Treatment of Energetic Wastes

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Treatment of Energetic Wastes by Open Detonation
at China Lake
Laurie Zellmer Thomas Boggs Therese
Atienzamoore Brenda Abernathy Eric Erickson
Robin Nissan Roxanne Quintana Andrew Chafin
30th Environmental Energy Symposium San Diego,
CA April 5 - 8, 2004
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• Participating Organizations
• NAWCWD China Lake
• NAWS China Lake
• Chemical Compliance Systems, Inc.
• URS Corporation
• W. Mitchell and Associates

3

• Main Topics
• China Lake and its OD Facility
• Permitting and the Original Health Risk
  Assessment (HRA)
• Efforts to Rework the HRA
• 1) Emissions Factors Database
• 2) Fate of Metals
• 3) Simulated OD Tests of Energetic-Contaminated
  Wastes
• Other HRA Requirements

4

• China Lake
• Located in Upper Mojave Desert
• - Arid climate
• - gt330 clear days per year
• Navys largest Research, Development, Test,
  Evaluation (RDTE) facility
• - Land (orange) 1,100,000 acres or 1700 square
  miles
• - Airspace (blue) 12,500,000 acres or 19,600
  square miles
• Minimal Encroachment
• - Little population growth
• - Mainly surrounded by BLM land

5

• China Lake Mission
• RDTE of weapons systems, software integration,
  and energetic materials
• In performing mission...
• Generate 100,000 to 300,000 pounds of energetic
  waste per year
• - Cannot transport off-CL
• - Must treat on-site

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Energetic Wastestreams Generated
Munitions - Expired/Excessed (Standard
Items) - RDTE (NonStandard Items) Laboratory
RD - Leftover scrap from mixes/casting - Energet
ic-contaminated trash (e.g. rags, gloves)
- Samples - Contaminated solvents
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• Current Method of Treatment
• Open Detonation - Primary method of treatment
• Rarely Open Burn Last OB Aug 98
• OD directly on ground (Waste is NOT buried)
• Range Limit 15,000 lbs Explosive Weight

8
View of OD Facility (One Mile to South 700 Feet
Above) Arid Mountainous Depth to Groundwater is
gt 400 feet
1400 Feet Above OD Facility
9
China Lakes North Range
Prevailing Wind
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• Permitting for China Lake OD Facility
• Currently operates under
• - RCRA (Hazardous Waste) Part A Interim Status
  Permit
• - Clean Air Act Title V Permit
• Permitting Requirements
• - Numerous!
• - Human Health Risk Assessment (HRA)
• HRA Addresses
• - Lifetime risk of developing cancer
• - Potential for chronic non-carcinogenic effects
• - Potential for acute non-carcinogenic effects
• Preparation of original HRA started in early
  1990s with direction from CA EPA

11
Original HRA Lack of Validated Data in early
1990s Lack of Standardized Guidance ? Use of
Overly Conservative Assumptions ? Inaccurately
Inflated Health Risks ? Severe Limitations in
Annual Event Treatment Amounts ?
12
Contd - Original HRA Conflict with Safety
Standards Environmental Regulations Safety
Standards for OD Activities emphasize Avoid
Excessive Unpacking of Waste Items Increased
handling ? Increases probability of incident
(injury/death) Example Leftover energetic mix
placed inside a velostat bag which is placed
inside a bucket Unpacking Removal of the
bucket To comply with inflated health risk
limitations Forced to Unpack Waste
Items Unacceptable! Rework Original HRA
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• Revisions to the Original HRA
• With expertise from our technical codes,
  initiated four major efforts
• 1) Emissions Factor Database
• 2) Fate of Metals (especially from casings)
• 3) Simulated OD Tests for Explosive-Contaminated
  Wastes
• 4) Alternative Technology Assessment (will not be
  discussed, but copies are available)
• Our New Approach
• - Science-based
• - Technically accurate
• - Data-driven
• - Regulatory agencies support!

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EFFORT 1 Emission Factor Database

• Very difficult to collect emission data from
  actual OD events
• - Extreme violence of the detonation prevents
  monitoring emissions at the source
• - Entrained dirt in the detonation plume prevents
  remote monitoring with optical methods until dust
  dissipated
• Turned to detonation tests in controlled
  environments for EF data
• - Bang Box
• - OBODi
• - Fly-through tests at DPG
• - Nevada Test Site

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Contd - EFFORT 1 Emission Factor Database
Huge Matrix of EF Data
EF Data from Over 100 Tests
1000 Compounds
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Contd - EFFORT 1 Emission Factor Database
List of 1000 compounds 1) California Assembly
Bill 2588, Air Toxic Hot Spots Information
Assessment Act (AB2588) - Compounds of health
concern 2) EPA Region IX Preliminary Remediation
Goals (PRGs) - Compounds of health
concern 3) China Lake 1996 original
HRA 4) Compounds from tests Huge matrix How can
we simplify?
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Contd - EFFORT 1 Emission Factor Database
Step 1 - Eliminate Compounds

• 1000 compounds
• Duplicates
• Pesticides / herbicides
• Pharmaceuticals
• Compounds with elements not in parent energetics
  (e.g. Sb, Se)

• 600 compounds remain
• 400 of these are of health risk concern (i.e. on
  the AB2588 and/or PRG lists)

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Step 2 - Combine tests into Energetic Families
with like emissions
Contd - EFFORT 1 Emission Factor Database
Propellants
Explosives
Melt Cast Explosives Melt Cast Explosives
A1 TNT based (Comp-B, Cyclotol, Octol)
A2 TNT / Aluminum (H-6)
Plastic Bonded Explosives (PBXs) Plastic Bonded Explosives (PBXs)
B1 Nitramine / binder
B2 Nitramine / binder / aluminum
B3 Nitramine / binder / aluminum / AP
Other Explosives Other Explosives
C1 e.g. PbN3, ammonium picrate
Gun Propellants Gun Propellants
IA Single base (NC)
IB Double base (NC / NG)
IC Triple base (NC / NG / NQ)
Rocket/Missile Propellant Rocket/Missile Propellant
IIA Double base with lead
IIB Double Base w/o Lead
IIC AP / binder / Al
IID AP / binder / Al / nitramines (gt50 AP)
IIE AP / binder reduced smoke
IIF Nitramine/Energetic Binder/Al/ lt20 AP
Miscellaneous
P Pyrotechnics
W Energetic Contaminated Wastes (ECW)
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Step 3 - Place each compound into 1 of 4 Quadrants
Contd - EFFORT 1 Emission Factor Database
Health Concern
1
2
Benzene
2-Chloropropane
Data
No Data
Carbon Dioxide
Graphite
4
3
No Health Concern
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Quadrant 2 How perform HRA for 250 compounds
that are of a health concern but without data?
Contd - EFFORT 1 Emission Factor Database

• First conducted a Health Risk Screening
• 1) Couple the likely concentrations of ALL
  Quadrant 2 compounds with their toxicities
• 2) Then rank the compounds to identify the
  compounds that contribute the most health risk
• 3) Focus on those compounds that contribute to
  the top 90 of health risks

25 Compounds
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Second, identified emission factors on a family
basis
Contd - EFFORT 1 Emission Factor
Database Quadrant 2
No
Can it be formed by this family?
Ignore for this family
Yes
No
Is it in the top 90 health risk?
Ignore
Yes
No
Surrogate EF Similar compound in same family?
Surrogate EF Similar compound, similar family?
Yes
No
Yes
SWAG CHEETAH, math treatment of other family,
etc.
Use for EF in HRA
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TNT (A1) Family - Quadrant 2(With Health Concern
but No Data)
Contd - EFFORT 1 Emission Factor Database
No
Can it be formed by this family?
Ignore for this family
2-Chloropropane
Yes
No
Is it in the top 90 health risk?
Ignore
Yes
No
Surrogate EF Similar compound in TNT family?
Surrogate EF Similar compound, similar family?
Yes
No
Yes
SWAG CHEETAH, math treatment of other family,
etc.
Use for EF in HRA
23
TNT (A1) Family - Quadrant 2(With Health Concern
but No Data)
Contd - EFFORT 1 Emission Factor Database
No
Can it be formed by this family?
Ignore for this family
Yes
No
Is it in the top 90 health risk?
Ignore
m-Xylene
Yes
No
Surrogate EF Similar compound in TNT family?
Surrogate EF Similar compound, similar family?
Yes
No
Yes
SWAG CHEETAH, math treatment of other family,
etc.
Use for EF in HRA
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Contd - EFFORT 1 Emission Factor Database
TNT (A1) Family - Quadrant 2(With Health Concern
but No Data)
No
Can it be formed by this family?
Ignore for this family
Yes
No
Is it in the top 90 health risk?
Ignore
Yes
No
Surrogate EF Similar compound in TNT family?
Surrogate EF Similar compound, similar family?
Yes
No
Yes
Nitropropane
SWAG CHEETAH, math treatment of other family,
etc.
Use nitromethane for EF in HRA
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Summary
Contd - EFFORT 1 Emission Factor Database

• Identified gaps in the test data
• Simplified management of the database
• Developed logical approach to identify surrogate
  compounds where data lacks but a health concern
  exists (Quadrant 2)
• - These compounds are commonly ignored!

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• EFFORT 2 Fate of Metals in Munitions
• Original HRA assumed that metal casings vaporize
  completely
• Major driver of acute and chronic noncancer risks
• Metal Casings are Designed to Fragment,
• NOT Vaporize

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Contd - EFFORT 2 Fate of Metals Three Types of
Metals in Munitions 1) Additives in
Energetics - Participate in detonation reaction
to form metal oxides - To increase performance
modify burn rate (e.g. Aluminum) - Included in
emission factor database (Effort
1) 2) Paints/Coatings - Very low
concentrations 3) Casings - No chemical
reaction Break apart
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Contd - EFFORT 2 Fate of Metals Proof that
Metals Casings Fragment 1) Test Data - Lethality
studies of weapons where 95 - 99 metal
recovered as fragments
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Contd - EFFORT 2 Fate of Metals Proof that
Metals Casings Fragment 2) Fragments from OD site
- Sharp edges No evidence of melting
Heavy or light case, steel or aluminum - No signs
of melting
Without melting No vaporization!
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Contd - EFFORT 2 Fate of Metals Proof that
Metals Casings Fragment 3) High Speed Photos (1
million frames/second) - Shows weapons fragmenting
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Contd - EFFORT 2 Fate of Metals
Proof that Metals Casings Fragment 4) Heat
Transfer Calculations Prove that OD
temperatures are not hot enough to melt or
vaporize the casing
Without melting No vaporization!
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Contd - EFFORT 2 Fate of Metals
Proof that Metals Casings Fragment 5)
Metallurgical Analysis of OD Fragment Prove that
OD temperatures are not hot enough to melt or
vaporize the casing
Thin feathery edge most susceptible to melting
Edge is not featureless
Rolled edge shows evidence of mechanical
deformation, not intense heat
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• Contd - EFFORT 2 Fate of Metals
• FACT Evidence that casings do not vaporize is
  overwhelming, but need to.
• Refine analysis to account for casing
  particulates
• Combine the amount of metal in the casing with
  available emissions test data
• Example Consider a steel rocket motor casing
  that contains Mn
• (0.4 lbs of steel / lb of energetic) x
• (0.006 lbs Mn / lb of steel) x
• (0.000067 lbs Mn emitted / lb Mn in steel)
• 1.61E-7 lbs Mn emitted / lb of energetic

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• Contd - EFFORT 2 Fate of Metals
• SUMMARY
• Calculations indicate that EFs for metal casings
  are FOUR orders of magnitude lower than the
  original HRA
• Chromium, Nickel, Molybdenum were not
  considered in original HRA, but are in the
  revised methodology

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• EFFORT 3 OD Tests for
• Energetic-Contaminated Waste (ECW)
• ECW Rags, gloves, plastic, aluminum foil, etc.
  contaminated with energetics
• Fuel-rich materials
• - Unlike energetics stoichiometric
• mixtures of fuel oxidizer
• Combustion of fuel-rich materials can generate
  toxic emissions (e.g. dioxins)
  Incinerators
• No emission factor test data for OD of ECW
• Small-scale chamber tests conducted at China Lake

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Contd - EFFORT 3 OD Tests for ECW
3 TESTS Detonator RP-501 Donor 225 g Comp A-3
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Contd - EFFORT 3 OD Tests for ECW
3 TESTS Detonator RP-501 Donor 225 g Comp
A-3 Propellant 140 g AP ECW Sample 11.0 g
Plastic 1.2 g Al Foil 0.4 g Glass 32.5 g Paper
Rags 5 g Acetone
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Contd - EFFORT 3 OD Tests for ECW

• Tests designed to maximize dioxin formation
• Used AP-based energetic
• - High fuel content
• - High chlorine content
• Representative of wastes treated at China Lake

As-Cast ECW AP Mix
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ECW Dioxin Emission Factors
Contd - EFFORT 3 OD Tests for ECW
Species Donor EF ECW EF Original HRA
TEQ as 2,3,7,8-TCDD 1.6e-13 2.0e-11 2.2e-8
Three orders of magnitude lower than original
HRA which used a medical waste incinerator model!
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SUMMARY
Contd - EFFORT 3 OD Tests for ECW

• Within experimental error, all carbon from the
  ECW is present as CO and CO2
• - Proves that reaction (afterburning) is complete
• Except for dioxins, treatment of ECW by OD is
  cleaner than the Comp A-3 donor
• - Likely an artifact of higher temperatures from
  the AP propellant
• The primary driver for health risks (i.e.
  dioxins) is significantly lower than predicted in
  the original HRA (medical waste incinerator model)

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Other HRA Requirements

• Emissions from Munition Components
• Circuitry found in the guidance control
  sections
• Very difficult to determine accurately
• Will add a small percent (to be negotiated) to
  the emissions for the ECW family

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• Contd - Other HRA Requirements
• Dust Emissions from the OD Crater
• Measure volume of craters
• Plot Crater Volume vs Explosive Wt
• For PM10 and PM2.5 emissions, analyze ash samples
  for particle size distribution
• For toxic compounds, use actual soil sample data

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• Contd - Other HRA Requirements
• Windblown Dust
• Use 39 acres includes sides of canyon
  disturbed area
• For PM10 and PM2.5 emissions, use 1985 EPA
  document
• Rapid Assessment of Exposure to Particulate
  Emissions from Surface Contamination Sites
• For toxic compounds, use actual soil sample data
• Dust from Grading
• Use 5.5 acres of disturbed area
• For PM10 and PM2.5 emissions, use EPA AP-42 EFs
  for heavy construction
• For toxic compounds use actual soil sample data

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Contd - Other HRA Requirements

• Reaction Volume
• EFs divided by the reaction volume
  Concentration of species at ground zero
• For simplicity use visual measurements of the
  dust cloud

Actual
Visual
Actual reaction volume is larger Reaction gases
are invisible Larger reaction volume produces
lower concentrations!
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• Contd - Other HRA Requirements
• Dispersion Models
• Upper level mushroom cloud stem of OD plume
• Open Burn/Open Detonation Dispersion Model
  (OBODm)
• Lower level of OD plume including dust
  entrainment
• Industrial Source Complex Short-Term (Version 3)
  (ISCST3)
• Meteorological Data
• Use 4 years of sequential hourly data
• Met station located 1 mile south 700 feet above
  the facility

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Contd - Other HRA Requirements

• Receptors
• Use fenceline receptors every
• 22.5 degrees
• Also occupational, residential, sensitive
  receptors on- and off-China Lake property

China Lake North Range
Occupational
School
Day Care
Hospital
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• Contd - Other HRA Requirements
• Toxicity Values
• Only for Quadrants 1 and 2 compounds
• Use published toxicity values from five sources
  in a priority manner
• Use surrogate compounds where no values exist
• Health Effects
• One in a million cancer risk
• Hazard index 1 for chronic acute non-cancer
  effects

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• Contd - Other HRA Requirements
• Exposure Routes
• Inhalation, ingestion, dermal contact with soil,
  human milk ingestion by infants
• Health Risk Calculations
• Oct 03 CAPCOA Air Toxics Hot Spots (AB2588)
  Program Guidance Manual for Preparation of Health
  Risk Assessments

49

• Conclusions
• China Lake has developed an innovative,
  science-based approach to address potential
  impacts on human health from OD activities
• Reworking of the original HRA lowers health risks
  by several orders of magnitude
• Because of the sites location and method of
  operation, OD can be environmentally friendly,
  especially at a facility like China Lakes