US Army Corps

of Engineers

Construction Engineering

Research Laboratories

Approved for public release; distribution is unlimited.

USACERL Technical Report 98/104

August 1998

Alternatives to Open Burning/Open Detonation

of Energetic Materials

A Summary of Current Technologies

by

James Stratta

Roger Schneider

Neal R. Adrian

Robert A. Weber

Bernard A. Donahue

U.S. Army Ammunition Plants (AAPs) and load,

assemble, and pack (LAP) facilities generate diverse

pyrotechnic, explosive, and propellant (PEP) production

wastes as part of munitions production activities. 

These energetic material (EM) wastes and EM

contaminated wastes (EMCW) continue to be

destroyed by open burning and open detonation

(OB/OD), the most common (“first generation”) method

of EM disposal. Incineration is a currently used,

feasible “second generation” treatment option, but has

enjoyed poor regulator and public acceptance.

Concerns for potential human health risk created by

OB/OD at Army installations as well as environmental

impacts on the air, soil, and water are forcing the Army

to identify and develop alternatives to OB/OD

treatment.

This document summarizes research initiatives by the

U.S. Army Construction Engineering Research

Laboratories (CERL) into several “third generation”

pretreatment and treatment technologies for EM and

EMCW, including: cryogenic cutting, supercritical CO2

extraction and hydrothermal oxidation, hydromilling,

wet air oxidation, hydrothermal oxidation,

biodegradation, and electrochemical treatment. Results

are also given from a waste generation survey of nine

Army Materiel Command (AMC) facilities, and of a

study that characterizes the emissions from burning

propellants under experimental conditions.
USACERL TR-98/104 1

SF 298
2 USACERL TR-98/104

Foreword

This study was conducted for U.S. Army Environmental Center (USAEC) under

Project 4A162720D048, “Industrial Operations Pollution Control Technology”; Work

Unit PE-TH6, “OB/OD Alternatives for Energetic Productions Waste.” The

technical monitor was Wayne Sisk, SFIM-AEC-ETD.

The work was performed by the Troop Installation Operation Division (UL-T) of the

Utilities and Industrial Operations Laboratory (UL), U.S. Army Construction

Engineering Research Laboratories (CERL). The CERL principal investigator was

Sharen A. Kloster. Walter J. Mikucki is Chief, CECER-UL-T; John T. Bandy is

Operations Chief, CECER-UL; and Gary W. Schanche is the responsible Technical

Director, CECER-TD. The CERL technical editor was William J. Wolfe, Technical

Resources.

COL James A. Walter is Commander and Dr. Michael J. O’Connor is Director of

CERL.
USACERL TR-98/104 3

Contents

SF 298 ............................................................... 1

Foreword ............................................................. 2

List of Tables and Figures ............................................... 6

1 Introduction ....................................................... 9

Background ........................................................ 9

Objective ......................................................... 11

Approach ........................................................ 11

Mode of Technology Transfer ......................................... 14

Metric Conversion Factors ............................................ 14

2 Characterization of Air Emissions and Residues From the Combustion of

M31A1E1 ........................................................ 15

Introduction ....................................................... 15

Source Document .................................................. 15

Tests of Environmental Contaminants from the Combustion of Energetics ........ 15

Conclusions ...................................................... 16

Future Research .................................................. 16

3 A Survey of Munitions Production Waste Generation at Army Installations . . 20

Introduction ....................................................... 20

AMC Installation Survey of EM ........................................ 20

Conclusions ...................................................... 24

4 Cryogenic Cutting of EM Production Wastes ........................... 25

Introduction ....................................................... 25

Source Document .................................................. 26

Cryogenic Cutting with High Pressure Liquid Nitrogen (LN2

) .................. 26

Conclusions ...................................................... 26

Future Research ................................................... 27

5 Hydromilling of EM ................................................ 28

Introduction ....................................................... 28

Hydromill Testing .................................................. 28

Safety Issues ..................................................... 35

Conclusions ...................................................... 35

Future Research ................................................... 35
4 USACERL TR-98/104

6 HTO of Energetic Wastes ........................................... 36

Introduction ....................................................... 36

Source Documents ................................................. 37

Alkaline Hydrolysis and HTO of M31A1E1 ................................ 37

HTO of Energetics Using AN and Potassium Dinitramide Phase Stabilized 

Ammonium Nitrate (KDN-PSAN) .................................. 39

Conclusions ...................................................... 40

Future Research ................................................... 40

7 SCCO2

 Extraction and HTO of EM .................................... 41

Introduction ....................................................... 41

Source Document .................................................. 41

SCCO2

 Extraction of M31A1E1 Propellant Components ..................... 41

HTO of SCCO2

 M31A1E1 Extracted Components .......................... 42

Conclusions ...................................................... 43

8 WAO Treatment of EM ............................................. 44

Introduction ....................................................... 44

Source Documents ................................................. 44

Alkaline Hydrolyzed M31A1E1 Treatability ................................ 45

NOSIH-AA2 and Alkaline Hydrolyzed NOSIH-AA2 Treatability ................ 45

AN and KDN as Oxidizers in WAO ..................................... 46

Conclusions ...................................................... 48

Future Research ................................................... 49

9 Compost Feasibility of EM .......................................... 50

Introduction ....................................................... 50

Source Documents ................................................. 50

Feasibility of Composting ............................................ 51

M31A1E1 and NIOSH-AA2 Biodegradation Studies ......................... 52

Regulations Potentially Applicable to Composting .......................... 52

Conclusions ...................................................... 54

Future Research ................................................... 54

10 Electrochemical Processing of Energetic Wastes ....................... 56

Introduction ....................................................... 56

Source Documents ................................................. 56

Electrochemical Deactivation of Energetic Materials for Fuel Cell Application ..... 57

Electrochemical Decomposition of M31A1E1 .............................. 58

Electrochemical Processing of NOSIH-AA2 ............................... 58

Conclusions ...................................................... 59

11 Summary and Recommendations .................................... 60
USACERL TR-98/104 5

Scope of the Munitions Production EM Generation ......................... 60

Assessment of M31A1E1 OB Combustion Products ........................ 60

Pretreatment Alternatives for EM ....................................... 60

Treatment Alternatives for EM ......................................... 61

Future Research Priorities ............................................ 63

Acronyms and Abbreviations ............................................ 64

References ........................................................... 67

Distribution
6 USACERL TR-98/104

List of Tables and Figures

Tables

1 Criteria pollutant and CO2

 emission factors from burning

M31A1E1 ................................................ 16

2 VOC emission factors from burning M31A1E1 .................... 17

3 SVOC emission factors from burning M31A1E1 ................... 17

4 VOC and NMOC emission factors from burning M31A1E1 ........... 18

5 Metal emissions factors from burning M31A1E1 ................... 18

6 SVOC content in residue from burning M31A1E1 .................. 19

7 Metal content in residue from burning M31A1E1 ................... 19

8 Tons of EM and EMCW generated from munitions productions

by installation ............................................. 21

9 LN2

 cutting of energetic material data summary ................... 27

10 M31A1E1 alkaline hydrolysis–carbon products .................... 37

11 M31A1E1 alkaline hydrolysis–nitrogen products ................... 38

12 M31A1E1 alkaline hydrolysis HTO products ...................... 38

13 SCCO2 extraction and HTO treatment of M31A1E1 ................. 42

14 COD destruction by WAO of propellants AN and KDN with

phenol, acetic acid, and biosludge (expressed as %) ............... 47

15 Nitrogen removal from liquid by WAO of propellants AN and

KDN with phenol, acetic acid, and biosludge (expressed as %)

........................................................ 48
USACERL TR-98/104 7

Figures

1 X-Y Table ................................................ 29

2 Cone-Cylinder I ........................................... 30

3 Cone-Cylinder II ........................................... 31

4 Tiered rotosieves .......................................... 32

5 Cylindrical rotobasket ....................................... 33

6 Drum mill ................................................ 34
8 USACERL TR-98/104
USACERL TR-98/104 9

1 Introduction

Background

U.S. Army Ammunition Plants (AAPs) and load, assemble, and pack (LAP) facilities

generate diverse pyrotechnic, explosive, and propellant (PEP) production wastes as

part of munitions production activities. These energetic material (EM) wastes may

consist of excess EM that exceeds production requirements, off-specification EM,

energetics potentially contaminated with foreign substances, or other production

materials contaminated with EM. In addition, EM contaminated waste (EMCW),

or solid wastes with potential EM content are treated similarly to EM. At most

AAP facilities, heterogenous EM and EMCW wastes continue to be destroyed by

open burning and open detonation (OB/OD), the most common (“first generation”)

method of EM disposal since production of such munitions began.

Concerns for potential human health risk created by OB/OD as well as for

environmental impacts on the air, soil, and water is forcing the Army to identify

and develop alternatives to OB/OD treatment. Regulatory requirements vary from

State to State, but are generally becoming more stringent. A major Army concern

is that munitions production at AAPs may be interrupted by State regulatory

requirements that may limit OB/OD disposal operations of production line wastes.

Such limitation would have a direct and adverse effect on the Army’s readiness that

would prove critical in time of national emergency.

At the onset of this research, the scope of the OB/OD problem was still unknown

even though the need to dispose of EM associated with the disposal of obsolete or

recycled munitions has long been recognized. Consequently, the U.S. Army

Construction Engineering Research Laboratories (CERL) evaluated the production

line waste generation at selected facilities. In addition, the chemistry of the

environmental emissions from the OB combustion of propellants burned within an

enclosure was characterized by capturing and analyzing the offgases and residuals.

To enhance the comparison of various treatment and pretreatment alternatives,

two propellants, the triple-base propellant M31A1E1 and the double-base

propellant NOSIH-AA2, were used as “standard energetics” throughout the various

research initiatives (cf. p 37).
10 USACERL TR-98/104

On 28-29 October 1992, CERL hosted a Workshop to gather experts in the area of

PEP production and EM and EMCW disposal to discuss more benign disposal

alternatives. Workshop participants observed that OB/OD alternatives must be:

• reasonably safe

• commercially available, or readily constructed

• cost-effective

• versatile in ability to handle a variety of energetics

• applicable to the Army’s need.

Workshop participants identified six primary treatment alternatives to OB/OD:

1. Incineration

2. Wet air oxidation (WAO)

3. Hydrothermal oxidation (HTO), or supercritical water oxidation (SCWO)

4. Electrochemical destruction

5. Biodegradation

6. Plasma arc destruction.

Incineration, which is considered a feasible “second generation” treatment option,

is currently used to treat an assortment of munition-related wastes at Army

installations. Tooele Army Depot (TEAD) has had experience with various

incineration technologies for years; the Ammunition Peculiar Equipment (APE)

1236 furnace at this location is capable of burning140-180 kg (300-400 lb) of EM per

hour. Past experience has shown incineration to be a safe and effective method of

EM treatment. Unfortunately, incineration has enjoyed poor regulator and public

acceptance—a trend that is not likely to change.

One of the underlying problems associated with the safe destruction of EM wastes

is converting the wastes into a suitable form for treatment and destruction. The

nature of EM wastes and its wide variance in shape and sizes require that process

input be regulated for necessary process control and overall safe operation. In

addition to waste segregation at point of generation, two EM pretreatment process

categories were identified as appropriate and compatible with most treatment

operations and are in need of further evaluation: (1) waste diminution and (2)

dissolution. Diminution is possible largely with hydromilling (cutting) with either

water or liquid nitrogen at very high pressures i.e., up to 380 MPa (55,000 psi). (A

notable difference between water- and liquid nitrogen-cutting is that the liquid

nitrogen process creates no secondary waste stream.) The dissolution of waste

appears most promising when it uses alkaline hydrolysis or supercritical fluid
USACERL TR-98/104 11

extraction. These two pretreatment process categories are part of the CERL

research initiatives described in this report.

These CERL research initiatives represent investigations into “third generation”

alternative pretreatments and treatments for EM and EMCW—efforts to assess the

feasibility of WAO, HTO, electrochemical destruction, and biodegradation as

environmentally friendly replacements for OB/OD and incineration.

Objective

The objective of this summary document was to identify CERL research initiatives

and accomplishments in defining environmentally benign alternatives to OB/OD

destruction of production-related EM.

Approach

This report summarizes investigations into nine areas of research:

1. Combustion Characterization. The PEP Thermal Treatment Evaluation and

Test (PEP-TTET) Facility at Dugway Proving Ground (DPG) was selected as

the test facility for this investigation because of its unique design and past

experience in performing the necessary open-air tests. Approximately 2.3 kg

of M31A1E1 propellant were burned in each of three separate tests. Sulfur

hexafluoride (SF6) was released during each test burn and used as a

simultaneous tracer to accurately determine the emission concentrations. The

weights of emissions for each of the three test burns were averaged and

related to the amount of M31A1E1 propellant actually burned and an

emission factor was developed. Where possible, the standard deviation for

each parameter was provided. The emission factors for airborne parameters

carbon dioxide (CO2

) and the criteria pollutants for airborne volatile organic

compounds (VOCs), semivolatile organic compounds (SVOC), nonmethane

organic compounds (NMOCs), and metals were measured and reported. After

each of the three test burns, the remaining residues were analyzed and the

concentrations of SVOCs and metals in the residues reported.

2. Waste Generation Survey. A questionnaire that addressed the key issues of

energetic waste production was developed and mailed to each of nine Army

Materiel Command (AMC) facilities. The data on each response was validated

and updated through site visits to each installation.
12 USACERL TR-98/104

3. Cryogenic Cutting. A Zero Added Waste Cutting, Abrading, and Drilling

(ZAWCAD) System was tested for use in the diminution (pretreatment) of

selected energetic materials: three propellant samples (M131A1E1, Benite,

and NOSIH-AA2), and three explosive samples (246 trinitrotoluene [TNT],

Composition B, and Composition A5). This research explored the applicability

and efficiency of ZAWCAD on prime, pristine EM samples, and using only

liquid nitrogen.

4. Hydromilling. CERL designed and constructed several pilot scale hydromills

(shown in Chapter 5, “Hydromilling of EM,” pp 29-34) that were tested with

EM and EM simulants at Lone Star Army Ammunition Plant (LSAAP). The

first hydromill tests involved two hydromill cutting systems used in tandem.

The first hydromill, the “X-Y Table” used a set of three rastering highpressure (380 MPa, or 55,000 psi) waterjets in line, with a 15.24 cm. (6-in.)

spacing and common pressurized water manifold to cut EM in a grid pattern.

This device can reduce the EM to chunks with a diameter no greater than 7.6

cm (3 in.). The EM from the X-Y Table was fed to a second hydromill, the

“Cone-Cylinder I,” which further reduced the size of the EM to sugar cube-size

chunks. Subsequent hydromill designs included the Cone-Cylinder II, Tiered

Rotosieves, and the Cylindrical Rotobasket, all of which resulted in the design

and construction of a pilot scale Drum Mill hydromill. Tests included the

cutting of TNT, Comp B, Comp 5A, Benite, M900 tracer composition,

M31A1E1 propellant, NOSIH-AA2 propellant, and other EM simulants.

5. Hydrothermal Oxidation (HTO). The triple-base propellant M31A1E1 was

initially pretreated by hydrolysis with sodium hydroxide for the purpose of

producing soluble products that could be processed further by HTO. HTO was

tested for its ability to successfully and safely convert M31A1E1 into

innocuous end products. The energetic material ammonium nitrate (AN) was

also evaluated as an oxidizing agent as part of the HTO process in treating

and disposing of more conventional waste materials. Experiments were

performed at varying temperatures, residence times, AN, hydrogen peroxide,

and carbon concentrations. Gaseous, liquid, and solid effluents were collected

and analyzed. Proposed reaction mechanisms for AN oxidation of the organic

compounds were presented.

6. Supercritical Carbon Dioxide (SCCO2

) Extraction and HTO. The solubility of

M31A1E1 in SCCO2 was examined by extracting a 207 mg sample for 6 hours

with CO2

 at 313K (40 EC) and 25.5 MPa (3700 psi). Liquid CO2 was pumped

through the M31A1E1 sample at a rate of 0.45 ml per minute. M31A1E1 was

extracted by a similar method. The extract was fed directly into an HTO
USACERL TR-98/104 13

reactor operating at 823K (550 EC), 345 MPa (5000 psi), and 4 mL/min (11 sec

residence time). The oxidant, hydrogen peroxide (H2O2

), was added in an

amount 30 times the stoichiometric requirement. The end products were

analyzed to determine if the extracted components from the M31A1E1 were

destroyed in the HTO reactor.

7. Wet Air Oxidation (WAO). A series of tests were conducted to evaluate the

treatability of M31A1E1 and NOSIH-AA2 by WAO. Alkaline hydrolysis, a

potentially important pretreatment step, was also evaluated as part of this

series of WAO tests. Two other propellants (AN and potassium dinitramide)

were examined as possible oxidizing agents in the WAO process. A number

of different metal alloys were evaluated to obtain information on the best

possible materials to withstand the highly corrosive environments anticipated

in full scale WAO systems.

8. Biodegradation. A literature review was done in the area of biodegradation

of explosives and propellants. Individual components of M31A1E1 and

NOSIH-AA2 were evaluated for biodegradation in the liquid cultures under

aerobic, nitrate-reducing, sulfate-reducing, and methanogenic conditions for

3 months. Tests results on these propellant specimens were based on visual

observations, loss of weight, and changes in tensile strength after exposure to

compost and soil slurries for 45 and 30 days, respectively. A review of

regulations at the Federal and State level was done to determine how

composting facilities for EM may best comply with regulations under Resource

Conservation and Recovery Act (RCRA) and hazardous waste regulations.

9. Electrochemical Treatment. A literature search was done into the physical and

electrochemical properties of energetic compounds, and into the electrochemical behavior of select energetic materials. Laboratory scale experiments on

the electrochemical behavior of nine energetic materials were performed. The

electrochemistry of nitrocellulose (NC), nitroguanidine (NQ), nitroglycerine

(NG), as well as the hydrolyzate of M31A1E1 was evaluated to determine if

NQ and NG can be reduced electrolytically at copper, silver, and gold

electrodes from aqueous carbonate solutions in the region of -0.8 to -1.0 volts.

Alkaline hydrolyzed NOSIH-AA2 propellant was evaluated in a series of

experiments to examine the electrolytic deposition of lead at both cathode and

anodes. Platinum, copper, and nickel were evaluated as possible working

electrode materials to determine if lead can be separated from the alkaline

solutions of NOSIH-AA2 at both the anode and cathode.
14 USACERL TR-98/104

Mode of Technology Transfer

It is anticipated that the information derived from this investigation will form the

basis for further research to develop and implement benign alternatives to OB/OD

destruction and incineration of production-related EM.

Metric Conversion Factors

The following metric conversion factors are provided for standard units of measure

used throughout this report:

1 in. = 25.4 mm

1 ft = 0.305 m

1 sq ft = 0.093 m2

1 cu ft = 0.028 m3

1 cu yd = 0.7645 m3

1 mi = 1.61 km

1 lb = 0.453 kg

1 gal = 3.78 L

1 psi = 6.89 kPa

1 ton = 0.907 metric ton

EF = (EC × 1.8) +32

1 BTU = 1.055 kJ

1 (short) ton = 907.185 kg
USACERL TR-98/104 15

2 Characterization of Air Emissions and

Residues From the Combustion of

M31A1E1

Introduction

The purpose of this research was to generate environmental emissions data from

the burning of energetics to support the development of benign alternatives to OB

and OD operations. The burning of propellant and testing of potential environmental contaminants was performed in the PEP-TTET Facility, also known as the

“Bang Box,” located at DPG, UT. 

Source Document

This research is more completely described in the report: Characterization of

Emissions Produced by the Open Burning Thermal Treatment of M31A1E1 Volume

I and II (Andrulis Research Corporation for CERL, January 1996).

Tests of Environmental Contaminants from the Combustion of Energetics

The triple-base propellant M31A1E1 was selected as a “common standard” for

testing because it contains three common energetic compounds (NG, NC, and NQ),

the common gelatinizer dibutylphthalate, and the stabilizer/gelatinizer centralite,

because it and has both good physical characteristics and representative thermodynamics. Consequently, M31A1E1 was the only energetic burned and tested as part

of this research.

The PEP-TTET Facility at DPG was selected as the test facility for its unique

design and past experience in performing such contained open-air tests. The PEPTTET Facility consists of a 1000 m3

 hemisphere and attached airlock. The

hemisphere is constructed of a plasticized fabric that stretches to accommodate

detonation-produced shock waves. Two regulated high-capacity blowers continually

inject filtered air into the Facility to inflate the hemisphere. A variety of state-of-
16 USACERL TR-98/104

Compound Average wt/wt Std Dev wt/wt

CO2 6.45e-01 1.18e-03

CO 1.66e-04 2.25e-05

NO 1.16e-03 2.59e-05

NO2 9.61e-05 8.40e-07

SO2 1.21e-03 6.05e-06

O3 2.91e-05 7.79e-07

Table 1. Criteria pollutant and CO2

 emission

factors from burning M31A1E1.

the-art air sampling and analysis equipment is available to characterize the

emissions from the combustion of energetics. Residues from the combustion were

also collected and analyzed. The limits on the amounts of energetic that can be

burned or detonated in the PEP-TTET Facility are 227 g of explosive and 2.7 kg of

propellants.

During this research, approximately 2.3 kg of M31A1E1 propellant was burned in

each of three separate tests. SF6

 was released during each test burn and used as

a simultaneous tracer to accurately determine the emission concentrations. The

weights of emissions for each of the three test burns were averaged and related to

the amount of M31A1E1 propellant actually burned and an emission factor was

developed. These emission factors related the weight of each emission parameter

to the weight of propellant burned. Where possible, the standard deviation for each

parameter was provided. Table 1 lists the emission factors for airborne parameters

CO2

 and the criteria pollutants. Tables 2, 3, 4, and 5 list emission factors for

airborne VOCs, SVOC, NMOCs, and metals, respectively. Tables 6 and 7 list the

residues remaining after each of the three test burns was analyzed for concentrations of SVOCs and metals in the residues, respectively.

Conclusions

The emission factors developed from the burning of M31A1E1 can be used to

determine the potential pollutants generated from the combustion of triple-base

propellants, their potential human health risk, and their potential environmental

impact on air, soil, and water.

Future Research 

Future research in this area should be

devoted to developing other EM emission factors data and using this information to ascertain the comparative

health risk associated with OB/OD and

other alternatives used to dispose of

EM.
USACERL TR-98/104 17

VOC Average wt/wt Std Dev wt/wt

CCL2F2 (F-12) <2.79e-07 ND

CH3CL <2.55e-07 ND

CCLF2

-CCLF2 (F-114) <1.21e-09 ND

CH3

-CH2CL <6.54e-08 ND

CCL3F (F-11) <5.84e-08 ND

CH2=CCL2

 (Vinylidene chloride) <1.03e-07 ND

CH2CL2

 (Methylene chloride) <6.40e-07 ND

CCL2F-CCLF2

 (F-113) <2.11e-08 ND

CHCL3

 (Chloroform) <6.60e-09 ND

CH3

-CCL3 (Methylchloroform) <2.81e-08 ND

benzene <8.85e-07 ND

CCL4 <4.42e-08 ND

toluene <1.92e-07 ND

ethylbenzene <1.84e-07 ND

m&p-xylene <6.67e-07 ND

styrene <1.78e-08 ND

o-xylene <3.12e-07 ND

p-ethyltoluene <2.87e-08 ND

Table 2. VOC emission factors from burning M31A1E1.

SVOC Average wt/wt Std Dev wt/wt

benzyl alcohol 3.91e-08 4.34e-09

a,a-dimethylphenethylamine <1.33e-08 ND

dimethyl phthalate 1.09e-07 8.38e-09

4-nitrophenol <6.31e-08 ND

diethyl phthalate 6.19e-08 6.57e-09

4-nitroaline <1.34e-08 ND

di-n-butyl phthalate <3.30e-07 ND

dimethoate <9.96e-08 ND

4-aminobiphenyl <1.33e-08 ND

butylbenzyl phthalate <7.92e-08 ND

bis(2-ethylhexyl) phthalate <1.23e-08 ND

di-n-octyl phthalate 7.33e-08 4.72e-09

Table 3. SVOC emission factors from burning M31A1E1.
18 USACERL TR-98/104

Compound Average wt/wt Std Dev wt/wt

Alkenes (olefins) 2.21e-06 5.25e-07

Aromatics 2.33e-06 1.36e-06

Total unidentified hydrocarbons 1.80e-05 1.26e-05

Total nonmethane hydrocarbons 2.17e-05 1.36e-05

1,3-Butadiene <8.07e-06 ND

benzene <1.40e-07 ND

toluene <2.11e-07 ND

TO-12 (NMOC) 9.18e-05 6.44e-06

Table 4. VOC and NMOC emission factors from burning M31A1E1.

Metal Average wt/wt Std Dev wt/wt

Aluminum <2.22e-07 ND

Antimony ND ND

Arsenic ND ND

Barium 3.82e-07 3.55e-08

Cadmium ND ND

Calcium 1.50e-05 9.39e-07

Chromium 3.38e-07 5.51e-08

Copper 4.42e-06 2.40e-06

Lead ND ND

Mercury <1.43e-09 ND

Nickel <8.36e-08 ND

Potassium 1.79e-03 1.92e-05

Sodium 7.57e-05 1.56e-05

Titanium 4.36e-08 2.25e-08

Zinc <7.47e-07 ND

Table 5. Metal emissions factors from burning

M31A1E1.
USACERL TR-98/104 19

SVOC Average ug/kg

benzyl alcohol 1300

2-methylphenol (o-Cresol) 1000

nitrobenzene 180

2-nitrophenol 100

dimethyl phthalate 67

2,6-dinitrotoluene 63

2,4-dinitrotoluene 66

diethyl phthalate 270

N-nitrosodiphenylamine 200

di-n-butyl phthalate 2500

butylbenzyl phthalate 580

bis(2-ethylhexyl) phthalate 2400

di-n-octyl phthalate 4400

biphenyl 47

Table 6. SVOC content in residue from burning

M31A1E1.

Metal ug/kg

Aluminum 340

Antimony BDL

Arsenic BDL

Barium 56

Cadmium 1.9

Calcium 7100

Chromium 15

Copper 14

Lead 14

Mercury 0.26

Nickel 6

Potassium 150000

Sodium 6400

Titanium 7.2

Zinc 82

Table 7. Metal content in residue

from burning M31A1E1.
20 USACERL TR-98/104

3 A Survey of Munitions Production Waste

Generation at Army Installations

Introduction

U.S. Army installations that manufacture munitions generate a significant amount

of EM. Disposal of this waste and outdated ammunition must comply with Federal,

State, and local regulations. Such regulations vary significantly from State to

State. In the past, most munitions waste has been disposed of by OB/OD.

However, OB/OD has become an environmental concern, and few disposal

alternatives have been yet developed. Failure to develop suitable disposal

alternatives that comply with all environmental regulations is likely to result in the

potential, or actual, termination of munition production operations during critical

times of national emergency. To assess the disposal requirements, an evaluation

of the scope of the EM generation is required. This is the first study to assess the

scope of EM generation. Based on this information, the Army will be better able to

assemble a strategy to develop the necessary technologies required to dispose of

these wastes in an environmentally acceptable manner.

AMC Installation Survey of EM

An EM waste generation survey was initially coordinated with AMC Headquarters

to determine the AMC installations most likely to need EM disposal alternatives

into the next century. Nine facilities were identified. A questionnaire to address

the key issues of energetic waste production was developed jointly between CERL

and AMC. This questionnaire was mailed to each of the nine facilities. After each

installation responded, the data on each response was validated and updated

through site visits to each installation. Table 8 summarizes the EM production

data for each installation.
USACERL TR-98/104 21

Installation EM* EMCW

Radford AAP 990 3700

Redstone

Arsenal 170 50

Lonestar AAP 160 140

Holston AAP 110 1200

Crane AAA 93 44

McAlester AAP 30 19

Iowa AAP 24 422

Milan 13 480

Lake City AAP 9 0

Table 8. Tons of EM and EMCW

generated from munitions

productions by installation.

Radford Army Ammunition Plant (RAAP)

RAAP manufactures TNT, NC, NG, and single- and

multi-based propellants. The current level of activity

is relatively low. EM waste is disposed of by either OB

or incineration; EMCW is disposed of by OB. OB of

EMCW comprises 47 percent of all waste disposal over

the 5-year period. OD activities are not conducted at

RAAP.

OB operations are conducted at the propellant burning

grounds, in an air curtain destructor (ACD) without air

pollution controls, and in a decontamination burning

pit. Ash is tested for hazardous constituents and is

then disposed of accordingly. Some OB operations are

close to the plant’s boundary, which is a navigable

waterway. The State of Virginia has cited RAAP for

the OB operations’ proximity to the waterway.

Redstone Arsenal

Most EM waste generated is production-related waste associated with the

production of rocket motors. The OB area is relatively small, and weather limits

its operations. OB occurs about 150 to 200 days a year. EM is not transported to

the burning ground until it is ready for disposal. The waste is normally disposed

of within 90 days. Ash is held in a permitted igloo, and is then tested for metals

and explosives. Metals from the burning operations go to a Defense Reutilization

and Marketing Organization (DRMO) for disposal. OD operations are very limited,

with only five firing points. OD operations are conducted approximately 50 days

a year. Redstone Arsenal received a Notice of Violation (NOV) for allowing ashes

to touch the ground in 1992.

Lonestar Army Ammunition Plant (LSAAP)

LSAAP produces high explosives, propellants, and pyrotechnics. LSAAP disposes

of EM and EMCW, and demilitarizes obsolete munitions. OB and OD operations

are carried out throughout the year. OB operations are conducted about 130 days

a year. Such operations occur on elevated pans that can burn either EM or EMCW

or on a large, on-grade burn pad with a leak-detection system. EM waste is

transported from the generation points to an EM storage building before disposal.

No EM waste is stored for more than 90 days. Ash is tested, then transported to a
22 USACERL TR-98/104

hazardous waste landfill as hazardous. Only EM or demilitarization items are

disposed of through OD. EM for OD are stored in igloos for up to 180 days. OD

activities occur about 140 days a year. The State of Texas increased its scrutiny of

LSAAP in recent years, but the plant has yet to receive an environmental citation.

Holston Army Ammunition Plant (HAAP)

HAAP manufactures RDX (cyclotrimethylenetrinitramine) and HMX (cyclotetramethylenetetranitramine) base explosives and explosive products made of RDX and

HMX. The EM generated is composed mainly of RDX and HMX. The EMCW

generated is primarily composed of paper, plastic bags, pallets, boxes, liners, piping,

and other items potentially contaminated with EM. EMCW disposal accounted for

92 percent of all material disposed of during the surveyed time.

All waste at HAAP is disposed of through OB; HAAP has no OD activities. EM is

burned in clay-lined, elevated pads. The burning is relatively clean, and generates

little ash. Any ash that remains is taken to an on-post landfill for nonhazardous

waste. The pans are drained to the wastewater treatment plant (WWTP). EMCW

disposal occurs either on pads or in large cages. Flashing is done outside the OB

grounds in decontamination ovens, or in one of the EMCW piles. HAAP has not

received an environmental citation since 1986.

Crane Army Ammunition Activity (CAAA)

CAAA produces and renovates conventional ammunition and ammunition-related

components. CAAA also receives, ships, and/or demilitarizes and disposes of

conventional and related munitions. The munitions production operations that

generate EM and EMCW include: (1) casting explosives, (2) press loading of

projectiles and boosters, (3) preparation of primers, (4) production of pyrotechnics

such as red phosphorus and illumination rounds, and (5) renovation of old rounds.

An APE 1236 deactivation furnace is used to dispose of small items such as fuses,

detonators, and small arms ammunition.

OB operations are carried out on the ammunition burning grounds (ABG) and the

old rifle range (ORR). The OB operation schedule varies due to weather throughout

the year, but usually disposal occurs more than 200 days per year. Ash is

temporarily stored on the facility, and is then disposed of in an offsite hazardous

waste landfill. OD operations are conducted on about 120 days from April until

November. No ash is removed from OD operations. Metal is removed for scrap.
USACERL TR-98/104 23

McAlester Army Ammunition Plant (MCAAP)

MCAAP activities include the production and renovation of conventional ammunition and ammunition-related components and the demilitarization and disposal of

conventional ammunition and related items. EM makes up approximately 1 to 2

percent of the total amount of waste disposed of by OB/OD. OB is regularly

scheduled for demilitarization operations, but not for production waste due to

variations in the production schedules. OB occurs about 200 days a year. EM from

production operations is stored in the original manufacturer’s container (or its

equivalent). EMCW is packaged in cardboard containers.

OD operations occur about 100 days a year. MCAAP has not received any NOVs

associated with OB/OD operations. An inactive APE 1236 is being upgraded.

Iowa Army Ammunition Plant (IAAP)

IAAP conducts LAP operations for ammunition such as small boosters, mines,

cratering charges, artillery rounds, missile warheads, and cluster bombs. EM waste

includes scrap explosives and propellants and sludges from wastewater treatment

operations and the processing of explosives, and a small amount generated from

developmental laboratories. EM is occasionally sold to approved buyers. EMCW

waste includes explosive-contaminated solvents, explosive-contaminated carbon,

and other EM-contaminated solid wastes such as paper, plastic, cardboard, and

wood.

OB and OD operations have been scaled back significantly since December 1992.

OB operations are restricted to flashing of EM-contaminated waste, and emergency

situations. OD operations are limited to ammunition, and only when immediate

disposal of the item is necessary because of safety considerations.

IAAP uses a combination of an explosive waste incinerator (EWI), a contaminated

waste processor (CWP), and a deactivation furnace to dispose of EM and EMCW

waste. The EM waste is held in igloos until it enters the incinerator unit. All ash

from the EWI is considered hazardous. EWI air-pollution control equipment

includes a cyclone and baghouse. IAAP has received no NOVs for OB/OD activity.

Milan Army Ammunition Plant (MAAP)

MAAP’s OB operations include the load, assemble, and pack of ammunition and the

demilitarization of obsolete, conventional ammunition. MAAP’s OB operation
24 USACERL TR-98/104

includes the disposal of wastes from demilitarized munitions, as well as from LAP

operations.

MAAP has facilities for both burning of waste and flashing of contaminated

material. Waste is stored in containers throughout the facility before disposal. The

waste goes into storage if it is not burned in 48 hours. Ash is routinely tested, and

if the ash is hazardous, it is disposed of offsite. All OD operations are conducted

underground, in one of two subareas of the ammunition destruction area. MAAP

has received no NOVs associated with its OB/OD activites.

Lake City Army Ammunition Plant (LCAAP)

LCAAP manufactures small caliber ammunition and associated explosive and

pyrotechnic materials, and demilitarizes selected obsolete, conventional munitions.

LCAAP is unique in that no EMCW that needs disposal is currently generated.

Contaminated gloves are cleaned and containers are recycled. The EM produced

is disposed of mostly through the explosive waste incinerator (EWI), with OB

operations now reduced to flashing and occasional nonroutine use. When the

survey was conducted, OB operations were conducted two to three times a week.

Chromium emission levels were of some concern at the EWI. OD operations are

conducted only in emergency situations.

LCAAP has two facilities for dealing with the liquid discharge from its munitions

production. A wastewater treatment plant neutralizes the wastes produced from

the pyrotechnics production, and the remaining nonhazardous solution is slowly fed

into the sewer. A neutralized explosive wastewater treatment plant (NEWTP)

deals with the wastewater produced from lead-based initiating explosives.

LCAAP has received no environmental citations.

Conclusions

The amount of EM and EMCW generated from munitions production activities is

significant. Data over a 5-year period for the nine Army installations showed the

total amount of EM and EMCW generated annually were 1600 and 6100 tons,

respectively.

Some installations are beginning to use alternative disposal methods, but OB/OD

continues to be the primary means of disposal. Pressures from some States have

forced installations to reduce OB/OD in favor of alternative disposal methods such
USACERL TR-98/104 25

as incineration. A realistic approach to establishing alternative energetic waste

disposal methods can be formulated based on this study, which has determined the

amounts and types of energetic wastes generated at U.S. Army installations.
26 USACERL TR-98/104

4 Cryogenic Cutting of EM Production

Wastes

Introduction

U.S. Army Ammunition Plants and LAP facilities generate diverse PEP production

wastes, which can take the form of EM or EMCW, “off-spec” product, EM

contaminated with foreign substances, or processing equipment and materials

contaminated with EM. The EM wastes may be contaminated with tramp metals,

rocks, glass, wood, and other extraneous materials. Diminution, or size reduction,

is an essential pretreatment step for all viable subsequent energetic waste

treatment options. The smaller the size of the individual pieces of waste, the

greater the treatability of the waste as well as the improved process control.

However, conventional bladed grinding or shearing equipment cannot be used to

effect diminution because of the unknown ingredients of these wastes.

Hydromilling with high pressure water up to 380 MPa (55,000 psi) was evaluated

as a possible size reduction, or diminution, technology. Hydromilling is promising,

but, since it produces a flow of water, it introduces another stream of materials that

requires collection and treatment before final disposal. Cutting with liquid nitrogen

pressurized up to 372 MPa (54,000 psi) produces a stream, which, after cutting,

evaporates and leaves no secondary waste requiring segregation and treatment.

The original energetic waste, cut into many small pieces, is the only material left

behind requiring final treatment and disposal.

The objective of this study was to investigate the use of the ZAWCAD System for

the diminution of selected energetic materials. The study tested three propellant

samples: M131A1E1, Benite, and NOSIH-AA2; and three explosive samples: TNT,

Composition B, and Composition A5. The study was done by Lockheed Martin

Idaho Technologies, Inc. (LMIT) personnel at the Idaho National Engineering

Laboratory, Idaho Falls, ID.
USACERL TR-98/104 27

Source Document

Cryogenic cutting of explosives and propellents using liquid nitrogen is described

in more detail in the report: Marcela R. Stacey, Cryogenic Cutting of Energetic

Material Production Wastes (Lockheed Martin Idaho, Inc. at the Idaho National

Laboratories, Idaho Falls, ID, for CERL, undated).

Cryogenic Cutting with High Pressure Liquid Nitrogen (LN2)

The ZAWCAD system, which has been used to cut many other materials, is similar

to other high-pressure cutting systems. The LN2

 can be pressurized up to 400 MPa

(60,000 psi), after which the LN2

 is ejected through a small orifice at velocities of

greater than 900 m/s (3,000 ft/sec). The system includes a cryogenic fluid supply

system (LN2

), a pressurization system, a temperature control system, a nozzle

system, a recovery system, and a manipulation system. The pressurization system

uses intensifiers with the potential to increase the pressure of the LN2

 from 100 to

400 MPa (15,000 to 60,000 psi). After pressurization, the LN2

 is cooled to less than

–140 EC. The LN2

 flow rates are variable from 1 to 10 L/min (0.25 to 2.5 gal/min).

The manipulation system, which is computer controlled, positions the material to

be cut beneath the jet, executes cuts of varying thickness, and varies the cutting

rate from 0.003 to 19 mm/second (0.0001 to 0.75 in./second). The ZAWCAD

enclosure is made of lexan panels of thickness from 1.3 to 4 cm (0.5 to 1.5 in.), with

top and bottom vents. The enclosure is evacuated with a recovery system which

filters the exhausted air at 3.5 sm3

/m (125 scfm).

The ZAWCAD system cut the selected explosives and propellent EM samples safely

and easily. The cryogenic jet easily passed through the specimens without any

detonation, deflagration, ignition, or scorching. Table 9 summarizes the data

gathered during this study. (A video is also available.) Note that this research

explored the applicability and efficiency of ZAWCAD on prime, pristine EM

samples, and using only LN2

.

Conclusions

LN2 cryogenic cutting is a very promising pretreatment diminution technology for

EM and EMCW. The ZAWCAD process, using cryogenic LN2

 cutting, is capable of

cutting the selected EM easily and safely without detonation, deflagration, ignition

or scorching. After processing with the cutting system, the explosive and propellant

materials were quite small and ranged in size from 0.008 to 6.1 mm (0.0003 to 0.24
28 USACERL TR-98/104

Parameters

Propellant Explosive

M31A1E1 Benite NOSIH-AA2 TNT Comp B Comp A5

LN2

 Pressure–MPa

(psi)

359 (52,000) 359 (52,000) 365 (53,000) 372 (54,000) 345 (50,000) 345 (50,000)

LN2

 Temperature–K

(EC)

148 (-125) 148 (-125) 151 (-122) 147 (-126) 147 (-129) 143 (-130)

Max Particle Size–mm

(in.)

5.0 (0.197) 0.5 (0.02) 6.1 (0.24) 3.0 (0.12) 0.2 (0.008) 0.96 (0.038)

Min Particle Size–mm

(in.)

0.008 (0.0003) 0.013 (0.0005) 0.02 (0.0007) 0.02 (0.0009) 0.1 (0.0038) 0.1 (0.0037)

Feed Rate–m/sec (

in/sec)

0.6 (0.25) 0.6 (0.25) 0.6 (0.25) 0.6 (0.25) 0.6 (0.25) 0.6 (0.25)

Table 9. LN2 cutting of energetic material data summary.

in.). These sizes are well-suited for processing in subsequent waste treatment

processes such as wet air oxidation, hydrothermal oxidation, incineration, and

composting.

While these limited tests were performed on pure propellent and explosive

specimens, future research should use actual AAP production wastes with the

assortment of adjunct materials that are found in these waste streams. This

suggests other areas for future research: adding solid carbon dioxide (SCO2

)

particles to the cutting jet, varying the feed rate, and expanding the array of EM

wastes.

Future Research

Future research should explore the effects of adding solid carbon dioxide (SCO2)

particles in the jet for abrasive augmentation. Additional areas of immediate future

research include cutting other EM and investigating associated factors such as

geometries (shapes and sizes) and contamination. Also, other future efforts towards

integrating the cutting process with disposal procedures would provide the Army

valuable information on a complete and self-contained waste treatment and

disposal system.
USACERL TR-98/104 29

5 Hydromilling of EM

Introduction

Alternative treatment technologies to OB/OD require that EM be reduced in size

to make the waste compatible with the EM feed mechanism, as well as with the

overall quality control requirements of the respective EM treatment systems.

Because EM production wastes can be contaminated with tramp metals, rocks,

glass, wood, and other extraneous matter, conventional metal-bladed grinding or

shearing equipment cannot be used safely to cut the EM into small pieces. One

solution is to use a narrow, high-velocity stream of water pressurized up to 380

MPa (55,000 psi) in a hydromill to cut EM safely. Based on concepts and advice

provided by AAP personnel, and industry and explosives experts, CERL designed

and constructed several pilot-scale hydromills that were tested with EM and

simulants at LSAAP.

Hydromill Testing

The first hydromill tests involved a pair of tandem hydromills. The first hydromill,

the “X-Y Table” (Figure 1) was a pilot-scale mill with a set of three, in-line,

rastering high-pressure waterjets with a 6-in. (15.2 cm) spacing and common

pressurized water manifold. Large pieces of EM, roughly the size of a loaf of bread,

were placed on a 19-in. (48.26 cm) square perforated platen. The X-Y Table was

designed to cut the EM in a grid pattern; the EM was held in place while the

manifold traversed over the platen in the X direction, was rotated 90 degrees, then

traversed over the platen in the Y direction. Additional cuts were possible to reduce

the EM to chunks the largest dimension of which would not exceed 3 in. (7.62 cm).

The cut EM from the X-Y Table was fed to a second hydromill. This hydromill, the

“Cone-Cylinder I” (Figure 2) was designed to receive the feed manually from the X-Y

Table and further reduce the size of the EM to sugar cube-size chunks. The ConeCylinder I is comprised of a 15-in. (38.1 cm) long, truncated sheet metal cone

surrounded by a wire mesh basket of uniform diameter. The cone and basket

rotated along the longitudinal axis, oriented 30 degrees from the vertical. Waterjets

positioned within the metal cone and spraying outward through slots cut EM
30 USACERL TR-98/104

Figure 1. X-Y Table.

passing downward over the outside of the cone within the basket. A 1 cm (0.5-in.)

space at the bottom between the cone and basket was intended to determine the

final dimension of the EM. While the X-Y Table worked well, the Cone-Cylinder I

hydromill did not work as intended. Surrogate materials and Comp B were forced

against the basket wall by the water jets and did not descend through the basket.

Subsequent hydromill designs including the Cone-Cylinder II (Figure 3), Tiered

Rotosieves (Figure 4), and the Cylindrical Rotobasket (Figure 5) have all contributed to improving the design of the cutting system. The tests have included the

cutting of TNT, Comp B, Comp 5A, Benite, M900 tracer composition, M31A1E1

propellant, NOSIH-AA2 propellant, and other EM simulants. The experience with

these systems has resulted in the design and construction of a pilot scale Drum

hydromill. The Drum Mill (Figure 6) is constructed of a substantially modified, 55-

gal, stainless steel drum. The Drum Mill has an internal oscillating waterjets

manifold and an internal fixed flight; the mechanism is tilted about 20 degrees from

the horizontal on its side. Like its predecessor, the Drum Mill must be loaded and

unloaded by hand.
USACERL TR-98/104 31

Figure 2. Cone-Cylinder I.
32 USACERL TR-98/104

Figure 3. Cone-Cylinder II.
USACERL TR-98/104 33

Figure 4. Tiered rotosieves.
34 USACERL TR-98/104

Figure 5. Cylindrical rotobasket.
USACERL TR-98/104 35

Figure 6. Drum

mill.
36 USACERL TR-98/104

Safety Issues

The high pressure waterjets of the hydromills represents a safety hazard even in

the absence of the EM. Waterjets, which can cut EM, plastics, and soft metals,

therefore present a potential hazard to humans particularly during system setup

and maintenance. Hydromilling can potentially generate flying objects that can

present a safety hazard. Care was taken to examine each series of tests and

evaluate any potential hazards and take appropriate control measures. These

control actions included: implementing appropriate lockout-tagout procedures,

using personal protective equipment, separating personnel from the testing area by

distance and shielding, isolating the hydromilling test area, installing hydromill

shields to limit waterjet induced projectiles, providing adequate area ventilation for

EM components, implementing appropriate electrical grounding and bonding with

associated continuity testing, collecting and appropriately disposing of all cutting

residues, and training staff on the operation of critical equipment.

Conclusions

Hydromilling of EM is being shown to be an effective and safe pretreatment

alternative. The Drum Mill is anticipated to provide a critical link in successfully

demonstrating that high pressure water cutting can reduce the size of EM feed to

meet a variety of treatment system demands.

Future Research

Future research requirements in the area include the design and construction of

safe and reliable feed and discharge assemblies that will make hydromilling a

continuous processor. These assemblies will include feed and discharge weighing

conveyors to control the quantity of EM in the mill and associated operating

parameter sensors. Once complete, a greatly enhanced variety of EM should be

processed to evaluate the mill’s capabilities. A full-scale pilot test of this Drum Mill

in association with a EM treatment system such as composting or hydrothermal

oxidation is needed.
USACERL TR-98/104 37

6 HTO of Energetic Wastes

Introduction

HTO, or SCWO, as it was earlier known, is one method of treating waste energetics

that may prove safe and effective. This process combines waste with an oxidant

(air, oxygen, hydrogen peroxide, or other oxidizing agents) in water at pressures

and temperatures above the critical point of water (647.3K and 22.12 MN/m2

 [374

EC and 217.7 atm]). This process has been successfully demonstrated in the

treatment of many waste streams. High destruction and removal efficiencies

(DREs) have been reported for a broad range of common solid and liquid wastes,

including chlorinated aromatic solvents. HTO has been shown to reduce these

relatively complex substances to simple and innocuous products such as water,

carbon dioxide, nitrogen gas, and inorganic salts. In HTO, the wastes and oxidant

are mixed in water above the critical point. Above the critical point, the water

solution has transport properties like that of a gas; mixing and reactions occur very

rapidly. Because the temperature of the reactions is lower than that normally

encountered in incineration, nitrogen oxides and char production are greatly

reduced. The heat of the reaction is absorbed by the process. HTO oxidation occurs

rapidly, in the order of only seconds or minutes. 

HTO operations have been examined by regulators and are considered to be “treatment operations other than incinerators.” This is important since HTO treatment

systems are not then subject to the same rigorous permitting process as is

incineration, and does not receive the negative stigma associated with incineration.

Public acceptance of HTO disposal operations can be expected to be far more

favorable than incineration, or the current OB/OD.

Research examined the ability of HTO to successfully and safely convert the triplebase propellant, M31A1E1, into innocuous end products. In addition, AN and

potassium dinitramide-AN mixtures were evaluated as oxidizing agents as part of

the HTO process in treating and disposing of more conventional waste materials.
38 USACERL TR-98/104

Product

Product 

ppm

C 

ppm (%)

formate (HCOO-

) 860 230 (3)

oxylate (O2CCO2

2-) 1100 310 (3)

cyanate (OCN-

) 3600 1000 (12)

urea (OC(NH2

)2) 5700 1100 (13)

propionate (CH3CH2COO-

) 6900 3400 (39)

TIC (CO3

2-,HCO3-

) 2500 2500 (29)

Total C 8600 (99)

Table 10. M31A1E1 alkaline hydrolysisBcarbon products.

Source Documents

The work on alkaline hydrolysis and HTO of M31A1E1 is detailed in the report:

Stephen J. Buelow, Research and Development for Alternatives to Open

Burning/Open Detonation of Waste Propellants, Explosives and Pyrotechnics:

Alkaline Hydrolysis and Supercritical Water Oxidation of M31A1E1 (Los Alamos

National Laboratory for CERL, undated).

The research on the use of energetics as HTO oxidizing agents is elaborated in the

report: Petra I. Proesmans, Li LAN, and Stephen J. Buelow, Use of Reclaimed

Ammonium Nitrate as an Oxidizer for the Hydrothermal Oxidation of Organic

Wastes (Los Alamos National Laboratory for CERL, undated).

Alkaline Hydrolysis and HTO of M31A1E1

The triple-base propellant M31A1E1 was initially pretreated by hydrolysis with

sodium hydroxide to produce soluble products that could be further processed by

HTO. The alkaline hydrolysis process was relatively simple. Approximately 1.2 g

of sodium hydroxide was added per gram of propellant and the mixture was heated

at 366K (93 EC), at Los Alamos altitude (2225 m, or 7300 ft) for about 30 minutes.

The reaction was vigorous, but not violent. Mass spectrometry of the hydrolysis

products revealed no detectable amounts of any of the propellant bases or other

primary components. Tables 10 and 11 show the carbon and nitrogen components

and mass balances of the alkaline hydrolysis products. These mass balances

account for essentially all the carbon and nitrogen and indicate that the components

of the M31A1E1 are completely converted to oxyanions of carbon and urea. Most

of the carbon is converted to carbonate and propionate. The bulk of the nitrogen is

given off as N2O gas, and the remaining nitrogen in solution is primarily nitrate

and nitrite.

Hydrolyzed solutions of M31A1E1

were processed within an HTO

reactor. Reactions were

conducted at 873K (600 EC) and

34.5 MPa (5000 psi). The HTO

reactor flow rate was 4 mL/min,

which resulted in a reactor

residence time of 11 seconds. The

hydrolysis product feed was

limited to 5 percent by weight
USACERL TR-98/104 39

Product

Product

ppm

N

ppm (%)

ammonium (NH4

+

) 310 240 (1)

nitrate (NO3

-

) 4200 950 (5)

nitrite (NO2

-

) 5900 1800 (10)

cyanate (OCN-

) 3600 1200 (7)

urea (OC(NH2

)2) 5700 2700 (15)

nitrous oxide (N2O) gas gas (64)

Total N (102)

Table 11. M31A1E1 alkaline hydrolysisBnitrogen

products.

Initial Hydrolysis

ppm

HTO (w/H2O2)

ppm (%)

HTO (w/10 x H2O2)

ppm (%)

Carbon

TOC 5853 (67) 0.8 (0.009) 0.1 (0.001)

TIC 2504 (29) 348 (4) 320 (4)

CO2

 (gas) (80) (82)

Nitrogen*

NO2

- 5940 (10) 29 (0.05) 138 (0.2)

NO3

- 4225 (5) 10 (0.01) 1017 (1)

OCN- 3565 (7) <1 <1 

OC(NH2

)2 5729 (15) <1 <1 

N2O (gas) (64) (2) (23)

* N2

 gas was not measured; NO, NO2, and CO were below the 100 ppb

detection limit.

Table 12. M31A1E1 alkaline hydrolysis HTO products.

because of plugging problems due to the

formation of insoluble sodium carbonate.

The concentration of H2O2

, the oxidizing

agent, was varied from a stoichiometric

ratio to a tenfold excess.

Table 12 lists the data obtained for the

two sets of oxidant conditions. The

combination of alkaline hydrolysis and

HTO of the M31A1E1 resulted in the

complete oxidation of the organic carbon

present. The organic carbon was

removed to below detection limits, which

represented a DRE of greater than 99.991 percent. CO2

 accounted for at least 80

percent of the total carbon product and was dependant on the amount of oxidant

present. Much of the nitrogen (64 percent) is lost as gaseous N2O in the initial

alkaline hydrolysis step. The urea was hydrolyzed to below detectable limits by

HTO. The destruction of nitrate and nitrite was incomplete and dependant on the

amount of H2O2

 present. Nitrate and nitrite destruction rates were greater with

less added oxidant. When the stoichiometric amount of oxidant was added, the

nitrate and nitrite acted as oxidizing agents and were reduced. However, where 10

times the stoichiometric amount of oxidant was added, the H2O2

 competed
40 USACERL TR-98/104

successfully as an oxidizer and significantly larger amounts of nitrate and nitrite

remained in solution. The major nitrogen product from the reduction of nitrate,

nitrite, and urea was assumed to be N2

 gas, which was not measured.

HTO of Energetics Using AN and Potassium Dinitramide Phase Stabilized

Ammonium Nitrate (KDN-PSAN)

The objective of this research was to provide a preliminary evaluation of AN and

KDN-PSAN as oxidizing agents for the destruction of organic wastes under HTO

conditions. AN and KDN-PSAN were used to oxidize methanol, acetic acid, and

phenol. These three compounds were selected as representative of three common

wastes, i.e., alcohol, organic acid, and aromatic compounds. Experiments were done

at varying temperatures and residence times, and with various concentrations of

AN, hydrogen peroxide, and carbon. Gaseous, liquid, and solid effluents were

collected and analyzed. Proposed reaction mechanisms for AN oxidation of the

organic compounds are presented. The results provide an evaluation of AN and

KDN-PSAN as oxidizers of organic wastes in HTO systems. 

The information from these tests show that AN is an effective oxidizer for the three

organic compounds tested. The relative oxidation rate of ammonia by nitrate was

comparable to that of phenol and much faster than that of methanol and acetic acid.

The phenol oxidation showed distinctly different chemistry from methanol and

acetic acid. Reactions were completed within 30 seconds at 773K (500 EC) and 345

MPa (5000 psi), and oxidation was only limited by the oxidizing agent. When

organic compounds are added in stoichiometric amounts to AN, nitrate oxidizes both

ammonia and the organic compound resulting in very low concentrations of

ammonia, nitrate, and organic carbon in the effluent. 

Major reaction products were N2

, N2O, NO, and CO2 (bicarbonate and carbonate).

Small amounts of CO, H2

, and residual ammonia and TOC were detected in the

effluent for higher than stoichiometric amounts of organics. Small amounts of

nitrite and residual nitrate existed when less than stoichiometric organic was

present. Formation of NO (a desirable product) decreased with increasing TOC feed

concentration. The resulting decrease in carbon removal efficiency was countered

by use of a co-oxidant system using H2O2

 in conjunction with AN. H2O2 was an

effective co-oxidizer for the destruction of organics. Formation of NO was prevented

using equivalent or excess amounts of H2O2

. The H2O2 may be a more effective

oxidizer for methanol and acetic acid than nitrate, while no preference for H2O2

 or

nitrate may exist for phenol oxidation.
USACERL TR-98/104 41

The effect of KDN on the reaction rates is significant. KDN can change the

chemistry of the reaction by providing an additional oxidizer in the form of NO2

.

Also, hydrolysis of KDN produces KOH, which is a strong base affecting the

reaction chemistry. The potassium ion itself can affect the reaction by acting as a

catalyst for various reactions.

Conclusions

Alkaline hydrolysis of M31A1E1 was successfully demonstrated as a pretreatment

process that can break down a triple-base propellant into simpler gaseous and

soluble compounds without trace of the original bases. The hydrolysis renders the

material safer to pump, or otherwise transport, to subsequent treatment processes.

HTO operations can successfully convert the carbon and nitrogen hydrolysis

products largely to carbon dioxide nitrogen gas, and nitrite and nitrate. The

alkaline hydrolysis-HTO combination is a viable total treatment process for at least

some EM.

Reclaimed AN and KDN-PSAN can be effectively and safely used as an oxidizing

agent in HTO systems for the destruction of waste organics. Aromatic compounds

are more easily oxidized by the nitrate than the more refractory organics such as

methanol or acetic acid. 

Future Research

Additional work needs to be performed at the pilot scale level to further evaluate

these operations with other energetics, methods of dealing with plugging problems,

and further defining reactant products. Work also needs to be performed with other

energetics and to further establish the effect of KDN on the overall reactions. Pilot

scale HTO system research would provide kinetic and scale-up information critical

for full scale design and performance.
42 USACERL TR-98/104

7 SCCO2 Extraction and HTO of EM

Introduction

Work performed by CERL has demonstrated HTO to be an effective method of

treating EM and generating innocuous end products. The purpose of this work was

to examine a technology for extracting ingredients from energetic wastes and then

immediately treating the extracted components in the HTO process. Since CO2

 has

the potential to act as a solvent above the critical point (304.2K [31 EC], 7.38

MN/m2

 [1073 psi]), this approach investigated SCCO2 extraction of components of

the triple-base propellant M31A1E1. Before this work, the SCCO2

 solubilities of the

M31A1E1 components were unknown.

The primary objectives of this effort were to determine:

• which M31A1E1 components are soluble and therefore extractable in SCCO2

• if the CO2-extracted components can be injected into a HTO reactor

• if the extracted components can be safely destroyed by HTO

• what effect the CO2

 solvent has on the HTO chemistry of M31A1E1.

Source Document

An elaborated account of this work is contained in the report: Steven J. Buelow,

Research and Development Alternatives to Open Burning/Open Detonation

Destruction of Waste Propellants, Explosives, and Pyrotechnics: Supercritical Carbon

Dioxide Extraction—Supercritical Water Processing of M31A1E1 (prepared for

CERL by Los Alamos National Laboratory, undated).

SCCO2 Extraction of M31A1E1 Propellant Components

The solubility of M31A1E1 in SCCO2 was examined by extracting a 207 mg sample

for 6 hours with CO2

 at 313K (40 EC) and 25.5 MPa (3700 psi). Liquid CO2 was

pumped through the M31A1E1 sample at a rate of 0.45 ml per minute. After

terminating the extraction procedure, a total 21 percent by weight of the propellant
USACERL TR-98/104 43

Product*

CO2

 Flow Rate

3mL/min mg

(%)

CO2

 Flow Rate

mL/min mg (%)

Carbon C C

 TOC 0.7 (9) 0.02 (0.2)

 TIC 4.4 (59) 0.7 (9)

Nitrogen C C

 NO3

- 24.4 (36) 15.2 (21)

 NO2

- 2.3 (4) 1.5 (3)

 N2O 10.6 (43) not observed

* NO, NO2

, and CO were below 100 ppb detectable

limit.

Table 13. SCCO2 extraction and HTO treatment of

M31A1E1.

had been extracted. NG and two

binders, dibutylphthalate (DBP) and

ethyl centralite (EC), had been

preferentially extracted from the

propellant. The balance of the

propellant remained behind in the

solid state. The three SCCO2

 soluble

components amounted to 22.5

percent of the original propellant,

indicating that nearly all of these

three components had been

successfully extracted. The other

primary base components, NQ and

NC, were not extracted. This was

not surprising since NQ is highly

polar and not likely to be soluble in

the relatively nonpolar SCCO2

 solvent, and NC is a medium molecular weight

polymer and also requires a more polar solvent to solubilize it.

A potential safety hazard was noted during the experiment. The extracted NG

tended to drop out of solution in the tubing after passing through the SCCO2

extraction equipment and the pressure regulator, where the pressure and

temperature were reduced below the critical pressure and temperature. The build

up of NG in this tubing, threads, and related assembly could lead to a possible

detonation because of the unpredictable nature and extreme sensitivity of NG. This

was not a problem when the SCCO2

 extract was fed directly to an HTO process.

HTO of SCCO2 M31A1E1 Extracted Components

M31A1E1 was extracted as described above by SCCO2. The extract was fed directly

into an HTO reactor operating at 823K (550 EC), 34.5 MP (5000 psi), and 4 mL/min

(11 sec residence time). The HTO reactor was gold-lined to prevent interference

from corrosion reactions. The oxidant, H2O2

, was added in an amount 30 times the

stoichiometric requirement. Table 13 lists the results of experiments at two

different SCCO2

 flow rates (3 and 1 ml/min). Carbon and nitrogen data are also

presented, but nitrogen gas (N2

) and CO2 analysis are not included. The rate of

reactions are not quantified; however most of the reaction products were noted

within the first few minutes of the extraction procedure.
44 USACERL TR-98/104

The data clearly show that the extracted components from the M31A1E1 were

destroyed in the HTO reactor. The NG was completely destroyed (converted to CO2

and inorganic carbon). The organic content was reduced to 9 and 0.2 percent of the

starting C concentrations for the two flow rates, respectively. Specifically, 91 and

99.8 percent of the starting C present as NG, EC, and DBP were converted to CO2

or CO3

-

. The lower CO2 flow rate resulted in a higher portion of organic carbon

being oxidized. The major nitrogen products were N2O and NO3

-

.

Conclusions

The results of this work indicate that it is possible to extract some propellant

components in SCCO2

. NG can be extracted from propellant M31A1E1 by SCCO2,

while NQ and NC cannot be extracted under the conditions of the test. The SCCO2

extract solution can then be further processed by direct injection into a HTO

reactor. The HTO end products include NO, NG, N3

, CO2, and inorganic carbon

compounds. The oxidation of the energetics in the HTO reactor appears to be

unaffected by the presence of large amounts of CO2

. Future research in this area

should include evaluation of SCCO2

 extraction and HTO treatment of other

energetics such as TNT, HMX, and RDX and other propellants.

Safety was identified as a concern in the SCCO2

 extraction of NG from the

M31A1E1 propellant requiring awareness and precautions to ensure its immediate

injection and reaction within the HTO reactor.
USACERL TR-98/104 45

8 WAO Treatment of EM

Introduction

WAO has been used successfully as a waste treatment method to destroy industrial

and municipal organic material for many years. This technology uses elevated

temperatures (of several hundred degrees celsius) in the presence of an oxidizing

environment to convert complex materials to simpler and less objectionable

compounds. Waste EM may be well suited for this method of destruction. A series

of tests were conducted to evaluate the treatability of M31A1E1 and NOSIH-AA2

by WAO. Alkaline hydrolysis, a potentially important pretreatment step, was also

evaluated as part of this series of WAO tests. Two other compounds (AN and KDN)

were examined as possible oxidizing agents in the WAO process. A number of

different metal alloys were evaluated to obtain information on the best possible

materials to withstand the highly corrosive environments anticipated in full-scale

WAO systems.

Source Documents

The research into alkaline hydrolyzed M31A1E1 treatability is detailed in the

report: Bench-Scale Wet Air Oxidation Shaking Autoclave Test Results for Triple

Base Propellant from the U.S. Army (Zimpro Environmental Systems Inc. for CERL,

14 September 1992).

The work in NOSIH-AA2 and alkaline hydrolyzed NOSIH-AA2 treatability is

covered in greater detail in the report: Bench-Scale Wet Air Oxidation Shaking

Autoclave Test Results on a Triple Base Propellant NOSIH-AA2 (Zimpro

Environmental Systems Inc. for CERL, 26 September 1993).

The use of future waste rocket propellents as oxidizing agents in the WAO process

was more completely reported in: Use of Ammonium Nitrate and Potassium Dinitramide as Oxidizing Agents for Wet Air Oxidation (WAO) of Organic Wastes

(Zimpro Environmental Inc. for CERL, 31 October 1995).
46 USACERL TR-98/104

Alkaline Hydrolyzed M31A1E1 Treatability

M31A1E1 is a rocket propellant containing NC, NG, and NQ. The WAO of alkaline

hydrolyzed M31A1E1 was evaluated for chemical oxygen demand (COD) and

destruction of hydrolyzed nitrogenous compounds. Oxidations were performed in

laboratory shaking autoclaves at temperatures of 553, 573, and 593K (280 EC, 300

EC, and 320 EC) for 60-minute residence times. Five metal alloys (316L Stainless

Steel, Alloy 20CB-3, Inconel 600, Titanium Grade 2, and Nickel 200) were

evaluated for corrosion at 553K (280 EC) for 200 hours. 

The physical appearance of the hydrolyzed propellant was dark brown and

contained about 8 g/L of total nitrogen and 32 g/L of COD. The majority of the

nitrogen was in the form of nitrite. The pH of the hydrozylate as well as the WAO

products were approximately 14. The destruction of COD ranged from 60 to 69

percent over the three WAO temperatures evaluated. Approximately half of the

remaining COD was attributed to nitrite, which increased by 25 to 50 percent

during the tests. In all the tests, organic nitrogen compounds appeared to be

destroyed. The level of ammonia was about an order of magnitude greater in the

WAO products than in the hydrolyzed feed and the levels of nitrate remained

approximately the same.

In all three tests, the oxidized WAO products were clear in color and lower in

suspended solids. The products as well as the feed did not have any Biochemical

Oxygen Demand (BOD). This lack of BOD was attributed to either a lack of

nutrients or salt toxicity. The relatively high salt content, and precipitation during

the initial test at 553K (280 EC), resulted in conducting the remaining two tests

(513 and 593K, or 300 and 320 EC) after diluting the propellant with distilled water

(1:1). The WAO gaseous products included oxygen (5 to 12 percent) and nitrogen

(86 to 91 percent). NO, CO2

, and CO were all below detectable limits. The Inconel

600 and the Nickel 200 were the only two metal alloys that showed no signs of

pitting or stress corrosion cracking after the 200 hours of testing.

NOSIH-AA2 and Alkaline Hydrolyzed NOSIH-AA2 Treatability

This research was designed to evaluate the ability of the WAO process to destroy

the NOSIH-AA2 propellant. The major components of this double-base propellant

are NG, NC. Oxidations at various temperatures were performed on a mixture of

propellant and distilled water, and propellant pretreated by alkaline hydrolysis. Six

different alloys (316L Stainless Steel, Alloy 20CB-3, Inconel 600, Titanium Grade

2, Nickel 200, and Hastelloy C-276) were evaluated for corrosion. 
USACERL TR-98/104 47

The NOSIH-AA2 was cut into 6 mm (0.25-in.) squares and mixed with distilled

water forming a 15 g/l mixture. The WAO tests were conducted at 473, 493, 513,

and 533K (200, 220, 240, and 260 EC). The solid propellant initially was light

brown and the oxidized product waters were clear yellow with less than 55 mg/L of

suspended solids. High levels of COD reduction was observed at all temperatures.

COD reduction rates ranged from 80 to 99 percent and increased with temperature.

The remaining COD was expected to be composed of low molecular weight

compounds such as volatile acids. The BOD of the product waters indicates the

WAO products can undergo further biological decomposition. The WAO products

contained lead concentrations in the range of 105 to 219 mg/L. Approximately 92

percent of this lead was soluble, which could be precipitated by pH adjustment. The

pH of the WAO products ranged from 1.4 to 1.9. The offgas contained CO2

 (11 to

13 percent), CO (1 to 78 percent), total hydrocarbons (179 to 314 ppm), methane (45

to 263 ppm), and nitrous oxide (<0.1 percent).

The NOSIH-AA2 propellant was hydrolyzed with sodium hydroxide at 378K (105

EC) and mixed with distilled water forming a 100 g/l mixture. The WAO tests were

conducted at 513, 533, 553, and 573K (240, 260, 280, and 300 EC). The oxidized

products were clear green, which was attributable to insolubilized copper. The

products contained 1,400 to 2,100 mg/L of suspended solids that had significant

amounts of precipitated lead. COD destruction ranged from 66 to 87 percent and

increased with increasing temperature. Approximately 7,500 to 9,000 mg/L of the

remaining COD was due to the nitrite-nitrogen and was expected to be amenable

to further biodegradation. The residual BOD levels of 100 to 8,400 mg/L provide

further evidence to support the potential for further biological degradation. The pH

of the hydrolyzed propellant was initially 13.8, but was reduced after WAO to 9.4

to 9.8. The offgas contained CO2

 (0.3 to 2.1 percent), CO (<0.1 percent), total

hydrocarbons (168 to 304 ppm), and NO (0.1 to 0.5 percent). 

The evaluation of the corrosion potential data of the six candidate metals revealed

that four of the six would have corrosion rates of less than 0.1 mm/year (5 mils per

year) and no localized corrosion. These four metals were 316L Stainless steel, Alloy

20CB-3, Inconel 600, and Titanium Grade 2.

AN and KDN as Oxidizers in WAO

The purpose of this study was to investigate the use of AN and KDN as oxidizing

agents in the WAO process. The decomposition of these compounds was expected

to liberate an oxidizing radical that could be used to oxidize other organic

compounds. AN, KDN, and AN-KDN mixtures were evaluated for their ability to
48 USACERL TR-98/104

AN - - -

AN + phenol 90 >93 >93

AN + acetic acid 5 22 77

AN + biosludge 70 82 74

KDN - - -

KDN + phenol >93 >93 >93

KDN + acetic acid 64 83 92

KDN + biosludge 86 90 >90

AN + KDN - - -

AN + KDN + phenol >96 >96 >96

AN + KDN + acetic acid 73 75 90

AN + KDN + biosludge >91 >91 >91

Table 14. COD destruction by WAO of propellants AN

and KDN with phenol, acetic acid, and biosludge

(expressed as %).

oxidize phenol, acetic acid, and biosludge in the WAO process. The use of these

oxidizing agents would allow the disposal of some potential waste rocket propellent

wastes in an environmentally acceptable manner.

A total of 36 different 60-minute WAO tests were performed in testing the oxidation

characteristics of AN and KDN. The temperature was varied from 513 to 573K

(260 to 300 EC) and the pH was adjusted at the start of each test in the range of 1.0

to 1.3. The test solutions with AN, KDN, and the mixture contained from 5 to 15

g/L of oxidant. In addition, five different metal alloys (316L Stainless Steel, Alloy

20CB-3, Hastelloy C-276, Inconel 625, and Titanium Grade 2) were evaluated for

corrosion at 573K (300 EC) for 120 hours.

Tables 14 and 15 summarize the data reflecting the destruction of COD and the

percent nitrogen removed from the product liquid. The data show that COD

destruction was high and that it increased with higher temperatures. The percent

removal of nitrogen from the liquid was also excellent.

Tests of the AN alone showed AN was exceptionally resistant to degradation when

the WAO was at, or below, 573K (300 EC) and when there were no reducing agents

present. The presence of phenol and biosludge were more effective than acetic acid

in enhancing AN decomposition. The wet air oxidation of AN alone, and AN with

acetic acid (as the reducing agent) produced the lowest COD removal rates and

lowest nitrogen removals of all tests.

Tests of the KDN alone and with

reducing agents showed COD

reductions of 67 to 82 percent and

LN2

 removals of 64 to >93 percent.

Offgases contained significant

levels of nitrous oxide as well as

nitrogen.

Tests that used the KDN-AN alone

showed the removal of nitrogen

from the liquid ranged from 54 to

66 percent. These two oxidants

together were somewhat more

resistant to degradation than KDN

alone, and less resistant than AN

alone. The AN did not appear to

inhibit the decomposition of the
USACERL TR-98/104 49

AN 3 9 13

AN + Phenol 69 86 87

AN + Acetic Acid 4 23 86

AN + Biosludge 61 86 93

KDN 67 65 67

KDN + Phenol 83 83 82

KDN + Acetic Acid 75 80 81

KDN + Biosludge 79 80 82

AN + KDN 54 56 66

AN + KDN + Phenol 79 80 84

AN + KDN + Acetic Acid 78 80 87

AN + KDN + Biosludge 78 82 85

Table 15. Nitrogen removal from liquid by WAO of

propellants AN and KDN with phenol, acetic acid, and

biosludge (expressed as %).

KDN. WAO tests with the three

reducing agents demonstrated

COD reductions of 73 to >96

percent and liquid nitrogen

removals of 78 to 87 percent. Offgases contained significant levels

of nitrous oxide as well as nitrogen.

The level of nitrogen in the offgas

increased significantly when

reducing agents were present in

the WAO process.

The pH of the feed solutions and

the WAO product effluents ranged

from 1.1 to 1.9. To identify

suitable construction materials for

a WAO system, tests were

performed on the five candidate

metals at 573K (300 EC) for 120 hours using AN + phenol, KDN + phenol, and AN

+ KDN + phenol. Based on these tests, Titanium Grade 2 was found to be the most

suitable, while Hastelloy C-276 and Inconel 625 were found the least suitable.

Conclusions

These research studies have clearly shown that WAO is an effective and safe

method of disposing of M31A1E1 and NOSIH-AA2. Alkaline hydrolysis

pretreatment was shown to be very successful in converting these propellants into

nonhazardous and/or simpler compounds that can be processed at higher feed rates

and successfully treated by WAO. Residual BOD values on some of the WAO

effluents indicate these treated wastes effluents can be degraded further

biologically.

The oxidants AN and KDN can be used successfully in the WAO processing of

phenol, acetic acid, and biosludge. The presence of these organic reducing agents

enhanced the decomposition of AN. KDN, when used as an oxidizing agent in the

WAO process, produces significant amounts of nitrous oxide in the offgas. The use

of AN and KDN WAO oxidizing agents provides an environmentally responsible

way to dispose of these energetic materials.
50 USACERL TR-98/104

The pH of the WAO process is usually very acid or very basic and presents a highly

corrosive environment for normal construction materials. Tests on a number of

metals produced varied results depending on the reactants and the WAO conditions.

Future Research

Future research indicated in the area of WAO includes:

• longer term testing for candidate construction materials

• evaluation of a broader temperature range of WAO

• evaluation of optimum pH conditions

• testing a greater array of waste energetics as oxidizing agents

• WAO testing of different EM

• combining treated WAO effluents with biological treatment such as activated

sludge or composting. 
USACERL TR-98/104 51

9 Compost Feasibility of EM

Introduction

Composting is considered an environmentally acceptable alternative for the

destruction of a wide assortment of waste materials. The Army has had success in

demonstrating that composting can be used as a feasible alternative in the

treatment of soils contaminated with EM in the cleanup of its military bases. Based

on this initial success in early work to remediate soils contaminated with explosives

and propellant, the feasibility of composting production line EM was evaluated.

Additional research was performed to determine the biodegradation potential of

triple- and double-base propellants in soil, water, and compost media. In addition,

the applicable regulations in those States having AMC installations that were

expected to generate EM, and that might use composting technology, were

examined. This was intended to provide some understanding of the regulatory

issues the Army would encounter in implementing compost technology.

Source Documents

The feasibility of composting of EM and EMCW was initially evaluated in the

report: Neal Adrian, Bernard Donahue, James Stratta, The Potential for

Composting Energetic Materials Production Wastes, Technical Report (TR) 95/35

(CERL, September 1995). This study included a literature search regarding the biodegradation of explosives and propellants, a review of research on the composting

of explosive contaminated soils, a discussion of case studies of composting of

explosives and propellants at Army installations, and a summary of research area

requirements.

CERL research into the biodegradation potential of the triple-base propellant

M31A1E1 and the double-base propellant NIOSH-AA2 is summarized in the report:

Neal Adrian, The Biodegradation of Propellants in Compost, Soil Slurries, and

Liquid Cultures, TR 96/83 (CERL, August 1996).

CERL evaluated safety and environmental issues in the report: Stephanie CastleWerner and James Stratta, Environmental Regulations Applicable to the
52 USACERL TR-98/104

Composting of Energetic Waste Materials (J.M. Stratta and Associates Inc. for

CERL, December 1994).

Feasibility of Composting

A review of the limited literature of the biodegradation of explosives and propellants

provides a variety of findings. TNT, the most studied energetic compound, has been

shown to biodegrade to varying degrees both aerobically and anaerobically. Both

RDX and HMX appear more susceptible to biodegradation under anaerobic, rather

than aerobic, conditions. NG has been shown to biodegrade aerobically in stepwise

fashion to glycerol dinitrates and glycerol mononitrates followed by the formation

of glycerol, which can be broken down aerobically and anaerobically. NQ

biodegrades anaerobically, but not aerobically, to a variety of products. NC is

generally considered to be recalcitrant to biodegradation, but susceptible to

biodegradation when chemically pretreated by alkaline hydrolysis and is also

subject to fungal degradation. NC concentrations have also been observed to be

reduced in composting, but the relative contributions of sorption, chemical, physical,

and microbial degradation were not determined.

Composting is a biological process resulting in the decomposition of organic matter

and generates relatively innocuous byproducts such as water, carbon dioxide, and

reduced waste volume. This process can be broken into four major microbiologically

important phases dictated by temperature: (1) the mesophilic phase, 298 to 318K

(20 to 45 EC), (2) the thermophilic phase >318K (>45 EC) , (3) the cooling phase, and

(4) the maturation phase. The greatest decomposition occurs in the thermophilic

phase. Several parameters are often controlled for optimum composting: moisture

content (40 to 60 percent), temperature (333K, or 60 EC), pH (6 to 8), and the

carbon-to-nitrogen ratio (26-35: 1). Oxygen is also important and the internal

oxygen content can be maintained by selecting a specific method of composting, and

also by artificially inducing air circulation.

Case studies of laboratory, pilot, and field composting efforts of soils contaminated

with explosives and propellants at Louisiana Army Ammunition Plant (LAAP),

Badger Army Ammunition Plant (BAAP), and Umatilla Army Depot Activity

(UMADA) are reported. These studies, of up to 5 months duration, demonstrated

the biodegradation and/or transformation of TNT, RDX, HMX, tetryl, and NC

during the composting process. However, the mechanisms of the transformation

within the compost process were not always demonstrated to be biodegradation. In

regard to composting, these case studies strongly support the transformation of
USACERL TR-98/104 53

explosives and propellants, a reduction of toxicity with time, and a need for high

substrate ratio of surface area to mass for optimum biodegradation.

M31A1E1 and NIOSH-AA2 Biodegradation Studies

The literature suggests that many energetic compounds are biodegradable.

However it is difficult to extrapolate the often varied results found in literature to

predict the biodegradation of actual energetics that contain additives such as

stabilizers, plasticizers, and ballistic modifiers. CERL performed research into the

biodegradation potential of M31A1E1 and NIOSH-AA2. This bench scale effort

used two propellants that have been used extensively in previous studies in

electrochemical reduction, HTO, and SCWO. The effort was designed to evaluate

the biodegradation of M31A1E1 (NQ, NG, and NC) and NIOSH-AA2 (NG and NC)

propellants in compost, soil slurries, and liquid cultures.

Individual components of M31A1E1 and NOSIH-AA2 were evaluated for

biodegradation in the liquid cultures under aerobic, nitrate-reducing, sulfatereducing, and methanogenic conditions for 3 months. It was found that NC was

partially biodegraded under anaerobic conditions and was somewhat less

biodegraded under aerobic conditions. The finding regarding the degradation of NC

is consistent with other studies, which also concluded that NC is somewhat

resistant to biodegradation. NQ was resistant to biodegradation, and NG had

degraded in both the experimental cultures as well as the controls. The lack of

biodegradation of the NQ was surprising in view of several reports indicating it is

easily biodegraded under anaerobic conditions.

M31A1E1 and NOSIH-AA2 were not biodegraded in the soil slurries or compost

piles to any appreciable extent. Tests results on these propellant specimens were

based on visual observations, loss of weight, and changes in tensile strength after

exposure to compost and soil slurries for 45 and 30 days, respectively. Although

some loss of weight was observed with time, the tensile strength increased with

time. The relative insolubility of the propellant formulations probably played a role

in the inability of organisms to aggressively breakdown these materials.

Regulations Potentially Applicable to Composting

Once it was apparent that composting was a potentially feasible disposal

alternative, CERL evaluated safety and environmental issues in a study that

examined applicable Federal and key State regulations. Those States where AMC
54 USACERL TR-98/104

installations generating EM and EMCW are located, do not have specific

regulations applicable to hazardous waste composting. In most cases, States follow

the provisions of RCRA for guidance and incorporate large sections of RCRA “by

reference” into State law. Composting would most likely be defined as a biological

treatment unit under RCRA and all regulations applicable to solid waste, hazardous

waste, and appropriate hazardous waste management units apply. Due to the

uncertainty regarding which type of hazardous waste management unit definition

is appropriate for composting EM and EMCW, two “best-fit” sets of regulations are

included as potentially applicable units operations: waste piles and containment

buildings.

Federal RCRA regulations that would generally apply to the composting of EM

would fall into several broad categories: (1) regulations for solid waste storage,

collection, and land disposal, (2) regulations for chemical, physical, and biological

treatment of hazardous wastes, and (3) either regulations for permitted hazardous

waste facility waste piles or containment buildings. These regulations cover such

elements as:

• safe collection of the wastes

• use of personal protective equipment

• hydrogeology of the site

• ground water monitoring

• ambient air quality effects

• design of the facilities

• facility operations

• monitoring operating parameters

• closure and post-closure

• leachate collection

• response plans

• inspections

• incompatible waste storage

• permitting.

The compost regulations in eight States (Alabama, Indiana, Iowa, Missouri,

Oklahoma, Tennessee, Texas, and Virginia) were evaluated based on the location

of select AMC facilities anticipated to continue operations and generate EM and

EMCW within these States. None had specific, well defined regulations dealing

with the composting of hazardous wastes. All can be expected to follow RCRA with

minor exceptions. Special attention must be paid to onsite disposal, offsite

transportation, permitting requirements, and public concern. UMADA, OR, has an
USACERL TR-98/104 55

NPL site contaminated with explosives from munitions demilitarization activities.

This site has been remediated by excavation and composting.

Conclusions

The open literature on a wide assortment of research provides promising, yet

sometimes conflicting, information that shows energetic materials to be

biodegradable. Work in recent years on the composting of explosives and

propellants in soils has shown that composting can successfully destroy explosives

and propellants. This technology offers promise for disposing of EM wastes in the

future. However, recent studies on M31A1E1 and NIOSH-AA2 failed to show largescale biodegradation in short-term, limited scope compost and soil slurry bench

tests.

Regulations at the Federal and State level applicable to composting are based

largely on RCRA regulations. In general, States do not yet have independent

hazardous waste compost regulations. Composting facilities for EM will have to

comply with hazardous waste regulations and regulations that apply to waste piles

or containment buildings defined under RCRA.

Future Research

Major areas for future research are:

1. Size reduction is identified as an extremely important element in the compost

process for the normally large-sized EM materials. Availability of substrate

to microorganisms is critical for substrate biotransformation. The smaller the

waste particle size, the more promising the compost process becomes.

Developing methodologies, such as ZAWCAD or hydromilling, to pretreat the

EM wastes and generate high surface area-to-mass ratios, are key to the

success of composting EM.

2. The toxicity as well as the biodegradation potential of the various propellant

and explosive additives are both critical in the biodegradation process.

Ballistic modifiers, stabilizers, and gelatinizing agents may be toxic or

inhibitory to micro-organisms. Defining the role such agents play and

determining how to make these additives more amenable to biodegradation

is essential in identifying the explosive and propellant wastes that are most

(or least) suitable for composting.
56 USACERL TR-98/104

3. Acclimation of microorganisms over time is another important factor needing

further examination. Microorganisms can develop the capability to degrade

what was once thought to be relatively recalcitrant compounds. To date,

essentially no work has been done to define the role time plays in this

acclimation process.

4. The role of extremophilic microorganisms, such as acidophiles and

alkaliphiles, is critical in developing microorganisms capable of the

biotransformation of relatively biodegradation resistant wastes. Identifying

select organisms capable of existing under potentially extreme environmental

conditions may prove helpful in developing a favorable compost microclimate.

5. Finally, identifying the optimum EM composting conditions and performing

long-term pilot-scale field tests are critical to demonstrating the efficacy of this

treatment method.
USACERL TR-98/104 57

10 Electrochemical Processing of Energetic

Wastes

Introduction

The overall objective of this work was to investigate the electrochemistry of selected

energetic compounds and to evaluate their potential use as reactants for fuel cells,

in which the environmentally safe destruction of the energetic compounds and

energy recovery are realized. Initial research focused on literature searches in the

area of physical and electrochemical properties of energetic compounds, and in

studying the electrochemical behavior of select energetic materials.

Source Documents

Basic background information on the electrochemistry of energetic wastes is

summarized in the report: Characterization of the Electrochemical Deactivation of

Select Energetic Materials for Possible Fuel Cell Applications (Exploratory Batteries

and Storage Batteries Departments, Sandia National Laboratories for CERL,

September 1992).

The electrochemical decomposition of the triple-base propellant M31A1E1 is

detailed in the report: Electrochemical Decomposition of M31A1E1 Energetic

Materials (Mequon Analytical for CERL, September 1992).

Research into the electrochemical processing of alkaline hydrolyzed NOSIH-AA2

triple-base propellant is elaborated in the report: Electrochemical Processing of the

Triple Base Propellant, NOSIH-AA2, Alkaline Hydrolyzed NOSIH-AA2, and Select

Lead (Pb) Compound Ballistic Modifiers (Mequon Analytical for CERL, September

1993).
58 USACERL TR-98/104

Electrochemical Deactivation of Energetic Materials for Fuel Cell Application

Fuel cells are electrochemical devices that convert chemical energy directly into

electrical energy. In fuel cells, fuels are continuously fed to the negative electrode

where they are oxidized, and an oxidant, typically oxygen from air, is fed to the

positive electrode where it is reduced. Unlike batteries, fuel cells are capable of

producing electrical energy as long as both the fuel and air are supplied to the

electrodes. If the energetic material can be oxidized, energy and benign reaction

products might be produced. The majority of energetic materials possess either

amine or nitro groups. In the case of materials having amino functionalities, these

can be used as fuels for the negative electrode while oxygen is supplied to the

positive electrode. In this case the electrochemical reactions occur spontaneously.

Since nitro groups cannot be oxidized further within the limits of these experiments,

they were studied as oxidants that were reduced at the positive electrodes. In this

case, the fuel cell was forced by applying energy to drive the electrochemical

reactions.

A literature review of select EM revealed electrochemical information already

available on key explosive and propellant compounds. The energetic compounds

searched were TNT, pentaerythritol tetranitrate (PETN), HMX, RDX, N-methylN,2,4,6-tetranitrobenzenamine (Tetryl), NG, NQ, and NC. These represent three

important classes of energetics: (1) nitroaromatics (TNT and Tetryl), (2) nitrate

esters (PETN, NG, and NC), and (3) nitramines (HMX, RDX, tetryl, and NQ). Much

information on related energetic compounds was also found; a significant amount

of research activity in this area has been conducted and reported in both

government reports and electrochemical-related journals.

The literature review showed that similarities in electrochemical behavior are

generally observed within groups of energetics that contain related chemical

structures. In general, nitroaromatics could be reduced at lower potentials than

nitrate esters, and the nitramines, particularly HMX, required the most negative

potentials. Certain compounds, however, are very sensitive in their electrochemical

behavior to pH, to the nature of the supporting electrolyte, and to the organic

solvent content. Almost all are reducible under some particular set of experimental

conditions. The nature of reduction products has been the subject of the most study

in the case of nitroaromatics, although nitrate esters and NQ have also been

investigated. Less is known about products from the cyclic nitramines.
USACERL TR-98/104 59

Laboratory scale experiments were performed on the electrochemical behavior of

nine energetic materials:

• nitrobenzene (NB)

• ortho-, meta-, and para-nitrotoluene (o-NT, m-NT, and p-NT, respectively)

• 2,4 DNT (Dinitrotoluene)

• 2,6 DNT (Dinitrotoluene)

• TNT

• 1,3,5-triamino-2,4,6-trinitrobenzene (TATB)

• NQ.

The electrochemical behavior of TNT, DNTs, NTs, and NB is similar, presumably

because of their structural similarities. In general, the initial starting materials

cannot be oxidized within the voltage working range of the supporting electrolyte

solutions. However, these materials can be reduced. This study described details

of the electrochemical behavior of these compounds and the conditions employed.

Electrochemical Decomposition of M31A1E1

In this research, the electrochemistry of NC, NQ, NG, and the hydrolyzate of

M31A1E1, were evaluated. The results of these experiments demonstrated that NQ

and NG can be reduced electrolytically at copper, silver, and gold electrodes from

aqueous carbonate solutions in the region of -0.8 to -1.0 volts. However, the

electrochemical reduction of NC in aqueous solution is hampered by the relative

insolubility of NC. The M31A1E1 hydrolyzate contains ingredients that are

reducible at a copper electrode at -0.7 to -1.0 volts and oxidizable at a copper

electrode at potentials near 0.0 to +0.5 volts. Computations are presented that

reflect the feasibility of the electrolytic destruction of the studied energetic material

solutions at rates of 1 to 10 L/hour.

Electrochemical Processing of NOSIH-AA2

A literature review of this propellant revealed very little electrochemical separation

information had ever been assembled on its ingredients. In this research, an

alkaline-hydrolyzed NOSIH-AA2 propellant was evaluated in a series of

experiments to examine the electrolytic deposition of lead at both cathode and

anodes. Platinum, copper, and nickel were evaluated as possible working electrode

materials. The results of these experiments show that lead can be separated from

the alkaline solutions of NOSIH-AA2 at both the anode and cathode. The
60 USACERL TR-98/104

experiments demonstrated that copper is a suitable cathode, but not anode

material, and nickel is a suitable cathode material.

Conclusions

The amount of information on the electrochemical characteristics of energetics is

generally limited. Electrochemical processing of EM is indicated as possible.

However, a significant amount of additional research is needed to identify electrode

materials, products and reactants, rates of reaction, process optimization, and

process-monitoring equipment.
USACERL TR-98/104 61

11 Summary and Recommendations

Scope of the Munitions Production EM Generation

CERL research efforts have resulted in a much improved definition of the scope of

EM production line waste generation and OB/OD disposal at nine key U.S. Army

Ammunition Plants. Prior to this work, no information existed to characterize the

amounts, types, or methods of disposal. This information shows that, based on a

5-year period, the average amount of production line-related EM and EMCW

generated at these nine Army installations were 1600 and 6100 tons per year,

respectively. OB is still the primary means of disposal, and pressures to cease

OB/OD activities vary by State. Alternatives other than incineration are in demand

to protect Army munition production facilities from production interruption due to

regulations impacting OB/OD disposal activities.

Assessment of M31A1E1 OB combustion Products

Air pollution emission factors and OB residue characteristics have been developed

for the combustion of the M31A1E1. Emission factors for VOCs, SVOCs, NMOCs,

and metals are available to be augmented and used for human health and

environmental risk assessments as well as to make better informed comparison and

choices among alternative treatment alternatives.

Pretreatment Alternatives for EM

Hydromilling continues to be evaluated as a promising technology to convert

heterogeneous EM waste streams into more homogeneous and safer inputs to EM

treatment systems. Progressing from the use of tandem high pressure hydromills

to the design and construction of a pilot scale Drum Mill, which uses 380 MPa

(55,000 psi) water to cut EM and EMCW, this technology is proven and merits

continued development. Future research needs to focus on: (1) development of a

continuous hydromill processor with an automatic feed system and discharge

assemblies, (2) expanding the range of EM and EMCW materials hydromilled, and
62 USACERL TR-98/104

(3) coupling the hydromilling with one or more alternative treatment options such

as composting or HTO.

Cryogenic cutting with high pressure LN2

 was also demonstrated to be an

extremely promising pretreatment method of reducing the size of EM. Initial tests

performed on a variety of selected munitions clearly demonstrated that a LN2

stream pressurized up to 400 MPa (60,000 psi) is capable of cutting EM into peasize pieces—an ideal size range for feed to subsequent EM destruction. The LN2

cutting was done safely without detonation, deflagration, ignition, or scorching. An

important benefit that this process offers is that, after cutting, the LN2

 evaporates,

leaving no residual secondary waste stream requiring collection, storage, and

treatment. Future LN2

 efforts should be directed toward: (1) the cutting of actual

production EM materials, (2) adding CO2

 particles as an abrasive to the cutting jet,

(3) varying the feed rate, and (4) expanding the array of EM production wastes.

Alkaline hydrolysis has been examined as a pretreatment alternative as part of

HTO, WAO, and electrochemical processing. In all cases, the alkaline hydrolysis

of the EM proved to generate a product that was easily and safely handled by

subsequent treatment alternatives. With HTO, M31A1E1 was hydrolyzed to

nitrogen and carbon compounds with no trace of the original NG, NC, or NQ base.

These nitrogen and carbon compounds were then successfully oxidized further by

HTO. M31A1E1 and NOSIH-AA2 were both hydrolyzed prior to the WAO studies.

The alkaline hydrolysis was successful in transforming the EM into less hazardous

compounds capable of further WAO treatment both safely and efficiently. The

alkaline hydrolyzate is also capable of being processed at higher feed rates than the

parent EM. Additional research in this area should address the use of alkaline

hydrolysis in association with a wider array of EM with other following treatment

options, particularly HTO, WAO, and composting.

SCCO2

 extraction has been demonstrated to be successful in the extraction of NG

from M31A1E1, while leaving NC and NQ behind. The extracted NG presents some

concern about safety, however, processing this substance appears manageable.

Future research could include examination of the SCCO2

 extraction of a wider array

of EM.

Treatment Alternatives for EM

HTO—formerly called “supercritical water oxidation” (SCWO)—was shown to be an

effective treatment for EM. In these studies M31A1E1 propellant was pretreated

by alkaline hydrolysis. The hydrolate and H2O2

 were fed into the HTO system. The
USACERL TR-98/104 63

combined alkaline hydrolysis-HTO process resulted in a greater than 99.991

percent destruction removal efficiency of the original propellant organic carbon

compounds. Most of the carbon was converted to CO2

. The nitrogen was converted

to N2O gas, nitrite, or nitrate. AN and KDN-PSAN were evaluated as possible HTO

oxidizing agents in place of H2O2

 in the treatment of conventional organic wastes

such as phenol, acetic acid, and methanol. These tests showed that reclaimed AN

and KDN-PSAN can be effectively and safely used as an oxidizing agent in HTO.

Additional HTO research needs to be done at the pilot scale level to: (1) further

evaluate these operations with other energetics, (2) explore methods of dealing with

plugging problems, and (3) further define reactant products and reaction kinetics.

WAO was shown to be a safe and effective method of treating M31A1E1 and

NOSIH-AA2. Alkaline hydrolysis was demonstrated to be a safe and effective

pretreatment step. Residual BOD values of some WAO effluents indicate that some

treated waste effluents can be further degraded biologically. The fact that the WAO

process pH was either very acidic or very basic presented a highly corrosive

environment for normal construction materials. AN and KDN were successfully

used as oxidizing agents in the WAO process in the treatment of phenol, acetic acid,

and biosludge. Future research in this area should focus on: (1) long term testing

of candidate construction materials, (2) evaluation of a broader WAO temperature

range, (3) evaluation of optimum pH conditions, (4) testing a greater array of

energetics as oxidizing agents, (5) testing WAO treatment of different EM, and

(6) combining treated WAO effluents with biological treatment such as activated

sludge or composting.

Composting has been demonstrated to be an acceptable form of treatment of soils

contaminated with explosives and propellants. Unfortunately, a review of literature

on this subject often produces conflicting information. Future pilot scale composting

work needs to be performed to evaluate the feasibility of composting EM. Proper

EM pretreatment is essential to ensure maximum size reduction for optimum

mixing and contact between the EM and the composting microorganisms.

Hydromilling, LN2

 cutting, or alkaline hydrolysis are excellent candidate

pretreatment steps.

Electrochemical decomposition and the use of intrinsic chemical energy in EM for

fuel cell development is a technology for which there is very limited information.

Significant additional research is required in the area of electrode materials,

products and reactants, rates of reaction, process optimization, and process

monitoring equipment.
64 USACERL TR-98/104

Future Research Priorities

Information presented within this document describes research essential to finding

environmentally benign alternatives to the OB/OD. Recommended areas for future

research are prioritized below:

1. The highest priority should be given to continuing the development of

hydromill pretreatment technology through the design, construction, and

testing of a continuous feed Drum Mill with automatic feed and discharge

assemblies. This system is essential to any treatment system and should be

tested as part of a complete treatment system including composting or HTO.

2. A high priority should be given to additional research in the development of

LN2

 cutting as a pretreatment step. Initial LN2 results have been very

successful in accomplishing the primary goal of safely cutting the EM into

small, readily processed pieces.

3. A high priority should be given to pilot scale EM composting research that

includes a carefully selected pretreatment step to minimize EM particle size

such as hydromilling, LN2

 cutting, or alkaline hydrolysis.

4. A high priority should be given to continuing the alkaline hydrolysis-HTO

processing at a pilot scale level with a wider array of EM materials.

5. A high priority should be given to the continued development of

electrochemical reduction cells for the decomposition of EM production wastes.
USACERL TR-98/104 65

Acronyms and Abbreviations

AAP Army Ammunition Plant

ABG ammunition burning grounds

ACD air curtain destructor

AMC Army Materiel Command

AN ammonium nitrate

APE ammunition peculiar equipment

atm atmosphere of pressure

BDL below detectable limits

BOD biochemical oxygen demand

CAAA Crane Army Ammunition Activity

cm centimeter

CO carbon monoxide

COD chemical oxygen demand

CWP contaminated waste processor

DBP dibutylphthalate

DNT dinitrotoluene

DRE destruction and removal efficiencie

DRMO Defense Reutilization and Marketing Office

EC ethyl centralite

EM energetic material

EMCW solid waste contaminated with EM

EWI explosive waste incinerator

ft/sec feet per second

gal/min gallons per minute

H2 hydrogen

H2O2 hydrogen peroxide

HAAP Holston Army Ammunition Plant

HMX cyclotetramethylenetetranitramine

HTO hydrothermal oxidation

IAAP Iowa Army Ammunition Plant

in/sec inches per second

KDN potassium dinitramide [KN(O2

)2]

KDN-PSAN potassium dinitramide phase stabilized ammonium nitrate

KOH potassium hydroxide
66 USACERL TR-98/104

L/min liters per minute

LAAP Louisiana Army Ammunition Plant 

LAP load, assemble, and pack

LCAAP Lake City Army Ammunition Plant

LMIT Lockheed Martin Idaho Technologies Inc.

LN2

liquid nitrogen

LSAAP Lonestar Army Ammunition Plant

m/s meters per second

m3

cubic meters

MAAP Milan Army Ammunition Plant

MCAAP McAlester Army Ammunition Plant

min minute

mL milliliter

mm/sec millimeter per second

NB nitrobenzene

NC nitrocellulose

ND not determined

NEWTP neutralized explosive wastewater treatment plant

NG nitroglycerin

NMOC nonmethane organic compounds

NO norous oxide

NO2 nitrite

NOV notice of violation

NQ nitroguanidine 

NT nitrotoluene

O3 ozone

OB open burning

OCN cyanate

OD open detonation

ORR old rifle range

PEP propellents, explosives, and pyrotechnics

PEP-TTET PEP Thermal Treatment Evaluation and Test Facility

PETN pentaerythritol tetranitrate

ppb parts per billion

ppm parts per million

psi pounds per square inch

RAAP Radford Army Ammunition Plant

RCRA Resource, Conservation, and Recovery Act

RDX cyclotrimethylenetrinitramine

SCCO2

supercritical carbon dioxide

scfm standard cubic foot per minute
USACERL TR-98/104 67

SCO2solid carbon dioxide

SCWO supercritical water oxidation

sec second

sm3

/m standard cubic meters per meter

SO2

sulphur dioxide

SVOC semivolatile organic compound

TATB 1,3,5-triamino-2,4,6-trinitrobenzene

Tetryl N-methyl-N,2,4,6-tetranitrobenzenamine

TIC total inorganic carbon

TNMOC total non-methane organic compounds

TO-12 EPA approved test method for NMOC

TOC total organic carbon

UMADA Umatilla Army Depot Activity

CERL U.S. Army Construction Engineering Research Laboratories

VOC volatile organic compounds

WAO wet air oxidation

WWTP wastewater treatment plant

ZAWCAD zero added waste cutting, abrading, and drilling system
68 USACERL TR-98/104

References

Adrian, Neal, Bernard Donahue, and James Stratta, The Potential for Composting Energetic

Materials Production Wastes, TR 95/35 (U.S. Army Construction Engineering Research

Laboratories [CERL, September 1995).

Adrian, Neal, Draft Technical Report (TR), The Biodegradation of Propellants in Compost, Soil

Slurries, and Liquid Cultures (CERL, March 1996).

Bench-Scale Wet Air Oxidation Shaking Autoclave Test Results for Triple Base Propellant from the

U.S. Army (Zimpro Passavant Environmental Systems Inc. for CERL 14 September 1992).

Bench-Scale Wet Air Oxidation Shaking Autoclave Test Results on a Triple Base Propellant NOSIHAA2 (Zimpro Passavant Environmental Systems Inc. for CERL, 26 September 1993).

Buelow, Steven J., LA-UR-93-412: Research and Development Alternatives to Open Burning/Open

Detonation Destruction of Waste Propellants, Explosives, and Pyrotechnics: Supercritical

Carbon Dioxide Extraction—Supercritical Water Processing of M31A1E1 (Los Alamos National

Laboratory for CERL, undated).

Castle-Werner, Stephanie, and James Stratta, Environmental Regulations Applicable to the

Composting of Energetic Waste Materials (J.M. Stratta and Associates Inc. for CERL,

December 1994).

Doddapaneni, Narayan, David Ingersoll, and Rudolph G. Jungst, Characterization of the

Electrochemical Deactivation of Select Energetic Materials for Possible Fuel Cell Applications

(Exploratory Batteries and Storage Batteries Departments, Sandia National Laboratories for

CERL, September 1992).

Roger Schneider, Environmentally Benign Alternatives to OB/OD Destruction of Energetic Material

Production Wastes—Workshop Proceedings, 28-29 October 1992 (Rho-Sigma Associates for

CERL, undated).

Huber, Calvin, Electrochemical Processing of the Triple Base Propellant, HOSIH-AA2, Alkaline

Hydrolyzed NOSIH-AA2, and Select Lead (Pb) Compound Ballistic Modifiers (Mequon

Analytical for CERL, September 1993).

Huber, Calvin, Electrochemical Decomposition of M31A1E1 Energetic Materials (Mequon Analytical

for CERL, September 1992).
USACERL TR-98/104 69

Schneider, Roger L., Bernard A. Donahue, and Robert A. Weber, Design, Construction, and Planned

Testing of Tandem High Pressure Waterjet Hydromills Used for the Pretreatment of Energetic

Material Production Wastes, paper presented at 19th Army Environmental R&D Symposium

(Williamsburg, VA, 1994).

Stacey, Marcela R., Cryogenic Cutting of Energetic Material Production Wastes (Lockheed Martin

Idaho, Inc., undated).

Use of Ammonium Nitrate and Potassium Dinitramid as Oxidizing Agents for Wet Air Oxidation

(WAO) of Organic Wastes (Zimpro Passavant Environmental Inc. for CERL, 31 October 1995).

Wilcox, James L., and Ben Entezam, Characterization of Emissions Produced by the Open Burning

Thermal Treatment M31A1E1, Volumes I and II (Andrulis Research Corporation for CERL,

January 1996).

Buelow, Steven J., LA-UR- 93-411: Research and Development for Alternatives to Open

Burning/Open Detonation of Waste Propellants, Explosives and Pyrotechnics: Alkaline

Hydrolysis and Supercritical Water Oxidation of M31A1E1 (Los Alamos National Laboratory

for CERL, undated).

Proesmans, Petra I., Li Luan, and Stephen J. Buelow, LA-UR-95-4138: Use of Reclaimed Ammonium

Nitrate as an Oxidizer for the Hydrothermal Oxidation of Organic Wastes (Los Alamos

National Laboratory for CERL, undated).

Schneider, Roger L., and Bernard A. Donahue, Environmentally Benign Alternatives to Open

Burning/Open Detonation (OB/OD) Destruction of Energetic Materials (EM) Production

Wastes, Paper presented at 19th IPS Christchurch, New Zealand (February 1994).
70 USACERL TR-98/104

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