Environmental & Energy Symposium - Apr 04 1 Treatment of Energetic Wastes by Open Detonation at China Lake Laurie Zellmer * Thomas Boggs Therese Atienzamoore

1Environmental & Energy Symposium - Apr 04

Treatment of Energetic Wastes Treatment of Energetic Wastes by Open Detonation at China Lakeby Open Detonation at China Lake

Laurie Zellmer * Thomas BoggsTherese Atienzamoore Brenda Abernathy Eric Erickson Robin NissanRoxanne Quintana Andrew Chafin

30th Environmental & Energy SymposiumSan Diego, CAApril 5 - 8, 2004


Participating Organizations

• NAWCWD China Lake

• NAWS China Lake

• Chemical Compliance Systems, Inc.

• URS Corporation

• W. Mitchell and Associates


Main Topics

• China Lake and its OD Facility

• Permitting and the Original Health Risk Assessment (HRA)

• Efforts to Rework the HRA

1) Emissions Factors Database2) Fate of Metals3) Simulated OD Tests of

Energetic-Contaminated Wastes

• Other HRA Requirements


China Lake• Located in Upper Mojave Desert

- Arid climate- >330 clear days per year

• Navy’s largest Research, Development, Test, & Evaluation (RDT&E) 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


China Lake Mission

• RDT&E 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


Munitions- Expired/Excessed

(Standard Items)- RDT&E (NonStandard

Items)

Laboratory R&D - Leftover scrap from

mixes/casting- Energetic-contaminated

“trash” (e.g. rags, gloves) - Samples - Contaminated solvents

Energetic Wastestreams Generated


Current Method of Treatment

• Open Detonation - Primary method of treatmentRarely Open Burn; Last OB Aug 98

• OD directly on ground (Waste is NOT buried)• Range Limit = 15,000 lbs Explosive Weight


View of OD Facility(One Mile to South & 700 Feet Above)

Arid & MountainousDepth to Groundwater is > 400 feet

1400 Feet Above OD Facility


China Lake’s North Range

Prevailing Wind


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


Original HRALack 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


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


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!


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


Huge Matrix of EF Data

Contd - EFFORT #1: Emission Factor Database

CHEMNAME TEST OD-1

CompB Bulk

TEST OD-2 Exp.D

Bulk

TEST OD-3 RDX

Bulk

TEST OD-4

TNT Bulk Surface

OD

TEST OD-5 TNT 10-m

AGL OD

TEST OD-6

20mm HEI Cart.

TEST OD-7 40mm

HEI Cart.

A1 C1 B1 A1 A1 IIA B1Acenaphthylene 0.00E+00 0.00E+00 0.00E+00 0.00E+00 0.00E+00 0.00E+00 0.00E+00Acetaldehyde a a a a a 0.00E+00 0.00E+00Acetic Acid a a a a a 0.00E+00 0.00E+00Acetone a a a a a 0.00E+00 0.00E+00Acetonitrile a a a a a 0.00E+00 0.00E+00Acetophenone a a a a a 0.00E+00 0.00E+00Acetylene a a a a a 1.80E-04 4.20E-05Acrolein a a a a a 0.00E+00 0.00E+00

Acrylonitrile a a a a a 0.00E+00 0.00E+00Allyl Chloride a a a a a 0.00E+00 0.00E+00Aluminum 0.00E+00 0.00E+00 0.00E+00 0.00E+00 0.00E+00 9.60E-04 1.50E-02Amino-2,6-Dinitrotoluene,4- 0.00E+00 0.00E+00 0.00E+00 0.00E+00 0.00E+00 0.00E+00 0.00E+00Amino-4,6-Dinitrotoluene,2- 0.00E+00 0.00E+00 0.00E+00 0.00E+00 0.00E+00 0.00E+00 0.00E+00Antimony 0.00E+00 0.00E+00 0.00E+00 0.00E+00 0.00E+00 0.00E+00 0.00E+00Arsenic 0.00E+00 0.00E+00 0.00E+00 0.00E+00 0.00E+00 0.00E+00 0.00E+00Barium 0.00E+00 0.00E+00 0.00E+00 0.00E+00 0.00E+00 0.00E+00 0.00E+00

~1000Compounds

EF Data from Over 100 Tests


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?



~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)

Step 1 - Eliminate Compounds


Step 2 - Combine tests into Energetic Families with like emissions

Melt Cast Explosives

A1 TNT based (Comp-B, Cyclotol, Octol)

A2 TNT / Aluminum (H-6)

Plastic Bonded Explosives (PBXs)

B1 Nitramine / binder

B2 Nitramine / binder / aluminum

B3 Nitramine / binder / aluminum / AP

Other Explosives

C1 e.g. PbN3, ammonium picrate

Gun Propellants

IA Single base (NC)

IB Double base (NC / NG)

IC Triple base (NC / NG / NQ)

Rocket/Missile Propellant

IIA Double base with lead

IIB Double Base w/o Lead

IIC AP / binder / Al

IID AP / binder / Al / nitramines (>50% AP)

IIE AP / binder reduced smoke

IIF Nitramine/Energetic Binder/Al/ <20% APP Pyrotechnics

W Energetic Contaminated Wastes (ECW)

PropellantsExplosives

Miscellaneous



No Health Concern

Health Concern

DataNo Data

12

4 3

Benzene

Carbon Dioxide

2-Chloropropane

Graphite

Step 3 - Place each compound into 1 of 4 Quadrants



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

Quadrant 2 How perform HRA for ~250 compounds that

are of a health concern but without data?


~25 Compounds


Second, identified emission factors on a family basis…


Quadrant 2

Can it be formed by this family?No

Ignore for this family

Yes

NoSurrogate EF: Similar compound in same family?

Surrogate EF: Similar compound, similar family?

SWAG: CHEETAH, math treatment of other family, etc.

Use for EF in HRA

YesNoYes

Is it in the top 90% health risk?

Yes

IgnoreNo


TNT (A1) Family - Quadrant 2(With Health Concern but No Data)



Yes

NoSurrogate EF: Similar compound in TNT family?



Use for EF in HRA

YesNoYes


Yes

IgnoreNo

2-Chloropropane





Ignore for this familyYes




Use for EF in HRA

YesNoYes


Yes

IgnoreNo

m-Xylene







Yes




Use nitromethane for EF in HRA

YesNoYes


Yes

IgnoreNo

Nitropropane


Summary• 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!



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


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


Contd - EFFORT #2: Fate of MetalsProof that Metals Casings Fragment

1) Test Data - Lethality studies of weapons where95 - 99% metal recovered as fragments



Proof that Metals Casings Fragment2) Fragments from OD site - Sharp edges; No evidence

of meltingHeavy or light case, steel or

aluminum - No signs of melting

Without melting… No vaporization!



Proof that Metals Casings Fragment3) High Speed Photos (1 million frames/second) - Shows

weapons fragmenting

• Shows initial case deformation/fracture

• Gases escaping• Case fragmentation


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!


Proof that Metals Casings Fragment5) Metallurgical Analysis of OD FragmentProve 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



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



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


EFFORT #3: OD Tests forEnergetic-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


3 TESTS

Detonator: RP-501

Donor: 225 g Comp A-3

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




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


ECW Dioxin Emission Factors

Species Donor EF ECW EFOriginal

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!



SUMMARY• 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)



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

Other HRA Requirements


Contd - Other HRA RequirementsDust 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


Contd - Other HRA RequirementsWindblown 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


Reaction Volume

• EFs divided by the reaction volume = Concentration of species at ground zero

• For simplicity use visual measurements of the dust cloud

Contd - Other HRA Requirements

Actual reaction volume is larger; Reaction gases are invisible

Larger reaction volume produces lower concentrations!

Visual

Actual


Contd - Other HRA RequirementsDispersion 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


Receptors

• Use fenceline

receptors every

22.5 degrees

• Also occupational,

residential, &

sensitive receptors

on- and off-China

Lake property

Contd - Other HRA Requirements

School

Occupational

Hospital

Day Care

China Lake North Range


Contd - Other HRA RequirementsToxicity 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


Contd - Other HRA RequirementsExposure 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


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 site’s location and method of

operation, OD can be environmentally

friendly, especially at a facility like China

Lake’s

Documents

Environmental & Energy Symposium - Apr 04 1 Treatment of Energetic Wastes by Open Detonation at China Lake Laurie Zellmer * Thomas Boggs Therese Atienzamoore