FEATURE

Hazardous material inventory

reduction at nuclear and high
hazard facilities
Trap Door Site (TA-22) hosts current Los Alamos National Laboratory (LANL) operations related to
detonator development. The Radioactive Liquid Waste Treatment Facility (TA-50) supports TA-55 and the
rest of the Lab by processing radioactive liquid waste. Designated as a Research and Development facility,
the LANL Plutonium Facility (TA-55) is capable of small lot manufacturing. These three facilities are
managed by the Plutonium Science & Manufacturing Directorate (ADPSM). An assessment of these
facilities as-is material at risk quantities has been completed. Within TA-55 and TA-50, EPIcode results
presented nine worse case scenarios for hazardous materials quantities, respectively. No opportunities for
long-termreduction in hazardous materials were necessary at TA-22. Achlorine generator that is acceptable
for use at TA-55 would eliminate the classication levels and protective action distances for chlorine.
Purchasing potassiumhydroxide and sodiumhydroxide in containers that weigh 40 pounds or less at TA-55
and hydrochloric acid in 5 gallon containers or less at TA-50 would eliminate classication levels and
protective action distances for these chemicals, as well. Pursuing these opportunities will result in a
signicant reduction of hazardous material containers; from 9 containers to 2. Sodium hydroxide inventory
at TA-50 and nitric acid inventory at TA-55 cannot be reduced based on mission-essential needs, i.e., without
increasing the overall risk to each facility. In the following report, a Hazardous Material Inventory
Reduction approach for ADPSM facilities is outlined, recommendations for future opportunities to reduce
chemicals are presented and hazardous material inventories that cannot be reduced based on mission-
essential need discussed. Initiatives of this type contribute to ADPSMscientic and technological excellence
by increasing operational safety.
By Michael E. Cournoyer,
Jonathan Tapia,
Vincent P. Worland,
Stephan Schreiber,
Dianne Wilburn
INTRODUCTION
Trap Door Site (TA-22) hosts current
Los Alamos National Laboratory
(LANL) operations relatedtodetonator
development. The Radioactive Liquid
Waste Treatment Facility (TA-50) sup-
ports TA-55 and the rest of the Lab by
processing radioactive liquid waste.
Designated as a Research and Develop-
ment facility, the LANL Plutonium
Facility (TA-55) is capable of small lot
manufacturing. These facilities are man-
aged by the PlutoniumScience &Man-
ufacturing Directorate (ADPSM). In
these facilities, engineered barriers pro-
vide the most effective protection from
radioactive and hazardous materials.
1
These barriers have been incorporated
through architectural and structural
design and employ differential pressure
zones, High-Efciency Particulate Air
(HEPA) ltration, gloveboxes and
radiation shielding in the design of the
facility. The Hazardous Materials Pro-
tection Program (HMPP) augments
these passive safety features in these
facilities by integrating knowledge
about hazardous materials with mea-
sures that provide appropriate exposure
controls. Accomplishments of the
HMPP have been previously reported.
2
A key element of the HMPP is to pro-
vide inventory information on hazar-
dous materials in quantities large
enough to pose a signicant risk to per-
sonnel or the environment inthe case of
an emergency release or re.
The Labs Emergency Operations
(EO) Division has been tasked with
identifying opportunities to potentially
decrease emergency planning,
response impacts, and risk by reducing
chemical inventory. DOEOrder 151.1,
Comprehensive Emergency Manage-
ment System, Chapter IV, requires an
Emergency Planning Hazards Assess-
ment (EPHA) for facilities that use or
store hazardous materials in amounts
that exceed specied screening thresh-
olds, as shown in Table 1.
Paraphrasing DOE Order 151.1, the
NFPA hazard ratings can be used for
initial screening to determine when the
Michael E. Cournoyer, Ph.D. is
afliated with Los Alamos National
Laboratory, Los Alamos, NM 87545,
United States (Tel.: +1 505 665 7616;
e-mail: mec@lanl.gov).
Jonathan Tapia is afliated with Los
Alamos National Laboratory, Los Ala-
mos, NM 87545, United States.
Vincent P. Worland is afliated with
Los Alamos National Laboratory, Los
Alamos, NM 87545, United States.
Stephan Schreiber is afliated with Los
Alamos National Laboratory, Los Ala-
mos, NM 87545, United States.
Dianne Wilburn is afliated with Los
Alamos National Laboratory, Los Ala-
mos, NM 87545, United States.
2 Division of Chemical Health and Safety of the American Chemical Society 1871-5532/$36.00
Elsevier Inc. All rights reserved. doi:10.1016/j.jchas.2011.04.001
acute health affects of a chemical are
severe enough to consider evaluation.
Although the system was developed
primarily to serve the needs of re
protection agencies, it is useful to any-
one involved in the handling of poten-
tially hazardous substances. The
systemidenties the hazards of a mate-
rial in terms of three principal cate-
gories: health, ammability, and
instability. It indicates the degree
of severity by a numerical rating that
ranges from four (4), indicating severe
hazard, to zero (0), indicating no
hazard. In general for each of the cate-
gories, levels 3 and 4 represent effects
that are the most severe, have the long-
est lasting impacts, impact the largest
area and/or involve the largest energy
release. For purposes of screening,
therefore, any chemical with a health
hazard rating of 0, 1, or 2 is presumed
not to represent a signicant toxic
health hazard to humans and may be
excluded from further analysis. Any
chemical assigned a health hazard rat-
ing of 3 based solely on cryogenic
properties and the resulting frostbite
hazard may likewise be excluded.
The fact that a substance is am-
mable, combustible, or explosive is
not by itself sufcient cause to analyze
it in an EPHA. However, a substance
should be considered a potential
release initiator or promoter if it is
combustible or capable of a violent
chemical reaction that could cause or
enhance the release of other hazardous
materials with the ability to cause
severe injury or death beyond the
immediate vicinity of the release. If a
substance meets the following condi-
tions, its ammable or explosive prop-
erties should be noted for possible
consideration in the EPHA as a factor
potentially inuencing the release of
existing toxic materials:
The substance is ammable or
explosive and capable of a violent/
energetic reaction (e.g., deagration,
explosion, etc.).
The energy available in the sub-
stance could cause signicant
damage to facilities/equipment and
disperse other substances stored or
used in close proximity to it.
A chemical reacting with other sub-
stances is not by itself sufcient cause to
analyze it in an EPHA. If an energetic
reaction involving substance A could
cause the release of hazardous material
B, then the reaction should be consid-
ered as a potential initiator during the
analysis of substance B. If an identied
reaction creates an acute inhalation
hazard as a by-product and if the quan-
tity created could be a signicant
hazard beyond the immediate vicinity
of the event, then the reaction and its
by-product should be considered for
analysis in the EPHA. If a substance
meets the following test, its chemically
reactive properties should be noted for
possible consideration in the EPHA, as
the source of a toxic release:
The substance will react with other
chemicals or materials used or
stored in the same location.
The reaction could be sufciently
energetic to cause signicant damage
to facilities/equipment and disperse
other toxic substances stored or used
in close proximity to it.
The reaction products are toxic and
pose an acute airborne hazard.
Based on information from ADPSM
facilities EPHA and corresponding
safety basis documentation, opportu-
nities for reducing chemical inventories
were identied. An Inventory Assess-
ment Report fromthe EODivision was
generated that listed chemical material
that could potentially be reduced. The
EPHAdenes the facility/project emer-
gency planning basis by quantitatively
analyzing the potential consequences
of airborne releases of hazardous mate-
rials. This includes the release quanti-
ties anddistances at whichanAlert, Site
Area, or General Emergency will be
generated, as shown in Table 2.
The Emergency Planning Guidance
(ERPG) Tables are used to determine
whether a facility could generate an
Alert, Site Area, or General Emergency
due to a chemical release.
3
The gui-
dance table lists the amount of chemi-
cals that will result in the ERPG/
Temporary Emergency Exposure Lim-
its level two (TEEL-2) exposure rates at
30 m, 100 m, and other distances up to
1000 m. The EPHA establishes the
Emergency Planning Zone for the facil-
ityandthe site, as well as determines the
consequences to individuals at the fol-
lowing evaluation points and classies
the release of hazardous materials
according to the classication criteria.
In some instances (such as explosion of
a pressurized system), the maximum
release may be the only plausible
release. In other instances (such as a
leak resulting from a puncture), several
different scenarios could be modeled to
correspond to the different release
events. As an added feature, the EPHA
documents the assumptions and meth-
ods used in the analysis.
The Site EPHA takes information
from each facility and summarizes it
into one document covering the entire
Laboratory. This document establishes
the requirements and standard meth-
ods for the development and mainte-
nance of the EPHA process used by
Emergency Management and
Response, Emergency Planning &Pre-
paredness, for emergency response.
Thus, issues specic to emergency
management are addressed by the Site
EPHA. The Emergency Prediction
Information Code Program (EPIcode)
provides emergency response person-
nel and emergency planners with a
software tool to help evaluate the
atmospheric release of toxic sub-
stances.
4
EPIcode allows fast estima-
tion and assessment of chemical
release scenarios associated with acci-
dents from industry and transporta-
tion. The software can also be used
for safety analysis planning purposes
on facilities handling toxic materials.
Table 2. Classication criteria.
Emergency planning zone
Alert >ERPG-2 at 30 m
Site area
emergency
>ERPG-2 at 100 m
General
emergency
>ERPG-2 at site
boundary
Table 1. EPHA screening thresholds.
Physical
state
Screening
thresholds
Unit of
measure
Gas 10 Pounds
Liquid 5 Gallons
Solids 40 Pounds
Journal of Chemical Health & Safety, January/February 2012 3
Calculations are carried out that deter-
mine the rate at which the chemical
material is released to the atmosphere,
release height, release durations, and
the form and properties of the chemi-
cal upon release. The release chemical
may be a gas, a vapor, or an aerosol.
Through the Lab Pollution Preven-
tion (P2) Program, engineering and
technical support is provided to
enhance the safety of hazardous mate-
rial operations, and assure that mission
work can be accomplished without reg-
ulatory-related delays. The P2 Program
provides a number of services to Lab
operations, including the Generator
Set-Aside FeeProgram(GSAF) funding
for process improvements. In the fol-
lowing report, a Hazardous Material
Inventory Reduction approach for
ADPSM facilities is outlined, recom-
mendations for future opportunities to
reduce chemical are presented and
hazardous material inventories that
cannot be reduced based on mission-
essential need identied.
HAZARDOUS MATERIAL INVENTORY
REDUCTION APPROACH
Based on the above criteria, the follow-
ing approach is outlined:
1. Obtain a listing of chemical con-
tainers at TA-55, TA-50, ARTIC,
andTA-22usingtheLabs chemical
inventory system (ChemLog).
Although not on the ChemLog
database, the 6000 pounds of con-
centrated nitric acid stored outside
of TA-55 will be included in this
assessment.
2. Identify hazardous materials in
amounts that exceed specied
screening threshold quantities at
ADPSM facilities.
3. Assess these remaining hazardous
materials against the second criter-
ion; an NFPA Health rating of 3 or
4.
4. Compare the hazardous materials
that meet both criteria against the
list provided by EO Division. If
there is a discrepancy between
the two lists, the NFPA Health
rating based on the manufactures
Material Safety Data Sheet
(MSDS) will take precedence.
5. Generate a list for worse case sce-
narios for hazardous materials
within ADPSM facilities that meet
or exceed chemical threshold
quantities.
6. Categorize as-is Material at Risk
(MAR) using the EPIcode. The
MAR is dened as the amount of
hazardous material available to be
acted on by a given physical
stress.
5
7. Generate a condensed ERPG
Table for worse case scenarios
within ADPSM facilities.
8. Update appropriate safety basis
documentation and operations
documents, if the MAR quantity
is incorrect or the hazard material
is not present.
9. Generate a disposal plan for redu-
cing the inventory, if opportunities
for long-term reductions in hazar-
dous materials that have an emer-
gency response impact arise.
10. Generate a memo indicating the
material is mission critical, if the
quantity of hazardous material is
mission critical and cannot be
reduced.
RESULTS
On February 8, 2011, a listing of che-
mical containers at ADPSM facilities
was downloaded, using ChemLog.
These three facilities store 6076 con-
tainers in 34 buildings, as shown in
Table 3.
Hazardous materials in amounts
that exceed specied screening thresh-
olds at TA-55, TA-50, and TA-22 have
been identied. Of the 221 chemical
containers screened, only 9 met the
second criterion; NFPA Health rating
of 3 or 4, as shown in Table 4.
The 141 and 14,260 pound contain-
ers of hydrochloric acid and sodium
hydroxide solutions equate to 13 and
4000 gallon containers, respectively.
The results in Table 4 were compared
against the list provided by EO Divi-
sion. There are two discrepancies
between the two lists. The EODivision
list includes four 55 gallons drums of
sodium silicate solution used at TA-50.
The MSDS was reviewed for the
sodium silicate solution purchased
from the Univar USA Inc. (17425
NE Union Hill Road, Redmond,
WA). The NFPA Health rating for
sodium silicate solution is 2. Thus,
these four 55 gallons drums of sodium
silicate solution do not meet the sec-
ond criterion.
The EO Division list also includes a
scenario for chlorine gas generation
due to a breach in a container at TA-
50. As shown in Table 4, there are no
longer any scenarios where chlorine
gas can be generated at TA-50. In the
past, large quantities of potassium per-
manganate had been stored in the
immediate vicinity of the hydrochloric
acid containers. If these solutions were
to mix, chlorine gas can be generated.
6
Five chemicals in 6 physical states
have beenidentied infacility chemical
quantities that meet or exceed chemical
threshold quantities. A condensed
Table 4. Threshold quantities.
TA Bldg. Chemical name Inventory (lb) NFPA health
50 248 Hydrochloric acid 141 3
50 1 Sodium hydroxide (25%) 14,260 3
55 3 Chlorine 40 4
55 3 Chlorine 40 4
55 127 Nitric acid, 6971% 6000 3
55 192 Potassium hydroxide 110 3
55 192 Potassium hydroxide 110 3
55 192 Potassium hydroxide 110 3
55 5 Sodium hydroxide 110 3
Table 3. Chemical inventory results.
Facility Buildings Chemical
containers
TA-55 20 3954
TA-22 9 1187
TA-50 5 936
Total 34 6077
4 Journal of Chemical Health & Safety, January/February 2012
ERPGTable for worse case scenarios is
shown in Table 5.
An inventory assessment of TA-55,
TA-50, and TA-22 for has been gener-
ated. The as-is MAR is compiled in
Table 6.
OPPORTUNITIES FOR LONG-TERM
REDUCTIONS IN HAZARDOUS
MATERIALS
Four opportunities for long-term
reduction in hazardous materials have
been found at TA-50 and TA-55, as
shown in Table 7.
No opportunities for long-term
reduction in hazardous materials were
necessary at TA-22. The 4000 gallon of
sodium hydroxide at TA-50 and 6000
pounds of nitric acid at TA-55 cannot
be reduced based on mission-essential
needs. Reducing either of these
volumes would increase the probabil-
ity of a hazardous material event to an
unacceptable level.
7
For example; the
Actinide Process Chemistry group uses
an aqueous nitric acid process to pur-
ify, stabilize, and produce plutonium
material that is suitable for long-term
storage or future applications. During
a run, over a hundred of gallons of
nitric acid are pumped directly to the
work area, daily. Replacing the 6000
pounds storage tank with 800 2.5 l
glass containers of concentrated nitric
acid would increase the likelihood of a
chemical spill because now the worker
would have to hand carry each con-
tainer of nitric acid.
8
DISCUSSION
A proposal on replacing 40 pound
cylinders of chlorine with a chlorine
generator will be submitted at the next
call for GSAF proposals. Replacing the
current 110 pound containers that
hold the potassium hydroxide and
sodiumhydroxide with containers that
weigh 40 pounds or less at TA-55 will
be analyzed. Replacing the current 13
gallon containers that hold the hydro-
chloric acid with 5 gallon containers or
less at TA-50 will also be analyzed. All
TA-22 chemical quantities are less
than the threshold needed for classi-
cation in Table 2. Thus, TA-22 has a
chemical category of Low Hazard and
its facility categorization is complete.
TA-50 and TA-55 have chemical quan-
tities greater than the threshold needed
for classication in Table 2. Thus, TA-
50 and TA-55 have a chemical cate-
gory of High Hazard and their facility
categorization is complete.
A primary objective throughout
ADPSM facilities is that operations
be conducted in a safe, deliberate,
and controlled manner. TA-55 has
the majority of chemical containers
and buildings followed by TA-22, as
shown in Table 3. Operations are rou-
tinely evaluated to identify and quan-
tify hazards inherent in work activities.
Hazards analysis of ADPSM facilities
Table 7. Opportunities for long-term reduction in hazardous materials.
TA Chemical name Opportunities
50 Hydrochloric acid Purchase in containers of 5 gallons or less
55 Chlorine Investigate the feasibility of a chlorine generator
55 Potassium hydroxide Purchase in containers of 40 pounds or less
55 Sodium hydroxide Purchase in containers of 40 pounds or less
Table 6. as-is material at risk (MAR) within TA-55 and TA-50.
Location Description Hazard MAR
(lbs)
No. of
containers
Alert
(lbs)
SAE
(lbs)
GE
(lbs)
TA-55-0192 Explosion: Full facility Potassium hydroxide 700 1 0.5 1
TA-55-0192 Explosion: Full facility Sodium hydroxide 700 1 1
TA-55-0127 Explosion: Full facility Nitric acid, 6971% 6000 1 267 6000
TA-55-0005 Explosion: Full facility Sodium hydroxide 882 1 1
TA-55-0003 Explosion: full facility Chlorine gas 87 1 0.2 87
TA-55-0003 LOC: full facility Chlorine gas 87 1 0.2 87
TA-55-0003 LOC: localized Chlorine gas 44 1 0.2 44
TA-50-0001 Breach of one drum Hydrochloric acid 365 1 4 365
TA-50-0001 Breach of four drums Hydrochloric acid 365 4 4 4 1460
GE: general emergency; SAE: site area alert.The optimal levels of reduction are highlighted in yellow.
Table 5. Chemicals within ADPSM facilities that meets or exceeds chemical threshold quantities.
No. Chemical
compound
CAS
number
State Solution
conc. (w/o)
TEEL-2
(mg/m
3
)
Threshold quantity (lbs) at a distance (m) of:
30 100 200 500 750 1000
550 Chlorine 7782-50-5 Gas 6 0.15 1 3 10 19 29
1335 Hydrochloric acid 7647-01-0 Liquid 37% 32 2.18 13 38 151 277 427
1335 Hydrogen chloride 7647-01-0 Gas 33 0.83 5 14 57 105 162
1830 Nitric acid 7697-37-2 Liquid 70% 62 268.00 1640 4650 18,500 34,000 52,500
2153 Potassium hydroxide 1310-58-3 Solid 2 50.50 309 878 3490 6420 9900
2392 Sodium hydroxide 1310-73-2 Solid 5 126.00 773 2200 8720 16,100 24,700
Journal of Chemical Health & Safety, January/February 2012 5
considers potential engineered and
administrative controls necessary to
address the hazardous aspects of the
chemicals and their use. The outcome
of these studies determines that certain
hazardous material inventories cannot
be reduced at TA-55 and TA-50 based
on mission-essential needs. Hazardous
materials in amounts that exceed spe-
cied screening thresholds at TA-55
and TA-50 listed in Table 4 are con-
sistent with amounts documented in
safety bases documents. A signicant
reduction of emergency planning and
response impacts will be achieved, if
hydrochloric acid, chlorine, potassium
hydroxide, and sodium hydroxide are
eliminated from the list. Evidence of
signicant reduction in EPHA hazar-
dous materials would consist of elim-
ination of classication levels and no
protective action distances for hydro-
chloric acid, chlorine, potassium
hydroxide, and sodium hydroxide.
Personnel at ADPSM facilities are
knowledgeable of hazards and risks
they face when working with each
hazardous material in amounts that
exceed the threshold, especially those
found in Table 4. When a measure is
proposed to improve the hazard con-
trol system of hazardous material
operations, all risk factors must be
considered and weighed. For example,
reducing the volume of hydrochloric
acid from 13 to 5 gallon containers
may remove the hydrochloric acid
from Table 5, thereby lowering the risk
to the public, i.e., Site-wide Alerts and
General Emergencies. However, this
means the worker must handle three
containers instead of one; this
increases the likelihood of a chemical
spill. This in turn increases the risk to
the operator. Thus, the overall risk to
the operation may not be lowered. On
the other hand, handling 5 gallon con-
tainers instead of 13 gallon containers
reduces the risk of ergonomic injuries.
Thus, the dispensing of hydrochloric
acid task must be reevaluated before
the volume of hydrochloric acid is
reduced from13 to 5 gallon containers.
No EPIcode calculations have been
performed on the Sodium Hydroxide
(25%) storage tank at TA-50, as shown
in Table 6. The TA-50 EPHAshould be
updated to include this container. For
reasons discussed in the Opportunities
for Long-Term Reductions in Hazar-
dous Materials Section, reducing the
volume of Nitric acid stored at TA-55
to the optimal level, 267 pounds, is not
practical.
In summary, the Labs performance
is judged against dened mission deli-
verables. Deliverables for Hazardous
Material Inventory Reduction consist
of an inventory assessment of hazar-
dous material facilities denoting
opportunities for long-term reduction
of hazardous materials and evidence of
signicant reduction of hazardous
materials. Within TA-55 and TA-50,
EPIcode results present 9 worse case
scenarios for hazardous material. An
inventory assessment of hazardous
material facilities under the manage-
ment of ADPSM has been completed.
No opportunities for long-term reduc-
tion in hazardous materials were
necessary at TA-22. A chlorine genera-
tor acceptable for use at TA-55 would
eliminate classication levels and pro-
tective action distances for chlorine.
Purchasing potassium hydroxide and
sodium hydroxide in containers that
weigh 40 pounds or less at TA-55
and hydrochloric acid in 5 gallon con-
tainer or less at TA-50 would eliminate
classication levels and protective
action distances for these chemicals,
as well. Pursuing these opportunities
will result in a signicant reduction of
hazardous material containers; from 9
to 2. Sodium hydroxide inventory at
TA-50 and nitric acid inventory at TA-
55 cannot be reduced based on mis-
sion-essential needs, i.e., without
increasing the overall risk to the facil-
ity. Initiatives of this type contribute to
ADPSM scientic and technological
excellence by increasing operational
safety.
ACKNOWLEDGEMENTS
The authors would like to acknowl-
edge the U.S. Department of Energy
and LANLs Plutonium Science &
Manufacturing; Environment, Safety,
Health, and Quality; Security and
Safeguards; and Nuclear and High
Hazard Operations directorates for
support of this work.
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