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OCR for page 172
11
Summary, Findings, and Recommendations
This chapter summarizes the operating characteris-
tics of the seven technology packages and then pre-
sents general findings and recommendations that have
broad applicability across the technologies. (Findings
specific to each technology package are presented in
Chapters 3 through 9.)
SUMMARY OF THE OPERATING
CHARACTERISTICS OF TH E TECH NOLOGY
PACKAG ES
Each of the seven proposed technology packages
represents a unique combination of technologies for
destroying assembled chemical weapons. In Chapters
3 through 9, these packages were examined in detail.
Because the information contained in those chapters is
quite extensive, the committee decided it would be use-
ful to highlight some of the key points in a general
summary. Thus, Table 1 1-1 has been developed to sum
marize the fundamental operational characteristics of
the seven technology packages.
GENERAL FINDINGS AND RECOMMENDATIONS
Because the munitions contain both chemical agents
and energetic materials in various configurations, the
destruction of assembled chemical weapons is an ex-
tremely complex undertaking. The committee has ex-
amined the packages proposed by the seven technol-
ogy providers in detail and evaluated them according
to the criteria set forth in Chapter 2. The following gen-
eral findings and recommendations are applicable to
all of them. Recommendations are listed at the end of
172
the section, with references to the associated findings.
These findings and recommendations should be con-
sidered together and not quoted out of context.
General Findings
General Finding 1. The chemistries of all four of the
primary technologies, (hydrolysis, SILVER II, plasma
arc, and SET) as proposed, can decompose the chemi-
cal agents with destruction efficiencies of 99.9999 per-
cent. However, each technology package raises other
technical issues that must be resolved. One of the cru-
cial issues is the identity and disposition of by-products.
General Finding 2. The technology base for the hy-
drolysis of energetic materials is not as mature as it is
for chemical agents. Chemical methods of destroying
energetics have only been considered recently. There-
fore, there has been relatively little experience with the
alkaline decomposition of ACWA-specific energetic
materials (compared to experience with chemical
agents). The following significant issues should be re-
solved to reduce uncertainties about the effectiveness
and safety of using hydrolysis operations for destroy
ing energetic materials:
· the particle size reduction of energetics that must
be achieved for proper operation
· the solubility of energetics in specific alkaline
solutions
· process design of the unit operation and the iden-
tification of processing parameters (such as the de
gree of agitation and reactor residence time) nec-
essary for complete hydrolysis
OCR for page 173
SUMMARY, FINDINGS, AND RECOMMENDATIONS
.
.
.
the characterization of actual products and by-
products of hydrolysis as a function of the extent
of reaction
the selection of chemical sensors and process con-
trol strategies to ensure that the unit operation
following hydrolysis can accept the products of
hydrolysis
development of a preventative maintenance pro-
gram that minimizes the possibility of incidents
during the cleanup of accumulated precipitates
"Neutralization" (i.e., decomposition and detoxifi-
cation) of chemical agents has been studied since
World War I as part of the chemical weapons defense
program for the protection of U.S. troops and protec-
tion in the event of accidental releases. Hydrolysis, the
first approach selected, was used on a large scale to
neutralize the satin (GB) in cluster bombs destroyed at
Rocky Mountain Arsenal in the 1970s.
However, the standard method of destroying explo-
sives and propellants has been open-air burning or deto-
nation. Because chemical methods of destroying ener-
getics have only been considered recently, there has
been relatively little experience with the alkaline decom-
position of ACWA-specific energetic materials (com-
pared to experience with chemical agents). Most of the
work on base hydrolysis of TNT focused on its precipi-
tation from "pink water" (see Appendix E). Almost all
of the literature on the base hydrolysis of other ener-
getic materials was conducted with dilute solutions that
were well within the solubility limits of these materi-
als. Even though, several undesirable products and pre-
cipitates resulted, the qualitative (rather than quantita-
tive) understanding of these reactions suggests that the
use of strong base is probably the most efficient way to
ensure that hydrolysis is driven to completion.
As shown in Appendix E, the reaction of some ener-
getics with bases is much slower than the reaction of
chemical agents. In most cases, the rate of reaction is
limited by the rate of dissolution of the energetic mate-
rials, which are only slightly soluble in water.
General Finding 3. The conditions under which aro-
matic nitro compounds, such as trinitrotoluene (TNT)
or picric acid, will emulsify in the aqueous phase and
not be completely hydrolyzed are not well understood.
Therefore, this type of material could be present in the
output stream from an energetic hydrolysis step.
173
In Appendix E, the products of pressurized alkaline
hydrolysis of some typical propellants are shown to be
dependent on the additives in the compositions. Some
additives in propellants P1-P5 did not completely re-
act. For example, diphenylamine (DPA) and centralite
precipitated as solid residues or appeared as emulsions
in the liquid phase. The most problematic component
was found to be dinitrotoluene (DNT). In experiments
performed with pure 2,4-DNT, only 7 percent of the
nitrogen was found as nitrite in the liquid phase. No
DNT was found in the solid residue. It is believed that
the DNT was not completely decomposed and might
still have been present as an emulsion in the aqueous
phase (Bunte et al., 1997~. Emulsified components,
such as DNT and DPA, would have to be removed be-
fore any subsequent unit operations (e.g., aerobic
biotreatment) could proceed. Compounds such as TNT
and tetryl (both of which are present in assembled
chemical weapons) as well as picric acid, nitrated
phenols, or nitrated cresols (all of which could be
formed during hydrolysis of the energetics in these
weapons) are expected to behave in a similar fashion.
General Finding 4. The products of hydrolysis of
some energetic materials have not been characterized
well enough to support simultaneous hydrolysis of dif-
ferent kinds of energetic materials in the same batch
reactor.
Lead stearate, an additive in M28 propellant, is in-
soluble in water at ambient temperature, but soluble in
hot alcohol (Sax and Lewis, 1987~. If lead stearate dis-
solves in hot alkaline solution, then the lead cations
could combine with other anionic substrates in a batch
reactor and precipitate out sensitive compounds. This
possibility is supported by the results of testing on pro-
pellant P3 (Bunte, et al., 1997) discussed in Appendix
E. For example, picric acid will be formed during hy-
drolysis of the TNT or tetryl contained in the M55
rocket bursters. If bursters and propellant are hydro-
lyzed simultaneously, lead from the propellant could
either precipitate out or form lead picrate. In the hy-
drated form, lead picrate is not particularly sensitive.
However, enough heat could be produced from this
exothermic process to heat and dehydrate the lead pi-
crate deposited on vessel walls. As indicated in the
TNT hydrolysis section of Appendix E, dry lead pi-
crate is an extremely sensitive explosive and is very
OCR for page 174
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OCR for page 178
178
ALTERNATIVE TECHNOLOGIES FOR DEMILITARIZATION OF ASSEMBLED CHEMICAL WEAPONS
dangerous to handle. Therefore, the committee believes
that, to avoid forming sensitive compounds such as lead
picrate, hydrolysis of bursters and propellant should be
performed in separate vessels.
General Finding 5. The primary chemical decomposi-
tion process in all of the technology packages produce
environmentally unacceptable reaction products.
Therefore, all of the packages are complicated pro-
cesses that include subsequent treatment stepts) to
modify these products.
General Finding 6. The waste streams of all of the
ACWA technology packages could contain very small
amounts of hazardous substances (besides any residual
chemical agent). These substances were not fully char-
acterized at the time of this report; therefore, all waste
streams must be characterized to ensure that human
health and the environment are protected. If more than
one phase (gas, liquid, or solid) is present in a waste
stream and, each phase should be characterized
separately.
All of the alternative technology packages appear to
be capable of meeting the current destruction efficiency
limits for agent and hazardous materials of regulatory
concern. However, they may create new pollutants that
could have adverse environmental effects. Therefore,
complete characterizations of the process effluents (sol-
ids, liquids, and gases) from the secondary-treatment
waste streams will be essential. Characterization may
require pilot-scale operation of the integrated processes
before a final conclusion can be determined on envi-
ronmental acceptability.
The waste streams of all of the proposed technology
packages (gas, liquid, and/or solid) may contain small
amounts of hazardous materials, even under normal
operating conditions (this is a characteristic of virtu-
ally any industrial chemical process). To ensure that no
toxic effluent is accidentally discharged, all waste
streams must be monitored. In the committee's opin-
ion, all of the packages are fundamentally capable of
being monitored to ensure the protection of human
health and the environment. (Although the detection
and analysis of trace substances can be done to very
low levels, no monitoring or analytical method can
guarantee a true zero level of any known or unknown
compound.)
General Finding 7. None of the proposed technology
packages complies completely with the hold-test-re-
lease concept for all gaseous effluents (both process
and ventilation effluents).
General Finding X. Hold-test-release of gaseous ef-
fluents may not ensure against a release of agent or
other hazardous material to the atmosphere. No evi-
dence shows that hold-test-release provides a higher
level of safety than current continuous monitoring
methods for gaseous streams with low levels of con-
tamination. Furthermore, none of the technologies pro-
vides for hold-test-release of effluents from ventilation
systems that handle large volumes of gases from con-
taminated process areas.
In an earlier report on alternative technologies the
NRC noted that,
The risk of toxic air emissions can be virtually eliminated
for all technologies through waste gas storage and certifi-
cation or treatment by activated-carbon adsorption. Ei-
ther of these options can be combined with methods to
reduce the volume of gas emissions (NRC, 1993~.
Some of the technology packages include hold-test-
release steps of gaseous process effluents (1) when the
effluent stream flow rates are relatively low or (2) when
the effluent streams occur in batches that can be easily
contained. For continuous gaseous effluent streams that
have high flow rates (e.g., from SCWO units and ex-
haust gas from biotreatment units), elaborate designs
would be required to incorporate a hold-test-release
step.
The committee believes that the hold-test-release
step Is not a panacea for ensuring that gaseous effluents
are free of agent or other hazardous materials. Some
low-concentration hazardous volatile materials may
adsorb onto internal tank surfaces or be absorbed into
liquids or solids in holding tanks where they may es-
cape detection. When the holding tank is vented to the
atmosphere, these undetected materials may be des-
orbed and released to the environment. To the com-
mittee's knowledge, no experiments have been per-
formed to demonstrate that these phenomena do not
occur. Moreover, if a process upset contaminates the
holding tanks, decontamination (and verification of
decontamination) may present significant technical
difficulties.
OCR for page 179
SUMMARY, FINDINGS, AND RECOMMENDATIONS
All of the ACWA technology packages include the
baseline continuous monitoring and filtering systems
(ACAMS and DAAMS) for air ventilation in process
areas where contamination is expected. To add hold-
test-release steps for this large volume of air flow
would be very difficult and probably would entail very
expensive (and impractical) design.
Continuous monitoring coupled with interlocks that
shut down the process quickly if concentration limits
are exceeded may be just as reliable as hold-test-re-
lease steps for protecting human health and the envi-
ronment, especially for large-volume effluent streams.
Whatever approach is adopted will require additional
testing to demonstrate its viability and effectiveness.
Tests may very well show that hold-test-release steps
do not ensure safety any better than simpler continuous
monitoring methods combined with robust process con-
trols (i.e., continuous performance assurance).
General Finding 9. Solid salts will be hazardous
waste, either because they are derived from hazardous
waste (see Chapter 2) or because they leach heavy met-
als above the levels allowed by the Resource Conser-
vation And Recovery Act Toxicity Characteristic
Leaching Procedure. Stabilization mixing waste with
a reagent or reagents to reduce the leachability of heavy
metals will probably be required before the salts can
be sent to a landfill. The potentially high chloride and
nitrate content of these salts will make the waste diffi
. . ...
cult to size, and treatability studies will be neces-
sary to determine a proper stabilization formula.
General Finding 10. Testing, verification, and inte-
gration beyond the 1999 demonstration phase will be
necessary because the scale-up of a process can present
many unexpected challenges, and the ACWA demon-
strations were limited in nature.
The reasons supporting this finding are discussed
below. The ACWA demonstrations tested only the
unit operations that DOD believed were most criti-
cal or least proven for that technolo~v nacka~e
.. ..
OF ~ O
However, other unit operations may also require addi-
tional development before full-scale implementation
can proceed.
Second, the accelerated ACWA schedule required
that the demonstrations be relatively short. Thus, the
longer-term reliability of the processes could not be evalu-
ated. In addition, the duration of the demonstrations
179
may have been too short to characterize fully the
steady-state operational behavior the huildun of trace
· . · . - .
. , ~
materials In recycling loops, and problems with corro-
sion. Longer lasting tests with the full range of materi-
als to be processed will be necessary for identifying the
best materials of construction.
Third, the demonstrations did not include interfac-
ing the unit operations into a complete system (i.e.,
when the output stream of one process step becomes
the input stream of the next) when unexpected prob-
lems often arise. For example, scheduling is especially
difficult to design when a batch or semibatch process
(e.g., the hydrolysis reactors) is coupled with a con-
tinuous process (e.g., the SCWO reactor). Incomplete
processing in one stage may cause contamination or a
materials incompatibility in a later stage. Also, a bottle-
neck can be created if one step does not achieve the
expected throughput. Therefore, for each piece of
equipment, the implications of operating with input
streams that are off specification, that are not moving
at the design flow rate, or that are completely blocked
must be tested.
Fourth, scale-up of a process is not always linear.
Although the scale-up of some types of standard chemi-
cal process equipment can be straightforward, the
scale-up of new equipment designs can raise problems
if not all parts of the process scale in the same way. For
example, many mass-transfer processes scale with
length. Surface wash-out, heat transfer, and other sur-
face phenomena scale with surface area. Homogeneous
chemical reactions scale with reactor volume. When
all these phenomena occur simultaneously (in a hy-
drolysis or SCWO reaction vessel), the different scal-
ing properties must be accommodated in the design.
Fifth, impurities that are not detected in small-scale
tests may be evident in larger scale tests. Because of
the limited quantities used in the small-scale and dem-
onstration-phase tests, trace impurities in the waste
streams may not be detectable. The impurities and
small amounts of intermediates that are produced in a
full-scale (or near full-scale) plant are not necessarily
the same as those observed during laboratory or bench-
scale experiments, or even during demonstration-scale
tests. Small excursions or variations in the conditions
under which a reaction is run can also alter the nature
or the amount of trace impurities that are produced.
Because the scale of the demonstration testing is
OCR for page 180
180
ALTERNATIVE TECHNOLOGIES FOR DEMILITARIZATION OF ASSEMBLED CHEMICAL WEAPONS
limited, the quantity of trace impurities in the reaction
products may be too small for detection analysis.
Operation at near full-scale would reveal trace impuri-
ties that mav require process chances to mitigate or
eliminate them.
--a ---1----- r
__c, _ _ _ _ ____ __~) _
Sixth, materials-handling equipment was generally
not evaluated during the ACWA demonstrations. In the
scale-up operations of waste treatment facilities, the
materials-handling equipment, such as equipment for
sizing and feeding waste, has been the weak link in the
operational chain. The materials-handling equipment
will have to be tested and evaluated prior to full-scale
implementation to ensure that integrated facilities
operate properly.
This additional testing, verification, and integration
could be done in a pilot-scale facility. However, even
the construction and operation of a pilot-scale facility
will not necessarily ensure a trouble-free start-up of a
full-scale facility. Industrial experience suggests that
unanticipated problems will occur at full-scale in spite
of pilot-plant experience.
General Finding 11. Although a comprehensive quan-
titative risk assessment (QRA), health risk assessment
(HRA), and ecological risk assessment (similar to as-
sessments performed for the baseline process) cannot
be completed at this stage of process development,
these assessments will have to be performed and re-
fined as process development continues.
All of the proposed destruction systems are in the
conceptual design stage, which means that many de-
sign details have not been developed. At this stage, only
qualitative risk assessments could be done, and all of
the technology providers prepared preliminary hazard
analyses that qualitatively describe potential accidents.
General Finding 12. The "optimum" system for a par-
ticular chemical weapons storage depot might include
a combination of unit operations from the technology
packages considered in this report.
The technology packages proposed for the ACWA
program address the destruction of assembled chemi-
cal weapons at the hypothetical depot described in the
REP. The actual depots under consideration have very
different munition inventories. For example, the Pueblo
Chemical Depot has only mustard-filled projectiles and
mortars in its inventory. The Blue Grass Army Depot
in Richmond, Kentucky, however, has a large inventory
of M55 rockets, which contain GB or VX. Some of the
components and processes in the proposed systems are
very effective for one or another portion of the overall
demilitarization process. Technology packages may
also differ in their applicability to particular munitions
and particular chemical agents.
This discussion notwithstanding, the committee's
task is to evaluate the technology packages, as pro-
posed, for the hypothetical depot. The committee did
not, therefore, consider "mixing and matching" com-
ponent technologies for specific sites or munitions.
General Finding 13. Some of the ACWA technology
providers propose that some effluent streams be used
commercially. New or modified regulations may have
to be developed to determine if these effluent streams
can be recovered or reused.
According to current Army standards, a solid mate-
rial that has not been subjected to 5X treatment can
only be disposed of in a hazardous-waste facility. If a
process under consideration produces a waste stream
that could be reused by, for example, a metal reclaimer
or a fertilizer plant, this waste stream would have to be
subjected to 5X treatment. To date, liquids and gases
from chemical demilitarization processing have not
been recycled or reused commercially; therefore, ex-
isting standards may have to be reexamined.
General Finding 14. An extraordinary commitment of
resources will be necessary to complete the destruction
of the assembled chemical weapons stockpile in time
to meet the current deadline using any of the ACWA
technology packages. This would demand a concerted
national effort. It is unlikely that any of the technology
packages could meet this deadline.
The chemical-hydrolysis destruction of bulk agents
at Aberdeen Proving Ground, Maryland, and Newport,
Indiana, are examples of how much time could be re-
quired to bring any of the alternative destruction sys-
tems from its present state of development to the pilot-
plant stage and finally to the production stage. The
schedules for the design, construction, and operation
of the destruction facilities at these two sites (see
Figures 1 1-1 and 1 1-2) indicate that the destruction of
munitions will be completed by the end of 2004. The
ACWA program is approximately three years behind
the Aberdeen and Newport schedules, and the develop-
ment of an acquisition design package for ACWA is
OCR for page 181
SUMMARY, FINDINGS, AND RECOMMENDATIONS
1996 1 1997 T 1998 | 1999 | 2000 1 2001 | 2002 1 2003 | 2004
1 1 1 1 1 1 1 1
181
1995
2005
2006
2007
· _ Complete NRC study of alternatives
1 1 ~ 1
~ complete 60% desian for acquisition roacknae
FIGURE l l-l Schedule for the Aberdeen Chemical Agent Disposal Facility as of January 6, 1999. Source: Adapted from Pecoraro,
1999.
not likely to begin before October 1999; for Aberdeen
and Newport, it began in November 1996.
The programs at Aberdeen and Newport are less
complex than those required for other sites because the
stockpiles at those two sites contain only bulk agents in
one-ton containers. Only one agent is stored at each
site, and there are no munitions to be disassembled and
no energetics to be treated. Thus, the committee ex-
pects that the development cycle at other sites such as
Richmond, Kentucky, and Pueblo, Colorado, could
take even longer because of modifications to the disas-
sembly process and the numerous interfaces between
unit operations. In addition, the number of munitions at
Pueblo suggests a much longer operating period than at
Aberdeen or Newport. Therefore, meeting the April
2007 CWC treaty deadline will be very difficult. (A
recent report [Arthur Andersen, 1998] concluded that
the baseline incineration technology will also have dif-
ficulty meeting the April 2007 deadline. This comm~t-
tee did not evaluate the methodology used by Arthur
Andersen to reach this conclusion.)
A "crash program" to expedite the implementation
of any of the alternative technology packages is possible,
1995
of course. However, this would require significantly
more financial resources than have been planned for
the disposal sites. (Note that the Aberdeen and New
port designs have already been put on a fast track to
conduct pilot-scale testing concurrent with the cons~uc-
tion of full-scale facilities to reduce the time to start-up.)
General Finding 15. The Dialogue process for identi-
fying an alternative technology is likely to reduce the
level of public opposition to that technology. The com-
mittee believes that the Dialogue has been and contin-
ues to be a positive force for public acceptance of alter-
natives to incineration. Although the Dialogue process
requires a significant commitment of time and re-
sources, it has been a critical component of the ACWA
program to date.
Reducing opposition by the general public or by or-
ganized interest groups could reduce the time and re-
sources required to obtain state and federal permits for
constructing and operating disposal facilities. For ex-
ample, the speed with which the Aberdeen facility re-
ceived permits can be partly attributed to the lack of
public opposition (Hammerberg, 1998~. The ACWA
2000
1996 T 1997 | 1998 | 1999
T T 1
2002 1 2003 T 2004
1
2001
2005
2006
2007
~ _ Complete N RC study of alter
Natives
Complete 60% design for acquisition package
~ Set up system and run pilot tests
Operating period
FIGURE l 1-2 Schedule for the Newport Chemical Agent Disposal Facility as of January 6, 1999. Source: Adapted from Pecoraro,
1999.
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182
ALTERNATIVE TECHNOLOGIES FOR DEMILITARIZATION OF ASSEMBLED CHEMICAL WEAPONS
process, as mandated by Congress, has provided a
unique opportunity for sidestepping the kind of con-
flict that has impeded progress in the baseline incinera-
tion program. The Dialogue process initiated by the
program manager for ACWA is a basis for building
trust between DOD officials and citizen and environ-
mental groups that have traditionally been opposed to
. . .
Incineration.
General Finding 16. Although the committee did
not have access to scientific data on the attributes of
a technology that would be most acceptable to the
public, input from members of the active publics and
previous research indicates that technologies with
the following characteristics are likely to stimulate
less public opposition:
· minimal emissions, particularly gaseous
.
continuous monitoring of effluents to verify that
the process is operating as designed (process
assurance measurement)
· provisions for representatives of the local commu-
nity to observe and participate in the process
assurance measurement
General Recommendations
General Recommendation 1. If a decision is made to
move forward with any of the ACWA technology pack-
ages, substantial additional testing, verification, and
integration should be performed prior to full-scale
implementation (see General Finding 10~.
General Recommendation 2. The sampling and
analysis programs at each phase of development should
be carefully reviewed to ensure that the characteriza-
tion of trace components is as comprehensive as pos-
sible to avoid surprises in the implementation of the
selected technology (see General Finding 6~.
General Recommendation 3. If a decision is made to
move forward with any of these technology packages,
health and safety evaluations should progress from
qualitative assessments to more quantitative assess-
ments as the process design matures. Quantitative
(QRA), health (HRA), and ecological risk assessments
should be conducted as soon as is practical. Early ini-
tiation of these assessments will allow findings to be
implemented with minimal cost and schedule impact.
(See General Finding 11.)
The QRA is a tool for managing risk in the design as
it becomes increasingly well defined. In the early
stages, QRAs can indicate the systems or unit opera-
tions that appear to be major contributors to risk at that
stage of design development. If a pilot-facility is con-
structed, preliminary quantitative, health, and ecologi-
cal risk assessments should be developed prior to the
completion of the pilot facility design. These analyses
should then be factored back into the designs and the
risk assessments completed before operation of the pi-
lot facility begins. If a full-scale facility is constructed,
preliminary risk assessments for the full-scale facility
should be developed prior to the completion of the fa-
cility design. The preliminary analyses should then be
factored back into the full-scale design. These risk as-
sessments should be completed before operation of the
facility begins. The QRA should include assessments
of public and worker risk, as well as uncertainties. The
specific protocol for the HRA and ecological risk as-
sessment will have to be determined in cooperation
with state and federal permitting agencies.
General Recommendation 4. Any of these technol-
ogy packages, or any component of these technology
packages, should be selected on a site-specific basis.
(See General Finding 12.)
General Recommendation 5. Whatever unit operation
immediately follows the hydrolysis of energetic mate-
rials should be designed to accept emulsified aromatic
nitro compounds, such as TNT or picric acid, as con-
taminants in the aqueous feed stream. (See General
Finding 3.)
General Recommendation 6. Simultaneous process-
ing of different types of energetic materials should not
be performed until there is substantial evidence that the
intermediates formed from the hydrolysis of aromatic
nitro compounds will not combine with M28 propel-
lant additives or ordnance fuze components to form
extremely sensitive explosives, such as lead picrate.
(See General Finding 4.)
General Recommendation 7. The Department of De-
fense should continue to support the Dialogue throughout
the current ACWA program and should seriously con-
sider the participation of the Dialogue in any follow-on
programs.
Representative terms from entire chapter:
energetic materials
