematoria must be a minimum distance from
dwellings (100 yards in London or 200 yards elsewhere in the United Kingdom (UK)). The
cremation process works at temperatures in excess of 600 °C. A crematorium can function
continuously for a period of several days or weeks, should the demand to cremate a large number
of fatalities arise. However, only one body may be cremated at any one time in each
crematorium. Coffins awaiting cremation require temporary storage in the committal room;
therefore, the necessary space and ventilation may present problems. In the UK, it is doubtful
whether a cremation order would be available quickly from the appropriate legal authority (the
coroner) for all fatalities following a chemical, biological or radiological (CBR) release.
Therefore, a storage facility at 4 °C would be required. A coffin alone may not provide
sufficient containment for a contaminated body, due to the likelihood of offgassing, aerosolized
agents, or leakage of fluids. Double-bagging of the body will be necessary, preferably in a body
bag specifically designed for CBR-contaminated bodies. Equipment that minimizes the time that
crematorium personnel spend near the coffin, or the resultant ash, should be utilized (catafalque,
hearth type) (Baker et al., 2008).
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6 CONCLUSIONS
This report reviewed literature on the destruction of CB agents and surrogates bound on
materials such as ceiling tiles, wallboard, carpet, fiberglass, aluminum, concrete, pumice, stone,
wood, stainless steel, laminate, asphalt, brick, and others. A summary table of the operating
conditions and results from the thermal and hydrolysate treatments discussed in this review are
presented in Appendix A. The log reduction, destruction efficiencies, F-, D- and Z-values, and
spore survivability are included in the summary table.
Incineration of materials contaminated with CB agents is widely reported in the literature.
Incomplete combustion of CB agents should not occur, provided that the temperature and
exposure time used are sufficient to decompose the organic chemicals to simple inorganic
chemicals. There is not a significant amount of literature on the destruction of CB agents at
MWCs and MWIs. The majority of the literature on the destruction of CB agents using
incineration involves the use of HWCs.
For the incinerator modeling presented, the incinerator models are calibrated using empirical
data collected from pilot-scale experiments, mechanistic data from experiments, or derived using
molecular modeling techniques. Denison et al. (2002) found that models are useful in simulating
incineration system upset conditions and failures that could lead to an agent release, so that
appropriate design and operational modifications can be made to mitigate such occurrences.
CB agents can readily be absorbed into porous materials and can lead to unexpected persistence
of the agent, even after measures have been taken to decontaminate. The results from this review
found that more porous materials are much harder to treat effectively than less porous materials
using thermal destruction methods. Compiling the operating conditions in this review could
facilitate the management of the waste generated during cleanup following a CB contamination
incident.
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Biological Agent Destruction via Waste Incineration. J. Appl. Microbiol. 2009, 109, 99-106.
Wood, J.P.; Lemieux, P.; Griffin, N.; Ryan, J.; Kariher, P.; Natschke, D. Thermal Destruction of
Bacillus anthracis Surrogates in a Pilot-Scale Incinerator 2006, Proceedings of the Air and
Waste Management Association Annual Conference and Exhibition, New Orleans, LA, June 20-
23, 2006.
Wu, C.-Y., Damit, B.; Zhang, Q.; Woo, Myung-Heui; Sigmund, W.; Park, H.; Marijnissen, J.;
Cha, C. Y.; Jimenez, A. RHELP Regenerative High Efficiency Low Pressure Air Purification
System. Defense Treat Reduction Agency. 2009.
Wu, Y.; Yao, M. Inactivation of bacteria and fungus aerosols using microwave irradiation. J.
Aerosol Sci. 2010, 41,7, 682-693.
Yesodharan. S. Supercritical Water Oxidation: An Environmentally Safe Method for the
Disposal of Organic Wastes. Curr. Sci. 2002, 82, 9, 1112-1122.
-------
Page 101 of 103
Zavitsanos, P. D.; Manion, T.; Rozanski, A.J. Thermobaric Materials and Devices for
Chemical/Biological Agent Defeat. US 8,118,955 B2, Feb. 21, 2012.
Zhang, Q., Damit, B.; Welch, J.; Park, H.; Wu, C.Y.; Sigmund, W. Microwave Assisted
Nanofibrous Air Filtration for Disinfection of Bioaerosols. J. Aerosol Sci. 2010, 41, 9, 880-888.
-------
Final Report on Thermal Destruction of CB Agents Bound on Materials
Appendix A
Summary Table of Thermal
Processes for CB Agent Destruction
-------
Final Report on Thermal Destruction of CB Agents Bound on Materials
Page A-l of A-3
Table Al. Summary of Test Conditions and Results for Thermal Processes
Test Conditions
Results
Reference
Incineration
Bench scale study with CWA simulant,
Malathion at an initial concentration of
300,000 |ig/L. Tested in an oven ramped
up to 400 °C (following hazardous waste
incinerator (HWI) temperature increases)
then maintained at that temperature for 30
minutes.
The Malathion concentration averaged 911 |ig/L at
175 °C after 30 minutes of exposure (99.7%
destruction).
Lemieux et
al., 2010
Pilot-scale rotary kiln incinerator, G.
stearothermophilus spiked on dry and wet
ceiling tile bundles. The incinerator
temperature was 804 - 827 °C.
Dry ceiling tile bundles had a 1 to 2 logio reduction
at 5 to 10 minutes and 6 logio reduction after 12
minutes. Wet ceiling tile bundles 35 - 38 minutes
for 6 logio reduction.
Wood et
al., 2006
B. subtilis ceiling tile samples were heated
in a quartz reactor operating at 150, 200,
250, and 315 °C, for various time intervals.
6 logio reduction at 2.5, 3, 6, and 21 min at 315,
260, 204, and 148 °C, respectively.
Lemieux et
al., 2005
G. stearothermophilus spiked on wet and
dry ceiling tile bundles tested in a pilot-
scale rotary kiln incinerator.
6 logio reduction in 6 and 30 min at 1,093 °C for
dry and wet ceiling tile, respectively. 6 logio
reduction in 13 and 38 min at 824 °C for dry and
wet ceiling tile, respectively.
Wood et
al., 2008
Dry heat oven tests conducted at 175 °C
with wallboard spiked with B. atrophaeus,
B. cmthracis (Sterne) and G.
stearothermophilus.
The D-values were 0.4, 0.2 and 0.3 min for B.
atrophaeus, B. anthracis (Sterne) and G.
stearothermophilus, respectively, on wallboard
Wood et
al., 2009
B. subtilis spiked on wallboard and ceiling
tile tested in the pilot-scale rotary kiln
incinerator
For B. subtilis, the Z values were 159 and 281 K for
ceiling tile and wall board, respectively. The 6
logio reduction for B. subtilis on wallboard occurred
at 1,700 sec at 600 °F, 2,700 sec at 500 °F, and
4,500 sec at 400 ° F.
Denison et
al., 2002
Test data compared to incineration model
for HD destruction.
A furnace temperature of 850 °C was required for
complete destruction of HD, which was comparable
to the model output.
Denison et
al., 2002
B. stearothermophilus spiked on medical
waste feed in the small medical waste
incinerator operating at 816 °C.
At least a five log reduction of the spores was
achieved, although viable spores were detected in
10 out of a total of 48 air emission test runs, and
spores were detected in 10 out of 27 available ash
samples.
Wood et
al., 2004
Plasma Systems
Thermal plasma test with the Montec
steam torch with B. stearothermophilus
spiked on fiberglass and other substrates.
At 90 kW power, the steam plasma produced a
99.94% or greater kill rate for B.
stearothermophilus on fiberglass substrates at
velocities up to 2 ft/s at a distance of linch from the
exit plane. At this same power level and at a
distance of 3 in, the percent kill ranged from 97% to
85% as the speed increased from 0.5 to 2 ft/s. At
the lower power level of 60 kW, the maximum
speed that would produce 99.94% kill at 1 in was
1.5 ft/s.
Farrar et
al., 2000
-------
Final Report on Thermal Destruction of CB Agents Bound on Materials
Page A-2 of A-3
Table Al. Summary of Test Conditions and Results for Thermal Processes (Continued)
Test Conditions
Results
Reference
Atmospheric Pressure Plasma Jet (APPJ)
effluent temperature of 175 °C tested with
Bacillus globigii.
Results indicate a seven-log kill of Bacillus globigii
spores in 30 s at 5 mm distance, which was ten
times faster than dry heat at the same temperature.
Rosocha et
al., 2003
Cold plasma test; exposures were
conducted at a system pressure of 30 torr,
exposure temperature of 70 °C, plasma-to-
sample standoff distance of 10 cm and
10% addition of oxygen or hydrogen to a
helium balance. The agents studied were
VX, HD, and GD on aluminum.
VX decontamination (99.9%) was achieved in 8 to
16 min of exposure, while under 2 min was required
for the more volatile HD and GD.
Herrmann
et al., 1999
Glow discharge at atmospheric pressure
and enhanced corona discharge at
atmospheric pressure with Pseudomonas
aeruginosa on nitrocellulose filter
membrane and in a liquid broth. B. subtilis
in Luria-Bertani and E. coli.
15 min was required to sterilize a sample of
Pseudomonas aeruginosa on nitrocellulose filter
membrane. For Pseudomonas in a liquid broth,
only half of the initial cells were killed in 15 min.
For B. subtilis in Luria-Bertani broth at 42 W and
after a 12-min exposure time, about 100 cells were
still alive as compared to complete kill in 8 min for
E. coli using ECDAP.
Laroussi et
al., 2000
OAUGDP testing B. stearothermophilus
spores on nitrocellulose, B. subtilis var.
niger, B. pumilus spores on paper, B.
subtilis on glass, and E. coli on glass and
polypropylene.
B. stearothermophilus spores on nitrocellulose,
were killed to five logs in 5.5 min. B. subtilis var.
niger spores took 4 min (to 4 logio reduction), while
it took only 2.5 min to inactivate approximately the
same number of B. pumilus spores on paper. B.
subtilis on glass, 3 logio reduction after 60 seconds
(D1 at 13 sec, D2 at 10 sec). E. coli on glass 70
seconds for 2 logio (D1 33 sec, D2 7 sec), E. coli on
polypropylene, 24 sec 5 logio, D1 6 sec, D2 2 sec.
Montie et
al., 2000
Microwave Irradiation
Microwave treatment for airborne B.
subtilis var. niger, Pseudomonas
fluorescens, and Aspergillus versicolor at
750 W, 385 W and 119 W for 1.5 minutes.
The survival rates of airborne B. subtilis var. niger
spores were shown to be about 35%, 44% and 35%
when exposed to the microwave irradiation for 1.5
min with 750 W, 385 W and 119 W power applied,
respectively. The airborne Pseudomonas
fluorescens was shown to have lower survival rates
of 5.8%, 12.2% and 21%. 12%, 20%, 25% rates at
respective powers were observed for airborne
Aspergillus versicolor exposure
Wu and
Yao, 2010
Microwave at 750 W for B. subtilis on
PAN nanofibers.
For B. subtilis at 750 W for 90 s, 2.7 log
disinfection on PAN nanofibers.
Zhang et
al., 2010
TP AC compound with anthrax-type spores
with standard microwave equipment at
moderate power.
A 5.5 out of a total of 6 log kill was achieved with
TP AC compound and anthrax type spores.
McFarland
et al., 2001
E. coli, MS2 bacteriophage, and B. subtilis
static on-filter tests and dynamic system
test with microwave irradiation.
Biological agents were able to be completely
destroyed by microwave irradiation within 2
minutes, with E. coli being the most sensitive and
B. subtilis endospores being the least sensitive. For
the dynamic system in-flight filtration coupled PAN
nanofiber filtration at 500 W of continuous
microwave application the system was able to
remove over 95% of viable MS2 virus and B.
subtilis.
Wu et al.,
2009
-------
Final Report on Thermal Destruction of CB Agents Bound on Materials
Page A-3 of A-3
Table Al. Summary of Test Conditions and Results for Thermal Processes (Continued)
Test Conditions
Results
Reference
Microwave and catalysts tested with
DMMP initially at 300 ppm and DES at
600 ppm.
The best DRE (>99.5%) was obtained from tests
using the alumina-based vanadium catalyst after 35
min at 300 W. DES removal was at steady state
after 10 minutes, 99% DRE at 300 W with the
alumina substrate.
Cha et al.,
2004
Autoclave
BDR material (carpet, wallboard, and
ceiling tile) spiked with G.
stearothermophilus tested with an
autoclave at various packing arrangements.
Autoclave cycles consisting of 120 min at 31.5
lb/in2 and 275 °F and 75 min at 45 lb/in2 and 292 °F
effectively decontaminated the BDR material. The
most effective spore destruction was obtained with
a loose packing arrangement, dry BDR material, a
higher autoclave operating pressure and higher
temperature, multiple autoclave cycles performed in
sequence, and bags cut open prior to loading.
Lemieux et
al., 2006a
Landfill Flare
Bench tests with N2 and CH4 were used to
simulate landfill gas with combustion air at
870 to 1,037 °C with aerosolized G.
stearothermophilus and B. atrophaeus
At a 0.2 and 0.6 second residence times, all spores
were inactivated in the flare.
Tufts and
Rosati,
2012
Direct Heat Application
F-value determination for G.
stearothermophilus, B. atrophaeus, and B.
anthracis.
The F-value at 200 °C for G. stearothermophilus
and B. atrophaeus is 1.3 and 1.1 min. The F-value
is 1.2 min for B. anthracis. Dry heat oven tests were
conducted at 175 °C, the D-values were 0.4, 0.2 and
0.3 min for B. atrophaeus, B. anthracis (Sterne),
and G. stearothermophilus, respectively
Wood et
al., 2010
Z-value determination for B. subtilis
spiked on wet ceiling tile and wallboard.
The Z values for B. subtilis spiked on wet ceiling
tile and wallboard were 159 and 281 K, respectively
Denison et
al., 2005
A thermal electric heating system in
continuous air flow with E. coli and B.
subtilis bioaerosols.
E. coli and B. subtilis bioaerosols were rendered
more than 99.9% inactive at 160 °C and 350 °C
wall temperature of the quartz tube.
Jung et al.,
2009
SCWO and Bioremediation of Hydrolysate
VX hydrolysate treated with SCWO with
air at temperatures to 600 to 650 °C under
about 275 bar pressure about 30 seconds.
The organic (about 99.99 %) was oxidized to water
and sodium salts as well as gaseous nitrogen.
Pearson
and Magee,
2002
MP A, a VX hydrolysate simulant treated
with SCWO.
Greater than 99% DRE of MP A was achieved at a
temperature of 550 °C, pressure of 27.6 MPa,
oxygen concentration of 200% stoichiometric
requirements, and reactor residence times of less
than 20 s.
Bianchetta
et al., 1999
Bioremediation of TDG (hydrolysate of
sulfur mustard) with Strain T09 bacteria in
an aqueous solution with at 30 °C.
70 h required to degrade TDG with Strain T09.
Bassi et al.,
2009
Immobilized Cell Bioreactor to treat TDG
mustard hydrolysate.
The effluent concentration from the bioreactor was
below detection for much of the test with 5 davs of
HRT and 120-200 davs of SRT.
Nurdogan
et al., 2012
-------
Final Report on Thermal Destruction of CB Agents Bound on Materials
Appendix B
Compiled References Worksheet
(Excel Attachment)
-------
Document Type Legend
A Technical Report, U.S. Government
B Technical Report, Contractor for U.S. Government
C Translated Foreign-Language Document
D Translated Foreign-Language Abstract
E Untranslated Foreign-Language Document
F Untranslated Foreign-Language Abstract
G Peer-Reviewed English Language Literature, post-1975
H Peer-Reviewed English Language Literature, 1925-1975
I Peer-Reviewed English Language Literature, pre-1925
J Government Website, with citations
K Government Website, without citations
L Non-Government Website, with citations
M Non-Government Website, without citations
N Book Chapter or Book, with peer-review and/or editorial oversight
O Book Chapter or Book, no peer-review nor editorial oversight
P Book Chapter or Book, peer review and editorial oversight unknown
Q Patent (United States)
R Patent (International)
S Thesis/Dissertation
T News Article
U Other
V Analysis Pending
B-l
-------
Search Terms
Chemical or biological agents
Cremation
Environmental impact
Hyd rolysate
Thermal destruction
Warfare agents
Risk
Incineration
Remains
Warfare agents
Warfare agents
Chemical or biological agents
Destruction
Destruction
Biosafety
Chemical or biological agents
Warfare agents
Incineration
Destruction
Chemical or biological agents
Incinerator
Autoclave
Emissions
Warfare agents
Destruction or Decomposition or Incineration
Thermal or Heating or (Hot (w) (Temperature or Air))
aerosol containment
Chemical or Biological Agent
warfare agents
Antharacis or Anthrax or Stearothermophilus
incineration
HD or Mustard
Building or Soil or Carpet or (Ceiling (w) Tile)
Concrete or Asphalt
B-2
-------
Literature Search Results
Article/Report Title
rhermal Destruction of
n of a building following a biological warfare agent (such as 8ocillu.
concrete, and wood, which would be removed from the building either before or after
llikely to have been decontaminated, the possibility exists for the presence of trace amc
Itechniqueforthe BDR is high temperature incineration, complete destruction of microbiological organisms in an incinerator
environment is not a certainty, due to heat transfer limitations and matrix effects. This paper describes experiments that were
performed in a pilot-scale rotary kiln incinerator to evaluate the thermal destruction of 8. ontbrocis surrogates (bacterial spores)
present within bundles of carpeting and ceiling tile. Another purpose of the experiments was to evaluate sampling and analytical
techniques to measure spores in the exhaust gas and material bundles. No spores were detected via any of the three sampling tra
the exhaust gas for the carpet burn tests conducted in July and August 2005, although the detection limit was determined ti
spores/dry standard ft3. Combustion of the nylon-6 carpet resulted in increased nitrogen oxide (NOx) emissions, with short-term
in emissions levelsfrom approximately 30 ppm baseline to roughly 150 ppm with each carpet bundle charged. The use of biologi
indicator strips to quantify thermal destruction of spores embedded within carpet and ceiling tile bundles was successful. Spores
at ceiling tile bundles took at least 35 minutes to completely destroy, possibly exceeding typical incinerator st
carpet, wallboard, int
lough the BDR is
lough a likely disposal
22
Existing Procedures and
Methodologies Discussed
al program ha
;d bytheU.S. EPA to
n of ch
Finally, model pr
iade to predict agent dc
nical /biological
Full Text File Name
n Thermal Destruction
Iresidue (BDR). 8. ontbrocis of Bacillus Anthracis
surrogates (bacterial spores) Surrogates in a Pilot-
present within bundles of Scale Incinerator
nical/biological agent Common porous I:
Information Source
Google Scholar
Destruction and Detectio
>mical Warfare
Agents
technology applies
compatability witH
objects.
Contaminated objects, ir
Detection o
Chemical Warfare
Agents
cal Warfare Agent
event of a terrorist attack with chemical warfare agents (CWAs), large quantitie:
¦d by thermal incineration during the site remediation process. CWAs in general i
decompose readily in a high temperature combustion environment. Potential difficulti
ig materials from a post-CWA event site remediation due to the refractory natui
igs, and the potential impacts that waste packaging at the site may have on the
jction in combustion systems. This paper reports on a study to examine the therr
:hion) in a laboratory reactor, analysis of the results using reactor design theory,
computer simulation of a foil-scale commercial hazardous waste incinerator processing ceiling
:hion. The heating rates thatthe reactor was subjected to were based on previously detei
;cale rotary kiln incinerator simulator, and are intended to simulate the thermal processi
inine trace amounts of CWAs.
e not particularly thermally stable and
> exist, however, in thermally processing waste
of many materials found inside and outside
=havior of these materials and residual agent
al decomposition of surrogate CWAs (in this ca<
id subsequent scale-up of the results to a
i surrogate CWAs (in
laboratory reactor.
IT3 Conference, San Francisco, CA
ss of wi
j of be
ision SupportTool
(DST) for Disposal of
ring from National
Emergencies
AFTER A BUILDING OR WATER TREATMENT/DISTRIBUTION FACILITY HAS GONE THROUGH DECONTAMINATION ACTIVITIES
FOLLOWING A CONTAMINATION EVENT WITH CHEMICAL/BIOLOGICAL WARFARE AGENTS OR TOXIC INDUSTRIAL CHEMICAL, THERE
WILL BE A SIGNIFICANT AMOUNT OF RESIDUAL MATERIAL AND WASTE TO BE DISPOSED. A CONTAMINATION EVENT COULD OCCUR
FROM TERRORIST ACTIVITY OR FROM A NATURAL DISASTER SUCH AS THE RECENT HURRICANE EVENTS IN THE GULF COAST WHERE
MOLD AND POLLUTANTS FROM DAMAGED CHEMICAL AND INDUSTRIAL FACILITIES HAVE RESULTED IN SIGNIFICANT QUANTITIES OF
CONTAMINATED MATERIALS. IT iS LIKELY THAT MUCH OF THIS MATERIAL Will BE DISPOSED OF IN PERMITTED LANDFILLS OR HIGH
TEMPERATURE THERMAL INCINERATION FACILITIES. DATA HAS BEEN COLlfCTED FROM THE OPEN UTERATURE, FROM STATE AND
FEDERAL REGULATORY AGENCIES, AND FROM WASTE MANAGEMENT AND WATER UTILITY INDUSTRY STAKEHOLDER GROUPS, TO
DEVELOP TECHNICAL GUIDANCE FOR DISPOSAL OFTHESe RESIDUES. THE INFORMATION BECOMES AVAILABLE, AND OLD
INFORMATION (SUCH AS CONTACT INFORMATION FOR KEY PERSONNEL) CHANGES. THE PRiMARY AUDIENCE FOR THIS TOOL Will BE: THESE RESIDUES.
1) EMERGENCY RESPONSE AUTHORITIES WHO HAVE TO DECIDE THE MOST APPROPRIATE DECONTAMINATION METHODS AND
DISPOSAL OF THE RESULTING RESIDUES; 2)STATE AND LOCAL PERMITTING AGENCIES, WHO HAVE TO MAKE DECISIONS ABOUT WHICH
FACILITIES Will BE AHOWEDTO DISPOSE OF THE MATERIALS: AND 3) THE WASTE MANAGEMENT AND WATER UTILITY INDUSTRY,
THAT NEEDS TO SAFELY DISPOSE OF DECONTAMINATION RESIDUES WITHOUT AFFECTING THE OPERATION OF THEIR FACILITIES AND
CONTAMINATED MATERIALS.
FROM STATE AND FEDERAL
REGULATORY AGENCIES, AND
FROM WASTE MANAGEMENT
AND WATER UTILITY INDUSTRY
STAKEHOLDER GROUPS, TO
DEVELOP TECHNICAL
GUIDANCE FOR DISPOSAL OF
A_D ECISION_SUPPO
RT_TOOL_FOR_DISP
0SAL_0 F_R ESI D U AL_
BUILDINGMATERIAL
Protection Agency cc
U.S. En\.
destroy bacterial spores bound tothi
ing time, temperature, pressur
lave process sequence
ve for tr
Commercial
S (anthrax) i
m type,n
vbactllus stearotbermopbilus biologi
ain time and temperature profile data associated with each Bl st
effectively
292°F effectively
275°F proved to be particularly effective, probably
pores of the materials, allowing better steam penetration. The results also indie;
le a significant impact on the effectiveness of the
terrorist attack. The purpose of the tests was
d sufficiently robust conditions to adequately
ait, packing density, packing orientation, autoclave bag integrity, and
iR from wallboard, ceiling tiles, carpet, and upholstered furniture, and
- (Bl) strips cc
trip. The results indicated
of 120 min at 31.5 Ib/in2
intaining 106 spores and thermocouples to
that a single standard autoclave cycle did
and 275°F and 75 min at 45 Ib/in2 and
:s consisting of 40 min at 31.5 Ib/in2 and
p pulled the condensed water out of the
packing density and material type of the
tion process.
(BDR). The BDR was intent
simulate porous materia
berately contaminated
h biological agents such
(anthrax) in a terrorist attai
.S. EPA R&D Program for
Disposal of Building
Decontamination Re:
it of a 1
>n process requir
on, landfill ing, ai
arnedforbuildir
^transportation hubs, or other structures where chemical or biological agents
formerly contained within the building, and although it has undergor
:es that no remaining traces of the contamination agent is present in ¦
in chemicals and decomposition by-products from the contaminating agent. The completion of the
BDR be sent for ultimate disposal. Likely disposal options include high temperature therma
toclaving. This paper describes EPA's current program to 1. consolidate available informatii
;idue disposal into technical guidance for responders, permitting agencies, and tl
tagaps.
nformatior
for building
for responders,
permitting agencies, and th
sposal industry; and 2.
perform experimental rese;
) help close existing datag
J_S_EPA_R_D_PR OG
RAM_FOR_D I SPOSAL
_OF_BUILD_DECON_
RESIDUE LEMIEUX_
_SYM_PAPER
(Destruction of pi
(Organophosphorus it
Icompounds in Flames III e:
The Destruction of DMMP di
id H2/02/Ar (0.26/0.13/0.61 by volume) flame dc
dimethyl methyl phosphonate (DMMP) st
and TM Pin
Hydrogen and Oxyi
le of
>n of DMMP,
>n of DMMP;
species found
HOPO, and H
>n of trimethyl phosphate (TMP) in H2/02/Ar flames was refined. The present
¦mfor hydrogen, oxygen, and phosphorus and Werner and Cool's mechanism for the
lechanisms for the destruction of both DMMP and TMP in a flame to be developed,
using the computer codes PREMIX and CHEMKIN-II, the computer modeling of the
>n profiles for all the
H2/02/Ar (0.26/0.13/0.61 by
volume) flame.
ts for th
is of ini
id refine
iDimethyl methyl phosphonate The Chemistry of the
(DMMP) and trimethyl Destruction of
phosphate (TMP) in H2/02/Ar Organophosphorus
flames. Compounds in
Destruction of
DMMP and TMP in a
Flame of Hydrogen
and Oxygen
B-3
-------
Literature Search Results
Relevancy Publication Full Text Article/Report Title
Score Year Available?
| 40 2012 Y IThermal Inactivation of
Surrogate Spores in a
Landfill Gas Flare
A bench-scale landfill fare system was designed and
waste into the landfill gas to pass through the flare and exit into the
flare were characterized and compared to full-scale systems. Geobi
spores that may serve as surrogates for Bacillus antbracis, the caus
these organisms would be inactivated or remain viable after passing
n ofthefl;
itential for land-filled biological spores that migrate from the Simulat
fironment as viable. The residence times and temperatures of the
'us stearothermophilus and Bacillus atropbaeus, nonpathogenic
re agent for anthrax, were investigated to determine whether
rough a simulated landfill flare. High concentration spore
m to simulate the fate of biological weapon (BW)-grade spores in
Types of waste Full Text File Name Information Source
\Geobacillus Thermal inactivation Google Scholar
\stearothermophilus and of Bacillus anthracis
Bacillus atropbaeus, surrogate spores
nonpathogenic spores that
may serve as surrogates for
3d for vi:
1 burner. All spores of S. stearothermophilus and 8. atropbaeus were inactiv;
re-entrained in landfill gas may not escape the landfill as viable, apparently be
a landfill flare.
Systematic
Methodology for Se
Decontamination
Decontamination Strategy
for Large Area and/or
iment Contaminate
gical Agents using s
Energy Arc Lamp
(HEAL)
Decontamination and recovery of a facility or outdoor area after a wide-area biological incident involving a highly persistent agent (eg
s anthracis spores) is a complex process that requires extensive information and significant resources, which are likely to be
I, particularly if multiple facilities or areas are affected. This article proposes a systematic methodology for evaluating informant
ictthe decontamination or alternative treatments that optimize use of resources if decontamination is required for the facility oi
the methodology covers a wide range of approaches, including volumetric and surface i
ation, and seal and abandon strategies. A proposed trade-off analysi:
appropriateness, efficacy, and labor, skill, and cost requirements of the various decontamination methods for the particular facility or
a needing treatment-whether alone or as part of a larger decontamination effort. Because the state of decontamination knowledge
technology continues to evolve rapidly, the methodology presented here is designed to accommodate new strategies and materials
changing inibrmati(
strategyfor the decontamination of large areas and or equipment contaminated with Biological Warfare Agents (BWAs) and Chemical
Warfare Agents (CWAs) was demonstrated using a High Energy Arc Lamp (HEAL) photolysis system. This strategy offers an alternative
potentially quicker, less hazardous, generates far less waste, and is easier to deploy than those currently fielded by the
Department of Defense (DoD). For example, for large frame aircraft the United States Air Force still relies on the combination of
(stand alone in environment), air washing (fly aircraft) and finally washing the aircraft with Hot Soapy Water (HSW) in an
lation site preparation), and requires large amounts of water (e.g., 1,600* gallons for a single large frame aircraft), and
generates large amounts of hazardous waste requiring disposal. The efficacy of the HEAL system was demonstrated using diisopropyl
methyl phosphonate (DIMP) a G seriesCWAsimulant, and Bacillus globigii (BG) a simulant of 8acillus antbracis. Experiments were
ilate the energy flux of a field deployable lamp system that could stand-off 17 meters from a 12m2 target area and
uniformly expose a surface at 1,360 W/m2. The HEAL system in the absence of a catalyst reduced the amount of 8. globigii by five
of magnitude at a starting concentration of 1.63 x 107 spores. In the case of CWA simulants, the HEAL system in the presence of
the catalyst TT07 effectively degraded miyip waved nntn a 1 on mm diameter Petri dish i
methodology covers i
range of approaches, incli
e efficacy of the HEAL
using diisopropyl methyl
phosphonate (DIMP) a G
series CWA simulant, and
Bacillus globigii (BG) a
logical Agents
ig a High Energy
rc Lamp HEAL
is: To ot
le dry thermal re
(Sterne) Spores
Spores of Oth
applications.
sds and Results: Tests were conducted in a pilot-scale incineratoi
stearothermophilus, Bacillus atropbaeus and 8. antbracis (Sterne) ar
icted in a dry heat cwen to determine the destruction kinetics for the same species
atropbaeus and G. stearothermophilus demonstrated similar thermal sensitivity, but £
G. stearothermophilus. For the dry heat oven tests conducted at 175 C, the D-valt
atropbaeus, 8. anthracis (Sterne) and S. stearothermophilus, respectively.
jsions: Bacillus anthracis (Sterne) possesses similar or less dry heat re
stearothermophilus.
Significance and Impact of the Study: Previous studies have demonstrated conditions under
rator environment. The data from this study may assist in the selection of surrogates
tmthtmia snores emhedded in building materials are completely inactivated
villus species for wi
biological indicators comprise
of spores of Geobacillus
stearothermophilus,
'us atropbaeus and 8.
ucis (Sterne)
compared to 8. atropbaeus ;
Decontamination Using i
Energy Arc Lamp
(HEAL) System
for quickly decontaminating large areas exposed to chemical and biological (CB) warfare agents can present significant
I, manpower, and waste management challenges. Oak Ridge National Laboratory (ORNL) is pursuing an alternate method tc
decompose CB agents without the use of toxic chemicals or other potentially harmful substances. This process uses a high energy ar
lamp (HEAL) system to photochemically decompose CB agents ewer large areas (12 m2). Preliminary tests indicate that more than 5
(99.999%) of an Anthrax spore simulant (Bacillus globigii) were killed in less than 7 seconds of exposure to the HEAL systen
jmbined with a catalyst material (TT02) the HEAL system was also effective against a chemical agent simulant, diisopropyl
methyl phosphonate (DIMP). These results demonstrate the feasibility of a rapid, large-area chemical and biologic:
require toxic or corrosive reagents or generate hazardous wastes.
energy arc lamp (HEAL)
m to photochemically
decompose CB agents.
cal Investigation:
Destruction of a
s Surrogate
Decontaminatioi
* (S. a
disposal option for such
ar 500 °C. A mode
s are compared tc
I through the U.S. mail system in 2001, highlighting the need to develop efficacious
ils contaminated with biological agents. Incineration of building decontamination
i the complete inactivation of bacterial spores via this technique is not a certainty,
ralius stearothermophilus (S. stearothermophilus; a surrogate for 8. anthracis)
/as also developed to predict survival of a bacterial spore population undergoing
obtained in a laboratory setting. The results of the
Residue
Bundles
Decontamin;
s: To ev
lus stearothermophilus spores on indoor
i dried on seven types of indoor surfaces ar
stearothermophilui
Spores on Indoor Surfaces
a Hydrogen
Peroxide Gas Generator
iurface materials using hydrogen peroxide gas.
Methods and Results: Bacillus anthracis, 8. subtilis, andG. stearotbermopbilus spores were dried o
sxposed to 1,000 ppm hydrogen peroxide gas for 20 min. Hydrogen peroxide exposure significantly
lubtilis, and G. stearothermophilus spores on all test materials except S. stearotbermopbilus on industrial carpet. Significar
Jifferences were observed when comparing the reduction in viable spores of 8. anthracis with both surrogates. The effectivs
gaseous hydrogen peroxide on the growth of biological indicators and spore strips was evaluated in parallel
Hydrogen peroxide gas.
7 days postexposure,
samples displayed growth,
elusions: Significant differences in
arved when comparing the mean li
lifcance and Impact of the Study: 1
efficacy of hydrogen peroxit
ride comparative information for tl
and G. stearotbermopbilus
types of
5or surfaces and exposed
.,000 ppm hydrogen
oxide gasfor 20 min.
id spore strips e*
>n of 8.
stearothermophilu;
hydrogen peroxide
gas genearator
Waste Inciner;
Review of Avai
|After a building has undergone a -
will need to be disposed. Althoug
remove the potentially bio-contar
to completely destroy all potentially
(EPA) conducts
a biological weapon such as 8. Anthracis, many of the interior building materials M
I prior to their removal, officials may decide to (h
In either scenario, the possibility exists that some of
nay be the best option for the disposal of such building
early 1990s, the US Environmental Protection Agency
ity tests at several medical waste incinerators (M Wis); these data have now been examined to
performance. Microorganisms were spiked into the waste feed and in test pipes, and subsequently
i, residue, and pipes using EPA conditional test methods. The results showed thatfor the most of the
i of the spores was achieved, although viable spores were detected in 10 out of a total of 48 air
detected in 10 out of 27 available ash samples.
DESTRUCTION
t EFFICIENCY OF
MICROBIOLOGICAL
ORGANISMS IN
MEDICAL WASTE
INCINDERATORS-
REVIEW OF
AVAILABLE DATA
B-4
-------
Literature Search Results
Verification of
Formal dehyde Vapor
Technologies for
Decontaminating Indoo
Surfaces Contaminated
Article/Report Title
To support the Nation's Homeland Security Program, this
Verification (ETV) project is conducted to verify the performance of co
d and porous indoor surfaces contaminated wi
Jen and unexpected chemical and biological te
must be prepared to rapidly mitigate harm to
public- and private-sector buildings that housi
responsibility-for protecting human health and the environment from
Agency must identify and evaluate the tools for i
porous indoor surfaces. A Blanket Purchase Agreement was es
performance of technologies that can potentially
i first phase tests incude fumigation technologies s
• each technology tested.
Protection Agency (EPA) Environmental Technology
nercially available products, methods, and equipmentfor
biological or chemical warfare agents. Due to the continuinj
srist attacks, the Agencyfirst responders and building
e public and the environment. The main targets of future
ie Nation's workforce and business activities.To fulfill the
ct laboratory-scale efficacy te
id formaldehyde
Full Text File Name
Information Source
Test OA Plan ¦
Verification i
Formaldehyde Vapor
Technologies for
Decontaminating
Contaminated with
Chemical Agents
(2,450 MHi) for _2 min at different output powers(700, 385 and 119 W). Control and exposed bioaerosols were collected by a
ioSampler or a mixed cellulose ester (MCE) filter,and the air samples were further cultured. As a comparison, liquid-borne exposure for
ie species was also conducted. Environmental scanning electron microscope (ESEM) and transmission electron microscope (TEM) were
sedto study the membrane surface morphologies and intracellular components of the microwave-treated and untreated microbes. The
irvival rates of airborne 8ocillus subtilis var niger spores were shown to be about 35%, 44% and 35% when exposed to the microwave
radiation for 1.5 min with high, medium and low power applied, respectively (p-value=0.37). In contrast, the airborne Pseudomonos
jorescen s were shown to have lower survival rates of 5.8%, 12.2% and 21% (p-value=0.0045). Similar patterns but higher survival
ites at respective powers were observed for airborne Aspergillus versicolor exposure (p-value 0.0001). For environmental bacterial
id fungal bioaerosols, 30-40% of them were shown to survive the high power microwave irradiation for 1.7 min. Outdoor bioaerosols
ere shown to have stronger survival than the indoor bioaerosols when exposed to the microwave irradiation. ESEM and TEM images
lowed visible damages to the microwave-irradiated microbes. The results obtained here can be used to develop microwave-based air
orilijatiiin toi-hnnlnotas eciwiallv tarootoH fru- hinliioii-al aa-«cnlt
ib-O-Sil EH-5. L
ie of its
environmentally friendly,
;s, and does not harm carpets or painted surfaces. The new reagent
anding requirements for decontamination in the civilian sector, including availability, low
ice, ease of application and deployment by a variety of dispersal mechanisms, minimal
id acceptable expense. Experiments to test the effectiveness of L-Gel were conducted
:e Liver more National Laboratory and independently atfour other locations. L-Gel was
«nst all classes of chemical warfare agents and against various biological warfare agent
i, including spore-forming bacteria and non-virulent strains of real biological agents. Testing
at I -Gel is as effective against chemical agents and hinlngical materials, including
Operations involving chemical agents sue
iil dings and a wide variety of processing equiprr
ost persistent being mustard. Materials that art
luipment), and wood. All of these materials exis
Many of the contaminated facilities have potentis
Much of the contaminated process equipment als
monetary value as scrap material if properly
g, storage, a
•dbyanuml
:y if they can be properly d(
be realized since the only acceptable
ntact heating, infrared
:ating, flaming, hot plasma,
it gases, C02 laser
Past efforts at resolving this situation have identified some
icepts which could be utilized with five having been evaluated under laboratory conditions. The
ve, chemical, and extractive removal schemes. Each of these technologies was evaluated based
transfer, safety, damage to existing materials, penetration depth, applicability to complex surfaces, co
sse comparisons hot gas technology was identified as the most suitable methodology.
Currently a full scale demonstration is in the design phase for implementation at Rocky Mountain Arst
minated with mustard and mustard degradation by- products from past demilitarization activitie
approximately eighteen inches thick, large metal storage tanks, process piping, motors, and pumps.
Efficacy of Liquid ai
Foam Decontamin;
Technologies for CI
Warfare Agents on
:h-scale testing was used to evaluate the efficacy of four
ie liquid chemical warfare agents sarin (GB), soman (GD), sulfur mustar
periodically measured for upto24h after applying one of four selected
idium phosphate, Allen Vanguard Surface Decontamination Foam (SDF1
EnviroFoamTechnologies Sandia Decontamination Foam (DF-200)].
on, performed well on nonporous and nonpermeable
typically
ised Decon Green™ performed
penetrate the polymer matrix. Ble;
Results suggest that the different cha
ngle formulation and a strategy for
n formulations on typical indoor surfaces follow
(HD), and VX. Residual surface contamination i
ination technologies (0.5%bleach soli
lilitary Decon Green™, and Modec Inc. i
ition technologies tested, except for the
surfaces. However, chemical agent resic
porous and permeable surfaces, especially for the more persistent agents, HD ar
:er than aqueous-based bleach or foams on polymeric surfaces, possibly because
ach and foams out-performed Decon Green for penetrating the highly polar cone
iracteristies needed for an ideal and universal decontamination technology mayk
complex facility will require a range of technologies.
I VX. S
lical agents, 0.5% bleach
phosphate, Allen Vanguard
Surface Decontamination Foam
'), U.S military Decon
Green™, and Modec Inc. and
EnviroFoam Technologies
a Decontamination Foam
(DF-200)].
Decontamination ofVX,
nd HD on a Surface
Modified Vaporizec
Hydrogen Peroxide
Vaporized hydrogen peroxide (VHP) has proven efficacyfor biologic;
y. Regarding chemical warfare agent
ia gas to VHP affords reactivity toi
on, VHP is also effective against HD and V
taining efficacy for HD (and bioagents) ar
it suitable for fumigant-type dc
st GD. Simple addition of
lg efficacyfor
for fumigant-type
Determination of the
Efficacy of Two Building
Decontamination
Strategies by Surface
Sampling with Culture an
titative PCR Analysis
is (i.e
e, paint
atrophaeus {"Bacillus
products, a foam
sampling methods and analyzed by cultui
present on the surface materials were also conducted to determine if
analysis. Culture results indicated that 105 to 106 CFU per sample we
n with the foam, no culturable 8. atrophaeus spores ¦
strategies for
referred to as BG), a Socillus a
e dioxide gas. Surface samples
uantitative PCR (QPCR). Additic
supplied with materials used in office
'osol releases of endospores of Bacillus
ads surrogate. Studies were performed using two
a collected pre- and posttreatment with three
aerosol releases with environmental background
interference with decontamination or sample
surfaces before decontamination. After
Domestic and workplace
endospores of Socillus
atrophaeus ("Bacillus subtilii
subsp. rige r," also referred t
Determination ofthe
Efficacy of Two
Decontaminatio
Strategies by Surface
able 8. atrophaeus was detected in 24 of 27 samples (89%). However, QPCR analysi
present after decontamination with both methods. Environmental background material hs
bition ofthe QPCR assay was observed. These results demonstrate the effectiveness of
utility of surface sampling and QPCR analysis for the evaluation of decontamination strategi
B-5
-------
Literature Search Results
37 2000
Article/Report Title
chemical Warfare Agent A "plasma dc
Full Text File Name
> currently no acceptable, none
adicals such as atomic oxygen
ational Laboratory (LANL), Albuquerque, NM, to study the PI
technology is targeted at sensitive electronic equipment for which there
ation. Chemical reactivity is provided by a downstream flux of reactive
hydrogen, produced in a capacitively coupled plasma. In addition, the decon chamber
:al agents from contaminated surfaces by vacuum, heat, and forced
agent byproducts are recirculated directly through the plasma, where they undergo further
Preliminary studies on actual chemical agents were conducted at the U.S. Army Dugway Proving Ground, Dugway,
inducted at a system pressure of 30torr, exposure temperature of 70 °C, plasma-to-sample standoff distance of 10
of oxygen or hydrogen to a helium balance. This exposure condition was based on optimization studies conducted
ilants. The agents studied were VX and soman (GD) nerve agents and sulfur mustard (HD) blister agent, as well as a
int. All agents were decontaminated off aluminum substrates to below the detection limit of 0.1% of the initial
;vel of approximately 1 mg/cm2. For VX, this level of decontamination was achieved in 8-16 min of exposure, while only
e dominant decontamination mechanism for all of the agents. However, an observed difference inth
i oxygen and hydrogen indicates that chemical reactivity in the liquid phase also plays an important r
convection. Once evaporated, agents
UT. Exposures we
cm, and 10% addi
at LANL on agent
le evaporation of Decontamin;
I chemical agents from Studies in the F
surfaces by vacuum, heat, and
forced convection. Once
evaporated,
agents and agent byproducts
[Vie Medical community has used cold plasma for several years. A cold plasma is an ionized gas in whi
nolecules are ionized, and is formed by passing an inert gas, such as argon or helium, over a sharp co
roltage and high frequency. An additional benefit in the Medical application ofthistechnology is enhs
destruction of infectious microbial agents without damaging healthy tissue. By expanding the cold pla
square meter or more, a general purpose decontamination device results with uses in the destruction
ind in assisting in the removal of radiological agents, while causing minimal or no damage to the com
approach is especially useful on porous surfaces. The use oflarge-area low cost applicators, utilizing ni
ndependent plasma emitters for CBRN d(
le Mail Sterilizer
Counters Biologic
lemical Warfare
Study on Plasma Agerr
Effect of a Direct-Currt
Atmospheric Pressure
Oxygen-PI asma Jet on
itivation off. coli
ig Bacterial Mutarr
;s Spores by Short-
Term Exposure in Axially
>n of bii
al agents (spores) on surfaces by tw
nditions, a steam plasma dc
m of 2.4 mph.
>11 fraction of the gas
he aim of this study
method for deco
xposed to HPV in s
5 range from 1.41
exposure period, before
efficacy of hydrogen pero>
ethis pathogen V
box enclosure, transferred to a quenching agent at timed intervals during
nerated. D-values were calculated from graphs of loglO survivors plotted against time and were found
1PV wasfound to be effective at deactivating spores of toxigenic CI. botulinum, non-toxigenic
iridium spp. and Geobocillussteorotbermophilus dried onto stainless steel surfaces. HPV could be used to decontaminate cabinets
rooms where CI. botulinum has been handled. The cycle parameters should be based on studies carried out with relevant spores of
organism, rather than based on inactivation data for G. steorotkermopkHus spores, which have been used in the past as a standard
ogical challenge for disinfection and sterilisation procedures. HPV could provide
hods, as it was rapid, residue-free and did not give rise to the health and safety concerns associated with other gaseoi
systems.
le for sti
:h openings provid
:k prevents the door from opening
Compendium of practical
ice-based reccwery
ry optior
mplemented followi
bydc
blowing a chemical incident. The identification ofthisgaphasle
icidentsto provide a frameworkfor choosing an effective recovs
ptions (techniques or methods for remediation) for inhabited ar
eveloped and is included in the chemical handbook. This paper f
actions are implemented during the recovery phase of a i
emediation strategies and recovery options that have been
r have been. Additional factors that can affect the approach taken
to the development of the UK Recovery Handbook for Chemical
y strategy. A compendium of practical evidence-based recovery
is, food production systems and water environments has also bee
esents the key factors that should be considered when developing
ingle-gene knockout mutants and physical methods using mesh and quartz glass are employed to discriminate plasma
ess their lethal effects generated in a Direct-Current atmospheric-pressure oxygen plasma jet. Radicals generated in
:ermined by optical emission spectroscopy, along with the 03 density measurement by UV absorptior
al effect is investigated by an infrared camera. The biosensors include three kinds of Escherichia coli
i their mutants, totalling 8 kinds of bacteria. Results show that oxidative stress plays a main role in thi
r than superoxide 0-2, neutral reactive oxygen species such as 03 and 02 (al g) are identified as doi
jestigation, an experimental facility was developed for quantifying the inactivation ofviablebioaerosol particle
lated air flow. The tests were conducted with Bacillussubtilis var. niger endospores. The thermal inactivation of aerosolized
as measured based on the loss of their culturability that resulted from a short-term exposure to air temperatures ranging from
>1,000 °C. The cross-sectional and longitudinal temperature profiles in the test chamber were determined for different heating
conditions. The characteristic exposure temperature (re) was defined using a conservative approach to assessing the spore
on. Experimentally determined inactivation factors (IF) were corrected to account for the temperature profiles in the axially
ir flow. The reported IF-values serve as the lower approximation of the actual inactivation. Two data sets obtained at different
s, 0=18 and 36 Lmin-1, represent different exposure conditions. In both cases, the thermal exposure of aerosolized spores
I no effect or only a moderate inactivation when the Te remained below ~200 °C for 18 L min-1 and ~250oC for 36 L min-1.
lues increased exponentially by about four orders of magnitude as the temperature rose by 150 °C. Depending on the flow rate,
led ~104 atTe>320 °C (Q=18 L min-1) or >360 °C (Q=36 L min-1). AtTe=375-400 °C, the spore inactivation obtained at both
s reached the limit of quantification established in this study protocol, which translates to approximately 99.999% viability loss,
igs were attributed primarily to the heat-induced damage of DNA and denaturation of essential proteins. Up to a certain level
=rmal exposure, these damages are repairable; however, the self-repair capability diminishes as the heat rises and then the
secomes totally irreversible. The data generated in this study provide an important reference point for thermal inactivation of
sistant spores in various biodefense/counterterrorism and air quality control applications.
Decontaminated surfaces
CBRN
Decontaminatii
using a Large-Ai
Information Source
Google Scholar
Keywords
agents, thermal
Atmospheric discharge co
id especially, different m
m system. A pi as
a appli
i been shown to be effective in the reduction of pathogenic bacteria and spores and in the
warfare agents, without the generation of toxic or harmful by-products. Cold plasmas may ah
cal "dirty bombs." For practical applications in realistic scenarios, the plasma applicator mus
i reasonably short dwell time. However, the literature contains a wide range of reported dw(
utes, needed to achieve a given level of reduction. This is largely due to different experiment
lods of generating the decontaminating plasma. We consider these different approaches anc
5m, and use this to develop requirements for a practical, field-deployable plasma
:ator with 12 square inches area and integral high voltage, high frequency generator is
Surface Decontamination This study reports on the efficacy of atmospheric oxygen-argon plasma for bio
lusing Atmospheric (agents, such as 8ocillus onthrocis (Sterne] (Anthrax), MS-2 bacteriophage, ani
Oxygen-Argon Plasma 02/min, 28 L Ar/min) on the B. a. spores revealed an average post-exposure It
3d a log 9.9 kill. The effectiveness of the oxygen-argon plasma
sis, specifically highly reactive oxygen atom or hydroxyl radicals. The met
A10-
iurface sterilization of infectious
exposure (RF power 77 W, 29.5 mL
(LR) value of 2.7, whereas a 20-second
5 be attributed to the generation of free
idical attack of the microorganisms is
Atmospheric oxygen-argi
plasma (a 10- second exp
(RF power 77 W, 29.5 ml
02/min, 28 LAr/min]).
Surface sterilization of
infectious agents, such as
iBocillus orthrocis (Sterne]
(Anthrax), MS-2
bacteriophage, and Ecoli.
B-6
-------
Literature Search Results
Article/Report Title
Study on Photolytic:
Photocatalytic
Decontamination of
Warfare Agents (CWAs)
Photolytic and photocatalytic
|(PFIB) vapors in air were carrii
germicidal lamp through eithc
atGB, GD an
tactions of sarin (GB), soman (GD), sulfur mustard (HD), cyanogen chloride (CK) and
d out. It was shown that vapors of GB, GD, HD and PFIB could be efficiently eliminate
photolysis or photocatalysis, but CK could hardly be done through photodegradatio
HD might possibly undergo a photo-induced polymerization under UV light irradiati
ds at "IT02 surface. 71
efficis
id to a cleavage of these molecules into small inorgani
:h photolysis and photocatalysis of GB vapor at static conditions were kinetically slowed down a
of GB molecule. It has been testified thatthe static photolysis approach could be applicable for
space. And that, a dynamic photocatalysis approach for decontamination of GB vapor was proved to be mucl
through photolysis, and it was also considered to be feasible for decontamination of air polluted by GB vapor.
n. Photocatalytic
ital results strongly
possibly limited by a
n of GB
Existing F
Methodologies C
; UV light from germicidal lamp
through either photolysis or
photocatalysis.
Types of Waste Full Text File Name
Sarin (GB), soman (GD), sulfur
mustard (HD), cyanogen
chloride (CK) and
perfl uoroisobutyl ene
(PFIB) vapors in air were
Information Source
Google Scholar
air polluted by
agents (CWAs)
the foil of 2001, anthrax-contaminated letters were sent to public figures in the United States. C
ere employed to decontaminate exposed buildings, objects,;
(posed objects and materials. The recommended surface che
ich as peroxides or chlorine bleaching agents. Such oxidizing agents are effective against a
ological agents. Knowing how these reagents affect various substrates would helpto antic
'e are examining the effects on typical museum materials of reagents likely to be used, inc
hypochlorite, and potassium peroxymonosulfate. Results so far show significant changes in
ved on metals such as copper, silver, iron, and brass. Color changes occurred with at I
dyed fabric swatches tested, and about half of the inks. Samples of aged yellowed paper an
rate and the tested reagent. The observed changes were generally less drastic than mi
affected, though, to preclude the use of these reagents on museum objects unless no
objects of le<
lain legible if the appropriate reagent is
appropriate for a specific situation and what conse
ss of pr
js fords
ire effective, but potentially damaging to
s, gels, and foams of oxidizing agents
i range of hazardous chemical and
i and to minimize any potential damage,
ig hydrogen peroxide, sodium
iiber of materials. Surface corrosion was
one reagent in about one-fourth of the
iched. Effects varied with both the
lave been expected. Enough materials
drastic alternative is available. It appears
ifulness. For example, most documents
foams of
j employed ti
;, objects, and
Security Workshop on
Transport and Disposal of
Wastes from Facilities
Contaminated with
Agents
Workshop on
Transport and
Disposal of Wastes
from Facilities
Contaminated with
from the "Homeland Security
Workshop on Transport and
Disposal of Wastes From Facili
Contaminated With Chemical
iological Agents." The
'orkshop was held on May 2i
2003, in Cincinnati, Ohio, and
objectives were to: Document
challenges faced when handlir
transporting, and disp
esfrom publi
privatt
facilit
lemical and biological agents.
Identify research needs and
opportunities for improving
federal, sta
order to fill
gaps in the current
ofthese waste
management challenges.
Surface Decontamin;
Warfare Agents Usin
Nonequilibrium Plasr
Off-Gas Monitoi
aTek is developing a surface
asma technology was tested ag
four loglO destruction of the DM MP
n technology that utili<
DM MP, a simulant for the ch«
i aluminum surface was achiev
solved data on the treatment off-gases. The
present in the gas phase. The technology is
ctive species generated in a nonequilibrium corona plasma,
al agent Sarin. GC-MS analysis showed that a greater than
i a 10 minute treatment. An ion-trap mass spectrometer
lata indicate that only non-toxic fragments of the broken
ig further refined to develop a product that will not only
Atmospheric-Pressure
Decontamination/Sterili;
i atmospheric-pressure plasma
ition/steriliz
ig agent, VX ne
¦r biological warfare agents, such as anthrax, musi
procedure for decontaminating such equipment. The apparatus may also be used for
to be decontaminated or sterilized are supported inside the chamber. Reactive
js are generated by an atmospheric-pressure plasma discharge in a He/02 mix!
ing in chemical reaction between the reactive species and organic substances."
mination without damaging most equipment and materials. The plasma gases
lize the loss of helium and the possibility of escape of aerosolized harmful subs'
e is currently no acceptable
le region ofthese items
i a closed-loop system to
i atmospheric-pressure
tion/steriliza
warfare af
le of major chemic;
>. Selected phenol-formaldehyde resins it
erties without decreasing strength props
id polyurethane resins impregnated in sc
•n yellow
ig phenol-formaldehyde ar
-e adequately
;d of all
al for this purpose w
major chemical warfare agent was
insional stability and strength
ne, red oak, and aspen impregnated with these
warfare agents. A polyurethane resin that performs
Reaction of CW Agents
Presence of 03, UV
ants for the chemical warfare (CW) agents HD, GB ar
(254 and 185 nm), 03 (0-2 wt% in air) and 03 + UV at 0 ar
mined. The simulation for HD wasfound to be most t
nless steel surfaces, were exposed to UV
ts of the simulants decomposition were
Systems Analysis of
Decontamination Opti
for Civilian Vehicles
if vehicles is especially challenging
sf which strongly adsorb chemical agents, and in the
:annot be exposed to reagents that may cause even
First, an assessment was performed to determine th
would be employed currently to decontaminate botl
:onducted to identify technology, capability, and da<
dentified gaps was developed includir
vehicles focusing on efficacy
id Security (DHS) Science and Technology Directorate
icontamination of the exteriors and interiors of vehicl
3 normal use following the release of a highly toxic chemical. The
:ausethey often contain sensitive electronic equipment, multiple materials sot
;e of aircraft, have very rigid material compatibility requirements (i.e., they
lor corrosion). A systems analysis approach was taken examine existing and
lemical threat to vehicles in terms of types of chemicals likely to be released,
contamination locations). Next, the state-of-the-art or expected practices that
a exterior and interior of vehicles were identified. Agaps analysis was then
i approaches. Finally, a roadmaptofill the
m or emerging technologies that could be usei
Systems Analysis of
Decontamination
Options for Civilian
RHELP (Regenerative Hig
Efficiency Low Pressure)
Air Purification System
llhis project aims to develop a RHELP (Regenerative-High Efficiency-Low Pressure) air purification system using a ni
Ion silicon carbide in a microwave oxidizer that can effectively decontaminate air containing aerosolized chemical a
agents. Nanofibermats of several materials were designed and fabricated using electrospinning process. Physical fi
showed performance (filter quality) exceeding military HEPA requirement. Multiple layers were found to have bett
single layer of the same thickness. Biological agent testing showed effectiveness of microwave irradiation todeacti
biological agents. System performance can be further enhanced by lowering face velocity during periodic microwa
minimize heat loss. Chemical agent testing showed excellent regeneration but destruction of the agent needsfurth
•amic nanofiber Regenerative-High Efficier
ogical (CB) Low Pressure (RHELP) air
i testing | purification system using i
' quality than ceramic nanofiber on silio
wide range of carbide in a microwave o*
RHELP (Regenerative
| Pressure) Air ||
Purification System
B-7
-------
Literature Search Results
Atmosphere Uniform
Discharge Plasma
(OAUGDP) for Sterilizatic
of Surfaces and Material
Article/Report Title
le New Decon Green™ formula. Four main
:erm stability; 3) homogeneity; and £
;e problems have been solved, but a<
:hemical Agent Resistant Coating
c as Bio agents do not
i such as DF200,
the subjective nature of this tes
il. Currently, contact hazard anc
icy on surfaces such as CARC wl
This study presents the further refinement of the original Decon Green™
problems were identified with the "Classic"; 1) limited capacity for non-traditional agents; 2) Ic
material compatibility, especially with paints, M40 Mask lenses, and HMMWV light housings,
the expense of decon efficacy of Chem Agents (not Bio agents) for soft/sorptive materials such
(CARC) paint. The Bio efficacy of New Decon Green™ remains comparable to Decon Green™ CI
penetrate/soften materials. Moreover, Chem efficacy still remains better than other peroxide-
especially for paint-penetrating HD. Finally, a simple model is presented to extrapolate measui
vels. Off-gassing data for HD and GD on CARC paint is also discussed along witf
ambiguous results, and the problem of relating the results to a true, accurate vapor hazard lev
raction (residual hazard) remain the only unambiguous tests to verify d
>stantial agent remains folio
3 medical, food processing, and heatin
infection, and sterilization technologie
struction by heat, formation of toxic by-products, costs, and inefficiency in performance.We report the results of a plas
One Atmosphere Uniform Glow Discharge Plasma (OAUGDP), which operates at atmospheric pressure in air and produce:
:ive species at room temperature. OAUGDP exposures have reduced log numbers of Gram negative and Gram positive I
aerial endospores, yeast, and bacterial viruses on a variety of surfaces. The nature of the surface influenced the degree
:h microorganisms on polypropylene being most sensitive, followed by glass, and cells embedded in agar. Experimental
>wed at least a 5 loglO CFU reduction in bacteria within a range of 50-90 s of exposure. After 10-25 s of exposure, n
leakage and bacterial fragmentation were observed. Vulnerability of cell membranes to reactive Oxygen species (ROC) is hypothesized.
Results from several noval OAUGDP configurations are presented, including a remote exposure reactor (RER) which uses transported
) sterilize material located more than 20 cm from the plasma generation site, and a second planar electrode
configuration developed for air filter sterilization. Applications of these technologie:
g surfaces compromised by biological warfare agents are discussed.
Existing P
Methodologies Discussed
Decon Green™, chemical
:h problems as
Types of Waste
CARC painted surfaces.
Full Text File Name
Information Source
Google Scholar
One Atmosphere
Discharge Plasma for
Atmospheric Pressure
et (APPJ) is a unique, capacitively-coupled rf,
dw of He/02 feed gas. The APPJ generates highly
:ed surface at high velocity. This may provide a mi
agents which, unlike trad
175 °C has been shown tt
of 4.5 sec at a standoff di:
tal, uniform discharge operating at
le species of oxygen
>n ofCBW
lal decon methods, is dry and nondestructive to sensitive equipment. The reactive effluent of the APPJ at
Bacillus globigii spores, a surrogate for Anthrax, with a D value (t'me to reduce viability by a factor of 10)
ce of 0.5 cm. This is 10 times faster than hot gas at the same temperature and requires 80% less energy
el of kill. This D value is also an order of magnitude better than achieved by other nonthermal plasma
tther discharges, the APPJ provides a downstream process which can be applied to all accessible surfaces
nated object to fit within a chamber. Through active cooling of the electrodes, the authors have also
it an effluent temperature of just 75 °C, making the decontamination of personnel a definite possibility. Th(
oxidize surrogates of the CW agents, Mustard and VX, and a collaborative effort is now proceeding with the
id Chem/Bio Center (ECBC, formerly ERDEC). Efforts are now being directed towards reducing the
isine- the working stand-off distance.
Technology for the
Destruction of Organic
Wastes
temperature:
pressure, aqueous-based technology for the oxidativ
waste streams. The process has been developed for applications in v
tion at LLNL since 1992, and is applicable to the destruction of virtually all solid i
sils and greases, detergents, organic-contaminated soils or sludges, explosives, chemic;
>. The process normally operates at 80-100 °C, a heating requirement which increases 1
objects or, for example, treatment of a wide area contaminated soil site. The driver for
i of catalysts to demonstrate the effectiveness of the technology for organics destructio
iddition, DCO is at a sufficiently mature stage of development that technology transfer
technology for the oxidativ
jction of the organic
RCRA Compliance Test
Destruction of VX in Ton
Containers in the Metal
Parts Furnace (MPF) at
lemical Agent
:ions Disposal
System (CAMDS), Tooele,
inducted atthe Chemical Agent Munitions Disposal System (CAMDS) using the metal parts furnace (MPF) system to
nal detoxification of steel ton containers containing a residual heel of chemical warfare agent, VX. This was done
Congressional mandate by the Department of the Army as part of an on-going program to dispose of existing stocks of obsolete
cal warfare agent munitions. Particulate matter, HCI, trace metals, VX, and CO emissions were all well within State of Utah permit
established for the MPF. Particulate emissions were <45 mg/dscm at 70% 02 (average was <10 mg/dscm (<0.004 grain/dscf] at
7% 02). Agent VX (the Principal Organic Hazardous Constituent) destruction and removal efficiency (DRE) exceeded the Resource
Conservation and Recovery Act (RCRA) min. of 99% with a >99.99999% DRE. No VX was detected in flue gases at anytime during the
program. HCI emissions were well below the RCRA limit of 4 Ibs/h with an average <6.75 x 10-4 Ibs/h. Results were reviewed and
accepted by the Utah Department of Environmental Quality and were verified by material and energy balance calcns.
Warfare (CW) Agents ar
Structurally Related
Compounds (Pesticides,
Residues and waste materialsfrom ongoing cleanup of the US's vast CW agent stockpile;
2012, present a major problem. These typically comprise contaminated cle
CW agents are structurally similar to widely used biocides, such as organophosphates malat
frequently contaminate man-made materials. A rapid, environmentallyfriendly remediation meth
contribution describes a very rapid remediation method using ambient pressure
jnder current treaty obligations by
on, chlorpyrifbs and phosmet, whicH
licrowave hydrolysis of contaminate!
other analyses
a 50g:
in 20 m
APPJ at 175 °C has been
shown to kill Bacillus globigi
spores, a surrogate for
:al parts furnace (MPF).
Conference: 1999 IEEE Internation
Conference on Plasma Science,
Monterey, CA (US), 06/20/1999-
06/24/1999.
Thermal Technology
:or the Destruction ol
Organic Wastes
Warfare Agents by a C
Atmospheric Pressure
(Dimethylmethylphosphonate) wi
efficiently d«
chemical and biological warfare (CBW) agents for the application of a portable
Ihe cold arc plasma jet is a low temperature, high density plasma that produces highly reactive species
a. Moreover, it is possible to maintain stable plasma without He or Ar. The discharge operated on N2-02
;h voltage pulse (23 kHz, 30% duty ratio) power was applied to the inner electrode. In the
3acillus subtilis and Escherichia Coli were chosen as simulants for biological agents and DMMP
hosen as a simulant for chemical agents. The experimental results showed that B. subtilis and E
DMMP was decomposed very well in the plasma effluent.
a portable
on system.
Conference Paper, IEEE In
Conference on Plasma Sci
ICOPS.
i in a highly energized state, contains radicals such as atomic oxygen, e
these reactive oxygen species (ROS) can destroy just about all kinds of c
s. These chemical modifications result in protein cleavage, aggregation
secondary and tertiary protein structures. These oxidative proteins are
e is known as protein degradation. Through these chemical reactions, t
id water. The emission spectroscopy of an arc-seed microwave plasma
(777.194 nm) indicating relatively high atomic oxygen content in the torch was d
process for the decontamination of biological warfare agents,
ant of Bacillus anthracis sporesfor biological agent and the ai
of atomic oxygen produced by the torch as well as a good
from the nozzle of the torch. We now extend the experimental effort to
i highly
at 4 cr
oxygen m
suits of experiments using dry samples sho
et samples. The results will be presented ar
Development of a Low-
Temperature Catalytic
tion System for
Destruction of Chemica
Warfare Agents
This project isto develop a low-temperature microwave catalytic oxidation system that will effectively i
aerosolized or gaseous chemical agents (CWAs). To protect personnel in shelters catalytic oxidation systems should (1) destroy CW As in
lir at low temperatures to avoid NOx formation, (2) remove sulfur dioxide produced from the oxidation of CWAs containing sulfur
rtoms, (3) operate for an indefinite period of time and (4) destroy biological agents at low temperatures. This system will be used to
iupply clean breathing air to a bunker or other facility in a war zone that has been contaminated with chemical weapons. This work will
>e performed in two phases Phase I of the experimental effort is to obtain the data needed to design and fabricate a prototype CWA
catalytic oxidation system. During Phase II work the prototype microwave air decontamination system will be constructed and tested
at CHA Corporation and at a selected location to demonstrate the effectiveness of the microwave air decontamination system.
Experimental results obtained to date indicate that microwave catalytic oxidation will be capable of destroying more than 99.5% of
B-8
-------
Literature Search Results
Document
Relevance
Relevancy
Publication
Full Text
Article/Report Title
Abstract
Existing Procedures and
types of Waste
Full Text File Name
Information Source
Notes
Keywords
TVoe
Score
Year
Available?
Methodologies Discussed
G
Medium
33
2003
Effects of Dimethyl
The impact of dimethyl methylphosphonate (DMMP) was studied in a premixed methane/oxygen/N2-Ar flame in aflatflame burner
Methane/oxygen/N2-Ar flame
Simulants of nerve agents,
Effects-of-Dimethyl-
Google Scholar
chemical or biological
Methyl phosphonate on
slightly under atmospheric pressure at two different equivalence ratios: rich and slightly lean. CH4, CO, C02, CH20, CH30H, C2H6,
in a flat flame burner slightly
dimethyl methylphosphonate
Methyl phosph on ate-
agents, thermal
Premixed Methane
C2H4, and C2H2 profiles were obtained with a Fourier Transform Infrared (FTIR) spectrometer. Gas samples, analyzed in the FT1R, were
under atmospheric pressure.
(DMMP).
on-Premixed-
destruction
Flames
extracted from the reaction zone using a quartz microprobe with choked flow at its orifice. Temperature profiles were obtained by
Methane-Flames
measuring the probe flow rate through the choked orifice. Flame calculations were performed with two existing detailed chemical kinetic
mechanisms -for organophosphorus combustion. DMMP addition caused all profiles except that of CH30H to move further away from
the burner surface, which can be interpreted as a consequence of a reduction in the adiabatic flame speed. Experimentally, the
magnitude of the shift was 50% greater -for the near-stoichiometric flame than for the rich flame. Experimental CH30H profiles were four
to seven times higher in the doped flames than in the undoped ones. The magnitude of this effect is not predicted in the calculations,
suggesting a need -for further mechanism development. Otherwise, the two mechanisms are reasonably successful in predicting the
effects of DMM P on the fl ame.
U
Medium
33
2001
N
Biological Weapons Agent
A synergistic, molecularly targeted microwave approach has demonstrated unprecedented kill of a broad range of biological weapons
Directed microwave energy in
Biological weapons agents
NA
Google Scholar
Conference paper.
chemical or biological
Defeat Using Directed
agents (BWA) using directed microwave energy in conjunction with a specially designed chemical compound called aTPAC.The BWAs
conjunction with a specially
(BWA).
agents, incineration
Microwave Energy
are first treated with the TPAC compound, a process that only takes a few moments, and then exposed to the microwaves. Using this
designed chemical compound
synergistic approach, significant kill of the BWAs is achieved using standard microwave equipment at moderate powers (< 1M W peak
called a TPAC.
and only a few hundred watts average) and exposure levels (/spl sim/few joules). This method is so effective and broad ranged that total
kill is achieved on vegetative bacilli and spores and vegetative growth anthracis and an unprecedented 5.5 out of a total of 6 logs of kill is
achieved on anthrax type spores, the hardest BWA to defeat. To put the anthrax kill rate in perspective, of the approximately one million
spores exposed to the microwaves in a given sample only three survived, even though the spores were given every opportunity to grow
after RF irradiation. The TPAC compound consists of two components, atransduction-polymer (TP) and an acceptor-chromophore (AC),
that work in conjunction to produce BWA defeat. The AC molecule is designed so that it easily penetrates the wall of the BWA and binds
to surface matrix targets. Upon microwave exposure, the TP emits a blue photon that activates-the AC producing saturated levels of
chemical radicals that are irreversibly bound to the target spore wall, resulting in lethal failure of the spore upon germination. The TP
molecule is resonant and thus responds to a given microwave frequency better than others. Its effectiveness also depends upon the rise-
time and width of the RF pulse. With optimization of the RF pulse and frequency, total kill of even anthrax spores is expected.
G
Medium
33
2000
N
Bacterial
Atmospheric pressure nonthermal plasmas can efficiently deactivate bacteria in gases, liquids, and on surfaces, as well as can
Atmospheric pressure
A large area plasma
Google Scholar
chemical or biological
Decontamination Using
decompose hazardous chemicals. This paper focuses on the changes to bacterial spores and toxic biochemical compounds, such as
nonthermal plasmas.
decontamination technology
agents, incineration
Ambient Pressure
mycotoxins, after their treatment in ambient pressure discharges. The ability of nonthermal plasmas to decompose toxic chemicals and
is described 1br
Nonthermal Discharges
deactivate hazardous biological materials has been applied to sterilizing medical instruments, ozonating water, and purifying air. In
decontaminating chemical
addition, the fast lysis of bacterial spores and other cells has led us to include plasma devices within pathogen detection instruments,
and biological warfare
where nucleic acids must be accessed. Decontaminating chemical and biological warfare materials from large, high value targets such as
materials from large, high
building surfaces, after a terrorist attack, are especially challenging. A large area plasma decontamination technology is described.
value targets such as building
surfaces, after a terrorist
G
Medium
33
1998
Y
On Modeling of the
A model -for evaporation of chemical warfare agents on the ground has been developed. The process of evaporation is described in three
Development of a model for the
Soils contaminated with
On modeling of the
Google Scholar
chemical or biological
Evaporation of Chemical
steps: 1. the immediate drop enlargement due to impact momentum is modeled using an empirical correlation from technical
evaporation of chemical warfare
Soman and Mustard agents.
evaporation of
agents, thermal
Warfare Agents on the
literature; 2. further enlargement caused by capillary spreading upon the surface and the simultaneous sorption into the substrate,
agents on the ground.
chemical warfare
destruction
Ground
modeled in three dimensions; 3. subsequent drying and redistribution of the sorbed material is described as a one-dimensional vertical.
agents on the ground
process. The -formulation of the flux in the soil takes into account vapour, liquid, solute, and adsorbed phases. The evaporation from the
surface is determined by the vapour concentration atthe surface and the conditions in the atmospheric viscous sub-layer close to the
droplet spots on the surface. Model results agree with the limited experimental data found in the literature. The model shows a very
rapid sorption and redistribution of chemical warfare droplets on sand. This effect gives a rapid decrease of the
evaporation, except -for a shorter initial period. However, a small residual evaporation exists for a rather long time from liquid, which has
penetrated down into the soil.
U
Medium
33
1998
N
Utilizing a One-
An innovative approach to the decontamination of chemical and/or biological warfare agents is described. This recently developed
One atmosphere uniform glow
Sel ected simul ants for the
NA
Google Scholar
Conference paper.
Destruction or
Atmosphere Uniform
technology involves utilizing a one atmosphere uniform glow discharge plasma (OAUGDP) as the decontaminant/sterilant. The plasma
discharge plasma (OAUGDP).
highly toxic agents were
Decomposition or
Glow Discharge Plasma
provides a very powerful but environmentally safe oxidizing and disinfecting technique without the use of strong chemicals (chlorine
exposed to the OAUGDP and
Incineration; Thermal or
For Chemical/Biological
bleach) or high temperatures (autoclaving). Initial laboratory results indicate a greater than six log kill of bacteria in under one minute,
the
Heating or (Hot (w)
warfare Agent
significantly faster than autoclaving. In addition, the highly ionizing nature of the plasma discharge is expected to quickly degrade
sterilizing/decontamination
(Temperature or Air));
Decontamination
chemical agents through energetic bond breaking mechanisms. The active species of the air plasma are nonpersistent and are expected
effect quantified.
Chemical or Biological
to revert to the components of atmospheric air. Selected simulants -for the highly toxic agents were exposed to the OAUGDP and the
Agent; Anthorocis or
sterilizing/decontamination effect quantified.
Anthrax or
SteorotkermopkHus; HD
or Mustard; Building or
Soil or Carpet or (Ceiling
(w) Tile); Concrete or
T
Medium
32
NA
Y
Radiological, Chemical,
NA
Atmospheric-pressure plasma
Stainless steel coupons
Radiological,
Google Scholar
The temperature of thisgas
chemical or biological
and Biological
jet (APPJ).
(disks).
Chemical, and
discharge
agents, thermal
Decontamination
Biological
typically ranges from 50°C to 300°C,
destruction
Using Atmospheric-
Decontamination
which allows
Pressure Plasmas
Using Atmospheric-
for plasma processing of sensitive
Pressure Plasmas
materials and
equipment at low temperatures and
processing of more robust surfaces
at higher
G
Medium
32
2007
Y
A Decontamination Study
A comprehensive decontamination scheme of the chemical and biological agents, including airborne
Plasma flame and electrolyzed
The plasma flame presented
A decontamination
Google Scholar
chemical or biological
of Simulated Chemical
agents and surface contaminating agents, is presented. When a chemical and biological attack
ozone water.
here may provide a rapid and
study of simulated
agents, destruction
and Biological Agents
occurs, it is critical to decontaminate facilities or equipments to an acceptable level in a very short
effective elimination of toxic
chemical and
time. The plasma flame presented here may provide a rapid and effective elimination of toxic
substances in the interior air
biological agents
substances in the interior air in isolated spaces. As an example, a reaction chamber, with the
in isolated spaces and
dimensions of a 22 cm diameter and 30 cm length, purifies air with an airflow rate of 5,0001 /min
electrolyzed ozone water for
contaminated with toluene, the simulated chemical agent, and soot from a diesel engine, the
surfaces.
simulated aerosol 1br biological agents. Although the airborne agents in an isolated space are
eliminated to an acceptable level by the plasma flame, the decontamination of the chemical and
biological agents cannot be completed without cleaning surfaces of the facilities. A simulated
sterilization study of micro-organisms was carried out using the electrolyzed ozone water. The
electrolyzed ozone water very effectively kills endospores of Bacillus atropbaeus ATCC 9372
within 3 min. The electrolyzed ozone water also kills the vegetative micro-organisms, fungi, and
G
Medium
32
2006
Y
Degradation of Chemical
This study determines the effectiveness of pulsed streamer discharges (PSD), a type of advanced oxidation technology (AOT) to clean
Pulsed streamer discharges
Water contaminated with
Degradation of
Google Scholar
chemical or biological
Warfare Agent Simulants
water contaminated with chemical agents. For the purpose of this study, experiments were conducted with G and H agent simulants to
(PSD).
chemical agents.
chemical warfare
agents, thermal
Using
determine the degradation kinetics and to determine the effects of various electrical and chemical parameters in the degradation of
agent simulants using
destruction
Gas-Liquid Pulsed
these contaminants. The energy efficiency of contaminant degradation shows that pulsed streamer discharges can be an efficient
gas liquid pulsed
Streamer Discharges
technology in treating water contaminated with chemical agents. The maximum energy yields of degradation of H and G agent simulants
streamer discharges
by the pulsed corona discharges are 0.029 and 0.008 molecules/100 eV, respectively, in the series configuration with ferrous sulfate salt
U
Medium
32
2004
Y
Computational Modeling
Incineration is being used or is planned as destruction for stockpiles of chemical warfare agents in the U.S. This paper presents the
Liquid Incinerator Chamber
Liquid chemical weapon agent
Computational
Google Scholar
Conference paper.
chemical or biological
of a Chemical Liquid
development of models for analyzing a Liquid Incinerator Chamber (UC) for destroying liquid chemical weapon agent (GB, HD, or VX)
(UC).
(GB, HD, or VX) from
Modeling of a
agents, incineration
Incinerator Chamber
drained from munitions containing in the US Army chemical weapon stockpile. The models predict complete destruction of the chemical
munitions.
Chemical liquid
agent when the incinerators and afterburners are operated as per standard operating conditions. Under normal operating conditions
Incinerator Chamber
B-9
-------
Literature Search Results
Article/Report Title
destroy any stockpiles of
xtension for up to 5 years to 2012. T
al weapons and agents—primarily h
ilyfrom World War I, in China from
years, more than 20 000 tonnes of agent hi
Although incineration is well p
of agent,
of the chemical weapon destruction technologies demonstrated for 1 kg or more of agent in order to
ie technologies proven to destroy chemical weapons to policy-makers and others concerned with reaching
ion of chemical weapons and agents. As all chemical agents are simply highly toxic chemicals, it is logical to
ihemical agents as being no different from the consideration of the destruction of other chemicals that can
truction, as that of any chemicals, requires the taking of appropriate precautions to safeguard worker safety,
>nment. The Chemical Weapons Convention that entered into force in 1997 obliges all States Parties to
weapons within 10 years from the entry into force of the Convention—by 2007—i
iration, plasma pyrolysis,
in metal technology,
hydrogenolysis, and destruction
ecause of se
id States had, along wi<
s consequently a tight timeline under the treaty for
i War II as well as in the United States—also have tc
=en destroyed in a number of countries and ewer 80
i and will be used in the United States to destroy ovi
las been paid particularly in the United States to alts
5 the United States. Much of the informati
of stockpiled
lemical weapons—notably in Europe
3 be destroyed. During the past 40
1 % of this has been destroyed by
•er 80% of the U.S. stockpile of
ernative technologies to incineration
report is based on U.S.
isian Federation, by far the largest stockpiles of chemical weapons and agents
h progress in destroying its stockpile of chemical weapons and agents and has
alternative technologies for the destruction of chemical weapons and agents,
faced with the destruction of chemical weapons and agents need to be made it
thus may well result in a decision to use different approaches from
information to enable countries to make their own informed and appropriate
Full Text File Name
Information Source
ation Process for
'd Projectiles at
aintained a stockpile of chemical warfare agents
i advice on how best to dispose of the stockpile. I
:il (NRC) established the Committee on Review at
process, a slightly simplifiec
Hons since World War I. The Army leadership has
t the request of the Under Secretary of the Army, the
:ion of the Army Chemical Stockpile Disposal Program
and counsel on the CSDP. This report is concerned with the technology
system that was used to dispose of mustard munitions on Johnston
-based technologies for possible use at Pueblo. The evaluation in this
tould also help the public and other non-Army
Decontamination Efficacy
of Three Commercial Off-
¦-Shelf Sporicidal
Agents on Medium-Sized
s Contaminated with
Surrogates of Bacillus
^sponse to wide-area contamination resulting from the release of
ust a few letters containing anthrax spores resulted in the
i Distribution Centers (Brentwood, Washington, DC; Trenton and
Jersey City, NJ) and American Media Inc. (Boca Raton, FL). Despite heavy contamination levels of several building interiors, remediation
of building interiors was achieved successfully by fumigation with chlorine dioxide (CD) or vapor hydrogen peroxide (VHP). A wide- area
si ease and contamination of building exteriors and the outdoors would likely exhaust the national remediation capacity. Cleanup could
ike years and lead to incalculable financial drain because of a delay in effective response. Additionally, agencies responsible for the
litigation of contaminated sites are exploring alternative methods for decontamination including combinations for the disposal of
ontaminated items, source reduction by vacuuming, mechanical scrubbing, and pH-adjusted bleach pressure wash. If proven effective,
pressure wash-based removal of anthrax sporesfrom building surfaces with readily available equipment will significantly increase the
sadiness of federal agencies to meet the daunting challenge of restoration and cleanup efforts following a wide-area biological release.
rvapor hydrogen
de (VHP).
ie of m
wave plasma bi
er for a I
warfare agents. The apparatus can purify th
transportation systems, and military vehicles contaminated with
licrowave plasma torch connected in series to a fuel injector ani
warfare agents in large quantities. Hydrocarbon fuel in gaseous c
>usly, generating a large volume of plasma flame in th
al and biological warfare agents that pass through the rea
organic compounds and eliminate soot from diesel engin
:e injected into the
ser. The apparatus
warfare agents. The apparatus c
ivave plasma torch ev
Present State of CBRN
Decontamination
Methodologies
Decontamin;
is report, the present si
te of the art of i
nation technologies
CBRN agents and ti
;. Decontamins
;ical and/or nuclear (CBRN)
:ussed. Advantages and disadvantages
Justrial chemicals (Ties) and the
c processes: physical, chemical,
from surfaces and include weathering,
and strippable coatings. In principle
physical removal and containment. Chemical, enzymatic and energetic methods aim
¦ to reduce or eliminate the toxicity of the compounds. The following chemical
(chlorine, peroxides and reactive gasses), nucleophilic substitution (alkaline
hydrolysis and oximes) and alternative chemical approaches. Some chemical decontaminants are effective but highly toxic and
ironmentally unsafe. An example is DS-2, that is currently being replaced by safer decontaminants such as, in The Netherlands,
GDS2000. An environmental friendly alternative for aggressive chemical decontaminants wasfound in the use of enzymes. Some
:ymatic decontaminants are commercially available. Most enzymes are only effective against GB and GD, however, some enzymatic
approaches towards destruction ofVX, HD and BWAshave been reported. Finally, directed energy methods, such as photochemical,
a violet radiation, plasma, and microwave radiation have all been demonstrated to disinfect surfaces. However, these methods are
generally applicable. Unfortunately, there is no single decontamination technology that is effective against all CBRN agents.
Therefore, there are still sufficient challenges for further innovative developments in the future.
ie present state of the art of
^contamination technologies i
scussed (physical, chemical,
lzymatic, and energetic
Decontamination
biological, radiolo
nuclear (CBRN) m
Present State of
CBRN
Decontamination
Methodologies
lodelsfor a pilot scale rotary kiln simulator for the incineration of
a computational fluid dynamics (CFD) model is presented,
a. The models predict complete destruction of the biological agent that
i afterburners are operated as per standard operating.
ADVANCEDM ODEU
NG_OF_INCINERATIO
N_OF_BUILDIN G_DE
CON_RESIDUE
Atmospheric GlowTechnologies (AGT) has developed an innovative means of safeguarding indoor environments using One Atmosphere
iform Glow Discharge Plasma (OAUGDP/supTM/). AGT has placed an atmospheric plasma device within HVAC duct work and is using
ictive chemical species present in the exhaust from this device to neutralize biological agents captured on filter media. This plasma
ifice, using air only, requires no additives. Importantly, since our design does not impede airflow, those flow rates typical for HVAC
systems can be maintained. The biological inactivation achieved by this system is broad-spectrum and includes bacterial endospores.
AGT routinely achieves neutralization of 6 logs of Bacillus otropkoeus (formerly 8. subtilis variant niger, ATCC 9372) endospores within
-20 minutes up to 2 feet downstream depending upon airflow parameters. Data correlating biological inactivation with electrical and
irflow parameters will be presented. Ongoing research indicates singlet delta oxygen plays a significant role in OAUGDP-based
iological neutralization. Liability of microorganisms was assessed using standard plate counts from filter media. All plates were
leubated for a minimum of 96 h at 37/spl deg/C in order to accurately quantify any surviving organisms. The ability to provide broad-
aectrum reduction of air-borne biological agents indicates that the use of a duct-mounted OAUGDP atmospheric plasma device can
provide a reliable, unobtrusive means of protecting hieh-risk buiidines.
An atmospheric plasma
device within HVAC due
a to neutralize biologies
agents captured on filte
planned as a primary destruction technology of stockpiles of
:hemical warfare agents (CWA) in the United States. Computer modeling tools may play an
mportant role in reducing the time, cost and technical risk of using incineration. A simulation
workbench is being developed to assist the chemical demilitarization community. The
workbench will consist of models for a Liquid Incinerator (LIC), Metal Parts Furnace (MPF), a
De-Activation Furnace System (DFS), and the afterburners and Pollution Abatement Systems
(PAS) for these incinerators. In this paper we present recent development of the component
for the MPF for the incineration of mustard. Both a transient zonal model and CFD
are presented. Results of several practical cases are presented including comparison wi
predict complete destruction of the chemical agent when the
i this paper we present
evelopment of the
lodels for the Metal Parts
ADVANCED
COMPUTATIONAL
MODELING OF
MILITARY
INCINERATORS
gaseous discharges have been found t
generate these discharges at atmospheric pressure
plasmas generated by such discharges are
Tofully understand the biophysical and biochemic;
i be effective agents for biologica
makes the decontamination process practical anc
:old makes their use suitable for applications whe
processes induced by the interaction of living eel
anced corona discharge at atmospheric pressure.
ind inexpensive. In addition, the fact
cells with gaseous discharges, a
different discharges: a
discharge at atmospheric
a discharge at
atmospheric pressure.
B-10
-------
Literature Search Results
Treatment of Q"
Agents and Cher
Weapons
Article/Report Title
he U. 5. Army has been directed by Congress to dispose of its approximately 24,800 ton stockpile of chemical weapons and chemical
/arfare agents (CWAs) by December 31, 2004 and has chosen to use incineration for this purpose(l]. This stockpile contains the
lustard gas, blister agents H, HD, and HT, and the organophosphorus nerve agents VX and GB. On Johnston Atoll a prototype disposal
facility, consisting of four separate process streams each containing a furnace, afterburner and air pollution control section, has been
'ucted, tested and is now operational. In spite of the fact that this facility has met all major performance goals, there is
ferable opposition to the use of incineration for disposal of that portion of the stockpile stored at eight sites in the continental U.S.
; paper we review what is known concerning the relevant chemical mechanisms for th
ants and related compounds. Focus is placed on the reactions associated wit
S. While there have been few kinetics studies using either agents or their simulants, the rel
iration (C1,F), fire suppression (C1,F) and fossil fuel combustion (S,N) contains significant inf
conjectures are offered as to what might be important elementary reaction pathways, for both tP
ided that the mustard agents, which are straight chain molecules, should react quickly in le
¦xides of sulfur and normal combustion products. Because of there structural complexity ant
>rve agent GB, of the strong P-F bond a similar conclusion for the nerve agents is not as well
temperature reactions of CWAs,
present in the agents—CI, F, M, O,
igh temperature
CWAs, simulants s
compounds.
Types of Waste
Full Text File Name
Information Source
is stockpile of mustard ga<
ster agents H, HD, and HT,
d the organophosphorus
rve agents VX and GB.
Decontamination of
Sensitive Weapon
Platforms and Systems
appliec
litary platforms and systems represents the first line of d(
lation approach generates secondary pollution and requir
t approach could also degrade material integrity of the treated platfc
not erode the integrity and not produce secondary contamination is
ernative for a number of pollutants in this project. A radiofrequenci
and protection for U.S. warfighters.
id systems. Altern
to assess the effective
cleanup of the staine
Raman analysis on Bi
ological aerosols, oil and grease, and paint-sts
croscopy, and aerosol monitoring techniques were usee
plasma technique was found to be useful in th
tain the surface structure intact. TTme-sequencei
or decomposed during the treatment. Optical e
i used to monitor the nanoparticles and charges emissions during th
wsthe reduction and or elimination of the antigens, although scann
agents remain unchanged by the plasma treatment. The technique
»nd reasonably easy to operate. The technique is not a line-of-sight -
organic contaminants and bioaerosols on a range of complex surfaces.
material. Raman
ass of the pi;
TESTING
NONTHERMAL
PLASMA FOR
DECONTAMINATION
OF SENSITIVE
WEAPON
PLATFORM SAND
SYSTEMS
Operated at 200 W power, the
temperature was about 160°C at the
e, and HO'Cat about 15mm
scanning mobility particle
>ntaminated surface. EUSA
5n microscopy indicates the morphology of the
produce secondary pollutants, isfairly safe to
i therefore it can be used to remove effectively
Aspects of a Polymeric
iff Base and its
Polymer Metal(II)
Complexes
Some new coordination polymers of Mn(ll), Co(ll), Ni(ll), Cu(ll),
ing formaldehyde and piperazine have been invest
I, spectral (FT-IR, 1H-NMR, and UV-Vis), and thermogravi
Mn(ll), Co(ll), and Ni(ll) polymer metal complexes are octahedra
tetrahedral, respectively. All compounds were screened for their
Staphylococcus aureus, Pseudomonas aeruginosa, Salmonella typhi,
Agar well diffusion method with 100 mu g mL-1 of each compour
Zn(ll) ol
ic analysis. UV-Vis spectra and magnetic mc
le Cu(ll) andZn(ll) polymer metal complexe:
rns, Agelastes niger, and Microsporum
Decontamination of
ical Warfare Agents
by Photocatalysis
Photocatalysis has been widely applied to solar-energy co
(TiO(2)), produces active oxygen species under irr
its but also different types of hazardous substance
i of chemical warfare agents (CWAs) undi
ication. Photocatalyst, typically titanium
Jet light, and can decompose not only conventional
s. We have recently started the study of photocatalytic
te of Pc
:e Scier
ipplica
is of se
photocatalytic studies applied to CWA degradation, t
compounds. The data indicate that photocatalysis, w
ous compounds. Unfortunately, there are not
cientific data using CWAs in the near future to
possibl
levelop useful
n methods for CWAs, and previou;
s obtained with CWAs and their simulant
ing power, certainly helps detoxification o1
CWAs due to the difficulty in
n systems that can reduce the damage
We w
Decontamination of the
ical Warfare Agent
ant Dimethyl
M ethyl phosphonate by
s of Large-Area Low
Temperature Atmospherii
Dimethyl methyl phosphonate (DMMP), a chemical
pressure plasma. The decontamination efficiency w
ively by means of gas chromatography. W
ited in 2 min, furthermore, with the ad
input power (<100 W) and temperature (<75 °C), th
mulant of the nerve gas GB
s measured qualitatively by means of Four
h helium gas only, 10g/m2 of DMMP on s
ition of 5% of oxygen gas, it
; plasma is eligible for nondi
atmospheric
pressure plasma (input power
:100 W] and temperature (<75
Process for Non-
: a temperature of;
ie second in an atmosphere
imical warfare agents. The process in
pressure in a substantially dryfirst hi
}out 560° C„ (b) re
;el for a period of at least about 15 m
i-condensible gases from the first hea
as to temperatures of at
sout 500° C. for a period of at
in-condensibl e gases from th
.0 mg/m3 at
rd temperatun
Decontamin;
in of
Warfare (CBW) Agents
an Atmospheric
Pressure Plasma Jet
(APPJ)
ie atmospheric pressure plasma jet (APPJ) is
locity effluent stream of highly reactive cher
ie effluen
i pressure, uniform glow plasma discharge that produces a high
ischarge operates on a feedstock gas (e.g., He/02 /H20), which flows
oaxial electrode powered at 13.56 MHz rf. While passing through the
lectron impact. Once the gas exits the discharge volume, ions and
ffluent still contains neutral metastable species (e.g., 0*2 , He* ) and
shown to be an effective neutral izer of surrogates for anthrax spores and mustard
ion methods, the plasma effluent does not cause corrosion and it does not destroy
suitable for decontamination of sensitive equipment and interior spaces,
idly degrade into harmless products leaving no lingering residue or harmful by-
le plasma effluent does not
>t destroy wiring,
aking it highly suitable for
>n of sensitive
ial Decomposition
of Sulfur Mustard (2,2'-
>rodiethyl Sulfide): A
ical WarfareAgent
alcns. of enthalpies and free energies for •
noncatalytic thermal destruction of this chemic
Environmentally robust decomposition/destruction i
ce of a catalyst. The preferable decompositior
formation of sulfur mustard is -36.86 kcal/mol for th
st energy C2 conformatior
tard using G2(MP2) theory have shown that
ss of 2,000 Kto insure intrinsic safety in the
leavages. The G2(MP2)-calculated enthalpy of
Corona Discharge PI
Reactor for
Decontamination
plasma to sterilize objects from ¦
ae highly effective in promoting <
til recently, plasma processes we
plasmas, or at pressures low enough to give large active volumes with high
of the corona reactor has allowed atmospheric pressure applicat
temperature. We developed and demonstrated the use of a prototype low
(CDPR), which generates photons, ionized molecules and other act
>ls. The reactor was used to treat several different types of material
its. The system's capacity for destroying these contaminants rapidly
toxic battlefield, medical, and industria
jxidation, enhancing molecular dissociation, or producing free
:re applied in either the high temperature environment of arc
ler electron energies and lower gas temperatures. The
ions of plasma processing at reduced power and low bulk gas
temperature, ambient pressure, corona discharge plasma
ive species, to decompose toxic chemical and biological
sthat were contaminated with chemical and biological agent
', effectively, and at a substantial energy savings was
B-ll
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Literature Search Results
Article/Report Title
We report herein the evaporation rates and me
n aluminum substrates. For systematic analysis, v
itics of a Drop chromatograph/mass spectrometry (GC/M S) ar
Sulfur Mustard steel and aluminum increased with temperaturi
ical Agent from angle measurement showed that the evaporatii
:eel and |steel surface. On the other hand, the evaporatic
:e of ch
t contact angler
nical warfare agents (CWAs) in th
g personnel safety ar
ihanism of a drop of distilled sulfur musta
e used a laboratory-sized wind tunnel, thi
i drop shape analysis (DSA). We found th
. The rates were also linearly proportiona
n of the drop of HD proceeded only by co
i of HD from aluminum proceeded by a c
id togas
tes of HD from stainl
le-dependent contac
Existing Pr
Methodologies Di
Determined evaporation rates
and mechanism of a drop of
Full Text File Name Information Source
Google Scholar
in of the site upon a
| Heating or (Hot (w)
I (Temperature or Air)
Stearotbermopbilus; HD
5-applies
is of plasma hav
if micro-organisr
:ans of electrical a
in 70 Wtoelimina
eligible. On the otl
iumsupplygas.lt
> by plasma have not been clearly explained. The goal of this study was to find the sterilization
or sterilization factors with the atmospheric pressure radio-frequency helium glow discharge. For the
iio colt was used. To begin with the sterilization study, the plasma characteristics were investigated b
diagnostics. Especially, the gas temperature was controlled under 50 °C by keeping the input power le:
mal effects. Contribution of the UV irradiation from the plasma was studied and it turned out to be
: wasfound thatthe sterilization was more effective up to40% with only 0.15% oxygen addition to the
lat the inactivation process was dominantly controlled by oxygen radicals, rather than heat or UV
Atmospheric pressure plasma
»dio-frequency helium glow
scharge.
NA Google!
Destruction for Disposal
smical Warfare
Agent VX by Blending wit
Lignin, Styrene and
Toxin of Vx type is mixed with
respectively. Thus prepared re
id 2,2'-a;
Warfare Agents i
ical Treatment
Processes
Soils
ieveral simple processes have been studied for the
extended single wash with water was effective in rs
surfactant did not improve removal efficiency. Soils
effective chemical process for the removal of Must
effective as hypochlorite in cleaning Mustard cot
/erall the most efficient process for the destructic
i of be
i Mus-
id Soman w
Na2C03 or NaOH were almost
effectively by treatment with Na2C03.
Na2C03 solution.
«v of the MDF-LSA
100 Spray
Decontamination System
DSTO were given a sample of the Modec Decontamination Foam (M DF)-LS<\ 100 Spray Decontamination System and two Force 1 Decon
products (surfactant and sodium hypochlorite) to evaluate and determine their effectiveness against chemical warfare agents (CWAs).
However a laboratory-based evaluation was not undertaken due to the age of the MDF-LSA 100 sample and therefore the sample s
ntegrity. As a result this report was prepared to provide a general cwerview of the history of the MDF-LS^ 100 Spray Decontamination
System as well as information regarding the decontamination systems which have since superseded it. This report also aims to provide
ief information on the two Force 1 Decon products. MDF-LSA 100, also referred to as DF-100 (Decontamination Foam -100), was the
i of each specific ch
3 2000, an enhances
aforementioned problems-
developed bySandia National Laboratories (SNL) during the late 1990s, to provide
Duld work effectively against all potential chemical and biological threats. Howe
al formulation was less than ideal as it required the pH to be adjusted for optim
and biological agent and the formulation wasfound to degrade sulfur mustard
>n of the DF-100 was developed, called DF-200 or MDF-LSA 200, which took intc
Development of Novel
lative Technologie
for Decontamination of
Warfare Agents: Electric
ig with Intrinsicall
jctive Polymers
¦eloped for
hemical or biological agents. Hen
:, alternative technology for
trically conducting polymers, such as polyaniline, can
iers, artillery pieces, etc.) and installations (e.g., build
ting elements to convert applied electric energy to the
ics high enough to thermally decompose the chemica
been established by the fact that applying household
le surface temperature to 120-180 degrees Celsius in
ergo several heating-cooling cycles without significan
>n of ch
id biological weapons have been ba
mical/biological, multipurpose, re-u
ting polymers. The basic concept is
or fabrics
r biological warfare agents on thi
ternating current to the polyanilir
few minutes. The system is very t
energy to thermal energy to
thermally decompose the
chemical or biological warfare
riped from the surface be
-e Of KHS05, KHS04 and K2S04. T
i. A method for
Surfaces that have come inti
biological warfare agents.
i surface exposed to
Routes of Photocatalytic
Destruction of Chemical
Warfare Agent Simulant;
:ed imitants of chemical warfare agents such as dimethyl methylphosphonate (DMMP), diethyl phosphoramidate (DEPA), pinacolyl
methylphosphonate (PMP), butylaminoethanethiol (BAET) were subjected to photocatalytic and sonophotocatalytic treatment in
>us suspensions ofTi02. Complete conversion of the same mass of imitants to inorganic products was obtained within 600 min for
DMMP, DEPA, PMP, but required a longer time for BAET. Sonolysis accelerated photodegradation of DMMP. No degradation was
ved without ultraviolet illumination. Final products of degradation wereP043-, C02 for DMMP and PMP, P043-, N03- (25%),
(75%), C02 for DEPA, and S042-, NH4+, C02 for BAET. The number of main detected intermediate products increases in the order
DMMP (7), DEPA (9), PMP (21), and exceeds 34 for BAET. Degradation of DMMP mainly proceeds through consecutive oxidation of
5xy groups and then the methyl group. Dimethyl hydroxymethyl phosphonate and dimethylphosphate testify to the parallel
:ion of the methyl group. Destruction of DEPA mainly starts with cleavage of the P-NH2 bond to form diethyl phosphate, which
transforms further into ethyl phosphate. Oxidation of a and p carbons of ethoxy groups to form ethylphosphonoamidate, hydroxyethyl
ethylphosphonoamidate and other products also contributes to the destruction. Photocatalytic degradation of PMP mainly starts with
:ion of the pinacolyl fragment, methyl phosphonic acid and acetone being the major products. Oxidation of BAET begins with dark
ization to disulfide, which undergoes oxidation of sulfur forming sulfinic and sulfonic acids as well as oxidation of carbons to form
al, aminobutane, etc., and cyclic products such as2-propylthiazole. A scheme of degradation was proposed for DMMP and DEPA,
:arting routesfor PMP and BAET. Quantum efficiencies of complete mineralization calculated as reaction rate to photon flux ratio
|NA ~**
Photocatalytic and
sonophotocatalytic
jus suspensions of TT02.
Atmospheric Pressure
Jet (APPJ).
as Off I Google Sc
surrogate for
B-12
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Literature Search Results
Article/Report Title
Agents Contained in a
)nd Means for
Pyrolysis of the Entire
Full Text File Name
Information Source
TOXCENTER
¦atingor(Hot(w)
(Temperature or Air)
Steorotkermopkilus; HD
or Mustard; Building c
Soil or Carpet or (Ceilir
(w) Tile); Concrete or
Decontaminat
Surfaces byPli
Discharges
atmospheric pressure a
;ical systems such
m plasma discharges for th
lating or (Hot (w)
(Temperature or Air)
Steorotkermopkilus; HD
De composite
Weapons
purpose of this study is to show that low-pressure p>
tained in unexploded ammunition produced during tl
laboratory scale. This paper presents the results obtaine
530 °C, at an initial pressure of 25 Torr (3.29 kPa), ai
olysis can be a suitable industrial technique to destroy the chems.
i First World War. For this, an exptl. study has been performed at
¦for chloropicrin, diphosgene, and phosgene at temps, ranging bet
i for reaction times ranging from 10 to 120 min. Under these con
chloropicrin and diphosgene are completely decomposed to form phosgene as
quasi-total destruction of phosgene should be obtained above 700 °C.T1
hydrodynamic and thermal problems are discussed.
lating or (He* (w)
(Temperature or Air)
Steorotkermopkilus; HD
of pollutants. Th
of flames, doped with
of destroying CWA in
lg of flame chemistry of organophosphorus compounds (OPC). This class
al warfare agents. (CWAs) such as the nerve agents GB GD and VX, stockpiles of which in the United S
ire scheduled for destruction by incineration or other technologies. Although high CWA destruction el
incinerator tests in the U.S. it is necessary to improve technology for achievement higher efficiency a
>wledge of detailed destruction chemistry of the CWA and simulants can be obtained by studying the
jlants and CWA and by the development of the combustion model which will include the chemical ms
e. Alkyl phosphates and alkyl phosphonates are typical organophosphorus compounds, that are simul
Studying th«
fames, dopi
CWA.
e objective of this invest
10% reduction in a know gas-bor
nicrobial population (D value) ar
he temperature over a range of 300-
.,100^(149-533^); (2) the effect of
ie carrier gas on this
me/temperature rel
3) the role, if any, thi
eat injury plays in th
>us temperature!
popi
Photocatalytic decontamination of sulfur mustard (HD) i
UV-A light was compared with that obtaine
igated. Decontamination efficiency wi
; found
Ti02 n:
as of
e size on photocatalytic decontamination of
Tze was increased from 11 nm to 1000 nm.
perties relative to larger ones. 100% of HD
only 24.7% of HD was found to be
>xide, sulfur mustard sulfoxide, thiodiglycol,
2 thiodiglycol were observed to be formed.
Military-Relevant Surfaces
Contaminated with
ical warfare Agent
inated. GC-MSdata indicated decontamination of HDto acetaldehyde, carbon i
I, etc. due tophotocatalysis. Without irradiation only hydrolysis products of HD like thiodiglycol were obsen
was conducted to develop methodsfor testing off-gassing from select military-relevant surfaces and to est:
off-gassing from a broad range of such surfaces. Vapor contaminated surfaces were investigated by exposi
rials to chemical warfare agent (CWA) simulants, and then monitoring the off-gassing concentration as a function of time.
Concrete, plastic, wood, steel and latex paint surfaces were contaminated with triethyl phosphate, 4-chlorobutyl acetate, 3-hepten-2-
trimethyl phosphate, and 2-isobutyl-3-methoxypyrazine. The testing process and simple analysis model provide test and analysi;
tods that will be used to test agent off-gassing and can serve as a standard for vapor hazard testing following vapor exposure. Us
imple model was justified, based on analyses of the measured off-gassing trends and the predicted trends of interaction betweer
compound and each surface.
Exposure to bacterial bioaerosols can have adverse effects on health, such as infectious diseases, acute toxic effects, and allergies. Thi
larch for ways of preventing and curing the harmful effects of bacterial bioaerosols has created a strong demand for the study and
svelopmentof an efficient method of controlling bioaerosols. We investigated the thermal effects on bacterial bioaerosols of
Simple model was employed,
I on analyses of the
) a surrounding temperature that ranged from 20 °C to 700 °C for about 0.3 s. Both £ coli and 8. subl
nore than 99.9% inactive at 160 °C and 350 °C of wall temperature of the quartz tube, respectively. A
ijury showed thatthe bacteria tended to sustain greater damage as the surrounding temperature inct
ation of E coli endotoxins was found to range from 9.2% (at 200 °C) to 82.0% (at 700 °C). However, t
n and morphology of both bacterial bioaerosols were maintained, despite exposure to a surround
the bacteria and endotoxins to a large extent inactive. This result could also be useful for developi
strategies for use in air purification or sterilization systems to control bioaerosols.
icreased, Gram-negative
I temperature of 700 °C.
;x paint surfaces wet
>utyl
phosphate, 4-chloro
acetate, 3-hepten-2-one,
trimethyl phosphate, anc
isobutyl-3-methoxypyra;
I (Temperature or A
Steorotkermopkilus; HD
or Mustard; Building c
Soil or Carpet or (Ceilir
(w) Tile); Concrete or
Asphalt
B-13
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Literature Search Results
Relevancy Publication Full Text Article/Report Title
Score Year Available?
\ 252005 I N[photoassisted Reaction of A photoassisted re;
Chemical WarfareAgent experimental resul-
VX Droplets Under UV germicidal lamp ov
Light Rrradiation could possibly initi;
;tion of O-ethyl S-(2-(diisopropylamino) ethyl] methylphosphonothioate (VX) droplets in air was
indicated thatVX droplets could be easily and chemically transformed into other compounds l
r sufficient time. Quantum chemical calculation results demonstrated that UV light less than 27
e photoreaction of VX and that both P-S and P=0 bonds in the VX molecule were lengthened. T
Existing P
Methodologies Discussed
>n of a lamp at a wavelength of less
liquid chromatography m
nerization of S-estersto C
id C-N
ntification of
der UV light
Types of Waste Full Text File Name Information Source
O-ethyl S-[2- NA Google Scholar
(diisopropylamino) ethyl]
methylphosphonothioate (VX)
droplets in air.
Sulfur Musts
Light Irradiat
germicidal lamp. The products detected upon
produced a kind of nontoxic heavy polymer, and this method seemed to be
photoassisted reaction of HD droplets would produce a series of products cc
proven to be even more toxic than HD. Therefore, it was not an effecti
led experimental results would indicate that two possible pathways might be involved in th
:ules may undergo a photochemical reaction upon absorbing photons of sufficient energy, ¦
olecules atthe primary step, or (2) HD molecules could be oxidized by the photogenerated
in of sulfur m
¦d (HD) in be
atHDm
id droplet states i
it the photoassisti
ar UV lig
F HD molecules in the gas phase
lation of air. Nevertheless, the
¦OCH2CH2CI groups, some of whicP
i of HD droplets. The
of HD molecules: (1) HD
> cleavage the C-S bond in
'gelling agents is used to detoxify chemical and biological agents by
Ited or contoured surfaces. Aqueous or organic solutions of oxidizing
material. Gel preparation is simple and suitable for field implementatior
applied quickly and uniformly ewer an area by a sprayer. After
id up for disposal.
Applica
m of a I
Catalytic
Reactor
(FTCMR) for the
Destruction of a Chem
Warfare Simulant
ncept is applied in the thermal oxidation of a chemical warfare
inary experiments under different DMMP feed concentrations ani
Jvantage of the FTCMR concept in the catalytic oxidation of
of DMMP in air was achieved at lower temperatures, with the FTCMR showing
plug-flow reactor (monolith) containing the same amount of catalytic metal. A
3 provide a better understanding of the fundamental transport phenomena
se of the Dusty-Gas formulation of transport, and incorporates continuum and
Knudsen diffusion, as well as viscous flow as the mechanismsfor gas transport through the porous membrane. The model is used for
dentifying the advantages of the FTCMR concept in comparison with the wall-coated catalytic monolith, and also for investigating some
of the limitations, which may exist in applying this concept for the complete oxidation of chemical warfare simulants. The results of the
support the superiority of the FTCMR concept ewer the more conventional plug-f
i study the flow-through catalytic membrane reactor (FTCMR) cc
ant, namely dimethyl methylphosphonate (DMMP), in air. Prelin
>r temperatures (373-573 K) h:
DMMP. Complete destruction of various i
iuperior performance when compared to a wall-co
Tiathematical model has also been developed in oi
underpinning the FTCMR operation. The model ma
i catalytic
aactor (FTCMR).
Thermal oxidation (373-573
K) of a chemical warfare
simulant, dimethyl
methylphosphonate (DMMP),
Decontamination: Recent
Perspective
(CBRN) decontamination is the removal of CBRN m
objective of the decontamination is to reduce radiation burden, salvage equipment, and material:
in place in preparation for protective storage or permanent disposal work a
al from equipment
nove loose CBRN cc
:ies. Decontaminate
principles of CBRN
(chemical, el
lation. Changes in ci
e. Therefore, di
dedication of large num
riew with emphasis on rs
al principles of CBRN
al effects of mi
¦e efficiently disinfected in be
vave power level was found to
ig, pose one of the biggest threats to public H
m was developed to disinfect air containing a
as benign surrogates of pathogens,were colic
er and dynamic in-flight tests were carried a
;ht tests, whereas 8. subtilis endospores wer
' determining the effectiveness of disinfectior
nanofibrous airfiltratior
nanofibrous
airfiltration for
endospores,as benign
surrogates of pathogens.
n of chemical warfare agents (CWA) from
of particular interest in recent years due to increase
of CWA from U.S. stockpile sites
tification of practical and effecti'
>ell as those resulting from deliberately appli
compared and contrasted. We then review various technologie
for surfaces that are difficult to clean. Discussior
chloroethyl)sulfide), VX (O-ethyl S-(2-diisopropyli
in personnel h:
acurity cc
iried munitions are also subjects for response planning. To
approaches, this paper reviews pathways of CWA degradation
ions and technologies; these pathways and technologies are
raditional and recent, with some emphasis on decontamination
3d to the major threat CWA, namely sulfur mustard (HD, bis(2-
inoethyl) methylphosphonothioate), and the G-series nerve agents. The principal G-
agentsare GA (tabun, ethyl N,N-dimethylphosphoramidocyanidate), GB (sarin, isopropyl methyl phosphonofluoridate), and GD (soman,
pinacolyl methyl phosphonofluoridate). The chemical decontamination pathways of each agent are outlined, with some discussion of
final degradation product toxicity. In all cases, and regardless of the CWA degradation pathway chosen for
. it will be necessary to collect and analyze pertinent environmental samples dur
ntof
major threat CWA on
surfaces, namely sulfur
mustard (HD, bis(2-
chloroethyl)sulfide), VX (O-
ethyl S-(2-
diisopropylaminoethyl)
methylphosphonothioate),
and the G-series nerve agents.
Comparative Study or
Photocatalytic Oxidati
of Four
Organophosphorus
ants of Chemica
Warfare Agents in
Aqueous Suspension c
Photocatalytic oxidation by oxygen of air w
phosphate (TEP), and diethyl phosphorami
I out for dimethyl methyl phosphonate (DMMP), trimethyl phosphate (TMP), triethyl
te (DEPA) in different
[e of organophosphorus compound
dependences are well approximated by one site Langmuir-Hii
organophosphorus compound. Parameters of the Langmuir-Hinsl
organophosphorus compounds atthe end of reaction was evident
ave sigmoidal shape. GC-MS technique was used to identify inte
imethyl phosphate and methyl phosphate in -
itermediates shows that photocatalytic oxida
photocatalytic
a case of TMPar
in proceeds prin
•e of the lack of adsorbed oxygen. These summit
ihelwood equation with competitive adsorption of oxygen and
alwood equation are reported. Complete mineralization of the
;d by the total organic carbon concentration profiles. These profiles
mediates of TEP and TMP oxidation. The main intermediates are
diethyl phosphate and ethyl phosphate in the case of TEP. The set o
h hvdroxvl
Dimethyl methyl phosphonate
(DMMP), trimethyl phosphate
(TMP), triethyl phosphate
(TEP), and diethyl
phosphoramidate (DEPA) at
different cc
| Warfare Agent Simulai
native Technologie
le Destruction of
lical Agents and
id approximately 3,40
ISolubility data are reported for ethyl phenyl sulfide (EPS) and 2-chloroethyl ethyl sulfide (CEES) in C02
. These two sulfide-based compounds are homomorphs for chemical warfare agents (CWAs). Both sulfide-CC
phase behavior. The maximum in the 100°C isotherm is approximately 2,600 psia for the CEES-C02 system
I psia for the EPS-C02 system. The Peng-Robinson equation of state (PREOS) is used to model both sulfide-C02 mixtures as well as
phase behavior of the 2-chloroethyl methyl sulfide (CEMS)-C02 system previously reported in the literature. The Joback-Lydersen
contribution method is used to estimate the critical temperature, critical pressure, and acentric factor for the sulfides. Semi-quantii
estimates of the phase behavior are obtained for the CEES-C02 and EPS-C02 systems with a constant value of kij, the binary inter;
parameter, fit to the 75°C isotherms. However, very poor fits are obtained for the 2-chloroethyl methyl sulfide-C02 system regard
Ithe value of kij. On the basis of the high solubility of EPS and CEES in C02, supercritical fluid (SCF)-based technology could be used 1
al Stockpile Disposal Program was established with the goal of destroying the nation's stockpile of lethal unit
U.S. Army has been testing a baseline incineration technology on Johnston Island in the souther
le planned disposal program, this baseline technology will be imported in the mid to late 1990s to continent
from 2 5 to 100°C. I Solubil ity data are reported for The max
i exhibit type-l ethyl phenyl sulfide (EPS) and 2- 100°C ist
sility in th
chemical weapons. Sine
Pacific Ocean. U
chloroethyl ethyl sulfide (CEES), i
a two sulfide based homomorphs t
sup for CWAs in C02 at ;
ive temperatures from 25 to 100°C. t
•ation technology is
le technology on Jol
proximately 2,600 psia for
a CEES-C02 system and
proximately 3,400 psia for
a EPS-C02 system.
id States disposal facilit
In early 1992 the Committee on Alternative Chemical Demilitarizatit
investigate potential alternatives to the baseline technology. This bo
destruction technologies to replace, partly or wholly, or to be used it
technologies that might be applied to the disposal program, strategi
[technologies that might be employed.
stockpile storage sit
rization Technologies
as formed by the Natior
> investigatior
aseline technology. The boot
sed to manage the stockpile,
B-14
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Literature Search Results
Relevancy Publication
Score Year
23 I 2006
Article/Report Title
Atmospheric-Pressure
Nonequilibrium Plasma it
Decontamination
ial Decompositio
of Dimethyl
M ethyl phosphonate o\
Manganese Oxide
Catalysts
atmospheric-pressure gas discharge system, slit discharge (SD), has been developed for the removing of biolc
mtaminants from the ambient air. The system consists of multiple plasma grids stacked perpendicularly to the
performance of the system has been tested using the surrogates of biological and chemical warfare agents. The
ssting will be presented. The experiments have been done using the "in-room" and "in-duct" scenarios, simulating the stand alone room
ir cleaner and the HVAC system. The efficacy of the system in removal of bacterial spores will be presented as a function of flow rate,
ischarge power, number of plasma grids, and concentration of the spores in the air. Sampling methods and associated challenges will
e discussed. Slit discharge (SD) is a promising technology in air-cleaning. Its performance is comparable with and often exceeds that of
ie convectional methods, such as dilution ventilation, filtration and ultraviolet germicidal irradiation. SD is an energy efficient, high
performance, and low cost technology for air decontamination with potential uses in industry, health care and household applications
•. decomposition of dimethyl methyl phosphonate (DMMP) has been studied over amorphous manganese oxide
(AMO) and AI203-supported manganese oxide catalysts. The reaction was carried out using air as the oxidant at temperatures between
.nd 400°C.The highest reaction rates occurred using temperatures of 400°C. Gas chromatography (GC) was used to examine
ant DMMP and other gas phase products. DMMP wasfound to oxidatively decompose ewer AMO and AI203-supported manganese
catalysts. The highest activity was observed using a catalyst prepared by precipitation of AMO on AI203. During the initial stages
iction, DMMP was completely removed from the gas phase. During this period DMMP was oxidized to C02, with no other gas
; products being observed. After a certain period of time (5 min-8 h), DMMP reappeared in the gas phase. The C02 concentration
MeOH began to -form, indicative of hydrolysis of DMMP. These results indicate that deactivation of catalysts occurs
pecies. Fourier transform infrared (FT1R) spectroscopy and ion chromatography (IC) were used to examine adsorbed
products on the surface of the catalysts. The IC analyses indicated that several products accumulate on the surface of the catalysts,
methyl methyl phosphonate, methyl phosphonic acid, and phosphoric acid. FT1R analyses showed that DMMP bonds strongly to
> acid sites on the manganese oxide surface via phosphoryl oxygen. The bare AI203 support was also examined in DMMP
decomposition reactions and showed high activity, with 100% DMMP removal from the gas stream for over 15 h. The major products
irved over AI203 were dimethyl ether and MeOH. No C02 was observed, indicating that DMMP is not oxidized ewer AI203. The GC,
nd FTIR results suggest that DMMP is dissociatively adsorbed ewer AI203. Finally, the resultsfor the thermal oxidation of DMMP
AMO are compared to results previously obtained using photo-assisted oxidative methods.
Existing Procedures and Types of Waste
Methodoloeies Discussed
Atmospheric-pressure gas
ischarge system.
decomposition of dimethyl
methylphosphonate (DMMP)
amorphous manganese oxide
(AMO) and AI203-supported
manganese oxide catalysts. Th
Full Text File Name
Information Source
Conference paper.
Destruction of Bacteria
an Atmospheric-
Capillary Electrode
Discharge Plasma
'action of plasmas with chemical and biological agents, in particular in <
much attention in recent years. Particular emphasis has been on the u
iperation in costly vacuum enclosures and thus facilitate the convenien
', atmospheric-pressure discharge plasmas are highly susceptible to ins-
uniform, large-volume discharge plasmas at or near atmospheric pressure rem;
maintain atmospheric-pressure plasmas ewer a wide range of operating conditio
subsequently licensed to PlasmaSol for development in various areas of applica-
patented capillary dielectric electrode discharge concept that employs c
lization of atmospheric-pressure plasmas as they do not
and low-cost treatment of large surface areas,
abilities and the generation and reliable maintenance of
in formidable challenges. A new concept to generate an
ns was developed at Stevens Institute of Technology anc
ons. The atmospheric-pressure plasma is produced
g a patented capillary dielectric electrode discharge concept that employs dielectric capillaries that cover one or both electrodes of
discharge reactor. The capillaries serve as plasma sources, which produce jets of high-intensity plasma at atmospheric pressure in a
riety of carrier gases under the right operating conditions. Spore-forming bacteria, in particular bacteria of the genera Bacillus, amonj
e most resistant microorganisms. The species Bacillus subtilis has received particular attention, as these bacteria are easy togrow in s
reproducible fashion under chemically well-defined conditions. Asa result, Bacillus subtilis has been the species of choice in many
*i experiments in the past. In this paper, we report the first experiments aimed atthe quantitative determination of the
>n of spore-forming bacteria, which are believed to be among the most resistant micro-organisms, using a novel atmospheric-
pressure plasma shower reactor whose design utilizes a patented atmospheric-pressure dielectric capillary electrode discharge plasma,
a established a straight forward protocol to prepare and characterize various bacteria including Bacillus subtilis on either glass or
iminum surface supports and analyze the samples after treatment by atmospheric-pressure plasma jets emanating from the plasma
actor using either in He or air (N/sub 2//0/sub 2/ mixture) as a carrier gas at varying power levels and exposure times. We used
i/eral Bacillus subtilis strains such as Bacillus subtilis var.niger ATCC 9372 in its three different colonial morphologies, 8acillus
btilis var. niger W 0235, and Bacillus subtilis W 0228 as prototypical examples of spore-forming bacteria. In some cases, we also usee
n-spore-forming bacteria {Pseudoirionos fluoresceins ATCC 1474) for selected experiments for reasons of comparison. We found
inificant reductions in colony-forming units ranging from 10/sup 4/ (He plasma) to 10/sup 8/ (air plasma) for plasma exposure times of
¦s than 10 minutes. We also measured the UV/VIS absorption spectrum of the spore suspension before and after several minutes of
plasma treatment. The UV absorption spectrum of a suspension of 8acillus subtilis showed a marked increase in the absorption of the
sample below 300 nm with a local maximum around 260 nm. This is attributed to the presence of extracellular
compounds that are released during the plasma treatment, most likely DNA, RNA, and proteins and thus verifies the destruction of the
by the plasma. The utilization of our plasma device in other sterilization and decontamination applications is currently also being
Atmospheric-pressure plasmas
produced using a patented
capillary dielectric electrode
scharge.
: self-sustaining reactive composition, method and c
ding at least one of a Group IV or Group V metal; a <
¦eaction togenerate heat sufcient to vaporize a thirc
r producing an elevated temperature sufficient to destroy the ch
inter core explosive driver With the self-sustaining reactive comi
:e for defeating
. a first
>n togenerate
jfficient to destroy
cal and biological agents.
THERMOBARIC
MATERIALS AND
DEVICES FOR
CHEMICAL
BIOLOGICAL AGENT
DEFEAT
Strud
logical Contamin;
jality (IAQ)
compromise
ificantly improved indoor air quality (IAQ) follow
for 10 minutes effectively sterilizes most items of active biological agents,
63 °C most insects, protozoa, bacteria, and fungi cease to fui
nd oxidizes harmful chemicals produce by biological organisn
difficult t
eat can be generated using
id air conditioning (HVAC)
/stem, portable electric-
lurning natural gas, propane,
' kerosene) can also generate
Contamination
Improve Indoor
Quality
ol Decontaminatic
logical Warfare
Agents for Complex
Platform Interiors
liquid technology for surface
objective of this project is to develop a novel laser
:ient surface decontamination without secondary contamination,
major goals are as follows.
o develop novel Laser Ablation Decontamination in Liquid (LADIL) technology for safe removal
>ut producing dangerous secondary pollutants.
1 the basic physical processes of laser ablation on a solid-liquid interface
ciency of surface-contaminated materials.
3. To optimize the cleaning process for efficient recycling of contaminanted materials. 4. To evalua
atmospheric-pressure plasma decontamination/sterilization chamber is described. The apparatu
ts from a surface wi
2. To Ot
Atmospheric-pressur
plasma
ion/steriliza and/or biological warfare agents, such
procedure for decontaminating such equipment. The ap
Items to be decontaminated or sterilized are supported
species are generated by an atmospheric-pressure plasr
ig agent, VX nerv
lout damaging
ie possibility of escape of ac
s currently no acceptable
¦ the region of these items
closed-loop system to
atmospheric pressure plasi
B-15
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Literature Search Results
Article/Report Title
Destruction of bacteria
using an atmospheric
capillary electrode
discharge plasi
The interaction of plasmas with chemical and biological agents, in particular in
received much attention in recent years. Particular emphasis has been on the i
require operation in costly vacuum enclosures and thus facilitate the convenier
However, atmospheric-pressure discharge plasmas are highly susceptible to in;
uniform, large-volume discharge plasmas at or near atmospheric pressure rem
maintain atmospheric-pressure plasmas ewer a wide range of operating conditi
subsequently licensed to PlasmaSol for development in various areas of applies
ligation of atmospheric-pressure plasmas as they do nc
and low-cost treatment of large surface areas,
abilities and the generation and reliable maintenance o
n formidable challenges. A new concept to generate ar
is was developed at Stevens Institute of Technology an
Existing Pr
MethodoloeiesDi
atmospheric pressure plasma
Full Text File Name Information Source
Destruction of Google Scholar
Atmospheric-
Capillary Electorde |
Discharge Plasma.pdf
methyl dioxophosphorane CH3P02, and monomethyl methylphosphonate PO(OH)(CH3)(OCH3).
el of the combustion chemistry of a hydrogen/oxygen bi
hemical warfare agents (CWAs), has been developed to
is employed to rt
imethyl methylphosphonate, a useful
thermal destruction of CWA stockpiles,
termediates in a low-pressure premixed
roperties of organophosphorus
nclude methyl metaphosphate CH30P02,
decompositior
DMMPin a Hydrogen
Oxygen Flame.
ADVANCED COMPUTER
SIMULATIONS OF
MILITARY INCINERATORS
ie US Army to destroy th
tain 3D furnace and cani
ie of the technologies being used by tl
ical Weapons Stockpile. In this paper i
ergeometrii
nistry. The destruction of chemical agent is predicted using non equilibrium chemistry models. M
lid Incinerator, Metal Parts Furnace, and a Deactivation Furnace System. Using computational ch(
e been developed that describe the incineration of organo-phosphorus nerve agent (GB, VX) and s
dels have been used to study a variety of scenarios to develop a deeper understanding of furnace i
;n processing munitions or equipment containing or contaminated by chemical agent. Model resu
obust systems that destroy chemical agent in a safe and efficient manner.
Emulations of
Source provided by EPA
during conference call on
10/16/14.
IMPROVED KINETIC
MODELS FOR HIGH-SPEED
COMBUSTION
SIMULATION
Report developed under an STTF contr
in computational fluit
pressure-dependent detailed chemical
performed v
dynami
namely: methane, ethylene, n-heptane, Jet A, n-d(
:al and quasi-steady-state (OSS) reduced mecha
anisms from the literature for ethylene, JP-8, ar
(ISVT) algorithm have been implemented and tested.
>11 goal of this STIR project has \x
odeling of hydrocarbon-fueled sc
for a JP-8 surrogate has been ere
opposed-jet burner at subatmospheric
trimethylbenze
IMPROVED KINETIC
MODELS FOR
HIGH_SPEED
COMBUSTION
SIMULATION.pdf
33 2001
26 2004
31 2006
study in'
:h pyrolytic:
s. We focus
cal warfare agents H, HD, and HT. We report our work on developing
for multiple chemical subsystems, using computational chemistry metht
iperimentsfor pyrolysisand oxidation oftwoalkyl sulfides: diethyl sulfide
;chanism has been developed to describe the pyrolysis and oxidation
alkyl sulfides that are
surrogates for chemical
warfare agents H, HD, ar
idelinesfor Mass N
:ality Management
ring Terrorist Incidents
olving Chemical Agents
Cremation of co
weapons
ry Affairs
Mortua
USNORTHCOM a
Department of Hi
Security Positioned for
Contaminated Mass
Fatality Management?
Emerging Concepts of
Mortuary Affairs Doctrine
for the 21ST Century
War Fghter
is for pc
al pdici
Mass fatalities from ch
Mass fatalities from
'tide reviews the definitions of biological weapons and mass casualties. In addition, it
ses the main operational and logistical issues of import in the medical management of mass
ties from the use of biological weapons. Strategies for medical management of specific
ic agents also are highlighted.
lobal War on Terrorism has emphasized homeland defense and security as a priority for the Nation. The United States Northern
(USNORTHCOM) recently attained its initial operational capability as the Department of Defense executive agent for
Defense. Terrorists have demonstrated the ability and willingness to obtain and use Weapons of Mass Destruction to further
Is. An unfortunate reality of the use of such weapons is the creation of contaminated remains. The recovery, identification, and
>n of such remains, including their decontamination, fells within the scope of Mortuary Affairs. This is a hugely sensitive issue.
RTHCOM and the Department of Homeland Security grapple with their transition to lead Homeland Defense ar
agencies, a seam in policy and capabilities may exist. USNORTHCOM's ability to provide support to meet surge
ig and processing human remains is not articulated or properly sourced. This paper looks at the threat posed w
rs that requires a synchronized response by USNORTHCOM and the Department of Homeland Security. Policies,
programs that highlight current government capability to handle domes
equirementsfor a
Department of Defense's (DoD)
Mortuary Affeirs program to
fatality management
emergencies
use of biological
NA
mass fatality
situation follow
weapon of mas
Emerging Concepts Google Sc
of Mortuary Affairs
Doctraine for the
21st Century War
Cremation, warfare
Safe Management of
logical agents pose a pot
¦nment investigation has
ie management of conta
antified a numbe
;s of the study ar
United Kingdom
of risk. This paper
as specific pathways
Safe Management of
a neglected area of study for be
l-hospital Management Emergency sil
Weapons of Mass from contami
d by chemical weapons of mass destruction add a r
difference between a hazardous materials inciderr
on to health care professionals, patients, equipment and facil
id to describe the procedures to be followed by emergency m
it and people. This review is designed to familiarize readers w
it affect the in-hospital management of incidents by chemica
:he potential for risk
:ies of the Emergency Department. Accurate and specific
¦dical personnel to safely care for a patient, as well as to
th the concepts, terminology and key operational
weapons.
concepts, terminology and key
affect the in-hospital
management of incidents by
chemical weapons
fatality management from
chemical and biological agents
B-16
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Literature Search Results
BIOLOGICAL RESPONSE
AND RECOVERY
SCIENCE AND
TECHNOLOGY
ROAD MAP
¦s taken, and how to safely dispose of the bodi
Medicine of the United States of America, searching
risks for public safety workers and funeral workers a:
of the dead and prevention of infection. A small but •
regarding the disposal of the dead and the contamini
Results. Victims of natural disasters usually die from
is extremely small. However, persons who are involv
NA
infectious agent, exposure to that
of the National Library of
Existing Pr
Methodologies Di
assess the risks of infection from
lis report categorizes key Contamina
ientific knowledge gaps,
antifies technology solutions
these gaps, and prioritizes
Full Text File Name Information Source
Infectious disease Google Scholar
The Convention on the Prohibition of the Development, Production, Stockpiling and Use of Q"
provides for the elimination of chemical weapons arsenals amassed during the Cold War. The
these deadly weapons, however, poses huge environmental problems. This book
Risks Associated with the Destruction of Chemical Weapons", hosted by the Uni\
former enemies NATO and Russia together to discuss, reflect on, and exchange t
environmentally friendly disposal of chemical weapons. This four-day workshop
America, Russia, and European countries. Most of them are recognized authoriti
related fields. The speeches by those who share the burden of this terrible under
the ethics, political and international law aspects of the destruction of chemical weapons,
pathogenesis, toxicity, and exposure to the polluted environment. Contributions were alsc
compendium of the workshop on the "Ecological
of Luneburg in October 2003, which brought the
Security and Cross-cutt
Elements of Biological
Non proliferation
Biosafety and Biost
in European Counti
linment have been in the spotlight in recent
¦ent oversight frameworks, thereby resulting
ccidental release of a biological agent, and increasedsafety of laboratory
:h Organization's (WHO)revised International Health Regulations (IHR(2005|),
id Nations Security Council Resolution (UNSCR) 1540 overlap in tl-
of practitioners and policymakers and
range of goals of
i The critical aspects of biosafety, biosecurity, and bioconti
years. There have also been increased international eff 01
safe pursuit of life sciences research, and to optimize cur
g terrorist/malevolent acquisition of deadly pathogens or i
workers. Our purpose is to highlight how the World Heah
the Biological Weapons Convention (BWC), and the Units
requirements with regard to biosafety and biosecurity in order to improve
maximize the use of national resources employed to comply with internationally-
these international instruments, which are linked by the common thread of biosafety and biosecurity,
essential pillars of international health security and cross-cutting elements of biological nonproliferati
Republic of Georgia to enhance biosafety and biosecurity in
The terms biosafety and biosecurity are widely used in different
of weapons of mass destruction. As a result, the biosafety and biosecurity issues should be considered interdisciplinary
based on multilateral agreements against proliferation of biological weapons, public health and
environmental protection. This publication presents information on both, international and national biosafety and
biosecurity legislation. Status of national implementation of the Biological and Toxin Weapons Convention, penalization
issues and measures to account for and secure production, use, storage of particularly dangerous pathogens
or activities involving humans, plants and animals where infection may pose a risk have been analyzed. Safety
and security measures in laboratories have been studied. Moreover, dual-use technology and measures of secure
transport of biohazard materials have been also taken into account. In addition, genetic engineering regulations, biosecurity
activities in laboratories and code of conducts have been investigated, as well.
Organic emissions from a chemical weapons incinerator have been characterized with an improved set of analytical methods tor
the human health risk assigned to operations of the facility. A gas chromatography/mass selective detection method with substai
al reduced detection limits has been used in conjunction with scanning electron microscopy/energy dispersive X-ray spectrometry i
Fourier transform infrared microscopy to improve the speciation of semi-volatile and non-volatile organics emitted from the incir
The reduced detection limits have allowed a significant reduction in the assumed polycyclic aromatic hydrocarbon (PAH) and
aminobiphenyl (ABP) emission rates used as inputs to the human health risk assessment for the incinerator. A mean factor of 17
Select agent research in the United States must meet federally-mandated biological surety
guidelines and rules which are comprised of two main components: biosecurity and biosafety.
Biosecurity is the process employed for ensuring biological agents are properly safeguarded
i against theft, loss, diversion, unauthorized access or use/release. Biosafety is those processes that
: ensure that operations with such agents are conducted in a safe, secure and reliable manner. As
such, a biological surety program is generally concerned with biological agents that present high
risk for adverse medical and/or agricultural consequences upon release outside of proper
containment. The U.S. Regional and National Biocontainment Laboratories (RBL, NBL) represent
expertise in this type of research, and are actively engaged in the development of programs to
address these critical needs and federal requirements. While this comprises an ongoing activity for
5f A Preliminary Assessment of Health Impacts (PAHI) study was conducted to look at potential human and environmental health in
health impacts for the due to the air and water emissions generated from the proposed Newport Chemical Agent Disposal Facility (NECDF) in Newport,
Newport Chemical Agent As an alternative to incineration, the NECDF will use a neutralization-based treatment process followed by supercritical water oxi
Disposal Facility to destroy the VX nerve agent stored in ton containers at the Newport Chemical Depot. There is no regulatory guidance on condi
an assessment of health impacts for this type of facility. Therefore, The U.S Army Center for Health Promotion and Preventive M
(USA CH PPM) designed a PAHI study based on bench-scale data and best engineering estimates that conservatively evaluate poss
health effects from the projected air and water emissions. The air portion of the PAHI focused primarily on estimating carcinoger
and noncarcinogenic hazards from direct and indirect exposures to the subsistence farmer, subsistence fisher, adult resident, anc
resident. The water portion of the PAHI evaluated potential human and environmental impacts using two different procedures in
decisions more effectively
during the response to, and
recovery from, biological
incidents. Fatality management
Safe and environment-friendly C
disposal of chemical weapons
for and secure productio
storage of particularly
dangerous pathogens or
infection may pose a
th Impacts (PAHI) study w,
and water emissions generated
¦ from the proposed Newport
Chemical Agent Disposal Facility
>1 (NECDF) in Newport, Indiana.
Destruction of US chemical weapons has begun a
i in the Pacific Ocean, and is scheduled to begin in
38% of the munitions had been destroyed
choice of technology, emergency management,
governments and activist groups to play a more
NA
le of the 8
sntinental United States, was completed on Johnston Island
uring the upcoming year. About 25% of the stockpile and
rer, the program has become controversial with regard to
s in large part due to efforts by some state and local
iking process that was once folly controlled by the US Army.
process on technology,
/e agent sto
lers at the r.
:al Depot.
Proceedings of the NATO ARW on
Ecological Risks Associated with the
Destruction of Chemical Weapons,
Luneburg, Germany, from 22-26
October 2003
State-of-the-Art in Google Sc
Biosafety and
European Countries
Evaluation of the Army Chemical warfare agents
Stockpile Disposal Program (Stockpile
Committee) of the National Research
(with comprehensive air pollution
control systems) as a safe and
effective procedure for destroying
B-17
-------
Literature Search Results
Article/Report Title
Chemical Warfare Agent NA
Disposal Public Health
Oversight
Existing I
Methodologies I
Disposal options are di
for chemical weapons i
Types of Waste
lical weapons.
Full Text File Name Information Source
Chemical Warfare Google Scholar
Agent Disposal Public
Health Oversight
andate to dispose of the current US stockpile of lethal unitary weapons (Pub
of 1986) has international implications and is responsible for a recent major
installations in the continental United States currently host aging stockpiles of cf
toxicology and physical properties of each agent are characterized, disposal opti
role of a programmatic health and environm
xisting community emergency planning and preparedness
99-145, Department of Defense
if available disposal
al warfare agents. The stockpile;
onsidered by the US Army are
process is outlined. Critical
mmunication of risk information
disposal option
the US Army ar
.timely disposal of the stockpile
health programs at ch(
weapon disposal facilit
(JACADS and TOCDF).
chemical agents and weapons involve unique hazards c
i storage stockpile, the disposal area, and the discovery i
have been developed to detect the presence of chemic
safety of the local population. Exposure limits for all ch
id picograms per cubic meter for general popul
are disposing of their
: handling extremely to
nd destruction of "four
;ing stockpile of ch
i prefers the latter
IS of CO
, Stockpile of ch
weapons.
i follow
d by th
Destruction Chemistry of
Organophosphorus
Compounds in Hydrogen-
Oxygen Flames
i sample tul
A review of the results of experimental studies of the destruc
hydrogen-oxygen rarefied flames is presented. These studies
Siberian Division of the Russian Academy of Sciences by soft
not considered part of the stockpile. M
! air, and these are used to help assure worker protection an
ire low, sometimes nanograms per cubic meter for worker c
ere are three types of monitoring used in the USA: alarm,
tively immediate real-time responses to agent leaks. Theyar
(generally a few minutes). Alarm monitors for the demilitari
desorption and simple gas chromatography. Alarms may nc
th the alarm monitor and analyzed in a laboratory by more
ofiles in flames,
methyl phosphonate and trimethyl phosphate—at
is of the indicated products a
hemistry of organophosphorus compounds modeling sarin in
performed at the Institute of Chemical Kinetics and Combustion <
tion probe molecular beam mass spectrometry. A method is desc
ate (including atoms and free radicals), and final organophosphorus compoi
istruction products of organophosphorus compounds—dimethyl
tified in various zones of an H2/02/Ar flame. Mass peak intensities proportic
isured. The inhibition and promotion phenomena of the flames are discovers
for the destruction of organophosphorus compounds in the flames is proposed. The results obti
processes involved in the incineration of chemical warfare agents and munitions and other toxi
i, for optimization of this technology, and also for understanding the inhibition and promotion mechanism
Proposed Modificatio
Support the Destructi
of Mustard Agents an
are stored, and where destruction of agents at
Chemical Stockpile Disposal Program (CSDP). The chemic
consists of 11.6%, by weight, of the total U.S. stockpile. T
necessary to eliminate the risk to the public from continu
;on, is one of eight U.S.
ethal unitary chemical agents ar
i munitions is proposed under tH
I agent inventory at UMDA
e destruction of the stockpile is
d storage and to dispose of obsc
Programmatic Envii
(FPEIS) for the CSDP that identifii
environmentally preferred alternative (i.e., the
significant adverse impacts). The FPEIS identifi
Impact Statement
isposal of agents and munitions as the
ironmentally preferred alterna
information that will be us
the development of
al analyses ar
DISPOSAL OF
CHEMICAL AGENTS
AND MUNITIONS
STORED AT
UMATILLA DEPOT
ACTIVITY
B-18
-------
Literature Search Results
Article/Report Title
HOW DO WE GET RID OF NA
THESE THINGS?:
DISMANTLING EXCESS
WEAPONS WHILE
PROTECTING THE
ENVIRONMENT
Warfare Agent
Degradation
PLANT OPERATION
Dioxin -formation from
d impregnated w
;o by the publi
tals Cu, Cd, Hg, ar
is (PCDFs), and
Types of Waste
lical weapons stockpile.
Full Text File Name
Information Source
Google Scholar
Keywords
warfare agents
agreement, the 1993 Chemical
Weapons Convention (CWC),
confronts the equally
-fundamental and pressing
ss of ns
oftheformatior
ecotoxicity of CW agent degradation products relevant ti
These parent CW agents indude several vesicants: sulfur mustards (undistilled sulfur mustard (H),
sulfur mustard (HD), and an HD/agent T mixture (HI)]; nitrogen mustards (ethyl bis(2-
chloroethyl)amine (HN1), methylbis(2-chloroethyl)amine (HN2), tris(2-chloroethyl)amine (HN3)],
and Lewisite; four nerve agents {OOethyl S.(2-(diisopropylamino)ethyl] methylphosphonothioate
(VX), tabun (GA), sarin (GB), and soman (GD)}; and the blood agent cyanogen chloride. The
degradation processes considered here include hydrolysis, microbial degradation, oxidation, and
photolysis. We also briefly address decontamination but not combustion processes. Because CW
agents are generally not considered very persistent, certain degradation products of significant pe
even those that are not particularly toxic, may indicate previous CW agent presence or
degradation has occurred. Of those products for which tl
and toxicity, only a few are both environmentally persistent and highly toxic. Major degradation
products estimated to be of significant persistence (weeks to years) indude thiodiglycol for HD;
Lewisite oxide for Lewisite; and ethyl methyl phosphonic acid, methyl phosphonic acid, and possibly
S.(2-diisopropylaminoethyl) methylphosphonothioic acid (EA2192)for VX. Methyl phosphonic
acid is also the ultimate hydrolysis product of both GB and GD. The GB product, isopropyl
methvlohosohonic acid, and a doselv related contaminant of GB. diisooroovl methvlohosohonate.
COMBUSTION AEROSOLS Combustion aerosols were measured in a 22 M W (thermal energy) municipal waste incinerator. Different types of waste fractions were
FROM MUNICIPAL WASTE added to a base-load waste and the effect on aerosol formation was measured. The waste fractions applied were: PVC plastic, pressure-
INCINERATION—EFFECT impregnated wood, shoes, salt (NaCI), batteries, and automotive shredder waste. Also, runs with different changes in the operational
OF FUEL FEEDSTOCK AND conditions of the incinerator were made. Mass-based particle size distributions were measured using a cascade impactor and the
protection policy
The fate of the degradatior
products from chemical
weapons.
oftheformatior
Today, disarmament diplomacy ha;
wrought unprecedented triumphs
across a wide range of global
Emphasis in this review is on those
potential degradation products
resulting from agent contact with
soil, water or the atmosphere after
buried chemical weapons
wastes, or potential spills i
CW agent degradation product;
and Toxicity of
Chemical Warfare
Agent Degradation
Microscopy (TEM) ar
2.5 |im). In general the
ere measured using a Scanning Mobility Particle Sizer. The plant is equipped w
letermined. The particle morphology was investigated by Transmission Electro
irticles was made by Energy Dispersive X-ray Spectroscopy (EDS). The mass-ba;
'eased the mass concentration of fine particles (aerodynamic diameter bel
i close to the reference PM2.5-value of 252 ± 21 mg/m (std.T,P). The total
runs spanning from 43 -10 to 87 - 10#/cm(std.T,P). The aerosols formed were
le fine particles are mainly composed by alkali salts, zinc, and lead. The heavy n
ut dioxins-polychlorinated dibenzo dioxins (PCDDs), polychlorinated dibenzofur
;ausing contamination in the environment because the adverse effects of these chemics
years. Possible dioxin-contamination has received much attention recently not only by
¦cause dioxins are known to be formed during the combustion of industrial and domestic wastes and
) exhaust gases from incinerators. Consequently, there is a pressing need to investigate the formatior
of these chlorinated chemicals to be able to devise ways to reduce their environmental
mall-scale incinerator was used for the experiments in the core references of this review. These
report the investigation of dioxin formation from the combustion of various waste-simulated samples, including different kinds i
rarious kinds of wood, fallen leaves, food samples, polyethylene (PE), polystyrene (PS), polyvinyl chloride (PVC), polyvinylidene
!, polyethylene tetraphthalate (PET), and various kinds of plastic products. These samples were also incinerated with inorganic
(NaCI, KCI, CuCI2, MgCI2, MnCI2, FeCI2, CoCI2, fly ash, and seawater) or organic chlorides (PVC,
pentachlorophenol)
> investigate th
>us organic and inorgani
a to incinerators. Among others, tf
ic hydrocarbons, toxic metals and i
generally not elevated in worker's
tent and/or the presence of different m
re polychlorinated biphenyls, dioxins, fu
d in worker's blood and urine and in persons living near ini
1 risk, respiratory symptoms, multiple pregnancy, congenit
However, these data do not provide univocal evidence th;
>xin formatior
is, chlorophenols, mono- at
;rators. The epidemiologic;
Study on the presence of
; vicinity of municipal waste
Mixed-i
What about the residuals? oxidation (MSO) and incinera
A comparative analysis of Department of Energy (DOE)
MSO and incineration technology (BDAT) for the same waste strean
prepared this report for the DOE Office of Em
ils from MSO ar
:oncerning final waste forms, or residuals, that resultfrom tf
systems. MSO is a technology with the potential to feat a ct
is. MSO was compared with incineration because incineratio
waste streams. The Grand Junction Projects Office (GJPO) ar
Restoration (OER). The goals of this
le regulatory is
icerns that MSO n
it technology for mixed
e implementation effort is ongi
i forth
xed waste in molten salt The goals of this study were to
tain segment of the waste streams at US objectively eval uate the
is the best demonstrated available anticipated residuals from MSO
I Oak Ridge National Laboratory (ORNL) and incineration, examine
*udy are to objectively eval uate the regul atory issues for these final
e final waste forms, and determine secondary waste forms, and determine
e disposal difficulties, is part of a larger secondary t
. A Peer Review Panel reviewed the
:e of the MSO Task Force.
esult from the
lation (MSO)
B-19
-------
Literature Search Results
Article/Report Title
from open-ai
The system w
•e developed at Sandia National
ould be wirelessly linked to one
mbined with integrated visual i<
iditions to adjust for changing r
a systems study of the problerr
lg of the polit
nissionsfrom open-burning/open-detona
in operations about process efficiency, al
i to regulators and neighboring communi
isor system uses instrument control hard
:ogether an array of sensors to monitor e
of implementing
emissions from open-
rials burning/open-detonation
(OB/OD) events. The system
)B/OD wou Id serve two purposes: (1)
Election operations about process
isorsto efficiency, allowing process
iitivity). optimization -for cleaner
Full Text File Name Information Source
NA Google Scholar
Keywords
warfare agents,
In the combustion facilities, halogens (CI, F, Br, I) sh
polychlorinated dibenzodioxins (PCDD), polychlorin;
polychlorinated biphenyls(PCB) and volatile heavy r
environmental effects. In this study halogens were t
contents of the combustion menu, flue gas, fly ash,
be considered with regard to the control of the compounds such as
dibenzofurans (PCDF), halogenated polyaromatic hydrocarbons (PAH),
ils formed as a result of incomplete combustion and caused adverse
rved in Izmit Hazardous and Clinical Waste Incinerator (IZAYDAS). Halogen
id filte
d. Result
filte
albywi
Dioxins and their surrogates
surrogates studied included I
and chlorophenols (CPs). The
quantity (TEQ). The correlate
correlation of LVOH
of the dioxins present und(
surrogate, but it can give a
from the memory effect ar
TEQ
yvere continuously monitored during the startup of two municipal waste in ciner
>w-volatility organohalogen compounds (LVOH) sampled by online systems, asi
changes in levels of LVOH, CBs, and CPs corresponded well with the trend of thi
>n of LVOH with TEQ was fairly good, whereas that of CBs and CPs with TEQ was
memory effect related to the delayed emission of less volatile comp:
ditions showed evidence of the memory effect, i.e., highly chlorinatei
. and LVOH decreased rapidly as the temperature rose. LVOH cannot
:k, and comprehensive warning of the presence of organohalogen cc
y kinds of organohalogen compounds, including dioxins.
jnd their surrogates
w EPA draft (TCO)
idance: prepared
EPA's recently published draft Risk Burn Guid
the total organics (TOs) that may be emitted from the combi
nonvolatile organic compounds) are determined using measi
ninary proof-of-concept tests have been pe
atric analysis (GRAV) procedures used to d(
8270semivolatile organic standard solutio
(ygenated, nitrogenated, and sulfonated hydrocarbons, in i
surement biases of the TCO and GRAV i
e TCO re
istion facilities complete a mass balance of Preliminary proof-of-concept
stinct fractions (volatile, semivolatile, and tests have been performed to
he boiling point (bp) range of each gain further knowledge of the
dge of the total chromatographable organics total chromatographable
jnvolatile organic fractions. A commercially organics (TCO) and gravimetr
:ontaining a variety of halogenated, analysis (GRAV) procedures
:ontaining only carbon and hydrogen, was used to determine the
g. TCO measurement biases observed for organic fractions.
is emerged o\.
entury as a viable strategyfor (a) reducing the volu
substantially the volume of chemical and biological hazardous wastes, (c) for destroying me
for producing energy. Facing an exponential rise in garbage production, policy-makers in th
as a waste-management option. By that time European nations had already made a strong
incineration has been employed in some form for centuries. However, in the last several de
public concerns about the health and ecological impacts of combustion facilities, the level o
control have all increased. Whether waste incineration poses a health risk has been the subject of
ntification of Emiss
Compaction has been suggested as an inter
s atthe site of generation and produces a mc
indicated that when partially compacted w
Compaction is not currently used in institut
specially designed anc
e. Compactior
objectives (DQOs) to
Disposal of WW II
mustard gas hydrolysate
;d for th
Since the issuance of the Environmental Protection Agency (EPA)'s Guidanci
ed. EPA National Exposure Research Laboratory, September, 1996) a great i
results of unspeciated mass organic determinations. Starting primarily atth
is to facilities for conducting stack emissions tests that included unspeciated n
acceptable risk. After several months of data collection experience, experirr
in the laboratory methods, and future structuring of the procedures of the r
methods for evaluating solid waste, physical /chemical methods (SW-846). 5
techniques will be presented with attendant data quality objectives (DQOs)
NA
le of wi
he performance of the incineration l
id to the release of infectious aerosols, which could pose a
;an be adequately controlled by a compaction device
compactor was challenged by compressing waste
i*ere released from the unit. Modifications to the design and
imorove svstem oerformance with reeard to the health and
for Total Organics (Draft guidance for total organics. 2nd
leal of variance has been observed regarding the measured
; end of 1997, the EPA Regions implemented requirements
iass quantitations as part of their demonstration of
antal observations have been made that allow refinements
lethods in a format similar to traditional SW-846 (Test
rd ed. September 1986] methods. Examples of procedural
:hat are used to observe the relative control of these
es forth
in be adequately
by a compaction
specially designed and
refinements in the laboratory
Conference publicatior
Presentation at the 70i
Meeting of the Air Poll
Association, Toronto, Ontario,
Canada, June 20-June 24,1977.
Hydrolybata,
B-20
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Literature Search Results
Document
Relevance
Relevancy Publication
Full Text
Article/Report Title
Abstract
Existing Procedures and
types of Waste
Full Text File Name
Information Source
Notes
Keywords
Tvoe
Score Year
Available?
Methodologies Discussed
T
Medium
29 2014
Eliminating Syria's
NA
Incineration of hydrolysis
Syria's chemical weapon
Eliminating Syria's
Google Sc
The effl uent from the Cape Ray
Hydrolysate,
chemical weapons
effuent
stockpile.
chemical weapons
lydrolysis operation will also be
incineration, warfare
ncinerated. The DF effluent will go to
effluent from the mustard hydrolysis
will goto a German government run
normally used to destroy old
chemicals weapons discovered
abandoned in Germany.
T
Medium
26 2008
Y
Destroying VX
NA
Incineration of VX hydrolysate.
VS hydrolysate (VXH)
Destroying VX
Google Sc
olar
Description oftransportaion ofVX
Hydrolysate,
lydrolysate from Indiana toTexas for
incineration, warfare
G
Medium
31 1998
N
Hydrolysis and Oxidation
Traditional chemical decontamination and disposal treatments for chemical warfare (CW) agents rely largely on base hydrolysis or
Hydrolysis or oxidaton of
Chemical war-fare agents.
NA
Google Sc
olar
Hydrolysate,
Process Effluents of Some
oxidation reactions in aqueous solution. Although often used as methodsfor decontamination or for disposing of relatively small
chemical warfare agents and
incineration, warfare
Chemical Warfare Agents
quantities of agent (often as a partial treatment together with open pit burning), these types of process have also been used in the US,
possible secondary treatments.
and Possible Secondary
UK and Canada, for example, to dispose of relatively large amounts of CW agent. The use of these chemical neutralisation treatments fo
Treatments
arge scale disposal was superseded in recent times by the use of incineration. In the 1950's, large quantities of mustard were destroyed
)y incineration (which is of course an oxidation reaction) in the UK. More recently, the Canadian stockpile was also disposed of by
ncineration as were the Iraqi stocks of mustard by UNSCOM. The US baseline technology is also, of course, based on incineration and
this, together with the existing incinerators in Germany and the UK, uses modern pollution abatement systems and is efficient and
effective. Nevertheless, there is considerable public opposition to incineration and alternative technologies are actively being sought in
U
Medium
27 2012
Y
Biological Treatment of
The Pueblo Chemical Agent-Destruction Riot Plant (PCAPP) is for demilitarization of chemical
Hot water and caustic hydrolysis
The PCD stockpile consists of
Biological_Treatment
Google Sc
WEFTEC conference proceedings.
Hydrolysate,
Chemical Agent
weapons stored atthe Pueblo Chemical Depot (PCD), Pueblo, Colorado. The PCD stockpile
to produce agent-free
projectiles and mortars
_of_Chemical_Agent
incineration, warfare
Hydrolysate by
consists of projectiles and mortars containing blister agents (93.4% of total stockpile), explosives
hydrolysate; biological
containing blister agents
_Hydrolysate_by_lm
Immobilized Cell
(4.2%), and propellants (2.4%). Agents are approximately 98% HD (distilled mustard, p, p"-
treatment of hydrolysate to
(93.4% of total stockpile),
mobilized_Cell_Biore
Bioreactor Technology
dichloroethyl sulfide), and 2% HT, a mixture of HD and T (bis-2-2-chlorethylthioethyl ether).
reduce organic content; and
explosives (4.2%), and
actor_Technology
Agent demilitarization involves; collection from munitions; hot water and caustic hydrolysis to
effl uent treatment to recover
propellants (2.4%). Agents are
produce agent-free hydrolysate; biological treatment of hydrolysate to reduce organic content;
water for reuse.
approximately 98% HD
and effluent treatment to recover water for reuse. The selected biotreatment process for the
(distilled mustard, p, p"-
lydrolysate is Immobilized Cell Bioreactor (ICB) technology. This paper describes the design of
dichloroethylsulfide), and 2%
CBs for PCAPP. The design is based on laboratory and pilot testing results, which defined
HT, a mixture of HD and T (bis-
organic loading rates, hydraulic retention times (HRT), aeration and nutrient requirements, and
2-2-chlorethylthioethyl ether).
G
Medium
30 1999
Y
Supercritical Water
Laboratory-scale, continuous-flow reactor tests were conducted to confirm the destruction
Supercritical water oxidation.
Methylphosphonic acid
Supercritical Water
Google Sc
olar
Hydrolysate,
Oxidation of
efficiency of methylphosphonic acid (MPA) and the effect of sodium hydroxide on MPA destruction
(MPA).
Oxidation of
incineration, warfare
M ethyl phosphonic Acid
efficiency under supercritical water oxidation (SCWO) conditions. Oxygen was used as the
Methylphosphonic
oxidant. The reaction temperatures ranged from 400 to 594 °C; the reactor residence times varied
Acid
rom 3 to 83 s; and the oxygen concentrations varied from 110 to 200% of stoichiometric
requirements. Fixed parameters included (1) a nominal pressure of 27.6 MPa (4000 psi), (2) a
MPA feed concentration of 1000 mg/L, (3) a feed flow rate of 25 g/min, and (4) a NaOH to MPA
molar ratio of 2:1. MPA destruction efficiencies (DE) of greater than 99% were achieved at a
temperature of 550 °C, oxygen concentration of 200% stoichiometric requirements, and reactor
residence time of less than 20 s. On the basis of data derived from 43 MPA experiments, kinetic
correlations for the DE of MPA were developed. The model predications agreed well with the
experimental data. Furthermore, data derived from 22 MPA/NaOH experiments indicated that
G
Medium
31 2002
Y
Supercritical water
Supercritical water oxidation provides a powerful means to transform toxic organic materials into
Destruction of VX hydrolysate
The article discusses VX
Supercritical water
Google Sc
The article descirbes destruction of
Hydrolysate,
oxidation: An
simple, relatively inert oxides. Over the past decade, our understanding of the fundamental chemistry of this process has increased
with supercritical water
hydrolysate.
oxidation An
VX hydrolysate with supercritical
incineration, warfare
environmentally
markedly. Many -fascinating research papers are appearing from laboratories around the world, on the use of the technique for the
oxidation.
environmentally safe
water oxidation. The reaction
safe method for the
decomposition of a variety of organic wastes.
method for the
products are
disposal of
This paper summarizes the important findings of few such studies, which are particularly relevant to the disposal of industrial waste
disposal of organic
reported to be carbon dioxide and
organic wastes
water containing organic
wastes
norganic salts. The liquid effluent
pollutants.
contains mainly a 1:1 molar mixture
of NaH2P04, Na2HP04 and Na2S04.
N
High
35 2007
IM
Review of Chemical Agent
NA
Secondary waste generation at
Secondary waste from
NA
Google Sc
olar
Hydrolysate,
Secondary Waste Disposal
chemical agent disposal
chemical agent disposal
incineration, warfare
and Regulatory
-facilities. Trial burns of
-facilities.
Requirements
secondary waste, compliance
T
Medium
32 2008
Y
Incineration ofVX
NA
A letter in response to the
VX hydrolysate
Incineration ofVX
Google Sc
olar
A letter to C&EN's discussing the
Hydrolysate,
lydrolysate
article "Destroying VX"
Hydrolysate
article "Destroying VX".
incineration, warfare
of VX hydrolysate.
T
Medium
27 2013
Y
DESTRUCTION
This paper analyses the complex process of chemical weapons destruction. It starts with sea dumping, the most simple and used
Discussion of incineration of
Syria's chemical weapon
DESTRUCTION
Google Sc
olar
Hydrolysate,
ACCORDING TO THE
method, now prohibited, continuing with conventional methods like hydrolisis and incineration, which have been used since the fifties.
hydrolysate produced from
stockpile.
ACCORDING TO THE
incineration, warfare
CHEMICAL WEAPONS
Finally, new technologies with specific applications are reviewed, like the use of explosives, biodegradation and supercritical water
demilitarization of Syria's
CHEMICAL
CONVENTION AND ITS
oxidation. Also, we discuss issues related to categories and deadlines for chemical weapons destruction in the Chemical Weapons
chemical weapon stockpile.
WEAPONS
APPLICATION IN SYRIA
Convention and possible modifications based on the need to complete Syria's chemical's stockpiles destruction before mid-2014.
CONVENTION AND
ITS APPLICATION IN
A
Medium
29 2001
Y
Chemical
NA
Discussion on chemical agent
Chemical weapons and
Chemical
Google Sc
olar
Hydrolysate,
Demilitarization-Assembl
destruction using various
hydrolysate.
Demilitarization
incineration, warfare
ed
processes including
Assembled Chemical
Chemical Weapons
neutralization. Processing of
weapons
Alternatives (ACWA):
hydrolysate waste.
Alternative.pdf
A
Medium
27 2007
Y
Chemical Demilitarization:
NA
Cost-beneift discussion for 8
VX hydrolysate waste.
Chemical
Google Sc
olar
Hydrolysate,
Actions Needed to
disposal options to treat 2
Demilitarization
incineration, warfare
Improve the Reliability of
million gallons of VX hydrolysate
Actions Needed to
the Army's Cost
waste.
Improve the
Comparison Analysisfor
Reliability of the
Treatment and Disposal
Army's Cost
Options
Comparison Analysis
for Newport's VX
for Treatment and
Hydrolysate
Disposal Options for
NEwports VX
Hvdrolvsate.odf
B-21
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Environmental Protection
Agency
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POSTAGE & FEES PAID
EPA
PERMIT NO. G-35
Office of Research and Development (8101R)
Washington, DC 20460
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