EPA/540/2-89/007
SUPERFUNDTREATABILITY
CLEARINGHOUSE
Document Reference:
Atlantic Research Corp. "Composting Explosives/Organics Contaminated Soils."
Technical report prepared for USATHAMA. 198pp. May 1986.
EPA LIBRARY NUMBER:
Super-fund Treatability Clearinghouse • EURS
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SUPERFUND TREATABILITY CLEARINGHOUSE ABSTRACT
Treatment Process: Biological - Composting
Media: Soil/Lagoon Sediment
Document Reference: Atlantic Research Corp. "Composting Explosives/
Organics Contaminated Soils." Technical report
prepared for USATHAMA. 198 pp. May 1986.
Document Type: Contractor/Vendor Treatability Study
Contact: Wayne Sisk
U.S. DOD/USATHAMA
Aberdeen Proving Ground, MD 21010-5401
301-671-2054
Site Name: Badger Army Ammunition Plant (Non-NPL - Federal
facility) and Louisiana AAP (NPL - Federal
facility)
Location of Test: Baraboo, VI and Shreveport, LA
BACKGROUND; Laboratory scale and pilot scale studies were conducted to
evaluate composting to treat sediments and soils containing explosive and
organic compounds. Sediment and soil from lagoons at Army ammunition
plants, located in Louisiana, Wisconsin and Pennsylvania contained high
concentrations of TNT, nitrocellulose, and.RDX, and moderate levels of HMX
and tetryl. Laboratory experiments using C-labeled tracers were used to
follow the fate of each explosive. Two types of composts (hay-horse feed
and sewage sludge-wood shavings) and three rates of sediment/soil addition
to the compost were utilized in these studies.
OPERATIONAL INFORMATION; Six 488 gallon tanks 5 feet in diameter and 4
feet in height were used as composters. These were placed in greenhouses.
Two drums of contaminated sediment from a dredging mound were used. The
composts were incubated at 60°C with continuous-aeration for 6-10 weeks.
Offgasses from the composts were monitored for C and at the completion of
the incubation, composts were analyzed for the explosives, extractable
C-labeled degradates and unextracted residual C.
PERFORMANCE; TNT degraded rapidly in all the sewage sludge composts but
breakdown in a hay-horse feed compost was adversely affected by the higher
rates of sediment addition. Cleavage of the benzene ring during TNT
breakdown did not appear to be significant.
RDX was almost completely degraded in composts amended with sediment
during 10 weeks of incubation. Increased rates of sediment addition
significantly decreased the rate of RDX breakdown in both hay-horse feed
and to a lesser extent in..sewage sludge composts. Substantial losses of
C from the composts as C02 demonstrated that RDX is completely
metabolized to natural products.
HMX did not degrade in the hay-horse feed composts, but levels were
reduced by 30-50% during 10 weeks of incubation in the sewage sludge
3/89-4 Document Number: EURS
NOTE: Quality assurance of data may not be appropriate for all uses.
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composts. HMX losses were lowest in the composts with the higher rates of
sediment addition.
Tetryl was highly susceptible to degradation by composting. 90-100%
tetryl was lost after composting for 44 days. Apparent rates of tetryl
breakdown were not strongly influenced.by the sediment loading rates.
The half-lives for TNT, RDX, and HMX using the hay-horse feed compost
were 1.6, 3.0, and 4.7 weeks, respectively. No loss of explosives in the
sewage sludge compost was observed during 7 weeks of composting.
Half-lives of TNT, RDX, HMX, and tetryl in the compost of manure mixed with
hay and saw dust were 1.0, 2.5, 3.3, and 1.2 weeks, respectively. In the
sewage sludge composts 92-97% degradation of cellulose occurred within 4
weeks. Leaching of explosives and heavy metals from the composts was
minimal. The economics of full scale composting are presented.
CONTAMINANTS:
Analytical data is provided in the treatability study report.
breakdown of the contaminants by treatability group is:
The
Treatability Group
W06-Nitrated Aromatic
and Aliphatics
CAS Number
118-96-7
121-82-4
135-HMX
479-45-8
9004-70-0
Contaminants
Trinitrotoluene (TNT)
Hexahydro-1,3,5-Trini tro-
1,3,5-triazine (RDX)
1,3,5,7-Tetranitro-
octahydro-1,3,5,7-
tetracyclooctane (HMX)
Tetryl
Nitrocellulose
3/89-4 Document Number: EURS
NOTE: Quality assurance of data may not be appropriate for all uses.
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AMXTH-TE-CR-86077
COMPOSTING EXPLOSIVES/ORGANICS CONTAMINATED SOILS
Richard C. Doyle
Jenefir D. Isbister
George L. Anspach
Judith F. Kitchens
ATLANTIC RESEARCH CORPORATION
Alexandria, Virginia 22312
May, 1986
Final Technical Report
Contract No. DAAK11-84-C-0057
Prepared for:
Commander
U.S. Army Toxic and Hazardous Materials Agency
Aberdeen Proving Ground, Maryland 21010
ATLANTIC RESEARCH CORPORATION
ALEXANDRIA.VIRGINIA • 22312
Approved for Public Release
Distribution Unlimited
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UNCLASSIFIED
SECURITY CLASSIFICATION of THIS PAGE r*»«n
REPORT DOCUMENTATION PAGE
READ INSTRUCTIONS
BEFORE COMPLETING FORM
• REPORT NUMBER
AMXTH-TE-CR-86077
2. GOVT ACCESSION NO.
1. RECIPIENT'S CATALOG NUMBER
4. TITLE fend
Composting Explosives/Organics Contaminated
Soils
5. TYPE. OF REPORT ft PERIOD COVERED
Final Report
«. PERFORMING ORG. REPORT NUMBER
7. AUTHOR^;
Richard C. Doyle; Jenefir D. Isbister;
George L. Anspach; Judith F. Kitchens
CONTRACT OR GRANT
DAAK11-84-C-0057
3. PERFORMING ORGANIZATION NAME AND ADDRESS
Atlantic Research Corporation
5390 Cherokee Avenue
Alexandria, Virginia 22312
10. PROGRAM CLEMENT. PROJECT, TASK
AREA ft WORK UNIT NUMBERS
P.E. 62720; Project No.
1L162704AF25; Task R91
II. CONTROLLING OFFICE NAME AND ADDRESS
DCAS
P.O. Box 7730
Philadelphia, Pennsylvania 19101
12. REPORT DATE
May, 1986
13- NUMBER OF PAGES
198
I*. MONITORING AGENCY NAME ft AOOMESSf" o»//er»n« '"M> Canlnltlnt Olllet)
U.S. Army Toxic and Hazardous Materials Agency
ATTN: AMXTH-TE-D
Aberdeen Proving Ground
Maryland 21010-5401
IS. SECURITY CLASS, (at Ihl, report;
UNCLASSIFIED
I3«. OECLASSIFICATION/DOWNGRADING
SCHEDULE
16. DISTRIBUTION STATEMENT (of
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EXECUTIVE SUMMARY
Laboratory scale and pilot scale studies were conducted to evaluate
composting as a decontamination method to treat sediments and soils
containing hazardous waste materials. All studies were conducted using
contaminated sediment/soil from U.S. Army installations. Sediment from
lagoons at Louisiana Army Ammunition Plant (LAAP) contained high concen-
trations of TNT and RDX, and moderate levels of HMX and tetryl. Soil from
Badger Army Ammunition Plant (BAAP) contained moderate to high levels of
nitrocellulose. The degradation of the explosives in these sedi-
ments/soils during composting was studied in a series of laboratory
experiments using l^C-labeled tracers to follow the fate of each explo-
sive. Two types of composts (hay-horse feed and sewage sludge-wood
shavings) and three rates of sediment/soil addition to the compost (10, 18
and 25% dry weight basis) were utilized in these studies. The composts
were incubated at 60°C with continuous aeration for 6-10 weeks. Offgasses
from the composts were monitored for l^C and at the completion of the
incubation, composts were analyzed for the explosives, extractable l^c-
labeled degradates and unextracted residual l^C.
TNT degraded rapidly in all the sewage sludge composts, but breakdown
in the hay-horse feed compost was adversely affected by the higher rates of
sediment addition. Accumulation of TNT transformation products (amino
derivatives of DNT) did not occur. Most of the l^C from degraded TNT was
recovered as unextracted residue. Cleavage of the benzene ring during TNT
breakdown did not appear to be significant.
RDX was almost completely degraded in composts amended with sediment
at the 10% rate during 10 weeks of incubation. Increased rates of sediment
addition significantly decreased the rate of RDX breakdown in both hay-
horse feed and sewage sludge composts; although the inhibitory effect was
much more pronounced in the hay-horse feed composts. Substantial losses of
l^C from the composts as ^C02 demonstrated that RDX is completely
metabolized to natural products.
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HMX did not degrade in the hay-horse feed composts, but levels were
reduced 30-50% during 10 weeks of incubation in the sewage sludge composts.
HMX losses were lowest in the composts with the higher rates of sediment
addition.
Tetryl was highly susceptible to degradation by composting; 90-100%
tetryl loss was demonstrated after composting for 44 days. Apparent rates
of tetryl breakdown were not strongly influenced by the sediment loading
rates. Recovery of l^C as l^CC^ or extractable degradates was insignifi-
cant. Most of the 14-C from degraded ring-labeled tetryl was found as
unextracted residue.
Nitrocellulose degraded rapidly with substantial evolution of
The patterns of I^CC^ evolution indicated that essentially all the
nitrocellulose was degraded within 4 weeks.
Pilot scale composting of the LAAP and BAAP sediments was carried out
using 500 gallon self-sustaining composts that were aerated intermittant-
ly. Breakdown of explosives in the hay-horse feed compost (11% LAAP
sediment) followed first order kinetics. The half-lives for TNT, RDX, and
HMX were 1.6, 3.0, and 4.7 weeks, respectively. No loss of explosives in
the sewage sludge compost (16% LAAP sediment) was observed during 7 weeks
of composting. A third type of compost (manure mixed with hay and saw dust)
was tested with the LAAP sediment (12% sediment). Loss of LAAP explosives
was greatest in this compost. Half-lives of TNT, RDX, HMX, and tetryl were
1.0, 2.5, 3.3, and 1.2 weeks, respectively. Nitrocellulose degradation in
hay-horse feed composts (15% BAAP sediment) was complete within 3 weeks.
In the sewage sludge composts 92-97% degradation occurred with 4 weeks.
Leaching of explosives and heavy metals from the composts was minimal and
should not constitute an environmental hazard.
Soil from Letterkenny Army Depot contaminated with TCE was tested to
determine the fate of TCE during composting. TCE was found to volatilize
from compost materials within a few hours when the temperature was held at
60°C.
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TABLE OF CONTENTS
Executive Summary . 1
I Introduction 10
A. Background 10
B. Objective 11
II Field Surveys 13
A. Badger Army Ammunition Plant 13
B. Louisiana Army Ammunition Plant 17
C. Letterkenny Army Depot 18
III Laboratory Scale Composting Trials 24
A. Materials 24
1. Composting Materials 24
2. Contaminated Sediments/Soils 24
3. Compost Seed 25
14
4. C-Radiolabeled Tracer Compounds 26
B. Analytical Methodology 27
1. Liquid Scintillation Counting 27
14
2. C-Product Identification and Quantitation 28
14
3. Residual C-Quantitation 29
14
4. Quantitation of C Trapped by Activated Carbon .... 29
5. Preliminary Extraction Trials 30
6. Tetryl Product Characterization 31
7. Analysis of NaOH Traps 31
8. Nitrocellulose Analysis 31
9. TCE Quantitation 32
C. Laboratory Composting Experiments 32
1. Experimental Design 32
2. Experimental Procedures 33
a. Compost Setup 33
b. Compost Monitoring 35
c. Compost Analysis 35
D. Results of Composting of Louisiana AAP Sediment 38
1. TNT 38
2. RDX 39
3. HMX 46
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A. Tetryl 49
5. Discussion and Conclusions 51
E. Composting of Badger AAP Sediment 52
1. Results 52
2. Discussion and Conclusions 55
F. TCE Volatility Tests (Letterkenny AD Soil) 56
1. Experimental Procedures 56
2. Results 56
3. Discussions and Conclusions 59
IV Pilot Scale Composting 60
A. EPA RCRA Research, Development and Demonstration Permit . . 60
B. Materials '. 61
1. Composting Materials 61
2. Contaminated Sediments/Soils 62
C. Composting Apparatus ,. 62
D. Experimental Design 63
E. Compost Setup 65
1. Sediment/Soil Preparation 65
a. Hay-Horse Feed and Sewage Sludge Composts .... 65
b. Manure Composts 65
2. Mixing Compost Materials and Sediment/Soil 67
a. Sewage Sludge Composts 67
b. Hay-Horse Feed Composts 70
c. Manure Composts 73
F. Analytical Methodology 73
1. TNT, RDX, HMX and Tetryl 73
2. Nitrocellulose 74
3. Gas Analysis 74
4. Heavy Metals and Pesticide Analyses 74
G. Composting Louisiana AAP Sediment 74
1. Monitoring and Sampling Procedures 74
a. Hay-Horse Feed and Sewage Sludge-Wood Chips Compost 74
b. Manure-Hay-Saw Dust Compost 75
2. Results 76
a. Hay-Horse Feed Compost 76
b. Sewage Sludge-Wood Chips Compost 82
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c. Manure Composts 84
3. Discussion and Conclusions 88
H. Composting Badger AAP Sediment 90
1. Monitoring and Sampling Procedures 90
2. Results 91
a. Hay-Horse Feed Composts 91
b. Sewage Sludge-Wood Chips Composts 92
3. Discussion and Conclusions 94
I. EP Toxicity 97
1. Sample Preparation 97
2. Toxicity Testing and Ames Assay 97
3. Results and Discussion 98
V Conclusions and Recommendations 102
VI Program Plan for Composting Demo and Economic Analyses 104
A. Composting Demostration at Badger AAP 104
B. Composting Demonstration at Louisiana AAP 104
C. Preliminary Design and Economics for a Full Scale Cleanup
of Badger AAP Soil by Composting 107
D. Preliminary Design and Economics for a Full Scale Cleanup
of Louisiana AAP Sediment by Composting 109
VII References 113
APPENDICES
A. Synthesis of 14C-RDX 114
B. Synthesis of 14C-HMX 117
C. Synthesis of C-Tetryl 118
14
D. Synthesis of C-Nitrocellulose 120
E. Analysis of TNT, RDX, HMX, and Tetryl in Sediment 121
F. Analysis of Nitrocellulose in Soil 123
G. Analysis of Trichloroethylene (TCE) in Soil 125
H. Analysis of TNT, RDX, HMX, 2A-DNT and 4A-DNT in Compost 126
I. Analysis of Tetryl in Compost 128
J. Analysis of Nitrocellulose in Compost 129
K. Analysis of Trichloroethylene (TCE) in Methanol 131
L. Temperature Records of Laboratory Composts 132
M. RCRA Permit Public Announcement and Fact Sheet 141
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N. Analysis of TNT, RDX, Tetryl, HMX, 2A-DNT and 4A-DNT in
Compost Leachates 163
0. Metal Analysis in Compost Materials and Soils 164
P. Metal Analysis in Leachate Samples 168
Q. Pesticide Analysis 169
R. Gas Sample Analysis 171
S. Daily Composting Facility Inspection Sheets 172
T. Louisiana AAP Sediment Pilot Scale Composting 176
U. Badger AAP Sediment Pilot Scale Composting 191-
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LIST OF FIGURES
1. Layout of the Nitrocellulose Wastewater Lagoons at Badger AAP . . 14
2. Photograph of Louisiana AAP Lagoon //4 17
3. Location of Sampling Sites at Louisiana AAP Pink Water Lagoons . 19
4. Schematic of C Bench-Scale Composting Apparatus 34
5. Outline of Louisiana AAP Laboratory Compost Analyses 36
6. Outline of Badger AAP Laboratory Compost Analyses 37
7. C02 Evolved from Louisiana AAP Composts Spiked
with Ring-UL 14C-RDX 45
8. C02 Evolved from Badger AAP Composts Spiked with UL C-
Nitrocellulose 53
9. Apparatus Used to Evaluate TCE Volatility from a Soil Compost
Mixture 57
10. Schematic of Pilot Scale Compost Apparatus 64
11. Photograph of the Louisiana AAP Soil Used for Composting .... 66
12. Compost Mixing Operation 71
13. Subsampling Sewage Sludge-Wood Chips Compost During Mixing ... 71
14. Subsampling Hay-Horse Feed Compost During Mixing 71
15. Composter Being Filled with Sewage Sludge-Wood Chips Compost . . 72
16. Composter Being Filled with Hay-Horse Feed Compost 72
17. Loss of TNT with Time (Hay-Horse Feed Compost) 80
18. TNT, 2A-DNT, 4A-DNT Concentrations in Hay-Horse Feed Compost
as a Function of Composting Time 80
19. TNT and Amino Compounds Concentrations in Manure Compost
as a Function of Composting Time 85
20. RDX, HMX and Tetryl Concentrations in Manure Compost
as a Function of Composting Time 86
21. Time Task Chart for Composting of Badger AAP Soil 105
22. Time Task Chart for Composting o.f Louisiana AAP Sediment .... 106
23. Layout of Full Scale Composting Plant at Badger AAP 108
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LIST OF TABLES
I Analysis of Samples Collected from Badger AAP 15
II Analysis of Samples from Lagoons at Louisiana AAP 20
III Average Levels of Explosives in the Louisiana AAP Sediment
Used in the Laboratory Composting Trials 25
14
IV Characteristics of C-Labeled Explosives Used in Laboratory
Composting Trials 26
14
V Methods of TLC Analysis Used for C-Explosive Products
Identification 28
14
VI Distribution of C in Louisiana AAP Sediment Composts Spiked with
14
Ring-UL C-TNT 40
VII TLC Analysis of the Benzene Extracts of Louisiana AAP Sediment
14
Composts Spiked with Ring-UL C-TNT 41
14
VIII Distribution of C in Louisiana AAP Sediment Compost Spiked with
Ring-UL 14C-RDX 43
IX TLC Analysis of the Acetonitrile Extracts of Louisiana AAP Sediment
14
Composts Spiked with Ring-UL C-RDX 44
14
X Distribution of C in Louisiana AAP Sediment Composts Spiked with
Ring-UL 14C-HMX 47
XI TLC Analysis of the Acetonitrile Extracts of Louisiana AAP Sediment
Composts Spiked with Ring-UL C-HMX 48
14
XXII Distribution of C in Louisiana AAP Sediment Composts Spiked with
Ring-UL 14C-Tetryl 50
14
XXIII Distribution of C in Badger AAP Soil Composts Spiked with UL
14
C-Nitrocellulose 54
XIV TCE Volatilization from Soil and Compost at 60°C 58
XV Analysis of the Louisiana AAP and Badger AAP Sediments 66
XVI Contents of Louisiana AAP Pilot Scale Composts 68
XVII Contents of Badger AAP Pilot Scale Composts 69
XVIII Concentration of Explosives in Pilot Scale Hay-Horse Feed
Composts Amended with 117. Louisiana AAP Sediment 79
XIX Concentration of Explosives in Pilot Scale Sewage Sludge
Composts Amended with 16% Louisiana AAP Sediment 83
XX Concentration of Nitrocellulose in Composts Amended with Badger AAP
Soil as a Function of Composting Time 93
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XXI Ames Assay Data on Extracts from Hay-Horse Feed and Sewage
Sludge Composts Amended with Louisiana AAP Sediment 99
XXII Ames Assay Data on Extracts from Manure-Hay Composts
Amended with Louisiana AAP Sediment 100
XXIII Ames Assay Data on Extracts from Composts Amended with
Badger AAP Soil 101
XXIV Capital Costs for Badger AAP Composting Plant 110
XXV Operating Costs for Full Scale Composting of Badger AAP Soil . . 110
XXVI Capital Costs for Louisiana AAP Composting Plant 112
XXVII Operating Costs for Full Scale Composting of Louisiana AAP
Sediment 112
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I. INTRODUCTION
A. Background
Operations at a number of military installations have resulted in the
release of toxic materials or hazardous substances onto soil or sediment
within these installations. These released substances include a variety
of explosives, solvents, pesticides and other organics, as well as a number
of inorganic materials, such as heavy metals and mineral acids. Concen-
trations of pollutants vary from low ppb levels up to the point where more
than half the weight of the sediments is composed of contaminants. Low
level contamination is generally found in soils around manufacturing and
handling facilities where release of the pollutants was inadvertent.
These lightly contaminated areas can account for the majority of the
contaminated land mass. Areas of heavy contamination are largely confined
to spillways and lagoons utilized over extended periods to channel and
contain wastewaters from the installations' operations, an accepted
practice at the time the facilities were constructed and operated.
Contaminants in some of the heavily polluted areas have been leached to
varying degrees. In some situations, contaminants have reached ground
water and are migrating horizontally toward potable water supplies. Near
term action is necessary at these sites to eliminate the source of ground
water pollution, i.e., remove or clean the contaminated sediments.
Ultimately all soil/sediments, including the lightly contaminated soils,
will have to be removed or decontaminated to be able to release the land for
unrestricted use.
Previous work has demonstrated that composting is an effective means
of degrading TNT and RDX. Composting can be setup as an on site treatment.
Compost materials (hay, straw, wood chips, manure, sewage sludge, etc.)
can be obtained locally at low or no cost, and composting facilities can be
rapidly constructed at minimal costs. Major equipment items needed to
handle the compost are off-the-shelf items that can be readily transported
from site to site as needed. Relatively few personnel are needed to
maintain a composting facility, and training for most of the personnel is
minimal. In short, composting has significant economic and portability
advantages over other currently available technologies. However, addi-
tional experimentation was deemed necessary to demonstrate the ability of
the composting process to handle the wide variety of contaminants found in
the lagoon sediments at various Army Ammunition Plants and depots.
10
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The previous work on composting of RDX and TNT was purposely designed
to avoid many of the complicating factors that will be encountered in an
actual composting operation. In these early studies, the contaminated
sediment was made by adding solutions of a single explosive to an
uncontaminated sandy soil that had a low adsorptive capacity. In the
present studies described in this report, the scope of the work was
expanded to examine the breakdown of TNT, RDX, tetryl, HMX, nitrocellu-
lose, and TCE in actual sediments from military installations. In some
cases, these sediments contained multiple contaminants, including the
contaminants being studied as well as other organics, pesticides, heavy
metals, etc. The explosives are not uniformly dispersed in the sediment,
but are found in large nodules as well as being adsorbed to the soil
surface. The sediments and soils used in the studies contained substan-
tially more clay and/or organic matter than the sand used in the initial
study, thus increasing possibility of strong adsorption of the contamin-
ants onto the soil. Both the presence of nodules of explosives and strong
adsorption of the explosives to the soil could protect the explosives from
microbial and chemical attack in the compost.
B. Objectives
The present experimental work, conducted under contract No. DAAK11-
84-C-0057 with USATHAMA, was aimed at studying the effects of multiple
contamination on the composting process. This work was divided into three
phases:
• field survey to locate and quantitate the contaminants in lagoon
or soil samples collected at three Army Installations described
in Section II
• laboratory tests presented in Section III to determine the fate
of each contaminant during composting
• pilot scale composting trials discussed in Section IV.
1]
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The primary objectives in the laboratory tests were to determine:
• if TNT, tetryl, RDX, and HMX in a Louisiana AAP sediment could be
simultaneously degraded by composting
• if nitrocellulose in a Badger AAP soil could be metabolized by
composting
• and to determine the fate of TCE in compost.
Within these objectives, information was obtained on the relative rates of
explosive breakdown and the resultant degradates were characterized.
Secondary objectives were to determine the efficiency of the composting
process as a function of contaminated sediment loading and the composting
materials.
The primary objectives of the pilot scale studies were to obtain
kinetic data on the loss of explosives during composting and to verify the
findings from the laboratory studies.
12
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II. FIELD SURVEYS
Field surveys were conducted at three different -installations to
determine the amount of hazardous materials or explosives in the soils or
lagoons and to identify which soils or sediments would be suitable for the
pilot-scale composting studies. The three installations which were
visited were Badger Army Ammunition Plant in Baraboo, Wisconsin; Louisiana
Army Ammunition Plant near Shreveport, Louisiana; and Letterkenny Army
Depot in Chambersburg, Pennsylvania. At each site, surface and ground
water samples were taken. Core samples were also taken at depths to 12
inches at various locations. These samples were packed in dry ice to
maintain the samples at 4°C and shipped via freight to ARC' s main
laboratories for analyses.
B. Badger Army Ammunition Plant
Badger AAP was visited on September 11, 1984 to locate potentially
contaminated areas and obtain samples for analysis. Badger has a series of
four large lagoons which receive nitrocellulose production waste waters
via a creek directly from the production lines. As shown in Figure 1, the
first lagoon encompasses 25 acres. This lagoon resembles a field with a
small stream trickling through it. The 25 acre lagoon ends in a sluice gate
which guides the water into another series of three lagoons which
eventually empty into Gruber's Grove Bay. The last two lagoons have been
dredged and the dredgings placed in mounds along the side of the lagoons.
All lagoons and dreding mounds support grass growth and are used for
grazing of cattle.
Samples were taken in the creek below the sewage treatment plant, at
the entrance to the 25 acre lagoon, at the gate from the 25 acre lagoon, in
the dredgings ponds and at the entrance to Gruber's Grove Bay. The
analyses of the samples are presented in Table I. The high level analysis
are understated because of problems with dilutions with the old nitro-
cellulose analytical method using the acidic sulfanilamide reagent. These
problems have been overcome with a modified analysis method (see Appendix
F).
13
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GRUBER'S GROVE BAY
Figure I. Layout of the Nitrocellulose Wastewater Lagoons at Badger AAP.
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Table I. Analysis of Samples Collected from Badger AAP **
Nitrocellulose
SamPle Concentration
# Site Description ppm
1 Top 6" of core, creek leading into 1,326.0
25 A pond
2 Bottom 6" of core, creek leading into 6,277.0
25 A pond
3 Skim top of sediment, creek leading into < 17.2*
25 A pond
4 Surface sample at end of right fork in 90.0
25 A pond inlet
5 Bottom 6" of core, at end of right fork in 518.0
25 A pond inlet
6 Top 6" of core at end of right fork in 148.1
25 A pond inlet
7 Surface samples at end of left fork in 88.8
25 A pond inlet
8 Bottom 6" of core at end of left fork in 3,498.0
25 A pond inlet
9 Top 6" of core at end of left fork in 592.0
25 A pond inlet
10 Surface sample from right side of sluice gate 1,690.0
in creek bed at far end of 25 A pond
11 Bottom 6" of core, creek bed at end of 25 A pond Sample jar broken in
shipment
12 Top 6" of core, creek bed at end of 25 A pond 5,867.0
13 Bottom 6" of core, east side of dredgings pit 3,148.4
(50 yds toward road from labeled site)
14 Top 6" of core, east side of dredgings pit 1,684.0
(50 yds toward road from labeled site)
15 Bottom 6" of core, 1' from marked sampling site Sample jar broken in
in dredgings pit shipment
** See Appendix F for Analysis Procedures
15
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Table I. Analysis of Samples Collected from Badger AAP (continued)
Nitrocellulose
Sample Concentration
# __ Site Description ppm
16 Top 6" of core, I1 from marked sampling 523.6
site in dredgings pit
17 Bottom 6" of core, final effluent before < 17.2
Gubers grove Bay
18 Top 6" of core, final effluent before < 17.2
Gubers Grove Bay
19 Bottom 6" of core, outlet of 84" line < 17.2
from treatment plant
20 Top 6" of core, outlet of 84"'line from < 17.2
treatment plant
21 Bottom 6" of core, approximately 1/2 way < 17.2
between treatment plant and pond #1, in creek bed
22 Top 6" of core, approximately 1/2 way < 17.2
between treatment plant and pond #1, in creek bed
23 Bottom 6" of core, dredgings pond north of #4 < 17.2
about 100' down from stake
24 Top 6" of core, dredgings pond north of #4 < 17.2
about 100" down from stake
* Detection limit for nitrocellulose in soil.
16
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B. Louisiana Army Ammunition Plant
Louisiana AAP was visited on September 13, 1984. Louisiana has 16
lagoons of approximately one-two acres each which contain varying amounts
of TNT, RDX, HMX and tetryl as well as some heavy metals. These lagoons
were used in the past to receive wastewater directly from the shell loading
operations. The water was trucked to the lagoons and dumped into the
lagoons from concrete spillways. As a result of these operations, the
heavily contaminated lagoons (4 and 9) show a high variance in concentra-
tion across the lagoon. The highest concentrations (up to 60-70%
explosives) are at the spillway while concentrations at the far end of the
lagoon are in the low ppm range. The effect of the high concentrations of
TNT and RDX is seen in Figure 2. The soil close to the spillway is red in
color with sparkling crystals of RDX.
Figure 2. Photograph of Louisiana AAP Lagoon #4
Looking Down on the Lagoon From the Spillway
17
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Both water and core samples were taken from these lagoons at the sites
shown in Figure 3. Data for TNT, RDX, HMX, tetryl, lead arid chromium levels
at the various sampling points in these lagoons are presented in Table II.
C. Letterkenny Army Depot
Letterkenny Army Depot was visited on September 20, 1984. This depot
has several pits containing paint scrapings and trichloroethylene from
refinishing and degreasing operations. These pits have been filled and the
solvents are migrating into the ground water. Several subsurface samples
were taken, packed to maintain the samples at 4°C and shipped to ARC's main
laboratory for trichloroethylene (TCE) analysis. These samples contained
TCE in the 1-2 ppra range. No excavation was performed, therefore, no
samples were taken at the 10-20 ft deep levels where the major portions of
the contaminants are located.
18
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,40
PROPOSED
COMPOST SITE
Figure 3. Location of Sample Sites at Louisiana AAP
Pink Water Lagoon
19
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Table II. Analysis of Samples from Lagoons at Louisiana AAP**
Sample TNT RDX HMX Tetryl Chromium Lead
# Sample Description (ppm) (ppm) (ppm) (ppm) (ppm) (ppm)
1 Lagoon #4
(Surface sample 16'6" W of 691,225 68,290 11,917 42,217 <7.2 53.6
spillway)
2 Lagoon #4
(Bottom 6" of core, 36' W of 107,583 32,493 7,363 337 <7.2 139.6
spillway)
3 Lagoon #4
(Top 6" of core, 36' W of 551,691 64,289 13,955 7,113 <9.8 45.0
spillway)
4 Lagoon #4
(Botton 6" of core, 36' NW 272,138 98,911 11,970 1,547 < 7.2 68.0
of spillway)
5 Lagoon #4 t
(Top 6" of core, 36' NW of 614,816 58,630 12,468 193 < 7.2 25.9
spillway)
6 Lagoon #4
(Bottom 6" of core, 70'N, 36'W 790 758 167 <0.3 < 7.2 <7.1
of spillway)
7 Lagoon #4
(Top 6" of core, 70'N, 36'W 1,453 1,653 554 <0.3 <7.2 <7.1
of spillway)
8 Lagoon #4
(Bottom 6" of core approx. half <1.6 18.7 7.8 <0.3 < 7.2 <7.1
way up the N side of lagoon
under 6" water)
9 Lagoon #4
(Top 6" of core approx. half 10.1 91.2 16.8 <0.3 < 7.2 <7.1
way up the N side of lagoon
under 6" water)
10 Lagoon #4
(Bottom 6" of core, 37.9 73.7 14.7 <0.3 < 7.2 <7.1
middle of lagoon)
11 Lagoon #4
(Top 6" of core, 40.8 72.6 27.2 <0.3 < 7.2 7.8
middle of lagoon)
12 Lagoon #4
(Bottom 6" of core approx. half 7.2 21.2 8.6 <0.3 <7.2 <7.1
way down W side of lagoon)
See Appendix E for Analysis Procedures
20
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Table II. Analysis of Samples from Lagoons at Louisiana AAP**
(continued)
Sample TNT RDX HMX Tetryl Chromium Lead
# Sample Description (ppm) (ppm) (ppm) (ppm) (ppm) (pom)
13 Lagoon #4
(Top 6" of core approx. half 21.8 65.6 12.1 <0.3 <7.2 <7.1
way down W side of lagoon)
14 Lagoon #3
(Bottom 6" of core, NE 44.9 353.4 69.7 <0.3 <7.2 <7.1
entrance)
15 Lagoon #3
(Top 6" of core, NE entrance) 99.5 531.4 1,451 <0.3 <7.2 31.1
16 Lagoon #4
(Water sample E side) Sample jar broken in shipment
17 Lagoon #5
(Bottom 6" of core at end <1.6 26.7 9.7 <0.3 <7.2 <7.1
of spillway from 4 into 5)
18 Lagoon #5
(Top 6" of core at end of <1.6 < 1.4 < 1.4 <0.3 <7.2 <7.1
spillway from 4 into 5)
19 Lagoon #9
(Surface, sample 42' W of 10,812 11,179 4,036 <0.3 8.0 41.S
spillway)
20 Lagoon #9
(Bottom 6" of core, 100' W 118.8 15.0 8.7 <0.3 <7.2 13.1
of spillway)
21 Lagoon #9
(Top 6" of core, 100'W <1.6 9.7 1.4 <0.3 <7.2 10.0
of spillway)
22 Lagoon #9
(Surface sample 66' N 12,449 29,871 6,316 <0.3 <7.2 28.3
of spillway)
23 Lagoon #9
(Bottom 6" of core, 70' NE 17.1 11.7 9.5 <0.3 <7.2 <7.1
of spillway)
24 Lagoon #9
(Top 6" of core, 70' NE 1,275 783 98 < 0.3 < 7.2 <7.1
of spillway)
25 Lagoon *'
(Bottom 6" of core, NW side 1,100 461 91.6 <0.3 <7.2 <7.l
across from spillway)
21
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Table II. Analysis of Samples from Lagoons at Louisiana AAP**
(continued)
Sample
#
26
27
28
29
30
31
32
33
34
35
36
37
38
Sample Description
Lagoon #9
(Top 6" of core, NW side
across from spillway)
Lagoon #2
(Bottom 6" of core, E side
side of lagoon)
Lagoon #2
(Top 6" of core, E side
of lagoon)
Lagoon #2
(Surface sample near
spillway under 1' water)
Lagoon #2
(Water sample near
spillway)
TNT RDX HMX Tetryl Chromium
( ppm) ( ppm) ( ppm) ( ppm) ( ppm)
Lead
( ppm)
< 1.6 2.6
124 728
158 646
23.3 <0.3 <7.2
94.4 <0.3
96.7 <0.3
Sample jar broken in shipping
<0.85pbb 0.21 <0.64ppb <5.3ppb
Lagoon #1
(Bottom 6" of core, 12' from 6;000 3,835
spillway)
Lagoon #1
(Top 6" of core, 12' from
spillway)
Lagoon #1
(Water sample from
near spillway)
Lagoon #10
(Surface sample 10' NW
of spillway)
Lagoon #10
(Bottom 6" of core, E side
of spillway at edge of water)
Lagoon #10
(Top 6" of core, E side
of spillway at edge of water)
Lagoon #10
(Water sample near spillway)
Lagoon #10
(Top 4" of core, 20' from
spillway)
2,056 1,145
541
198
< 0 . 3 <7 . 2
83
0.32 5.8 1.7 <5.3ppb
98,034 28,358 7,120 10,039
7.6
377 119
747 253
117.6 16.4
25.4 <0.3 <7.2
64.4 <0.3 <7.2
8.5
1.3
53.7
26.2
11. 1
9.2
22
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Table II. Analysis of Samples from Lagoons at Louisiana AAP**
(continued)
Sample TNT RDX HMX Tetryl Chromium Lead
st Sample Description (ppm) (ppm) (ppm) (ppm) (ppm) (ppm)
39 Lagoon #15
(Bottom 6" of core, 2' W 3,661 349 50.7 15.1 <7.2 < 7.1
of spillway)
40 Lagoon #15
(Top 6" of core, 2' W 13,858 376 5 0.3 <7.2 < 7.1
of spillway)
41 Lagoon #15
(Surface sample, 1' E of 42,122 11,915 2,676 3,446 11.1 27.1
spillway)
42 Lagoon #15
(Water sample 3' W of 6.2 1.8 0.2 < 5.3ppb
spillway)
43 Lagoon #9
(Water sample near spillway) 0.12 0.24 1.31 <5.3ppb
* Not Analyzed
23
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III. LABORATORY SCALE COMPOSTING TRIALS
A. Materials
1. Composting Materials
Two types of composts were utilized in these studies, and were
designated hay-horse feed compost and sewage sludge compost. The hay-
horse feed composts were composed of 48% (dry weight basis) chopped alfalfa
hay, 48% Purina Sweetena horse feed and 4% seed compost. The seed compost
was material from a previously composted mixture of hay and horse feed.
The seed was added to provide the microorganisms necessary to initiate
rapid composting. The sewage sludge composts were composed of 44% pine
wood shavings and 56% sewage sludge from the Arlington Wastewater
Treatment Facility in Arlington, Virginia. The sewage sludge was a mixture
of primary and secondary sludge with ferric chloride and lime added.' The
ash content was 35-40%. The sludge itself served as a microorganism seed.
The moisture content of all materials was determined by drying
subsamples at 65°C. Materials were sealed in plastic bags to maintain
their moisture level. The hay, horse feed, and wood shavings were stored
at ambient temperatures; the sewage sludge and hay-horse feed compost seed
were maintained at 5°C until used.
2. Contaminated Sediments/Soils
Selected samples from the field survey were pooled for use in the
composting trials. Nine samples from Louisiana AAP (sample numbers 1, 2,
3, 4, 5, 19, 22, 34 and 41, Table II, Section II) were selected to obtain
the highest possible concentrations of TNT, tetryl, RDX, and HMX. The
results of explosives analyses of this pooled sample are presented in Table
III.
24
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Table III. Average Levels of Explosives in the Louisiana AAP
Sediment Used in the Laboratory Composting Trials.
Explosive
TNT
RDX
HMX
Tetryl
Average
114,600
64,205
7,043
5,022
Concentration (ppm)
Standard Deviation
9,971
9,863
1,021
1,271
Four samples of the BAAP soil (sample numbers 2, 4, 12, and 13,
Table I, Section II) were pooled to get the highest possible nitrocellulose
concentration. Analyses of this pooled soil indicated that nitrocellulose
was present at 10,252 ppm (standard deviation 1892 ppm). All samples of
soil from Letterkenny AD were pooled to yield one composite sample.
Pooled samples from Louisiana AAP and Badger AAP were air-dried
at ambient temperatures by spreading them on aluminum foil in a dark hood.
The dried samples were ground and stored in amber bottles. Because of the
explosives present in the sediments, oven drying was not considered
feasible. Therefore, additions of sediment to composts were based on the
air dried weight of the sediments.
3. Compost Seed
A 50:50 mixture of chopped alfalfa hay and Purina Sweetena horse
feed was watered to approximately a 60% moisture content, inocculated with
fresh horse manure, and allowed to compost for 26 days. The compost was
self-sustaining with temperatures ranging from 32-75°C. Samples of this
material were stored in sealed plastic bags at 5°C until used to seed the
hay-horse feed composts.
25
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4. l^C-Radiolabeled Tracer Compounds
l^C-labeled explosives were utilized in all studies as an
analytical tool to follow the fate of each explosive in the composts.
Uniformly ring-labeled l^C-TNT, uniformly-labeled hexamethylene tetra-
mine, and uniformly ring-labeled N,N-dimethylaniline were obtained from
Pathfinder Laboratories. The radiolabeled hexamethylene tetramine was
used to synthesize uniformly ring-labeled RDX and HMX (Appendices A and B).
Uniformly ring-labeled tetryl was synthesized from the ^C-N,N-dimethyl-
aniline (Appendix C). Uniformly-labeled ^C-cellulose purchased from
DuPont NEN Products was utilized to synthesize uniformly-labeled nitro-
cellulose (Appendix D). The purities and specific activities of these
compounds are presented in Table IV. The specific activity of TNT was
based on the total activity of the material per unit weight of TNT. The
specific activities of the other explosives were calculated as the total
activity of the material per unit weight of the material (explosive and
impurities).
Table IV. Characteristics of ^C-Labeled Explosives Used in
Laboratory Composting Trials
Compound
TNT
RDX
HMX
Tetryl
Nitrocellulose
Labeling Specific Activity
Position ( yCi/mg) Purity
Uniform
Uniform
Uniform
Uniform
Uniform
ring
ring
ring
ring
20.
0.
0.
0.
0.
96
381
198
076
158
85
94
53
88
.8
.8
.4
.2
-
Major
Impuritv
-
HMX (4.0%)
RDX (40.3%)
-
Cellulose
(less than 10%)
26
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B. Analytical Methodology
1. Liquid Scintillation Counting
All quantitation of ^C was accomplished using liquid scin-
tillation counting (LSC); however, two methods of quench correction were
employed. Routine measurements, used to assay ^C-explosive stock
solutions, condensates from composts, acid and base traps, and TLC
scraping, were made with the counting window set at 300-655. The lower
limit of the window was set to avoid all chemical fluorescence. The H
number (used in conjunction with a 13?cs external standard) was utilized to
measure quench, and the counting window was automatically adjusted for
spectrum shift using the automatic quench control option. A calibration
curve to relate the H number to counting efficiency was constructed using
sealed quenched and unquenched standards.
The H number was found to be somewhat inaccurate when counting
compost extracts or samples from the Tri-Carb oxidizer. The high
concentration of organics in the compost extracts and the highly basic
ethanolamine in oxidizer samples result in a shift in the Compton
distribution which is not completely predicted by the H number. Therefore,
all these samples were counted with window settings of 75-655, not using
the automatic quench control. A known quantity of l^C-activity was then
added to each sample as an internal standard, and the samples were
recounted. Increase in the measured activity of each sample was used as
the counting efficiency.
All samples, whether using the H number or the internal standard
quench correction, were counted in Beckman Ready-Solv MP cocktail until a
2a error of 2% was obtained or until counting time reached 15 minutes.
Calculations for background subtraction, quench, dilution, concentration,
and subsampling were done using a program run on an HP-3000 computer or a
TI-58 programmable calculator to minimize computational errors.
27
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2. 14-C-Product Identification and Quantitation
Product characterization of the compost extracts and purity
assays for radiolabeled TNT, RDX, HMX and tetryl were accomplished using
thin layer chromatography. Silica gel plates were used for all analyses.
The TLC methodology and solvent systems used are presented in Table V.
Authentic standards were run adjacent to the samples, and spots were
identified by comparing Rf values with those of the standards. Radioactive
spots were visualized by autoradiography and were quantified by scraping
and liquid scintillation counting.
Table V. Methods of TLC Analysis Used for ^C-Explosive
Products Identification
Compound
TLC Analysis
Procedure
Solvent Systems
TNT
RDX
HMX
tetryl
purity check
2-dimensional linear
linear
linear
2-dimensional linear
compost extracts circular
benzene:hexanes:pentane:acetone
(50:40:10:3)
petroleum ether:ethyl acetate:hexanes
(160:80:25)
acetonitrile:methylene chloride (25:75)
acetonitrile:methylene chloride (25:75)
benzene:hexanes:pentane:acetone (50:40:10:3)
petroleum ether:ethyl acetate:hexanes
(160:80:25)
benzene:methylene chloride:acetonitrile:
hexanes (40:40:5:5)
28
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The following standards were used for TLC product identifi-
cation:
TNT analysis: 2,4,6-trinitrotoluene (TNT)
2-amino-4,6-dinitrotoluene (2-amino-DNT)
4-araino-2,6-dinitrotoluene (4-amino-DNT)
2,6-diamino-4-nitrotoluene (2,6-diamino-NT)
2,2' ,6,6'-tetranitro-4,4' -azoxytoluene (tetra)
RDX and HMX
analysis: hexahydro-1,3,5-trinitro-l,3,5-triazine (RDX)
1,3,5,7-tetranitro-l,3,5,7-tetrazocine (HMX)
Tetryl
analysis: N-methyl-N,2,4,6-tetranitroaniline (tetryl)
3. Residual l^C-Quantitation
i
Radioactivity remaining in the compost after solvent extraction
(residual l^C) was determined by combusting duplicate subsamples of the
dried, ground compost, collecting the resultant CC>2 released, and quanti-
tating the l^C activity associated with the C02 using LSC. After solvent
extraction all compost samples were freeze dried and then finely ground
(0.050 inch screen) in a hammer mill. Subsamples were combusted in a
Packard Tri-Carb oxidizer, which automatically collects and dispenses the
^C02 released into a scintillation vial for counting. Oxidizer operation
and efficiency were checked by combusting samples spiked with a known
quantity of ^C-nitrocellulose. Sample carry over was measured by
combusting several blank samples (non-radioactive cellulose) randomly
placed in each run. All data were corrected for carry over (background),
combustion efficiency, and counting efficiency.
4. Quantitation of ^C Trapped by Activated Carbon
Random subsamples of carbon from the air intake end of the trap
were combusted and the ^C released was quantitated by LSC. The combustion
procedure used for carbon was the same as employed for residual l^C £n the
compost (as described in the previous section).
-------
5. Preliminary Extraction Trials
Tests were conducted with all l^C-labeled explosives to evaluate
procedures for extracting the explosives out of the different composts. In
these tests, sediment spiked with a l^C-explosive was mixed either with
composting materials to give a time zero compost or mixed into composted
materials to simulate a sample having undergone composting. Both hay-
horse feed and sewage sludge composts were utilized. The proposed protocol
for the LAAP sediment was to extract three times with acetonitrile.
Recovery of TNT with acetonitrile as the extractant was somewhat low (75-
85%) for use in a radiolabeled metabolism study. It was determined that
extraction with methanol:benzene (1:3) followed by three benzene extrac-
tions gave consistently good recovery of TNT. RDX and HMX were adequately
extracted with acetonitrile.
Acetonitrile extraction of composts spiked with l^C-tetryl was
partially effective in solubilizing the l^C, but analysis of the extracts
showed that very little of the l^C was associated with the parent tetryl
molecule. Initially, it was believed that tetryl was not stable in
compost, and efforts were initiated to isolate and identify the l^C-
products in the acetonitrile extracts (Section III-B-6). However, it was
discovered that tetryl was not stable in the acetonitrile compost
extracts. Benzene, methylene chloride, acetone, and ethanol were tested
as extractants. Benzene was found to be an acceptable solvent to extract
tetryl out of compost.
Extraction trials using acetone to recover nitrocellulose from
compost containing BAAP soil gave mixed results. Recovery of ^C from
hay/horse feed compost spiked with ^C-nitrocellulose was 66-69%, but
recovery from sewage sludge composts ranged from 19-25%. Acetone is the
only known solvent that readily solubilizes nitrocellulose; therefore,
other solvents were not tested as extractants.
These studies demonstrated that sonication of samples during
extraction increased the extraction efficiency. Therefore, the standard
procedure used to extract all explosives was to extract four times @ 35-
40°C using sonication.
30
-------
6. Tetryl Product Characterization
HPLC (Appendix H) and TLC (Section III-B-2, linear one dimen-
sional analysis using benzene:methylene chloride:acetonitrile:hexanes
(40:40:5:5) analyses of time zero extracts of LAAP-sediment composts
spiked with ring-labeled l^C-tetryl separated 20-30 isolated containing
the l^C label. The last of these isolated eluted with retention times of
greater than 30 minutes. Initially it was believed that tetryl was not
stable in compost and fractions were collected from HPLC separation and
characterized by GC-MS. Only one compound produced a GC peak. It was
tentatively identified as dimethyldinitrophenylenediamine. During this
study, it became apparent that the l^C products in the acetonitrile compost
extract were not stable, suggesting that tetryl was not stable in the
extract. Extraction trials using benzene demonstrated that tetryl does
not degrade immediately in compost materials.
7. Analysis of NaOH Traps
Tests were conducted to confirm that the ^C activity in the NaOH
traps predominantly resulted from trapped l^CCb. Subsamples of traps
containing a substantial amount of i^C were reacted with sufficient BaCl2
to precipitate all 1^C02 as Ba 14C03. The solutions were centrifuged, and
an aliquot of the clear supernatant was assayed for l^C activity. Results
demonstrated that in more than 95% of the samples, all 14-C activity
resulted from 1^C02 evolved from the composts. In no instance was a
substantial amount of l^C found in a NaOH trap that could not be attributed
to 1^C02. Therefore, all ^C activity detected in the NaOH traps is
reported as 1^C02.
8. Nitrocellulose Analysis
No method currently exists to separate and purify nitrocellu-
lose; therefore, radiochemical quantitation of l^C-nitrocellulose is not
possible. A non-specific colorimetric test (Appendix J) that is a
modification of the USATHAMA method for soil analysis was used to quantify
nitrocellulose.
31
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9. ICE Quantitation
Unlabeled reagent grade TCE was used for all 1'aboratory tests.
TCE in soil, compost, or cold traps was.extracted into methanol, placed in
sealed containers, and maintained at 5°C until analyzed. Quantitation of
TCE in the methanol was by gas chromatography using a Hall detector
(Appendix K).
C. Laboratory Composting Experiments
1. Experimental Design
Separate experiments were set up to study the fate of individual
explosives (TNT, RDX, HMX, and tetryl) in the LAAP sediment and of
nitrocellulose in the BAAP sediment during composting. In each experi-
ment, a measured quantity of one of the explosives containing the l^C-label
was added to the LAAP or BAAP sediment. This spike did not measurably
change the concentration of explosive in the sediment (except for
nitrocellulose where the concentration was increased by approximately
20%), but introduced the l^C-label which was utilized to follow breakdown
of the single explosive.
Each experiment was setup with three independent variables. The
first variable was sampling time. Compost samples were extracted and
analyzed for explosives immediately after being setup (time zero) and
after a given period of composting. The second variable was compost
materials; two types of composts, hay-horse feed and sewage sludge-wood
chips, were utilized. The third variable was sediment loading level. The
contaminated sediment was added at levels equivalent to 10, 18 and 25% of
the total dry weight of the compost.
Duplicates of all compost treatments were setup except the time
zero composts which had only one replicate. Data were analyzed in a two way
analysis of variance. Time zero data were used to determine the effect of
composting on explosive concentration. Differences between means were
assessed where appropriate using the Student-Newman-Keuls Multiple range
test. No statistical tests were performed to compare explosives remaining
after composting to recovery from time zero composts. Rather, an average
30% decrease in explosives attributed to composting was considered a
significant reduction in terms of decontaminating the sediment.
32
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2. Experimental Procedures
a. Compost Setup
Individual composts were setup in 1-quart Mason jars. The
hay-horse feed composts (50 g dry weight) were watered to obtain a moisture
content of approximately 65% (wet weight basis). The sewage sludge
composts (70.2 g dry weight) contained 59% moisture and did not require
additional water.
Aliquots (5.6 - 23.2 g) of the LAAP or BAAP sediment were
weighed into beakers to be individually added to separate composts. Each
aliquot was spiked with a l^C-labeled explosive in a small (less than or
equal to 0.5 mL) amount of solvent (benzene for TNT and tetryl, aceto-
nitrile for RDX and HMX and acetone for nitrocellulose). The solvent was
allowed to evaporate at ambient temperatures for 1-2 hours. Each soil was
throughly mixed and then added to a quart jar containing compost materials.
Soil remaining in the beaker was washed into the compost with 5 mL of water
and the treated composts were thoroughly mixed. Any l^C activity remaining
in the beakers was dissolved in 5 mL of acetonitrile for RDX, HMX, TNT and
tetryl or acetone for nitrocellulose and was quantitated by LSC. The final
compost mixtures had moisture contents of 55 to 60% and contained 10, 18,
or 25% sediment (dry weight basis).
A ring of 1/4-inch O.D. polyethylene tubing with holes
drilled at 1/4-inch intervals was positioned underneath the compost in
each jar, and a thermocouple was inserted into the center of each compost.
The jars were stoppered, placed in an incubator held at 60°C and connected
with tygon tubing to the aeration system illustrated in Figure 4. Air was
continuously drawn through this apparatus to aerate the compost. Air
entering the compost was first scrubbed with NaOH to remove CC>2. Offgasses
from the compost were scrubbed through 1.8 N H2S04 (to collect volatile
amines) and through NaOH (to collect 1^C02). The offgasses were then
passed through a drying tube (€3804) and a tube of activated carbon to trap
volatile aromatics.
33
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riiiocoiip IL' ami
'Ilit;[lit 1 blur Meier
• IV-ilor.Ui.-il
Tub IUK
Tup
N.n III
Trap
Carbon Trap
To
V-ic iiui
Tu be
Figure 4. Schematic of l^C Bench-Scale Composting Apparatus
-------
b. Compost Monitoring
Temperatures in each compost and air temperatures in the
incubator were checked and recorded daily. Air flow rates through the
aeration system were checked and adjusted as needed several times a day.
Water was added to the composts on an "as needed basis" to maintain
microbial activity.
Water condensate collected in the first dead trap down
stream from the compost in the aeration system was removed as needed to
prevent spillover into the H2S04 traps. The NaOH traps were replaced as
needed to prevent saturation of the traps. The indicator Tropalein-0 was
added to the NaOH traps to provide a visual warning of when the traps were
near the saturation level. Subsamples of both the water condensates and
the NaOH traps were assayed for l^C-activity using LSC.
c. Compost Analysis
The analyses for all LAAP and BAAP composts are outlined in
Figures 5 and 6. Radioactivity in the water condensates and NaOH traps was
quantitated every 1-4 days during composting. Periods of composting
varied with the explosive being studied. Composts spiked with l^C-TNT were
incubated 36 days, those with l^C-HMX or ^C-RDX were composted 70 days;
composts containing l^C-tetryl were composted 44 days and compost contain-
ing l^C nitrocellulose were composed 42 days. After the composting period,
the composts were removed from the incubator, sealed, and stored at 5°C
until extracted. The acid traps were subsampled to quantitate their l^C-
content. A number of carbon traps from the hay-horse feed and sewage
sludge composts for each explosive were analyzed (combustion and LSC) for
the presence of l^C. Radiation levels were at or near background on all
carbon traps, tested. l^C-activity was assumed to be negligible for all
carbon traps and the remaining traps were not analyzed.
Prior to extraction the composts were removed from cold
storage and allowed to warm to ambient temperature. The composts were then
extracted in the Mason jar in which they were composted. Sufficient
solvent was added to cover the compost materials in the jar. Each compost
was extracted four times at 35-40°C using sonication (Ultrasonic genera-
tor, Model 2705, used on highest setting). Extracts were vacuum filtered
35
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14
C-COUPOST
HO
CONOENSATE
EXTRACT
SOLVENT EXTRACTION
14
c-ACTivmr by use
CONCENTRATION
14
C-ACTIVrrV/SPOT
byLSC
COMPOST SOLIDS
Figure 5. Outline of Louisiana AAP Laboratory Compost Analyses
36
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NrrnOCILLULOSK
ANALYSIS USMQ
COLORHMTmC MCTHOO
Figure 6. Outline of Badger AAP Laboratory Compost Analyses
37
-------
through Whatman No. 1 or No. 2 filter paper. With some hard to filter
samples a prefilter (Whatman No. 4) was used to speed up the filtration
process. The extracts were combined and brought up to a given volume using
the extract solvent. The solvents used for each explosive are as follows:
TNT: Benzene:Methanol (3:1) 1 extraction
Benzene 3 extractions
HMX: Acetonitrile
RDX: Acetonitrile
Tetryl: Benzene
Nitrocellulose: Acetone
The combined extracts for each compost were subsampled to
quantitate the ^C-activity in the extract (LSC). An aliquot (50-120 mL)
from the extracts was evaporated to dryness at 35-40°C using a nitrogen
stream. The residue was washed with an appropriate solvent (benzene for
TNT and tetryl, acetonitrile for RDX and HMX,) and the volume of the wash
was reduced (evaporation under N2) to approximately 0.5 mL. These concen-
trates were analyzed by TLC, using autoradiography and LSC to locate and
quantitate all radioactive constituents in the extract. Identir ;ation of
the parent explosive and selected degradates or impurities was made by
comparing Rf values with authentic standards.
The compost solids remaining after extraction were freeze
dried, ground in a hammer mill to pass a 0.050-inch screen, and combusted
to quantitate the residual l^C-activity.
D. Results of Composting of Louisiana AAP Sediment
1 . TNT
Composting of the LAAP sediment composts spiked with ring-
labeled l^C-TNT proceeded normally. All composts appeared to have
composted. Anaerobic conditions or build up of organic acids were not
observed. Throughout the 36 day composting period, compost temperatures
remained, within 2°C of the incubator temperature.
38
-------
The distribution of l^C recovered from the composts is sum-
marized in Table VI. The results of the TLC product identification of l^C
extracted from the composts are given in Table VII. Losses of TNT due to
composting were significant for all treatment combinations. The slowest
rates of TNT loss occurred in the hay-horse feed composts amended with LAAP
sediment at rates of 18 and 25%. TNT loss in these composts was greater
than or equal to 60%. Significantly higher rates of TNT loss were found in
the hay-horse feed compost with 10% sediment and in all the sewage sludge
composts, where greater than or equal to 99% on the average of TNT was lost
within 36 days. Accumulation of TNT transformation productions was
minimal. Less than 2% of the l^C was recovered as 2-amino-4,6-dinitro-
toluene and less than 1% as 4-amino-2,6-dinitrotoluene. The 2,6-diamino
analog of TNT could not be identified on the TLC because of streaking of
organics from the origin. An area of the TLC plates encompassing the 2,6-
diamino-4-nitrotoluene location was assayed for l^C. Less than 1.4 % of
the total activity could be associated with this compound. No other
dominant ^C-labeled compound was isolated from the compost extracts.
Loss of TNT was closely correlated to a reduction of the
extractable l^C and an increase in the residual 14C. Losses of 14C02 were
generally low (less than or equal to 2.4% average value) indicating little
to no cleavage of the benzene ring in TNT. Overall loss of l^C as ^C02 was
statistically higher in the sewage sludge composts where TNT loss was
greatest. Other volatile losses of l^C were inconsequential.
Extraction of time zero samples indicated that the extraction
procedures were effective. Overall recovery of !^C average 102.0% with a
standard deviation of 6.9%.
2. RDX
LAAP sediment composts spiked with ring-labeled ^C-RDX were
initially placed in the bottom of the incubator only a short distance above
the heating coils. As a result the composts received excessive heat.
During the first six days of the composting temperatures in the compost
ranged from 63-75°C (Appendix L), and the composts turned black on the
bottom. On day six of the study, the composts were raised off of the bottom
of the incubator. Temperatures in the compost thereafter were generally
39
-------
Table VI. Di stribution of
in Louisiana AAI> Sediment Composts Spiked with Ring-UL
Compos t*
HHF
SS
HHF
SS
Amount of
Sediment
Added
(dry wt %)
10%
18%
25%
10%
18%
25%
10%
18%
25%
10%
18%
25%
l^C Recovered (% of
Composting
Time (days) l^C02
0
0
0
0
0
0
36 0.7b**
36 0.3b
36 0.9b
36 2.4a
26 1.9a
36 2.2a
H20
Condensate
_
-
-
-
-
-
0.0a»»"
O.Oa
O.Oa
O.Oa
O.Oa
O.Oa
Acid
Trap
-
-
-
-
-
O.Oa
O.Oa
O.Oa
O.Oa
O.Oa
O.Oa
added)
Extract
88.2
93.0
91.8
89.6
89.2
98.6
7.8a
30. 8a
21. 6a
1.4b
1.6b
2.3b
Unextrac ted
Residual
9.5
5.4
11 .5
8.5
7.4
6.9
100. 3a
75. 2a
77. 8a
94. 4a
97. 4a
97. 6a
Total
97.7
98.4
103.3
98.1
96.6
105.5
108.8
106.3
100.3
98.2
100.9
102.1
* HHF - hay-horse feed composts; SS - sewage sludge composts
""'•- Values followed by the same letter are not significantly different at the 5% levels of probability
according to the Student-Newman-Kuel multiple range test. Data from samples composted zero days
were excluded from statistical analyses.
-;.-.'.-;.- Value less than 0.05%
-------
Table VII. TLC Analysis of the Benzene Extracts of Louisiana AAP
Sediment Composts Spiked with Ring-UL ^
Compost t
HHF
SS
II1IF
SS
Amount of
Sediment
Added
(dry wt %)
10%
18%
25%
10%
18%
25%
10%
18%
25%
10%
18%
25%
Composting
Time (days)
0
0
0
0
0
0
'36
36
36
36
36
36
TNT
84.5
84.0
90.9***
80.3
77.0
85.2
1 . 9b*****
21. 9a
14. 9a
NDb
NDb
0.3b
1^
2-amino*
DNT
ND**
ND
ND
ND
ND
ND
1 . la
1.9a
1 .Oa
O.lb
0.3b
0.5b
+C Recoverec
4-amino*
DNT
ND
ND
ND
ND
ND
ND
0.4a
().8a
0.7a
0. Ib
0.4b
0.3b
1 (% of added)
2 , 6 -di ami no*
NT
ND
ND
ND
ND
ND
ND
1 ,/,-;.-;.-;<*
ND
ND
0.5
0.4
0.6
Tet ra*
ND
ND
ND
ND
4.7
ND
0 . 4 a
1 .4a
1.6a
NDb
NDb
0.3b
Origin
ND
0.6
0.9
1.6
1 .2
2.0
4 .0
2.0
1.8
0.6
. 0.4
0.2
t HHF - hay-horse feed compost; SS - sewage sludge compost
* 2-amino DNT = 2-amino-4,6-dinitrotoluene
4-amino DNT = 4-amino-2,6-dinitrotoluene
2,6-diamino = 2,6-diamino-4-nitrotoluene
tetra = 2,2',6,6'-tetranitro-4,4'-azoxytoluene
** ND = Not detected
•A-V.--.V xwo tailed spot on chromatO'gram, may include the tetranitroazoxy toluene and an unknown impurity
-A--A-.V* Indistinct spot which may include 2,6-diamino-4-ni trotoluene
-.v-,',-;.-,v-A- Values for TNT composted 36 days followed by the same letter are not significantly different at the
5% level of probability according to the Student-Newman-Kuel multiple range test
-------
55-65°C. Individual composts tended to maintain a temperature consis-
tently higher or consistently lower than the incubator temperature. No
evidence of anaerobic conditions or organic acid build up was observed.
The results from composting l^C-RDX are presented in Tables VIII
and IX. RDX was substantially reduced in all composts. The rate of
breakdown appeared to be inhibited by increased rates of sediment
addition. This inhibitory effect was readily apparent in the hay-horse
feed composts. In the sewage sludge compost, average losses of RDX were
decreased somewhat by increased sediment addition, but these differences
were not statistically significant (5% level of probability).
In composts where greater than 50% of the RDX was degraded, a
substantial quantity of the ^C was evolved as ^CC^ (31-64% of the 14C
from degraded RDX). The rates of l^CC^ evolution are illustrated in
Figure 7. The large percentage of l^C evolved as 1^C02 demonstrated that
breakdown of the RDX molecule was extensive. The radiolabeled carbon from
degraded RDX that was not volatilized as 1^CC>2 was largely recovered as
residue that could not be extracted from the compost with acetonitrile.
l^C found in the water condensate or acid traps was less than or equal to
0.4% of the added carbon for any sample. No substantial quantities of any
l^C-degradate were found in the compost extracts. Small quantities (less
than 2%) of l^C were found in a single spot in the TLC analysis of the
sewage sludge composts. The spot had an Rf of 0.12 indicating the presence
of compound(s) more polar than RDX (Rf=0.87). No attempt was made to
identify the constituent(s) of this spot.
l^C-HMX was present as an impurity in the ^C-RDX used to spike
the composts (4.0% HMX by radiochemical analysis). Recoveries of l^C-HMX
in the solvent extracts suggested that HMX was degraded during the 70 days
of incubation. Losses of HMX were inversely related to rates of sediment
addition. In the hay-horse feed composts, approximately 75% reduction of
HMX occurred in the 10% sediment composts, but no loss of HMX was observed
in the composts with 18 or 25% sediment. HMX losses in the sewage sludge
composts amended with 10, 18 and 25% sediment were 65, 52, and 35%,
respectively.
42
-------
Table VIII. Distribution of l*C in Louisiana AAP Sediment Composts Spiked with Ring-UL ^C-RDX
Compost*
I111F
SS
HHF
SS
Amount of
Sediment
Added
(dry wt %)
10%
18%
25%
10%
18%
25%
10%
18%
25%
10%
18%
25%
14C Recovered (% of
Composting
Time (days)
0
0
0
0
0
0
70
70
70
70
70
70
14C02
_
-
-
_
-
-
4 6. 5 a**
4.0c
0.8c
37. 2a
24. 2b
26. Ob
H20
Condensate
_
-
-
_
-
-
O.lb
O.lb
O.lb
0.2a
0.2a
0.2a
Acid
Trap
-
-
_
-
-
0.2
0.1
0.0
0.2
0.1
0.1
added)
Extract
94.0
86.5
83.1
93.1
89.2
98.6
5.6b
70. 9a
69. 5a
11. Ob
15. 5b
25. 4b
Unextracted
Residual
12.6
14.4
25.0
9.6
29. 7b
24. 4b
25. 8b
54. 6a
66. 8a
46. 6a
Total
99.1
97.5
114.2
108.2
82.1
99.5
96.2
103.2
106.8
98.3
* HHF - hay-horse feed compost; SS - sewage sludge composts
*<• Values followed by the same letter are not significantly different at the 5% level of probability
according to the Student-Newman-Kuel multiple range test. Data from samples composted zero days
were excluded from statistical analyses.
-------
Table IX. TLC Analysis of the Acetonitrile Extracts of Louisiana AAP
Sediment Composts Spiked with Ring-UL
Compost*
HHF
SS
HHF
SS
Amount of
Sediment
Added
(dry wt %)
10%
18%
25%
10%
18%
25%
10%
18%
25%
10%
18%
25%
14C
Composting
Time (days) RDX
0
0
0
0
0
0
70
70
70
70
70
70
90
83
80
89
85
92
4
67
65
8
12
21
.3
.5
.1
.7
.8
.3
. 6b****
.3a
.8a
.7b
.8b
.2b
Recovered (
HMX
3
3
3
3
3
4
0
3
3
1
1
2
.6
. 1
.1
.4
.7
.9
.8c
. 3a
.3a
.4bc
.9b
.6a
% of Added)
Origin
0
0
0
0
0
0
0
0
0
0
0
0
.1
. 0***
.0
.0
. 1
.8
.2a
.3a
.4a
.2a
.4a
.4a
Rf 0.12
ND**
ND
ND
ND
ND
ND
ND
ND
ND
0.6
0.3
1.2
* HHF - hay-horse feed composts; SS - sewage sludge composts
-;.-;.- ND = Not detected
*-;.--;,- Value less than 0.05%
•"•« Values followed by the same letter are not significantly different at the 5% level
of probability according to the Student-Newman-Kuel mtil ti pie-range test. Data from
samples composted zero days were excluded from statistical analyses.
-------
50-
£ 40H
CM
O
a
ca
O 30
ui
O
>
ui
O
10-
14C02 EVOLVED FROM C-RDX
30 40 50
TIME (DAYS)
6O
HHF-10
SS-10
SS-20
SS-30
HHF-20
HHF-30
70
Figure 7. ^C02 Evolved From Louisiana AAP Composts
Spiked with Ring-UL 14C-RDX
-------
The average overall recovery of C was 99.5% with a standard
deviation of 8.8%. The efficiency of the extraction procedure, as
determined by time zero extracts, varied somewhat, but was generally high
(90.8% average recovery with a standard deviation of 5.6%).
3. HMX
LAAP sediment composts spiked with ^C-HMX composted normally
with temperatures ranging from 57 to 64°C. One replicate of the hay/horse
feed compost with 18% sediment dried out after 49 days of composting and
could not be effectively rehydrated. Anaerobic conditions or the build up
of organic acids were not detected.
The interpretation of the data from the composts spiked with
14C-HMX is complicated because HMX accounted for 53.4% of the 14C in the
spiking solutions and RDX accounted for 40.3% of the l^C. Summaries of the
data are presented in Tables X and XI. Approximately 30-50% of the HMX in
the sewage sludge composts was lost during composting. The breakdown of
HMX appeared to be related to the rate of sediment addition to the compost,
but differences in HMX degradation between sediment loading rates were not
significant at the 5% level of probability. No HMX breakdown was observed
in the hay-horse feed composts.
RDX degradation in the sewage sludge composts was similar to but
somewhat slower than that observed in the composts spiked with l^C-KDX
(Table IX). The breakdown of RDX in hay-horse feed composts was slow at all
levels of sediment addition (less than 25% breakdown in 70 days).
In this study it was not possible to distinguish between l^C from
HMX and RDX after the parent molecule was altered. Breakdown products for
both RDX and HMX include 1^CC>2, and residues in the compost that could not
be extracted with acetonitrile. No radiolabeled degradates were found in
the solvent extracts. Volatile losses of l^C other than as 1^CC>2 were
small.
A radiolabeled impurity in the 14C-HMX spiking solution was
found at an Rf of 0.44 on the thin layer chromatograph. The impurity was
not identified, but it did appear to breakdown during composting.
46
-------
Table X. Distribution of 14C in Louisiana AAP Sediment Composts Spiked with Ring-UL 14C-HMX
Compost*
HHF
SS
HHF
SS
Amount of
Sediment
Added
(dry wt %)
10%
18%
25%
10%
18%
25%
10%
18%
25%
10%
18%
25%
!4c Recovered (% of
Composting
Time (days)
0
0
0
0
0
0
70
70
70
70
70
70
• 1
H20
1^C02 Condensate
_
- -
-
_ _
-
-
0.4b** O.lb
0.6b O.lb
0.6b O.lb
31. la 0.6a
14. 6b 0.2a
13. 4b 0.2a
Acid
Trap
_
-
-
_
-
-
O.Ob
O.Ob
O.Ob
0.2a
O.la
O.la
added)
Extract
83.1
87.5
79.8
83.0
76.6
82.7
76. 8a
74. 8a
71.6b
27. Id
34. 2d
43. 3c
Unextracted
Residual
10.5
9.4
15.8
18.2
15.0
12.3
19. Ob
20. 6b
27. 6b
42. 8a
50. 6a
43. 6a
Total
93.6
96.9
95.6
101.2
91.6
95.0
96.3
96.1
99.9
101.8
99.7
100.6
•'•• HHF - hay-horse feed composts; SS - sewage sludge composts
•'•"«- Values followed by the same letter are not significantly different at the 5% level of probability
according to the Student-Newman-Kuel multiple range test. Data from samples composted zero days
were excluded from statistical analyses.
-;.-•:.-* Values reported as 0.0% were less than 0.05%
-------
Table XI. TLC Analysis of the Aceonitrile Extracts of Louisiana AAP
Sediment Composts Spiked with Ring-UL
Compost*
HHF
SS
HHF
SS
Amount of
Sediment
Added
(dry wt%)
10%
18%
25%
10%
18%
25%
10%
18%
25%
10%
18%
25%
l^C Recovered
Composting
Time (days)
0
0
0
0
0
0
70
70
70
70
70
70
HMX
42.2
45.7
42.1
45.0
41.6
47.3
44. 5 a***
43. 2a
41. 7a
21. 6b
23. 4b
30. 6b
RDX
37.6
37.6
33.9
34.3
31.0
31.1
30. 2a
29. 4a
27. 8a
3.7c
9.4b
10. 4b
(% of added)
Origin
0.2
0.1
0.1
0.1
0. 1
0.2
ND""""
0.1
0.2
0.5
0.1
0.6
Rf 0.44
3.7
4.0
3.6
3.6
3.9
4.2
2.2
2.2
1.9
1.2
1.2
1.7
Normalized Recovery (%)**
HMX
_
-
_
_
-
101. la
98. 4a
94. 8a
49. 2b
52. 8b
69. 7b
RDX
-
-
83. 4a
81. 2a
76. 8a
11. 2c
29. 4b
32. 5b
* HHF - hay-horse feed composts; SS - sewage sludge composts
** HMX and RDX normalized to average recoveries from time zero composts
•»••<• Values followed by the same letter are not significantly different at the 5% level of probability
according to the Student-Newman-Kuel multiple range test. Data from samples composted zero days were
excluded from statistical analyses.
**-;.-*
= Not detected
-------
The overall recovery of *C was very good, with an average
recovery of 97.9% and a standard deviation of 3.6%. - The extraction
procedure gave consistent recoveries of l^C. Average recovery from time
zero samples was 82.1% with a standard deviation of 3.7%.
4. Tetryl
Composts containing LAAP sediment spiked with l^C-tetryl com-
posted normally with no indication of organic acid build up and no evidence
of anaerobic conditions. Temperatures in the composts (55 -61°C) tended to
be somewhat lower than the incubator temperature (59-62°C).
The distribution of ^C from ring-labeled ^C-tetryl breakdown
during 44 days of composting is presented in Table XII. Loss of tetryl was
substantial and did not vary significantly with composting treatments.
Extracted l^C-tetryl accounted for an average of 3.7 and 2.6% of the total
added radioactivity in the hay-horse feed and sewage sludge composts,
respectively. However, some error in the final tetryl levels resulted from
inadequacies of the extraction and TLC methodologies. Extraction effi-
ciency as indicated by l^C extracted from the time zero composts was low
(42-68% recovery) in the sewage sludge composts, and tetryl recovery from
the 44 day composts may be similarly low. The TLC procedure used for the
compost extracts did not separate l^C-tetryl from its primary impurity
(unidentified) found in the spiking solution (7.5% of the total activity).
Thus, it is not possible to determine if a portion or all of the l^C
reported as tetryl was tetryl or an impurity. Despite - these errors, 90-
100% loss of tetryl was demonstrated.
Loss of i^C-tetryl was accompanied by an increase in the l^C in
the unextracted residue. Extractable l^C was primarily composed of l^C-
tetryl; only small quantities (£0.6% of the total l^C) of any individual
degradate (unidentified) were solvent extracted. l^C recovered as ^COo
accounted for 1.6-5.0% of the total l^C. Because of the impurities present
in the spiking solution (10.4%) it cannot be determined if any I^co2
evolution resulted from tetryl breakdown. The overall recovery of l^C was
good. Average recovery was 94.3% with a standard deviation of 6.7%.
49
-------
Table XII. Distribution of C Louisiana AAP Sediment Composts
Spiked with Ring-UL 12 Condensate
_
-
-
_ _
-
-
5.0 0.1
3.0 0.1
2.1 0.0
3.2 0.2
3.4 0.1
3.9 0.1
14C Recovered (% of Added)
Acid
Traps
_
-
-
_
-
-
0 . 0**
0.0
0.0
0.0
0.0
0.0
Extract
84.0
78.4
81.8
45.6
56.9
68.1
0.1
4.6
7.6
3.2
4.3
1.8
14C-tetryl
83.7
77.2
81.1
41.9
53.1
64.4
ND***
4.0
7.1
2.7
3.8
1.2
Unextracted
Residual
11.3
8.6
9.4
50.4
24.9
21. 1
84.2
89.2
90.1
92.6
96.0
96.5
Total
95.3
87.0
91.2
96.0
81.8
89.2
89.4
96.9
99.8
99.2
103.8
102.3
* HHF - Hay-horse feed compost; SS - sewage sludge compost
"•• Values less than 0.05%
-»-*•« ND = N0t detected by TLC analysis
-------
5. Discussion and Conclusions
The laboratory studies demonstrated that compos'ting effectively
eliminated the major contaminants in the lagoons at Louisiana AAP. Both
the type of composting material and the level of sediment addition
significantly influenced the rate at which the explosives were destroyed.
The sediment generally had an adverse effect on degradation of
explosives by composting. This effect was most pronounced in the hay-horse
feed composts, and may have retarded breakdown to a lesser degree in the
sewage sludge composts.
The two primary contaminants in the sediment, TNT and RDX,
responded similarly to the composting treatments. Breakdown was most
rapid in the hay-horse feed composts amended with sediment at the 10% level
and in the sewage sludge composts. Breakdown of these compounds in the
hay-horse feed composts was significantly retarded by the 18 and 25% levels
of sediment addition. Increased sediment additions may also have slowed
TNT and RDX breakdown in the sewage sludge composts; however, data were
insufficient to determine if the increased sediment addition slowed the
rate of explosives degradation. Losses of tetryl were substantial in all
treatments. After composting for 44 days, tetryl levels were reduced by
>92% in every treatment. Data on HMX clearly demonstrated that HMX is
susceptible to degradation during composting. However, the rates of
breakdown were slow in the sewage sludge compost (30-50% in 77 days), and
no loss of HMX was observed in the hay-horse feed composts.
Accumulation of toxic or otherwise undesirable degradation
products during the composting of LAAP sediment was not observed. l^C-RDX
degradation resulted in extensive metabolism of the molecule as indicated
by the substantial release of 14co2. Only one unidentified compound
attributed to RDX metabolism was extracted from the composts, and no build
up of this compound was evident. Similarly, only one degradate of HMX
breakdown was found by TLC analysis. Several unidentified spots appeared
in the TLC analyses of extracts from the ^C-TNT study. Also the 2- and 4-
amino derivatives, and the tetranitro azoxy analog of TNT were detected.
51
-------
However, in all cases relatively small percentages of the degradates or
transformation products were found. The formation of these products may be
incidental to breakdown of the explosives, or, these products may be short
lived intermediates in the degradation of the explosives.
Evolution of 14C02 from ring-labeled 14C-TNT and ^C-tetryl was
limited. These results indicate that cleavage of the ring may have
occurred, but the rate of ring degradation is probably very low. It is
hypothesized that the intact ring from TNT or tetryl is incorporated in
natural humic substances.
E. Composting of Badger AAP Sediment
1. Results
Composts containing BAAP soil composted extremely well. Temp-
eratures in the composts ranged from 66-77°C (Appendix L), and after 42
days of composting the composts were very dark in color and substantially
reduced in volume. Elevated temperatures of this magnitude in composts
consisting of either 50 or 70 g of organic materials demonstrated that the
BAAP soil or some component(s) of the soil significantly enhanced the
composting process. Anaerobic conditions in the composts did not occur but
the build up of organic acids may have occurred in one replicate each of the
hay-horse feed compost containing 10 and 18% soil. Both of these composts
had the smell of lactic acid. At the conclusion of the compost study the
acid smell could no longer be detected.
Breakdown of nitrocellulose began within the first week of
composting as indicated by the release of 14C02 from UL 14C-nitrocellulose
(Figure 8). 1^C02 evolution rates were initially very high. After 3-4
weeks, the rates of i^CC^ release began to decline. The cumulative losses
of l^C from the composts as ^CC^ accounted for 43-74% of the total
activity added to individual composts. Small quantities of l^C were
recovered in the acid traps and in the water condensatesfrom the hay-horse
feed composts, and more than 1% of l^C was recovered from the condensates
of the sewage sludge composts (Table XIII).
52
-------
14
C EVOLVED AS CX>2 (%)
0
|O
o
0)
o
Jj^
o
1
en o>
o o
1 1
«*j
o
1
Crc
-------
Table XIII. Distribution of C Badger AAP Soil Composts
Spiked with UL ^C-Nitrocellulose
Compost*
HHF
SS
HHF
SS
Amount of
Sediment
Added Composting
(dry wt %) Time (days)
10%
18%
25%
10%
18%
25%
10%
18%
25%
10%
18%
25%
0
0
0
0
0
0
42
42
42
42
42
42
!4c Recovered (% of added)
i
H20
1^C02 Condensate
-
-
60
65
59
44
48
55
.5 a**
.Oa
.6a
.Ob
.7b
.6b
-
-
0.4b
0.5b
0.5b
l.Oa
1.2a
1.2a
Acid
Trap
0.
0.
0.
0.
0.
0.
2a
2a
la
4a
4a
2a
Extract
67.2
66.4
68.8
22.0
24.8
19.1
1.8a
2.2a
1.4a
2.4a
2.6a
1.6a
Unextrac ted
Residual
43
42
44
88
84
89
25
27
32
65
60
62
.5
.4
.9
.8
.0
.9
.4b
.6b
.6b
.8a
.Oa
.Oa
Total
110.7
108.8
113.7
110.8
108.8
109.0
88.3
95.5
. 94.2
113.6
112.9
120.6
* HHF - hay-horse feed composts; SS - sewage sludge composts
"•'•• Values followed by the same letter are not significantly different at the 5% level of probability 33
determined by the analysis of variance
-------
After composting for 43 days very little of the *C could be
extracted into acetone. Essentially all of the l^C activity remained as
bound residue in the compost or had been lost as 1^C02. Analyses of the
extracts for nitrocellulose recovered less than 1.5% of the explosive
initially added to the composts.
Overall recovery of l^C averaged 106.2% with a standard devia-
tion of 12.4%. The extraction procedure gave consistent recoveries within
each type of compost, but recoveries were low. Average recoveries out of
the hay-horse feed composts were 67.5% (standard deviation 1.2%) and 22.0%
(standard deviation 2.9%) out of sewage sludge composts.
2. Discussion and Conclusions
The addition of Badger AAP soil to composts enhanced the
composting process and resulted in elevated temperatures in the composts
i
throughout the 42 day composting period. Under these highly thermophilic
conditions, nitrocellulose was rapidly degraded, releasing a substantial
portion of its carbon as C02- Such high losses of CC>2 demonstrate that the
metabolism of nitrocellulose is extensive; degradates with a structure
similar to the parent compound are not expected to occur to any significant
extent. The shape of the 14-C02 vs time curves indicates that most of the
nitrocellulose had degraded within the first 3-4 weeks. Further releases
of 1^CC>2 after the fourth week would increasingly result from the secondary
metabolism of l^C which had been incorporated into the microbial biomass
when the nitrocellulose was metabolized. The extensive breakdown of
nitrocellulose was further confirmed by the very low recovery of l^C in the
solvent extracts and the low levels of nitrocellulose found in the extract.
Even after these values are corrected for extraction efficiency, greater
than 90% nitrocellulose degradation is indicated. The nitrocellulose
assay is a non-specific colorimetric test with numerous interferences.
The compost extracts are highly colored and contain numerous short chain
organic acids and nitro groups, which can result in false positive readings
in the nitrocellulose assay when nitrocellulose levels are low. Given the
dramatic losses of ^CC>2, the low recovery of ^C in the solvent extracts
and the likelihood for false high readings from the nitrocellulose
determinations, it appears that nitrocellulose is completely degraded
within six weeks of composting.
55
-------
Nitrocellulose is not toxic, and any degradates resulting from
its breakdown are not expected to be toxic or otherwise harmful. Recovery
of l^C in the condensates, especially condensates from the sewage sludge
composts, suggest that some low molecular weight materials which may have
resulted from nitrocellulose degradation are volatilized from the com-
posts. Loss of these materials is not considered to constitute any
environmental or health hazards.
F. TCE Volatility Tests (Letterkenny AD Soil)
1. Experimental Procedures
TCE volatility tests were run to determine the rate at which TCE
would be lost from a soil-compost material mixture. An apparatus was set
up to collect TCE volatilized out of soil and compost samples. A diagram
of the apparatus is presented in Figure 9. A one-quart Mason jar was used
to hold the sample. The materials to be tested were placed in the jar then
57 jjL of TCE was added using a syringe. The opening was immediately
stoppered, and hooked up to the aeration system as shown in Figure 9. The
jar was placed in an incubator held at 60°C. Air was continuously pulled
through the sample jar and then through a liquid nitrogen cold trap to
collect the volatilized TCE. After an appropriate period, the cold trap
was washed with methanol, and the contents of the jar were extracted twice
with methanol. TCE in the methanol washes was quantitated using GC
analysis (Appendix K). This system was tested initially by placing TCE in
an empty flask. Then TCE losses from soil and compost were tested.
2. Results
All volatilization tests are summarized in Table XIV. Trapping
efficiency of the apparatus was good (approximately 96.5%). TCE losses
from soil after 1.5 hours of incubation were nearly quantitative. Less
than 0.05% of the TCE remained in the soils. Composting materials and soil
were mixed together and watered to simulate materials just beginning to
compost. Within 3 hours 94.6% of the TCE had volatilized from the compost
materials and only 0.1% remained in the compost. This test was repeated
using hay and horse feed that had been composted 26 days. No TCE was
detected in the compost after 3 hours incubation at 60°C. Recovery of TCE
56
-------
AIR
COMPOST SAMPLE
VACUUM
ACTIVATED CARBON
DEWAR FLASK (LIQUID N )
2
Figure 9. Apparatus Used to Evaluate TCE Volatility
From a Soil Compost Mixture
57
-------
Table XIV. TCE Volatilization From Soil and Compost at 60°C
t_n
Oo
TCE Recovery (%)
Materials
Nothing
Nothing
in Flask
Lakeland sand (16.7 g)
Soil from
Hay (25 g)
Composted
Letterkenny (16.7 g)
horse feed (25 g) and LAD soil (16.7 g) 100 mL H20
hay and horse feed (140.4 g at 64.4% mixture)
Incubation
Time (hours)
1.
1.
1.
1.
3.
3.
5
5
5
5
0
0
Cold
96
96
99
94
94
87
Trap
.2
.9
.8
.4
.6
.8
Flask
ND
ND
0.
0.
0.
ND
05
05
1
-------
from the cold trap was 87.8%. The somewhat low overall recovery apparently
resulted from water build up in the cold trap. At some point during the
test the ice in the cold trap blocked air movement. After that TCE
volatilized from the compost was lost through the air intake opening.
3. Discussion and Conclusions
TCE contaminated soil added to composts would result in rapid
and near quantitative loss of TCE to the atmosphere as thermophilic
temperatures in the composts were reached. Further investigation on the
fate of TCE in composts is not warrented.
59
-------
IV. PILOT SCALE COMPOSTS
A. EPA RCRA Research, Development and Demonstration Permit
The Resource Conservation and Recovery Act designates that waste from
munitions manufacturing and loading operations is a K044 hazardous waste.
Experiments aimed at treatment of a hazardous waste requires a RCRA permit.
The 1984 RCRA amendments provide a distinction between commercial disposal
operations and research and development.
In December of 1984, ARC wrote Mr. John Skinner of EPA's Office of
Solid Waste asking for guidelines for obtaining a RCRA R&D permit. In
January, 1985, ARC representatives met with EPA Office of Solid Waste
personnel to discuss composting of LAAP and BAAP sediment. EPA personnel
agreed at this time that composting of these sediments would be an
appropriate subject for a RCRA R,D&D permit. The actual application1for
the RCRA R,D&D permit was submitted on 5 February, 1985. EPA completed the
initial review of the application on 15 April, 1985 and sent ARC a list of
questions. ARC responded to these questions on 19 April, 1985. The permit
application and answers to the questions were submitted to an EPA
consultant for technical review. Additional questions sought by the
consultant were answered by ARC on 25 April, 1985.
The major question then became the reactivity of the sediment.
Several tests on the LAAP and BAAP sediments were performed at ARC and the
Bureau of Mines. These tests included:
Gap Test
DDT Test
Bureau of Explosives Impact
Thermal Stability Test
Electrostatic Discharge Test
Autoignition Test
Detonation Test
60
-------
These tests were run on air dried sediment at the following concentrations
of explosives in the sediments (dry weight basis).
LAAP BAAP
Nitrocellulose 1.03%
TNT
RDX
HMX
Tetryl
11.5%
6.0%
0.16%
0.5%
All reactivity tests on these sediments were negative. These test results
were submitted to EPA on 20 May, 1985.
A draft RCRA R.D&D permit was issued by EPA Region III on 30 May, 1985
and a public hearing announced for 1 July, 1985 (see Appendix M) . The
public hearing held on 1 July, 1985 and a 30 day comment period produced no
comments that warranted hold-up or denial of the permit. Thus, EPA Region
III issued ARC the first RCRA R,D&D permit No. VAD 06 112 2156 on 1 August,
1985.
B. Materials
l._ Composting Materials
Three composting mixtures were used in these studies, hay-horse
feed, sewage sludge-wood chips, and horse manure-hay-saw dust. The hay-
horse feed composts were composed of approximately 50% (dry weight basis)
chopped alfalfa hay, and 50% Purina Sweetena horse feed. The microbial
seed for this compost was provided by soaking the hay in a water slurry of
horse manure.
The sewage sludge compost consisted of equal volumes of wood
chips (25-35% moisture) and sewage sludge (65-70% moisture). The sewage
sludge was obtained from the Arlington Wastewater Treatment Facility in
Arlington, Virginia. The sewage sludge was a mixture of primary and
secondary sludge with ferric chloride and lime added. The ash content of
the sludge was 35-40%. The sludge provided the microbial seed for the
sewage sludge-wood chip composts.
61
-------
The horse manure-hay-saw dust compost was a combination of horse
manure from two stables; one using saw dust as bedding, the other using hay
as bedding. The relative quantities of saw dust to manure could not be
determined. The amount of hay was adjusted by mixing the manure from the
two stables to give adequate porosity in the compost. Although no
quantitative information on the manure-hay-saw dust compost was obtained,
visual inspection indicated that manure comprised greater than 50% of the
dry mass. No additional materials were added for seed. The manure from one
of the stables was relatively old and did not contain the available
nutrients as would be found in fresh manure. As a result of the lack of
nutrients, sufficient Purina Sweetena horse feed was added to dilute the
compost 19.8% after 19 days of composting.
2. Contaminated Sediments/Soils
Contaminanted sediment was collected from Badger AAP and
Louisiana AAP for pilot scale composting. Two drums of Louisiana sediment
were taken from lagoon #4 near the spillway. The Badger sediment was taken
from the dredgings mound (two drums) and from near the sluice gate at the
end of "lagoon #1 (one drum). The sediment from the sluice gate was
extremely wet due to the heavy rains the night before collection. It was
not used in the composting study because the drier soil from the dredgings
mound contained sufficient nitrocellulose.
C. Composting Apparatus
Six 488 gallon 304 stainless steel tanks measuring 5 feet in diameter
and 4 feet in height were used as composters. These tanks were placed in
two 19- x 9-ft Janco greenhouses located within a concrete lined pit and
surrounded by a six foot high fence. Three tanks were placed in each
greenhouse. Each tank was covered with a plywood cover with galvanized
steel inner facing. The outside of each compost tank was covered with
fiberglass insulation. A perforated wooden platform was placed on wooden
blocks three inches from the bottom of each composter. Woodchips were used
to fill the space at the bottom of the tank to provide insulation and to
adsorb leachate as it was produced during composting.
62
-------
As shown in Figure 10, each compost tank had a 2 inch drain near the
bottom of the tank which led to a leachate collection system and provided
a means of pulling air through the composts. A ball valve in the aeration
line to each tank provided individual aeration control. A port was placed
in each aeration line so that the air velocity could be measured from each
tank and air samples could be taken for analysis. A valve was positioned
in each line so that water condensate could be drained from system. The air
lines from all six composts tied into a single line from one blower. The
blower was intermittently operated by an adjustable timer.
D. Experimental Design
Two sets of pilot scale composting experiments were initially
planned. In the first set of experiments, hay-horse feed and sewage
sludge-wood chips composts were evaluated with Louisiana soil. Three
composters of each compost material were formulated; two of these
composters contained the LAAP sediment (Tank 1 and 2 for hay-horse feed and
4 and 5 for sewage sludge-wood chips) and one composter served as a control
(Tank 3 for hay-horse feed and 6 for sewage sludge-wood chips). For these
studies7 the hay-horse feed composts were housed in one greenhouse and the
sewage sludge-wood chips in the other greenhouse. Based on the results of
the laboratory studies, the hay-horse feed composts were amended with LAAP
contaminated soil at the 11% level while the sewage sludge-wood chips
composts contained 16% sediment.
In the second set of similar experiments, Badger AAP soil was added to
two composts containing hay-horse feed and two sewage sludge-wood chips
composts. Both composts types contained 15% by weight of the Badger
nitrocellulose contaminated soil.
The first pilot study using LAAP sediment indicated that effective
destruction of the explosives occurs in composts that can maintain very
high levels of microbial activity (high temperatures) for extended periods
(greater than 6 weeks). Sewage sludge-wood chip composts are biologically
too stable to provide the environment needed for extended high levels of
microbial activity. Therefore, a second LAAP compost study was conducted
using horse manure, hay, and saw dust as composting materials.
63
-------
ELEVATED TANK LID
1 FIBERGLASS INSULATION
I/ /
AIRFLOW
t/s-
STAINLESS
STIIL -*•
TANK
4'
1
*
1
A
/
f
d
t
\
r
\
i pi
r
////////// /////////
1 1 /
1 1 ' [_J _ / 1 /
^~~T^ ^_^ i~ n~r^
- — X x y^" * i-y ^—
/r^ f ^ COMPOST ^ ^^ _^
{ ^~ / ~^~- ' S^* ^^~~~" \
' ^^.— Jt\ - }
-------
The manure composts were not replicated. One control and one treated
compost were set up. LAAP sediment was added to the treated compost at
11.8% by weight; no sediment was added to the control. After composting
for 11 days compost temperatures dropped rapidly in the treated compost.
This loss of microbial activity was associated with the toxicity of the
LAAP sediment. Adjustments in the aeration failed to increase the
temperature in the treated compost. Therefore, after 19 days of composting
a small amount of compost (34 Ib dry weight) was removed from the composts
and 90 Ib (dry weight) of Purina Sweetena horse feed was added.
E. Compost Set Up
1. Sediment/Soil Preparation
a. Hay-Horse Feed and Sewage Sludge Composts
The volume of sediment/soil needed to setup four composts
was too large to allow all the sediment/soil to be homogenized. Therefore,
two drums each of the contaminanted sediment from LAAP and BAAP soil were
designated as "A" and "B". Each drum was individually mixed by mixing in
a 1-cubic yard cement mixer. Approximately half a drum of soil was mixed
in the cement mixer and then dumped into a plastic tub. The remaining soil
in the drum was mixed in the mixer and also dumped into the tub. Soil in
the tub was then mixed by hand. Then the soil was shovelled back into the
cement mixer and remixed (in two batches). The partially mixed LAAP
sediment in the plastic mixing tub is shown in Figure 11. Subsamples were
taken from each drum to quantify the explosives and heavy metals
contamination levels, and sediment/soil from only one drum was mixed into
any one compost. The analyses of these sediments are presented in Table
XV. For the LAAP compost studies, Barrel A was used in Tanks 2 (hay-horse
feed) and 5 (sewage sludge-wood chips) and Barrel B in Tank 1 (hay-horse
feed) and 4 (sewage sludge-wood chips). In the BAAP composting studies,
Barrel A was used in the sewage sludge-wood chip composts and B in the hay-
horse feed compost.
b. Manure Composts
LAAP sediment in drums A and B remaining after the hay-
horse feed and sewage sludge composts set up was pooled, air dried, and
crushed and sieved (2 mm) by hand. The sieved sediment was throughly mixed
65
-------
Figure 11. Photograph of Louisiana AAP Soil
Used for Composting
Table XV. Analysis of the Louisiana AAP and Badger AAP
Sediments
Concentration Mg/g
TNT RDX HMX Tetryl
LAAP-A 460,388 62,405 8,450 17,076
LAAP-B 322,735 67,749 9,001 3,961
LAAP-C 321,263 52,343 7,500 8,430
BAAP-A
BAAP-B
Nitrocellulose
56,382
49,950
66
-------
and then subsampled for explosives analyses. Explosives concentrations
(Table XV) were somewhat lower than those previously measured in drums A
and B. This discrepancy is believed to result from sieving the pooled
sediment. Some particles cemented together by high concentrations of
explosives were rejected by the sieving.
2. Mixing Compost Materials and Sediment/Soil
a. Sewage Sludge Compost
The composts were prepared by mixing small preweighed
batches of sewage sludge, wood chips and contaminated sediment/soil in a
one-cubic yard cement mixer. Approximately equal volumes of sewage sludge
and wood chips were weighed out. These weights were corrected for
moisture, and the appropriate amount of sediment needed for the batch
(corrected for moisture) was calculated. All calculations were handled
automatically by using a TI-58 programmable calculator. The calculated
weight of sediment soil was then mixed with the sewage sludge and wood
chips in the cement mixer. Fourteen to 15 batches were mixed to fill each
composter. The composters were filled for the LAAP sediment study. The
composters were partially filled for the nitrocellulose (BAAP soil) study
(12 batches) to allow for easier handling and sampling of the material.
Delays in initiating the pilot scale studies caused by
obtaining the EPA RCRA R,D&D permit forced a very rapid setup of the LAAP
composts. As a result, estimates of the moisture levels in the sediment
were used when mixing the compost. Small errors in the estimates resulted
in adding sediment at slightly higher rates than intended. A summary of
the materials used to construct each compost for LAAP and BAAP composts is
given in Tables XVI and XVII.
The mixing operation is shown in Figure 12. All operations
were carried out on a liner to avoid spills of the contaminated sediment/
soil. Materials in 55 gallon drums were weighed on a balance which was
accurate to 0.5 Ib. The materials were then dumped into the cement mixer
using a fork lift and drum tipper. The cement mixer was started, and the
compost materials were mixed for 2-3 minutes. With the mixer still
running, the compost was dumped into metal bushel baskets. The baskets
67
-------
Table XVI. Contents of Louisiana AAP Pilot Scale Composts
00
Hay (Ib) Horse feed (Ib)
Tank 1 250
Tank 2 238
Tank 3 236
Sewage Sludge(lb)
Tank 4 1344
Tank 5 1348
Tank 6 1232
Horse Manure (Ib)
250
238
236
Wood Chips(lb)
688
595
618
Sediment (Ib)
45
53
55
Sediment (Ib)
128
146
176
Sediment (Ib)
Total Dry Weight (Ib)
501
484
423
Total Dry Weight (Ib)
999
1020
936
Total Dry Weight (Ib)
% Sediment Addition
10.8
12.1
11.6
% Sediment Addition
15.5
15.9
16.9
% Sediment Addition
Tank 5
Tank 6
1419
1181
64
0
518
392
11.8
0.0
-------
Table XVII. Contents of Badger AAP Pilot Scale Composts
Hay (lb)* Horse feed (lb)" Sediment (lb)" Total dry weight (lb)" % Sediment Added
Tank
Tank
Tank
Tank
1
2
4
5
215
221.3
Sewage Sludge
331.5
342.6
216.9
223.2
Woodchips
260.6
292.2
76
78.2
109.0
107.1
508
523
702
742
15
15
15.7
14.4
" Dry weights
-------
were placed in the metal feed trough, seen in Figure 12, to contain any
materials spilled from the basket. A subsample of material was removed
from each batch as shown in Figure 13 and 14. The subsamples were mixed
together in a plastic cement pan, and then three subsamples of this
composts were taken for later analysis.
The baskets of mixed compost were hand carried and dumped
into the composters. The sewage sludge compost tank being filled is shown
in Figure 15. The partially exposed bamboo poles and blue thermocouple
wire show how the thermocouples were initially positioned in the LAAP
sediment composts. Fixed positioned thermocouples were removed from the
LAAP sediment composts after four weeks. A thermocouple probe was used in
placed of the fixed position thermocouples in the BAAP soil composts.
After the composter tanks were filled, a pillow stuffed with styrofoam
packing material was laid on the composts to prevent excessive heat loss
from the surface. •
b. Hay-Horse Feed Composts
The alfalfa hay was coarsely chopped in a hammer mill and
weighed into 55 gallon drums. Before being mixed into the compost the hay
was soaked for 2-14 hours in a dilute water slurry of horse manure.
The hay-horse feed, and sediment/soil were mixed in small
batches in a cement mixer as previously described for mixing the sewage
sludge composts. The manure soaking solution was drained from the hay
immediately before the hay was used. An amount of horse feed was weighed
out to equal the weight of hay in a drum (dry weight basis). Based on these
weights, an appropriate amount of sediment/soil was weighed out. Depend-
ing on the weight of hay in a drum, either 1/2 or 1/3 of the volume of each
component was dumped into the mixer and mixed. Each drum of hay and the
corresponding amounts of horse feed and sediment/soil were considered a
batch in the mixing process. Nine batches of hay were mixed to fill each
composter.
Calculations to determine the weights of sediment/soil to
add to each were performed in a TI-58 programmable calculator to avoid
computational errors. Sampling was as described for the sewage sludge
composts. The loading of one of the hay-horse feed compost in the
composter tank is shown in Figure 16.
70
-------
Figure 12. Compost Mixing
Operation
Figure 14. Subsampling Hay-
Horse Feed Compost
During Mixing
Figure 13. Subsampling
Sewage Sludf
Wood Chips
Compost Duri
Mixing
-------
\
Figure 15. Composter Being Filled with Sewage
Sludge-Wood Chips Compost
Figure 16. Composter Being Filled With Hay-
Horse Feed Compost
72
-------
c. Horse Manure Compost
Horse manure from the two stables was mixed by hand with
pitch forks and rakes in proportions that gave a mixture with sufficient
hay to provide adequate porosity for aeration of the compost. Weighed
aliquots of this mixture were blended with the previously processed LAAP
sediment in a cement mixer. The final compost contained 11.8% LAAP
sediment by weight. Subsampling the compost from the cement mixer was as
previously described. Thirteen batches of soil amended compost were
required to fill Tank 5. No sediment was added to the Control compost which
was placed in Tank 6. A polyethylene liner was placed over the compost in
each tank. Numerous slits in each liner allowed for uniform aeration. The
liner also helped to prevent rapid moisture losses from the top of the
composters.
F. Analytical Methodology
All analyses for the pilot scale composting conform to USATHAMA's
quality assurance program. These analyses are described below and in the
appropriate appendices.
1. TNT, RDX, HMX, and Tetryl
Triplicate LAAP compost samples were weighed into tared Mason
jars and stored at 5°C until extracted. Samples were extracted and
analyzed for TNT, RDX, HMX, and TNT transformation products according to
the method in Appendix H. Replicate samples were also taken for moisture
determination (dried 48 hours at 65°C). Additional triplicate sets of
samples from week seven hay-horse feed and sewage sludge composts and from
week 0-8 horse manure composts were collected for tetryl analysis. These
samples were stored at 5°C, and then extracted and analyzed according to
the method in Appendix I.
Leachate samples pooled over each week of composting were
subsampled and stored at 5°C until analyzed (Appendix N).
73
-------
2. Nitrocellulose
Replicate samples of compost were weighed into tared Mason jars
.and dried for 72 hours at 55°C. Percent moisture was calculated from the
weight loss. The dried samples were extracted as described in Appendix J
to quantitate nitrocellulose.
3. Gas Analysis
Gas samples were obtained from the headspace above each compost
and from a port placed in the aeration system to allow for sampling of the
atmosphere pulled through the compost. These samples were monitored for
C02, N2, NH3, and CH4 by GC (Appendix R). Gas samples were not taken from
the manure composts.
4. Heavy Metal and Pesticide Analyses
Samples of compost materials and compost from the hay-horse feed
and sewage sludge composts were dried (48 hours at 65°C) and finely ground
in a micro-mill. Subsamples were analyzed for heavy metals (Appendix 0).
Selected subsamples were also analyzed for pesticides (Appendix Q).
Leachate samples pooled by week were subsampled, acidified (pH less than or
equal to 2.0), and stored (5°C) until analyzed. Heavy metals were
quantitated in these samples according to the methods presented in
Appendix P.
G. Composting Louisiana AAP Sediment
1. Monitoring and Sampling Procedures
a. Hay-Horse Feed and Sewage Sludge-Wood Chip Composts
Daily compost inspection sheets were filled in to conform
to the EPA RCRA R.D&D permit. Included in this inspection were the
security of the facility, the integrity of the composters, composter
aeration plumbing, greenhouse liners, hazardous waste storage facilities,
the availability of safety equipment, and volumes of leachate and
condensate. Temperatures throughout each compost were measured and
recorded on a daily basis. The air flow through each compost was measured
every day and adjusted, if needed. If all composts needed substantial
74
-------
increases or decreases in aeration, the length of time the blower ran
during a 15 minute cycle was altered appropriately. A ball valve on each
aeration line was utilized to individually adjust the air flow through each
compost.
Air samples were collected weekly. Samples were taken from
the headspace above each compost when the blower was not on to determine
the composition of gases released by the compost. Samples were also taken
from the aeration plumbing (Figure 10) when the blower was running.
Compost samples were collected from each compost on a
weekly basis. Fifteen to twenty grab samples were removed from each
compost using a sampling device that consisted of six-inch double hinged
wing on the end of a 5-foot shaft. Samples were taken from throughout the
pile at varying depths and were pooled. Two subsamples for explosives
analysis and three subsamples for moisture determination were removed from
the pooled sample and the remaining compost was returned to the compost
tank.
Initially the composts were not mixed because spacial
sampling of the compost was planned after three weeks of composting. After
two weeks, it became apparent that the compost had to be watered and mixed
every 1-2 weeks to maintain desired levels of microbial activity. Composts
were mixed and watered by hand. At times, a portion of the compost was
removed to facilitate proper mixing.
b. Manure-Hay-Saw Dust Compost
Monitoring, leachate collection, temperature measurements,
and aeration adjustments were as described for the hay-horse feed and
sewage sludge composts. Composting conditions were adjusted to obtain the
highest possible compost temperatures in the treated compost. Aeration in
the control compost was utilized to hold its temperature range near to the
temperatures in the treated compost. No air samples were collected.
75
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Compost samples were collected after 0, 10, 19, 31, 42 and
56 days. The 0- and 56-day samples were collected while loading and
.unloading the compost. On the other sampling days, a cross sectional area
of the compost was sampled by digging a trench across each compost through
the center of the pile. The removed compost was homogenized and then
subsampled for individual analyses.
Composts were mixed and watered if needed after 7, 19, 34,
and 42 days of composting. After the 7-day mixing the treated compost
(Tank 5) began to cool. Attempts to increase the temperature by adjusting
the aeration were unsuccessful; temperatures were less than 40°C by day 11
(Appendix T). To revive Tank 5, 38 Ib (dry wt) of compost were removed and
90 Ib of Purina Sweetena horse feed and 8 Ib (dry wt) of fresh horse manure
were mixed into the compost on day 12 of the study. Compost temperatures
recovered within a few days.
2. Results
a. Hay-Horse Feed Composts
Materials in the hay-horse feed composts were well com-
posted during the 7-week trial. Variations between tanks appeared to be
random with no indications of the contaminated sediments inhibiting the
composting process, relative to the control tank. Mass reductions
attributed to composting were 66.1% in Tank 1, 46.5% in Tank 2, and 56.8%
in Tank 3 (control).
During the first three weeks of composting, average compost
temperatures (see Appendix T)were in the moderate range (38-55°C) and
variation in temperature within each tank was extreme. This variation was
found to result from two parameters which were not properly controlled, the
rate of air flow .and the distribution of air flow. The air flow rate was
initially set based upon previous experience with composting organic
wastes to stabilize and reduce their mass. After the first week of
composting the air flow rates were significantly reduced. A small increase
in the average temperature of the composts resulted, with average
estimated temperatures ranging from 45-55°C (see Appendix T, Table T-l).
76
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The uneven air flow seriously impaired the performance of
the composts. The insulating pillow channelled most of the air flow into
a limited portion of each compost. The presence of the thermocouple wires
and the bamboo stakes to which the thermocouples were attached tended to
push the pillow up and away from the compost. As a result, much of the air
flow was directed into the compost in the area around the thernocouples.
The excessive air flow in these regions rapidly dried the compost material,
which in turn reduced microbial activity and resulted in decreased
temperatures. These "cold spots" would slowly expand into the surrounding
compost. Typically 30% of each tank was cold and inactive most of the time
during the first three to four weeks of composting. It should be pointed
out that this cooling phenomena largely centered around the area where the
thermocouples were positioned, thus average compost temperatures during
the first four weeks of composting may be underestimated.
The compost drying and cooling problem caused by uneven air
flow initially was too slight to notice (first week of composting), but
progressively worsened. When the cause of the problem was identified, the
insulating pillows were removed (after 3 1/2 weeks of composting).
Temperature and moisture variability within each tank was substantially
reduced by removing the pillows; however, compost along one edge of each
tank still tended to dry rapidly and be somewhat cooler than the bulk of the
material in the tank. When the tanks were emptied at the conclusion of the
experiment, the cool edge was found to largely occur over an unsealed seam
in the aeration board at the bottom of the tank.
In the original experimental design, detailed sampling
around each of nine carefully positioned thermocouples was to occur after
three weeks of composting to provide information on explosives breakdown
relative to compost temperature and position in the compost pile. Drying
and cooling of the composts negated any results obtained from this type of
sampling. Also, settling and shifting within each compost moved the
thermocouples substantially within short time intervals. Therefore, after
four weeks of composting the thermocouples were removed and temperature
readings were obtained with a removable probe. Given that the composts had
to be watered and mixed frequently to counter the effects of the cool spot,
the use of a probe was much more practical than attempting to maintain
fixed thermocouples in each compost tank.
77
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Numerous probe readings were taken in each tank on a daily
basis to determine compost temperature. Three readings were taken in the
center of each tank: one reading near the bottom of the compost, one at the
center of the compost, and one between the center and the upper surface.
Four to eight readings were taken at mid-depth approximately mid-way
between the center and the outer edge of the tank. One or more readings
were taken mid-depth about six inches from the edge of the tank.
Average compost temperatures obtained using the probe after
the insulation pillows had been removed generally ranged from 52-62°C.
After seven weeks, all hay-horse feed composts were highly active and
capable of continued composting.
The loss of explosives during seven weeks of composting is
summarized in Table XVIII. Concentrations are corrected for loss of
compost mass. Mass loss was assumed to be linear with time, with losses
beginning after one week of composting. Variation in the data is somewhat
high due to the difficulty in obtaining representative samples; however,
losses of TNT, RDX, and HMX conform to first order kinetics. The log of TNT
loss with time in Tank 1 is illustrated in Figure 17. The first order rate
constants and half-lives for TNT, RDX, and HMX losses are given below:
Compost
Tank 1
Tank 2
Explosive
TNT
RDX
HMX
TNT
RDX
HMX
K*
0.393
0.246
0.151
0.495
0.211
0.146
Half-life
(wk)
1.8
2.8
4.6
1.4
3.3
4.8
* Values calculated using least squares regression.
78
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Table XVIII.
Concentrations of Explosives in Pilot Scale
Hay-Horse Feed Composts Amended with 11%
Louisiana AAP Sediment
Explosive Concentration (ppm)*
Tank
1
2
Composting
Time (wk)
0
1
2
3
4
5
6
7
0
1
2
3
4
5
6
7
TNT
39337
19986
13521
8841
8627
NA
4760
2535
53019
25083
37075
4933
17830
NA
4088
897
2-amino**
DNT
_
172
328
265
246
184
-
107
27
353
429
436
534
509
20
199
4-amino***
DNT
_
74
143
129
70
34
-
10
28
162
190
217
151
135
23
25
RDX
3483
2698
2261
2044
2011
1250
435
637
3677
3504
3049
2099
2736
NA
992
563
HMX
510
347
413
391
437
479
86
163
640
496
528
474
676
NA
246
160
* Adjusted for loss of compost weight
** 2-amino-4,6-dinitrotoluene
*** 4-araino-2,6-dinitrotoluene
NA - Not Analyzed
- Not Detected
79
-------
OQ
C
33 f
0) O
v; to
I CO
w
O O
TNT CONCENTRATION
M COMPOST (PPM
H
a
H
ro
m g
Q. »-••
rt
n :r
o
3 H
•o H.
o g
CO ft)
TUT CONCCMnuTION (C/C I
k - -
CONCENTRATION OF TNT AMINO COMPOUNDS IN COMPOST IPPM)
Tl
ca
c
fD
t—*
OO
rt
HO O 5C
H- m en o
3 rt it (u
(0 O en rt
O fa rt) H
en O
H
23
3
T3
O
cn
H- C
fo ft en o O
m 02;
•n cx H- p
n -
-------
TNT degraded most rapidly with an average half-life of 1.6
weeks. Losses of TNT were initially accompanied by small .increases in the
2- and 4-amino dinitrotoluene derivatives (Figure 18). Neither the 2- or
4-amino dinitrotoluene accumulated in the compost, and both compounds
decreased with increased length of composting. RDX degraded with an
average half-life of three weeks. HMX breakdown was slowest with an
average half-life of 4.7 weeks. Tetryl was quantitated only in the 7-week
samples; therefore, rates of tetryl breakdown are not available. After 7
weeks of composting, tetryl levels were reduced j>93% as shown below:
Tetryl (ppm)
Compost
Tank 1
Tank 2
0 Week*
360
1895
7 Weeks
18
125
% Reduction
95.0
93.4
* Values based on concentrations in the sediment.
Loss of explosives in compost leachate was very low as
expected, given the low solubility of explosives in water. Concentrations
of explosives in the leachate are given in Appendix T (Tables T-9 and T-
10). HPLC analysis of the leachate produced a multitude of peaks. Some
of the natural organic products in the leachate have retention times on the
HPLC chromatograph that cannot be distinguished from those of the
explosives. Reported concentrations of explosives in the leachate may
therefore be overestimated.
Metal analyses of the LAAP sediment and the composting
materials are presented in Appendix T. Metal concentrations in the hay and
horse feed were as expected for natural uncontaminated materials. The
sediment had elevated levels of lead and chromium, and low levels of
mercury were detected. Leachate during the first week of composting was
slightly acidic and the concentration of zinc in the leachate was
relatively high, eg. 618 ppm (Appendix T, Tables T-3 through T-5). All
subsequent leachates were alkaline and loss of metals from the compost via
leachate was low. Small losses of copper and zinc were observed throughout
the study. The formation of soluble ammonium complexes with copper and
zinc is thought to be responsible for these losses.
81
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b. Sewage Sludge-Wood Chips Composts
Good composting conditions for explosives degradation were
not achieved in the sewage sludge composts. As discussed in the previous
section, the initial use of high aeration rates and problems in getting
uniform air flow through the composts decreased the overall microbial
activity and prevented the composts from reaching temperatures substan-
tially above 50°C during the first 3 1/2 weeks of composting (Appendix T,
Table T-l). This problem was intensified by the contaminated sediment
which appeared to inhibit the composting process. During the first several
weeks of composting, the aeration rate in the control tank had to be
increased to hold its temperature down in the same range as the tanks
amended with the contaminated sediment.
Removal of the insulation pillows reduced the localized
drying and cooling problems within each compost tank. However, the average
temperatures of the sewage sludge composts did not increase after the
pillows were removed. Apparently, readily useable energy sources in the
compost had been largely exhausted by that time. Solutions of sugar and
then molasses were mixed into the tanks several times during the sixth week
of composting in an attempt to increase microbial activity, but no
increases in temperature resulted. The mass losses for Tanks 4, 5, and 6
(control) during seven weeks of composting were 17.3, 14.6, and 32.8%,
respectively.
No loss of explosives during composting could be confirmed.
Sampling the sewage sludge composts was difficult, and variation between
subsamples was high. Concentrations of explosives showed both increases
and decreases during the 7-week composting period (Table XIX). No
significant differences in the explosives concentration among weeks could
be detected by analysis of variance testing at the 5% level of probability.
The concentrations of explosives reported in Table XIX are corrected for
compost mass loss assuming a constant rate of loss beginning after two
weeks of composting.
82
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Table XIX. Concentrations of Explosives in Pilot Scale Sewage Sludge
Composts Amended with 16% Louisiana AAP- Sediment
Explosive Concentration (ppm)*
Tank
4
5
Composting
Time (wk)
0
1
2
3
4
5
6
1
0
1
2
3
4
5
6
7
TNT
28928
20740
30654
15200
28675
16574
11766
9860
49544
53846
78412
47121
42650
48032
45615
11032
2-amino**
DNT
698
1790
538
799
743
889
389
798
923
1809
640
692
971
814
756
749
4-amino***
DNT
395
792
217
308
277
325
121
263
289
832
236
321
377
276
272
200
RDX
6819
6177
8339
7028
6449
7552
4891
4428
6577
8464
10239
7252
8001
7849
8603
513
HMX Tet
1008 5.
587
1473
1265
1181
1318
888
1313
915 24'
1154
1852
1219
1448
1263
1369
515 2-
* Adjusted for loss of compost weight
** 2-amino-4,6-dinitrotoluene
*** 4-amino-2,6-dinitrotoluene
83
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Leachate from the composts contained apparent low levels of
explosives throughout the experiment (see Appendix T, Tables T-ll and T-
12). As previously discussed (in the previous section) the organics from
the compost materials leached from the compost produced a large number of
peaks during HPLC analysis. Analysis of the control compost demonstrated
that some of these peaks coincided with peaks attributed to the explosives.
Therefore, explosives concentrations in the leachate may be overestimated.
Metal analyses of the sewage sludge indicated that the
sludge was relatively clean (Appendix T, Tables T-16 through T-8). Compost
from this operation would not have metal concentrations that would
restrict the use of this material as a soil amendment. Leachate from the
sewage sludge composts was alkaline (pH 8.4 - 8.9) and solubilization of
metals in the leachate was limited to relatively low concentrations of
copper and zinc. These metals readily complex with ammonia to form water
soluble species under basic conditions.
c. Manure Composts
Initially the LAAP sediment inhibited composting and the
treated compost only marginally maintained thermophilic temperatures.
Mixing after 10 days upset the compost and horse feed had to be added to
affect compost recovery. After recovery (21 days) the treated compost
produced thermophilic temperatures until the termination of the study (56
days). The mass reduction resulting from composting was 31.5%. The
control compost was very well composted. Readily available energy sources
were exhausted in the control and temperatures dropped below 50°C after 43
days of composting. The total mass reduction was 48.7%.
Explosives levels in the compost decreased rapidly, approx-
imating first order kinetics. TNT, tetryl, and HMX concentrations
decreased substantially within the first 10 days of composting (Figures 19
and 20). RDX levels remained relatively constant during the first 19 days
of composting and then dropped dramatically as the microbial activity in
the compost increased after day 21 of the experiment. Listed below are the
first order rate constants and half-lives of each explosive.
84
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35.00O--
30,000
• TNT
2- & 4- AMINO DNT'S
Figure 19. TNT and Amino Compounds Concentrations in
Manure Compost as a Function of Composting Time
85
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7000-
6000-
5000
a.
a
a 4000
E
o
u
- 3000
c
o
o
c
o
u
2000
1000-
• - RDX
• - HMX
A - TETRYL
Figure 20. RDX, HMX and Tetryl Concentrations in Manure
Compost as a Function of Composting Time
86
-------
Explosive Kf Half-life (wks)
TNT 0.678 1.0
RDX 0.280 " 2.5
HMX 0.211 3.3
Tetryl 0.576 1.2
* Values calculated using least square regression.
The relative rates of loss of the explosives were similar to those found in
the hay-horse feed composts, but overall decontamination was noticeably
faster in the manure compost. After 56 days of composting, RDX levels were
reduced 94% and HMX was decreased by 81%. Tetryl levels were reduced 91%
within 27 days, and after 31 days, concentrations were too low to be
quantitated. The TNT concentration was reduced from 31021 ppm in the
compost at time zero to 138 ppm in 56 days, a 99.6% reduction. The 2- and
4-amino-dinitrotoluenes did not accumulate in the compost as the result of
TNT loss. Collectively these amino derivatives decreased 60% during the
first 10 days of composting, remained constant through the 27th day of
composting, and then decreased to 124 ppm (97% overall decrease) by the
56th day of composting.
Mobilization of explosives via the compost leachates was
negligible. No explosives were detected in leachate collected during the
first two weeks of the study. Between 0.2 and 2 ppm of TNT, RDX, and HMX
was found in the week 3 leachate, but only 200 mL of leachate was produced.
With increased length of composting,increased numbers and concentrations
of organics from the manure were found in the leachate. These compounds
interfered with explosives quantitation and resulted in falsely inflated
explosives levels. Some RDX and/or HMX may have been in week 4-8 leachate,
but interferences in the leachate did not permit accurate quantititation
(Appendix T, Table T-13).
87
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3. Discussion and Conclusions
Composting conditions in hay-horse feed composts were sub-
optimal during the first 31/2 weeks of the 7-week trial due to improper
aeration. Despite these conditions TNT, RDX, and HMX degraded rapidly.
Rates of breakdown could be adequately represented by first order kinetic
and half-lives of 1.6, 3.0, and 4.7 weeks were found for TNT, RDX, and HMX,
respectively. Insufficient data was collected to model tetryl breakdown,
but tetryl concentrations decreased 94% during 7 weeks of composting.
Rates of loss were as good as or better than those indicated by the
laboratory studies. Previous work in this area (Isbister e_t al_. , 1982) had
also indicated that artifically maintained laboratory scale composts tend
to underestimate the rate of explosives loss in larger self-sustained
composts.
Losses of explosives during 7 weeks of composting in sewage
sludge composts were erratic and generally low. Such results are
completely contrary to the findings from the laboratory studies where
explosives breakdown were generally faster in the sewage sludge compared
to the hay-horse feed compost. In the laboratory studies, all composts
were externally heated to maintain a temperature at or near 60°C. In the
pilot scale composts, temperatures resided largely in the 48-52°C range.
This temperature difference appears to be the key element in the
susceptability of the explosives to degradation via composting. The high
temperatures in the laboratory studies may reflect higher levels of
microbial activity needed to effectively degrade the explosive. The high
temperature could be necessary for the proliferation of specific thermo-
philic organism involved in the breakdown of these explosives. Increased
temperatures may be necessary to alter the physical state of the explosives
to render them susceptable to chemical or microbial attack. Another
alternative is that at elevated temperatures the explosives are not
chemically stable in the compost environment. Mechanisms of explosive
loss are not sufficiently understood to evaluate the means by which the
temperatures regulate the breakdown of explosives.
88
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The manure compost was highly successful in decontaminating the
LAAP sediment; RDX, HMX, and TNT levels were reduced 94.4,.81.2, and 99.6%,
respectively, within 8 weeks of composting. Tetryl concentrations were
reduced below the detection limit (80 ppm) after 27 days of composting.
The manure compost was initially inhibited by the high concentrations of
explosives and was completely upset after 10 days of composting. Un-
doubtedly if this inhibitory effect is lessened or eliminated, the rates of
decontamination will be improved.
The build up of TNT transformation products (amino derivatives
of TNT) was not observed in any of the composts. In the hay-horse feed
composts, a small increase in the 2- and 4-aminodinitrotoluene levels
coincided with large decreases in TNT. However, the concentration of amino
derivatives decreased with increasing the length of composting. Suffici-
ent data are not available to determine if the formation of amino
derivatives is an intermediate step in the loss of TNT or if this is an
ancillary reaction. In either case, the amino compounds appear to be short
lived in the compost.
Leaching of hazardous materials from the composts does not
appear to present any significant environmental hazard. The volume of
leachate from well managed composts is relatively small, and could easily
be collected and added back to the compost. Explosives concentrations in
the leachate were either low or not detected. The high levels of natural
humic materials leached from the composts interfered with the analyses and
could have resulted in falsely inflated explosives levels. It is not
certain that explosives were actually present in the leachate. Leachates
for the most part were alkaline; thus losses of heavy metals were minimal.
Small amounts of copper and zinc were solubilized as ammonium complexes.
Leachates also contained moderate concentrations of iron, apparently
present as organic chelates.
Sewage sludge and wood chips were not adequate materials to
compost the LAAP sediment. Sewage sludge has a high ash content and its
organic fraction is partially stabilized at the waste water treatment
facility. As a result, sewage sludge composts have relatively low energy
reserves available for microbial activity when compared to hay-horse feed
89
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or manure -hay composts. The lower energy reserves result in shorter
intervals during which composts can be maintained at temperatures above
60°C. In addition, the decreased availability of energy makes the sewage
sludge composts more susceptable to the inhibitory effects of LAAP
sediment and hinders the recovery of composts when the microbial activity
is temporarily upset.
The use of hay and horse feed as composting materials was
successful in decontaminating LAAP sediments, and the subsequent use of
manure mixed with bedding materials gave significantly improved results.
All of these materials are well suited for composting. They are easily
aerated and have large reserves of readily available energy with a
favorable nitrogen to carbon ratio for maintaining high microbial activity
over extended periods of composting (greater than two months). Although
the hay-horse feed compost probably provides a better microbial nutrition
source, the cost of hay and horse feed for large scale composting is
prohibitive. The improved performance of the manure compost over the hay-
horse feed compost was largely related to better compost mixing and better
daily management. Additional experience in the operation of composts for
explosives destruction should lead to further substantial increases in
decontamination rates. Improvements in compost formulation and mixing
should reduce or eliminate the inhibitory effects of the explosives on
microbial activity.
H. Composting Badger AAP Sediment
1. Monitoring and Sampling Procedures
Daily inspections to conform to the requirements of the permit
were as described in Section IV.G. 1. Temperature readings were taken daily
using a thermocouple probe. Several temperature readings were taken to
estimate the overall condition of the compost. Three readings were taken
in the center of each compost, near the bottom, midway up the pile and
between the middle reading and surface of the compost. Four to eight mid-
depth readings were taken midway between the center and the outer edge of
the composts, and at least one mid-depth reading was taken 6 inches in from
the outer edge at a point adjacent to where temperatures in the compost
were near the average. The air flow was adjusted as needed to maintain
appropriate compost temperatures.
90
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Air samples were collected weekly. Samples were taken from the
headspace above each compost when the blower was not on to determine the
composition of gases released by the compost. Samples were also taken from
the aeration plumbing (Figure 10) when the blower was running.
Composts were sampled at time zero and then after three and four
weeks of composting. Preliminary tests indicated that large quantities of
substances which interfere with the nitrocellulose analysis are produced
in the compost during the initial composting process (first two weeks).
Therefore, no compost samples were taken after one and two weeks of
composting. The sampling procedure consisted of digging a narrow (8-inch)
trench across the compost to the bottom of the composter. Then a 1- to 2-
inch layer was removed from the wall of the trench. This material was
thoroughly mixed, and three subsamples were removed for nitrocellulose and
moisture analysis. The remaining compost was returned to the composter.
2. Results
a. Hay-Horse Feed Composts
The hay-horse feed composts amended with Badger AAP sedi-
ment composted extremely well. The earlier problems associated with cool
spots due to the pillows, thermocouples and air diffuser board were fixed
by eliminating the pillows and fixed thermocouples, and sealing the crack
in the diffuser boards. Temperatures in these composts were significantly
higher than those observed in the LAAP composts. Once thermophilic
temperatures were reached, Tank 1 ranged from 65-83°C and Tank 2 ranged
from 62-86°C (see Appendix U, Table U-l). The air flow rates in the hay-
horse feed composts were maintained between 700 and 1200 linear feet per
minute (about six times that utilized for the LAAP composts). This high
air flow was necessary to maintain the temperature low enough so that the
compost would not catch on fire. As a result of the high temperatures and
air flow, the composts tended to dry out very quickly. Therefore, to
maintain microbial activity, each hay-horse feed compost was watered and
mixed twice weekly.
91
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The nitrocellulose concentrations in the compost as a
function of composting time are presented in Table XX. The initial concen-
tration of nitrocellulose in the compost was 6655 to 8176 ppm. After three
weeks of composting, the nitrocellulose levels in both of the hay-horse
feed composts were below the detection limit of 25 Mg/g-
The pH of all leachates was in the basic range from 8.1 to
9.0. The only metals detected in the leachate were small amounts of iron,
copper and zinc (Appendix U, Tables U-3 and U-4).
b. Sewage Sludge-Wood Chips Composts
The sewage sludge-wood chip composts amended with the BAAP
sediment composted better than that observed for the LAAP sediment amended
composts. Temperatures in the BAAP sewage sludge-wood chips compost were
generally in the 60+°C range (see Appendix U, Table U-l). Air flow was only
100-200 linear feet per minute and the compost did not generate the
extremely high temperatures that were observed in the hay-horse feed BAAP
compost.
The nitrocellulose in the zero time composts were 1449 to
5687 Ug/g- The 1449 number is way below the calculated amount of
nitrocellulose mixed in the compost. This low time zero nitrocellulose
value is due to problems with the analysis. The "A" barrel BAAP soil
contained another substance which tended to gel during the nitrocellulose
hydrolysis and give artificially low nitrocellulose values. Composting
for three weeks led to a decrease in the nitrocellulose concentration to
below the 100 Ug/g detection limit in one case. Small increases in the
nitrocellulose concentrations were observed after four weeks of compost-
ing. These increases could be due to organic acids which react with the
color reagent. In any case, a significant decrease in the nitrocellulose
concentration was observed in both sewage sludge-wood chips composts.
Only small quantities of zinc, iron and copper were found in the sewage
sludge leachates in spite of relatively high levels of Pb, Ba and Cr in the
original compost material.
92
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Table XX. Concentration of Nitrocellulose in-Compost Amended
with Badger AAP Soil as a Function of Composting Time
Nitrocellulose in ug/g*
HHF
HHF
SS
SS
Tank #
1
2
4
5
Calculated
NC Input
8435
8430
7350
6779
Analysis of
Time Zero Compost
8176
6655
1449
5687
Analysis of
Week 3 Compost
<25
<25
100
184.9
Analysis of
Week 4 Compost
NA
NA
117.2
202.7
* Detection limit for NC in hay-horse feed composts is 25 Ug/g-
Detection limit for NC in sewage sludge-wood chips compost is 100
93
-------
3. Discussion and Conclusions
Nitrocellulose is rapidly degraded in both hay-horse feed and
sewage sludge-wood chips composts. In fact, the addition of the BAAP soil
containing the nitrocellulose enhances the composting process over that
observed for controls (no explosives contamination). Leachates were not
analyzed for nitrocellulose because of the insolubility of nitrocellulose
in water. Only small quantities of iron, copper, and zinc were found in the
leachate.
Several studies have been conducted to determine the ability of
mesophilic microorganisms to breakdown esterified celluloses. In essence,
the literature indicates that these microbes cannot attack esterified
cellulose. This information led to the question as to whether the
thermophilic compost microbes were actually attacking the nitrocellulose
or if the observed degradation was simply due to thermal decomposition. To
resolve this question, literature was gathered on the thermal degradation
of nitrocellulose. Thermal degradation studies on nitrocellulose were
conducted by Leider and Pane (1981). They measured both the -ONC>2 ester
content and molecular weight of nitrocellulose after thermal aging at
various temperatures for various times. The loss of -ON02
product) is described by the second order rate constant.
C(0) - C(t)
C(t)
where k£ is the second order rate constant
C(0) is the initial concentration
C(t) is the concentration after time, t.
The molecular weight degradation is first order and described by the
following equation:
1 = 1 + kt
Mn(t) Mn(0)
k: is the first order rate constant where Mn(0) is the initial number
average molecular weight
Mn(t) is the number average molecular weight at time, t-
94
-------
Rate constants calculated from their data are as follows:
k2(T)
T°C _ (nitrate ester loss)/day _ (molecular wt degradation)/day
80
90
100
1.
5.
2.
3
8
2
X
X
X
10~4
10~4
10-3
4.
8.
3.
8
9
5
X
X
X
10
10
10
-7
-7
-6
Using the rate constants for nitrate ester loss, the degradation predicted
from thermal decomposition was compared to the compost degradation after
three weeks. The compost degradation was 108 and 24 times faster than that
due to thermal effects alone at 80°C and 90°C, respectively.
After comparing the thermal degradation rates with the com-
posting degradation rates of nitrocellulose, it was concluded that the
degradation observed during the composting process is due to the action of
11
thermophilic microorganisms in the compost and not due to thermal aging.
The major problem associated with using composting as a method
to clean up nitrocellulose contaminated soils and sediments is in
analysis. No specific method to identify and quantitate nitrocellulose
exists. Methods in current use require that the nitrocellulose be
hydrolyzed to produce nitrite which can be determined with color reagents
or specific ion electrodes. The Badger soil contains some other substance
which produces a gel during the hydrolysis reaction yielding false low
concentrations for nitrocellulose. The color reagents also react with
organic acids and formaldehyde) which are often produced during the
composting process,giving a false high concentration for nitrocellulose.
Nitrite specific ion electrode was evaluated for quantitation of the
nitrite produced from hydrolysis of nitrocellulose during this study.
However, use of an electrode to determine nitrite is also subject to
several interferences from compost breakdown products. These problems
combined with the different solubility characteristics of the various
grades of nitrocellulose make this explosive an analytical nightmare.
New research in the forensic identification of nitrocellulose
has been based on size exclusion chromatography. Lloyd (1984) used
reductive mode electrochemical detection with a pendant mercury drop
95
-------
electrode coupled with size-exclusion chroraatography to detect as little
as lOOyg of nitrocellulose. Some effort was expended during this contract
to use size-exclusion chromatography, coupled with electrochemical detec-
tion for nitrocellulose with some success. However, funds vere not
available for analytical methods development during this contract and the
effort had to be abandoned before it could be perfected. It is recommended
that further investigation be conducted to develop a method that is
specific for nitrocellulose.
The BAAP sediment composted extremely well in both the labora-
tory scale and pilot scale tests. The composting technique for nitrocel-
lulose is ready for a field demonstration at Badger AAP. A demonstration
and costs for the demonstration and full-scale treatment facility are
presented in Section VI. Composting is an economical method of decontam-
inating BAAP soil and could be used to process wastewater should the
facility be put back into operation. Local materials, eg. corn stalks and
cow manure, would make excellent compost materials for inexpensively
decontaminating this soil.
96
-------
I. EP Toxicity - Ames Assay of Compost Leachates
1. Sample Preparation
Water extracts (leachates) of the pilot-scale composts were
prepared as described in the EP Toxicity Test Procedures in 40 CFR 261 App.
II (one hay-horse feed, one sewage sludge-wood chips and one manure-hay-
saw dust compost). A water extract (leachate) was also prepared from
control composts which were not contaminated with explosives. These
extracts served as control compost leachates for the Ames tests. All
extracts were centrifuged to remove large particulate matter, filtered
through Whatman No. 50 filters, 0.45 U and 0.2u Gelman sterile membrane
filters. Sterility of the extracts was monitored by spotting filtered
extracts on nutrient agar plates.
2. Toxicity Testing and Ames Assay
Five Salmonella tester strains, TA1535, TA1537, TA1538, TA98 and
TA100, were obtained from B. Ames, Department of Biology, University of
California, Berkeley. The liver homogenate (Aroclor-induced S-9) was
obtained from Litton Bionetics, Inc., Kensington, Maryland. The mutagen
assay was performed as described by Ames e£ a_l. (1975). Replicate extracts
were tested in duplicate. Control mutagens not requiring S-9 activation
were 2-nitrofluorene (obtained from Aldrich Chemical Company and with
TA1538 and TA78), and N-methyl-N'-nitrosoguanidine (MNNG) (obtained from
Sigma Chemical Company and used with TA1535 and TA100). 2-Aminoanthracene
(Aldrich Chemical Company) was used as the positive control mutagen for
metabolic activation with S-9.
Preliminary testing of the compost extracts indicated that the
sewage sludge-wood chips compost extracts were toxic to the tester
strains at 100 yL/plate. Extracts of the hay-horse feed and manure-hay-
saw dust composts inhibited the growth of the tester strain lawns at
100 PL/plate. Based on these observations, each of the leachates was
tested at 50 ML/plate in the incorporation assay. Spot testing of the
leachates at 50yL on each of the tester strains showed slight inhibition
of the bacterial lawns but no increased colony formation around any of the
'spots' on the tester strain lawns.
97
-------
3. Results and Discussion
Data from Ames testing of duplicate extracts of -each compost are
presented in Tables XXI through XXIII. Each leachate was tested in the
incorporation assay at 50 PL/plate. One set of tests was run without
addition of the rat liver metabolic activating enzymes, with a second set
of identical tests performed with the addition of the metabolic activation
system (S-9 fraction of an Aroclor induced rat liver). As shown in the
Tables, the compost extracts tested at 50 ML per plate gave no mutagenic
responses in the plate incorporation assays with tester strains capable of
detecting frame-shift mutations (TA1537, TA1538, TA98) or tester strains
detecting base-pair substitutions (TA1535 and TA100).
Mutagens used to demonstrate positive reactions in the tester
strains included MNNG (N-methyl-N1-nitro-nitrosoguanidine), 2AA (2-amino-
anthracene), 2NF (2-nitrofluorene) and 9AA (9-aminoacridine).
In general, a negative result in the Ames test is defined as the
absence of a reproducible increase at least equal to, or greater than,
twice the number of spontaneous revertant histidine-independent colonies.
These compost extracts did not elicit a mutagenic response in any of the
tester strains indicating that neither mutagenic substances nor promuta-
gens (substances mutagenic only when metabolized) detected by this assay
are present in the water extracts of composts used to decontaminate
sediments from LAAP and BAAP.
98
-------
Table XXI. Ames Assay Data on Extracts From Hay-Horse Feed and Sewage Sludge
Composts Amended with Louisiana AAP Sediment
>£>
vfc
TA1535
No S-9 S-9
No S-9
TA1537
S-9
No S-9
TA1538
S-9
No S-9
TA98
TAIOO
S-9
No S-9
S-9
Tank 1
LAAP
HIIF
Tank 2
LAAP
HIIF
Tank 3
Control
HIIF
Tank 4
LAAP
SS/WC
Tank 5
LAAP
SS/WC
Tank 6
Control
SS/UC
K.'VI-I i ion
I'ub 1 1 iwi- Conl rol
16, 12
10
13
9, 9. 9
13
9, 13
17. 15
16. 10
14. 12
14, 13
13, 16
13. 16
15. 12
13
10 MB
MNNC
250
30
43
45
29
29
19
35
49
31
23
21
25
29
34
29
27
25
25
-
16
12
11
10
8
10
9
10
7
6
7
5
6
5
10
12
6
7
4
4
8
7
6
-
8
10
12
8
10
12
9
10
11
11
7
6
6
7
6
9
10
2.5 pg
2AA
228
28
36
40
38
42
50
40
37
49
50
53
28
30
14
12
5
30
17
18
15
16
9
1 1
35
27
21
10 MB
2NF
391
30
30
31
35
30
26
23
27
26
17
25
21
23
25
29
23
21
23
J2
2.5 pg
2AA
958
30
28
52
40
JO
27
28
25
23
28
24
30
21
18
16
83
19
17
17
15
24
25
23
31
31
I0pg
2NF
557
53
87
85
J7
41
81
73
71
89
70
78
89
80
82
79
60
57
59
61
44
2.5 pg
2AA
1055
118
107
110
93
115
135
1 10
91
90
90
83
90
81
84
95
102
95
96
80
75
86
83
10 pg
MNNG
1008
139
157
163
154
100
181
175
190
143
137
103
131
121
168
127
135
160
124
155
128
113
146
110
2. 5p g
2AA
TNTC
-------
Table XXII. Ames Assay Data on Extracts From Manure-Hay
Composts Amended with Louisiana AAP Sediment
o
o
TA1535
No S-9 S-9
TA1537
No S-9 S-9
TA1538
No S-9 S-9
TA100
No S-9 S-9
Tank 5
LAAP
Manure-
Hay
Tank 6
Manure-
Hay
Control
Reversion
Positive Control
16
11
15
15
13
13
18
19
18
10 pg
MNNG
65
17
18
15
20
28
25
15
24
20
-
-
-
12
10
8
7
9
10
8
10
12
50 yg
9AA
800
34
30
24
-
31
32
25
25
27
lOug
2AF
95
27
20
18
21
21
20
16
22
18
10 ug
2NF
TNTC
81
77
65
52
64
63
76
80
52
lOug
2AF
TNTC
160
134
139
142
131
150
123
132
120
10. yg
MNNG
515
158
183
183
201
189
179
192
163
173
2.5
2AA
530
-------
Table XXIII. Ames Assay Data on Extracts From Composts
Amended with Badger AAP Soil
TAI535
No S-9 S-9
TAI537
TA1538
No S-9
TA98
S-9
TA100
No S-9
S-9
No S-9
S-9
No S-9
S-9
Tank 7 12 20
BAAP 17. 11
HHF
Tank 8 16, 16
BAAI' 14, 16
IIIIK
T.uik 9 12, 11
I1AAI' 14, 14
ss/wi:
. Tank 10 7 , l>
JIAAI' H, /
SS/WC
H. V,'l s j.MI 1 )
I'D.. II i vi- ('mil nil Ml p )',
HNNC
2r>()
25
25
29
35
44
53
45
33
34
30
27
15
19
18
21
25
-
6
5
7
7
8
11
9
10
5
5
d
''
H
1 1
H
10
t,
-
7
7
13
15
12
10
13
7
8
5
6
5
10
2 .5 p «
2AA
228
26
41
10
13
42
44
18
26
6
8
12
8
17
29
8
10
27
10 pg
2NK
191
25
19
35
39
41
45
28
33
31
29
25
23
21
25
19
17
12
2-5 PB
2AA
958
33
31
40
40
41
21
23
10
12
15
12
12
14
II
10 MB
2NF
557
38
25
25
25
34
21
19
25
41
44
43
49
55
80
74
44
2.5 pg
2AA
1055
68
80
78
60
62
68
68
71
74
76
78
70
90
8)
10 pg
MNNC
1008
13)
153
134
156
116
136
110
115
123
1 J6
107
107
124
136
112
118
II 0
2 • 5 pg
2AA
TNTC
-------
V. CONCLUSIONS AND RECOMMENDATIONS
Breakdown of both the LAAP (TNT, RDX, HMX, and tetryl) explosives in
hay-horse feed and manure composts was highly successful. Explosives
degradation was relatively fast, and no toxic or objectionable degradates
accumulated in the composted materials. The materials in the hay-horse
feed compost are expensive; however, horse manure and other similar
materials can be obtained at minimal or no cost in the locality of military
installations.
Nitrocellulose in BAAP soil enhances the hay-horse feed composting
significantly. Thus, any fairly high energy material, such as cattle
manure, would be effective as a composting material to degrade nitrocellu-
lose.
No breakdown of explosives in the LAAP sediment-sewage sludge
composts was observed in these studies and loss of nitrocellulose in sewage
sludge composts was somewhat slower than in hay-horse feed compost. The
energy content of sewage sludge is not adequate to sustain high temperature
composting conditions for extended periods of time. Sewage sludge
composts also do not recover well if upset by toxic materials or
unfavorable composting conditions. Further work with sewage sludge
compost as a means to degrade explosives is not warranted.
In summary, it is recommended the following activities be pursued to
bring composting to a full-scale treatment process for contaminated lagoon
sediment:
• No additional work using sewage sludge-wood chips should be
pursued for degradation of hazardous materials because of the
limited energy source available in these materials.
• Composting LAAP sediment with hay and horse feed or manure and
bedding materials (hay, saw dust, etc.) has been shown to be an
effective decontamination procedure. It is recommended that
composting be tested in a full scale demonstration at LAAP.
102
-------
TNT is the major contaminant in the LAAP sediments. Although TNT
is rapidly lost during composting, the mechanism of TNT loss and
the fate of the TNT molecule are not known. It is recommended
that laboratory studies be conducted (prior to or concurrent
with the LAAP demonstration) to investigate the mechanism(s) of
TNT loss, to identify degradates, and to determine the fate of
these degradates in the environment. This information will be
helpful, if not essential, in obtaining a delisting of composted
explosives.
Nitrocellulose in the BAAP soil increases the rate of compost-
ing. Thus, composting should provide an inexpensive method for
decontamination of BAAP soil. It is recommended that composting
of nitrocellulose proceed to a demonstration at BAAP.
103
-------
VI. COMPOST DEMONSTRATION AND PRELIMINARY FULL SCALE
COMPOST DESIGN AND ECONOMICS
A. Composting Demonstration at Badge-r AAP
A time-task chart for a field demonstration of composting as a means
of degrading ".itrocellulose from BAAP soil is presented in Figure 21. The
BAAP demonstration program will take approximately 15 months to complete
including the following:
obtain EPA RCRA R.D&D permit
develop a better method to quantitate nitrocellulose in soil and
compost
- site preparation
- evaluation of three full scale composting scenarios
- evaluation of compost curing methods
- final design and economics for full scale clean-up of BAAP soil
by composting.
The total cost of this field demonstration program is $298,892 including
$57,791 for materials of construction.
B. Composting Demonstration at Louisiana AAP
Demonstration of the composting technique for decontamination of TNT,
RDX, HMX and tetryl from LAAP sediment will require 14 months to complete
as shown in Figure 22. The demonstration program should include the
following tasks:
- obtain Superfund approval
identify and determine the fate of composted TNT
- site preparation
evaluate three rates of sediment loading during full scale
composting operations
evaluate the need for benefits of recomposting (optional)
- evaluate compost curing methods
104
-------
TASK DESCRIPTION OCT NOV DEC JAN FED MAH AI'H J1AY .IUN Jill. ADC SKF 0(;T NOT_ DKC
'lask I Site Selection & Soil Analysis ^ — -^»
Task II Obtain R.D&D Permit ^ ^
Task III NC Analytical Method Development ^ ^
'lask IV Site Preparation ^ ^
l.isk V Composting at BAAP ^ ^
A. Compost @ 40% Sediment for 3 weeks ^ T*
II. Compost @ A0% Sediment for 2 weeks V ji
then add 40% more sediment + 20% new
compost materials and compost for 2
additional weeks
C. 30% Compost A + 40% sediment + 30% ^-~A
new compost and compost for 3 weeks
Task VI Compost Curing Studies ^ *
T.isk VII Sampling and Analysis
A. Sampling arid Analysis of Compost A ^ T»
li. Sampling and Analysis of Compost II 'F it
C. Sampling and Analysis of Compost C ^ •
Task Vlll Design and Economics for Pull Sc.ile Cleanup * ^
'l.isk IX Reporting
A. Monthly Technical and Financial A A A A AAA A A A A A A
II. Final Report ^P .
Figure 21. Time Task Chart for Composting of Badger AAP Soil
-------
TASK DESCRIPTION
PROGRAM MONTH
'86 '87
Jul. Aug. Sept. Oct. Nov. Dec. Jan. Feb. Mar. Apr. May
June July Aug.
Task I
Task II
Task III
- Task IV
Site Selection and
Soil Analysis
Obtain R.D&D Permit
Identify and Determine the
Fate of Composted TNT
Site Preparation
Task V Composting
Task VI Recoraposting (Optional)
Task VII Sampling and Analysis
Task VIII Compost Curing
Task IX Design and Economics for
Full Scale Cleanup
Task X Reports
A Monthy Technical and
Financial
B Final Report
Figure 22. Time Task Chart: for Composting of Louisiana AAP Soil
-------
- final design and economics for full scale and curing methods
clean-up of LAAP sediment by composting.
The total cost for this field demonstration program is $458,424 including
$72,786 for materials of construction.'
C. Preliminary Design and Economics for a Full Scale Cleanup of BAAP Soil
by Composting
In performing this preliminary design and economics for a full scale
cleanup of BAAP soil by composting, several assumptions were made. These
assumptions are listed below:
- twenty-five acres of soil contaminated to a depth of 2 feet must
be cleaned up (80,700 cubic yards)
- density of the soil is approximately 2500 Ib/cubic yard
soil moisture at field saturation level is approximately 44%
- compost materials consist of manure, hay or other bedding
material obtained locally at little or no cost
density of the composting materials is approximately 200 lb/
cubic yard
compost materials moisture is approximately 65%
soil amended to compost at a level of 40%
- compost moisture maintained at 50-65%
- composting time for complete degradation of nitrocellulose is 2
to 3 weeks
composting will be conducted on a concrete pad with a roof to
minimize leachate problems
windrow-forced aeration composting is used with the material
turned 2 times per week
The layout of a full scale compost system is shown in Figure 23. This
system consists of 24 windrow composts. Each windrow is 6 feet in height,
14 feet at the base, 3 feet across the top and 140 feet in length and
contains 264 cubic yards of material. At 40% sediment addition, each
compost will initially contain 17.8 tons of soil (dry wt basis) and 26.7
tons of compost materials. After composting for two weeks, the compost
will be remixed with the addition of 17.8 tons of soil and 5.3 tons of new
107
-------
o
00
120'
LEACHATE POND
O
o
o
LEACHATE
"DRAIN
ROOF
o
a
^/SUPPORT
140'-
.- AIR CONTROL
U VALVE
BLOWER
-va>
O
COMPOST
WINDROW
o
500*
o
— — --LEACHATE FLOW
— AIR FLOW
TO BLOWER
Figure 23. Layout of Full Scale; Composting Plant at Badger AAP
-------
compost materials. With 24 windrows in simultaneous operation, cleanup of
the 80,700 cubic yards of BAAP soil will required 9 years. The capital cost
for the system are presented in Table XXIV. Operating costs are presented
in Table XXV. Costs fo-r decontamination of 80,700 cubic yards of BAAP soil
are estimated to be $2,620,200 compared to $8,070,000 to $16,140,000 for
fuel for incineration (no capital or labor).
D. Preliminary Design and Economics for a Full Scale Cleanup of
Louisiana AAP Sediment by Composting
Several assumptions were made in completing the design and economics
for a full scale cleanup of explosive contaminated lagoons at LAAP by
composting. These assumptions are as follows:
- a total of 5 acres of land (lagoon bottom sediments) contamin-
ated to a depth of 2 feet must be cleaned up (16,133 cubic yards)
density of the sediment (dry) is 2500 Ib/cubic yard
- Moisture levels in the sediment are approximately 50% at
saturation
composting materials (manure, straw, hay and other bedding
materials) can be obtained locally at little or no cost
density of the composting materials is approximately 200 lb/
cubic yard
moisture in the composting materials is 60-65%
- contaminated sediment will comprise 20% of the initial compost
dry weight
composting time for the complete destruction of explosives is 6
weeks
composting will be conducted on a concrete pad with a roof to
minimize leachate problems
- window-forced aeration composting is used with materials being
turned and mixed 1 to 2 times per week.
The full scale composting facility for treatment of the LAAP sediment
will be identical in design but twice as large as the BAAP site (Figure 23).
Windrow size will also be the same and each compost will contain 264 cubic
yards of composting materials (267 dry tons). Contaminated sediment will
comprise 20% of the initial dry mass of each compost (11.4 tons of
109
-------
Table XXIV. Capital Costs for Badger AAP Composting Plant
Leveling, grading of land 3,200
Concrete pad with 1-ft x 1-ft troughs 300,000
Roof and support trusses 106,000
Aeration system
Piping 13,500
Valves 4,900
Blower 18,000
Metal for aeration system cover 19,300
Liner for leachate pond 33,400
SCARAB composter 35,000
Front end loader 20,000
$535,300
Table XXV. Operating Costs for Full Scale Composting
of Badger AAP Soil
Operators
3 people for 9 years @ 20,000 540,000
Benefits @ 25% salaries 135,000
Analysis
1 person for 9 years @ 20,000 180,000
Benefits @ 25% salaries 45,000
Maintenance @ 3,000/year 27,000
Electricity @ 2,000/year 18,000
Miscellaneous @ 3,000/year 27,000
Compost materials 890,200 cubic yards @ 50/40 cubic yards 1,112,900
$2,084,900
110
-------
sediment/compost). Destruction of the explosives will be complete with 6
weeks and the compost will be removed from the concrete pad and transported
to an adjacent area for final curing. Continuous operation of 48 windows
will decontaminate the estimated 16,133 cubic yards of sediment in 4.2
years. Capital costs and operating costs for this facility are presented
in Tables XXVI and XXVII. The estimated total costs for sediment
decontamination by composting (16,133 cubic yards) are $2,431,150, com-
pared to fuel costs of $1,613,300 to $3,226,600 for incineration (capital
and labor costs for incineration not included).
11J
-------
Table XXVI. Capital Costs for Louisiana AAP Composting Plant
Leveling, grading of land
Concrete pad with l~ft x l~ft troughs
Roof and support trusses
Aeration system
Piping
Valves
Blower
Metal for aeration system cover
Liner for leachate pond
SCARAB composter
Front end loader
6,400
500,000
212,000
27,000
9,800
36,000
38,600
66,800
35,000
20,000
$951,600
Table XXVII.
Operating Costs for Full Scale Composting
of Louisiana AAP Sediment
Operators
3 people for 4.3 years @ 20,000 258JOOO
Benefits @ 25% of salaries 64,500
Analysis
1 person for 4.3 years @ 20,000 86,000
Benefits @ 25% of salary 21,500
Maintenance @ 6,000/year 25,800
Electricity @ 3,000/year 12,900
Miscellaneous @ 6,000/year 25,800
Compost materials 788,040 cubic yards @ 50/40 cubic yards 985,050
$1,479,550
112
-------
VII. REFERENCES
Ames, B.N., J. McCann and E. Yamasaki (1975) "Method of detecting
carcinogens and mutagens with the Salmonella/mammalian-microsome
mutagenicity test, (Mutation Research., 31, 347-364.
40 CFR 261 App. II, EP Toxicity Test Procedures.
Isbister, J.D.; R.C. Doyle and J.F. Kitchens (1982) "Engineering and
Development Support of General Decon Technology for the U.S. Army's
Installation Restoration Program, Task II, Composting of Explosives"
USATHAMA Contract DAAK11-80-C-0027.
Leider, H.R. and A.J. Pane (1981) "Degradation of the Molecular Weight
and Nitrate Ester Content of Cellulose Nitrate on Thermal Aging",
NTIS DE81 029875.
Lloyd, J.F.D. (1984) "Detection of Differentiation of Nitrocellulose
Traces of Forensic Science Interest with Reductive Mode Electro-
chemical Detection at a Pendant Mercury Drop Electrode Coupled
with Size-Exclusion Chromatography," Anal. Chem., 57, 1907-1912.
113
-------
Appendix A
Synthesis of 14C-RDX
was synthesized via the processes outlined by Bachmann e_t a_l.
(1951). This process is carried out by nitrating hexamethylenetetramine
dinitrate with 98% nitric acid in the presence of acetic anhydride and
ammonium nitrate.
The experimental setup used for this synthesis is shown in Figure A-
1. The reaction vessel was a 25 mL, 3-necked, round-bottomed flask. The
flask was supported in a water bath. Stirring was provided with a 1/4- x
1/16-inch magnetic stir bar and a water driven, magnetic stirrer located in
the water bath under the flask. Reagents were added via two 2 mL disposable
pipets which were mounted in teflon sleeves in the right and left side
necks. The flow of liquid was controlled by a bulb on each pipet. Solid
reagents were added via a small funnel located in the center neck.
The ^C-hexamethylenetetramine dinitrate was made as follows. 0.43 g
of reagent grade hexamethylenetetramine was placed in a 10 mL beaker.
Approximately 0.5 mCi of ^C-hexamethylenetetramine (purchased from Path-
finder Laboratories) in 0.75 mL of methylene chloride was added to the
beaker and the solvent evaporated. The beaker was placed in an ice salt
bath on a water driven, magnetic stirrer. Then 0.47 mL of 70% nitric acid
was added to the hexamethylenetetramine in the beaker with stirring. The
mixture was maintained at 5°C for 15 minutes. The precipitated l^C-
hexamethylenetetramine dinitrate was collected by vacuum filtration and
dried in a vacuum oven at 20°C.
To prepare the RDX, 0.5 g ammonium nitrate and 0.3 mL of acetic acid
were added to the three-necked, round bottomed flask and warmed to 75°C.
To this mixture, 0.3 mL of acetic anhydride and 0.16 g of 14C-hexamethy-
lenetetramine dinitrate were added. 1.45 mL of acetic anhydride, 0.26 mL
of 98% nitric acid and 0.49 g hexamethylenetetramine dinitrate were
alternately added to the flask via the pipets or funnel over a 15 minute
time period while maintaining vigorous stirring. The mixture was allowed
to remain at 75°C for an additional 15 minutes. The mixture was then cooled
114
-------
PIPET
TEFLON SLEEVE
WATER BATH
Figure A-l.
Apparatus Used to Synthesize Small
Amounts of 1
-------
to 60°C, and the precipitated RDX was filtered from the hot mixture with a
Millipore filter and 0.45p teflon filter disc. The crude 14C-RDX was
recrystallized from acetone. The resultant product had a purity of 90% and
a specific activity of 0.38uCi/mg.
Reference
Bachmann, W.E.; W.J. Horton; E.L. Jenner; N.W. MacNaughton and L.B. Scott
(1951), "Cyclic and Linear Nitramines Formed by Nitrolysis of Hexamine,"
J. Amer. Chem. Soc. , 73, 2769-2773.
116
-------
Appendix B
Synthesis of
was synthesized according to the method of Solomon and
Silverman (1978). The reaction vessel shown in Figure A-l was used in the
synthesis except the funnel was replaced with a third pipet.
Three mixtures were prepared as follows:
1. Heel: 0.04 g l^C/reagent grade hexamethylenetetramine was
dissolved in 5.1 g glacial acetic acid and 0.04 g acetic
anhydride.
2. 38% hexamethylenetetramine solution: 0.2 g ^C/reagent grade
hexamethylenetetramine was dissolved in 3.3 g glacial acetic
acid.
3. 56.4% HN03/NH4N03 solution: 0.37 g NH^NOs was dissolved in
0.48 g HN03.
The reaction was initiated by placing the "heel" solution in the
reaction vessel and heating to 45°C in a water bath. The hexamethylene-
tetramine solution, 0.33 g of the 56.4% HNC>3/NH4N03 solution and 1.1 g
acetic anhydride were then alternately added to the heel over a period of
approximately 20 minutes. The reaction mixture was allowed to age for 6
minutes. The remainder of the 56.4% HN03/NH4N03 solution was then added
alternately with 1.6 g of acetic anhydride over a period of 15 minutes. The
mixture was then aged for 30 minutes. After the aging process, the mixture
was added to 3.5 mL of water and heated to 110°C for one hour to decompose
linear nitramine by-products. The mixture was then cooled, filtered
through a 0.45 U teflon filter and air dried. The resultant product had a
specific activity of 0.198 M Ci/mg.
Reference
Solomon, I.J. and L.B. Siverman (1978), "Process for Preparing Cyclo-
tetramethylenetetramine," U.S. Patent No. 4,086,228.
117
-------
Appendix C
Synthesis of ^C-Tetryl
Tetryl wac synthesized according to the procedures outlined by
Clarkson £t al. (1950). The reaction was carried out in a 25 mL, three-
necked, round bottomed flask fitted with a thermometer in the left neck and
a 2 mL pipet in the right neck. The flask arrangement was placed on a water
driven magnetic stirrer in a water or ice bath. Stirring was accomplished
with a 1/4-in x l/16~in magnetic stir bar.
Two solutions were prepared - a solution of dimethylaniline in
concentrated sulfuric acid (D.M.A.S.), and the nitrating acid. D.M.A.S.
was prepared by first mixing 0.6 mL of reagent grade N,N-dimethylaniline
with 100vi Ci of 14C-N,N-dimethylaniline (from Pathfinder Laboratories,
Inc.). The 14C-N,N-dimethylaniline mixture was then added to 1.8 mL 96%
sulfuric acid in a 5 mL beaker while stirring and cooling. The nitrating
acid was prepared by adding 3.6 mL of 99% sulfuric acid to 2.5 g crushed ice
in a 20 mL beaker. The mixture was stirred and cooled in an ice bath. Then
2.3 mL of 98% nitric acid were added to the sulfuric acid/water mixture.
The nitration reaction was carried out by placing 2.4 mL of the
nitrating acid in the 25 mL flask. The D.M.A.S. solution was slowly
dripped into the nitrating acid from the pipet while maintaining the
temperature of the reaction between 30 and 35°C. A red color was produced
with the addition of the D.M.A.S. When the addition was complete, the
reaction vessel was placed in a 90°C water bath until the temperature
reached 60°C. The temperature continued to rise on its own but was not
allowed tc exceed 100°C (cool with an ice bath). The solution turned
purple followed by separation of tetryl and violent evolution of brown
fumes. After completion of the fume-off, the mixture was heated in a water
bath (70°C) for 30 minutes to clarify the solution and expel the residual
oxides of nitrogen. The mixture was then cooled and the precipitated
tetryl collected with a Millipore filter and a 0.45 U teflon filter disc.
118
-------
The tetryl was purified by suspending it in 20 mL of water and blowing
steam through the water for 30 minutes. After cooling, the tetryl was
filtered and vacuum dried. The resultant l^C-tetryl had a specific
activity of 0.0755p Ci/mg.
References
Clarkson, C.E.; I.G. Holden and T. Malkin (1950), "The Nitration of
Dimethylaniline to Tetryl, 2:4:6: N-Tetranitromethylaniline. The Course
of the Reaction," J. Chem. Soc., 1556-1562.
119
-------
Appendix D
Synthesis of l^C-Nitrocellulose
l^C-Nitiocellulose was prepared by a method similar to the laboratory
procedure used at Picatinny Arsenal (1966) using the mixed acid method for
13.4% N nitrocellulose.
.25 mCi of l^C-cellulose (10.3 mg) from tobacco was mixed with 718 mg
of microcrystalline cellulose. The cellulose was placed in a 50 mL beaker
and the nitrating acid mixture was added. This mixture consisted of 13.7
mL 98% H2S04, 5.7 mL 90% HNOa and 3.3 mL of distilled water. The nitration
mixture was placed in a water bath and the temperature was maintained at
34°C for 30 minutes.
The reaction was then quenched by dumping the nitrocellulose and
mixed acids into 100 mL of distilled water and filtering with a Buchner
funnel using a 1.6 \i pore glass fiber filter. The filtrate was then washed
with 3 x 100 mL portions of distilled water. After washing, 0.5 mL of H2S04
and the filtrate were added to 100 mL water. This solution wiis placed in
a 90°C water bath for approximately 60 hours. When the acid boil was
completed, the nitrocellulose was filtered again and the 100 mL of fresh
distilled water was added. The pH was adjusted to 8.5 with Na2C03 and the
nitrocellulose mixture was placed back on the 90°C water bath for an
additional hour. At this point the nitrocellulose was filtered, washed
with 2 x 100 mL portions of distilled water, and dried in a vacuum oven at
40°C. Yield was 1.09 g nitrocellulose. The specific activity was 0.158 U
Ci/mg.
Reference
Encyclopec'.ia of Explosives and Related Items (1966), Vol. :2. C102.
120
-------
Appendix E
Analysis of TNT, RDX, HMX and Tetryl in Sediment
TNT, RDX, IIMX, and tetryl were extracted from the Louisiana sediment
by the following procedure. Fifteen mL of HPLC grade acetonitrile were
added to a weighed amount (approximately 1 g) of air dried sediment. The
mixture was thoroughly shaken to extract the explosives from the soil and
then centrifuged. The liquid was carefully removed from the soil with a
Pasteur pipet and placed in a 100 mL volumetric flask. The sediment was
extracted three additional times with acetonitrile and the extracts
combined in the 100 mL volumetric. If high levels of the explosives were
expected, the extract was brought up to 100 mL with acetronitrile. If low
levels of explosives were expected, the extract was brought up to 100 mL
with distilled water.
i
Analysis of the samples were accomplished using a HPLC consisting of
a LKB 2150 HPLC pump, a Perkin-Elmer LC55 UV detector and a HP 5380 GC data
system, computer controller and integrator. To accomplish the separation
of the explosives, 4.6 mm I.D. x 25 cm 5 ym sphericalODScolumn purchased
from Alltech was used with a mobile phase consisting of 51% methanol, 2%
dioxane, 0.5% acetonitrile and 46.5% high purity water which was 0.004 M in
n-hexylamine and 0.004 M in tetramethylammonium hydroxide buffered to pH
7.5 with phosphoric acid. The mobile phase flow rate was 1.3 mL/min. The
injection volume was 20 \iL using a Valco 6-port valve with 20 y L loop.
Detection of the explosives was a 232 nm. Under these conditions the
retention time and detection limit were as follows:
Retention Time Detection Limit
Explosive (min) (ppm in soil)
nMX
RDX
Tetryl
TNT
2A-DNT
4A-DNT
3.5
4.7
6.9
7.8
8.5
9.2
24.77
31.60
26.79
29.99
30.89
26.26
121
-------
Solutions containing high levels of explosives were diluted with
distilled water or distilled water/acetonitrile so as to-maintain a 1:1
acetonitrile:water mixture.
The explosives were quantitated by comparing the HPLC peak areas to
that obtained for solutions containing known amounts of the explosives.
The concentration of the explosives in the sediment is calculated as
follows:
Expl. in soil ( yg/g) = ppm in soln x 100 x dilution factor
wt of soil, g
122
-------
Appendix F
Analysis of Nitrocellulose in Soil
A sample of dried soil (approximately 1 g) was weighed into a 20 mL
tube. The soil was extracted twice with 2 mL of methanol thereby the
methanol was added to the soil and shaken. The slurry was centrifuged and
the liquid carefully drawn off the top of the soil with a Pasteur pipet.
This procedure removes free nitrates and nitrites which will interfere
with the nitrocellulose test from the soil.
The washed soil was then extracted with 3 mL of acetone. The soil was
shaken with the acetone, centrifuged and the acetone withdrawn with a
Pasteur pipet and placed in a graduated centrifuge tube. The extraction
was repeated twice and the extracts combined. Three mL of 1 N sodium
hydroxide were added to the combined extracts. The tubes were placed in a
30°C water bath under a stream of nitrogen until the volume was less than
3 mL (but not less than 2 mL) . A blank and standards containing from 20 to
160 yg nitrocellulose were also prepared at this time.
Approximately, 2-3 mL of nitrate/nitrite free distilled water were
added to each tube. The solutions were acidified to pH 2.2 with 3 N H2S04
and brought to 25 mL with nitrate/nitrite free distilled water. If high
levels of nitrocellulose are expected, dilution using nitrate/nitrite free
distilled water was done at this time. The samples were analyzed within
15-30 minutes after acidification.
A Hach Nilraver 3 powder pillow was then added to the blank and each
standard. The color development was allowed to proceed for 10 minutes, but
not more than 15 minutes. The spectrophotometer wavelength was set at
540 nm and the Hach DR2 spectrophotometer set to 100%T with the blank. The
absorbancfe of the standards was then measured and a standard curve of
nitrocellulose vs absorbance was constructed.
123
-------
The powder pillows were then added to the samples. After the
appropriate time, the absorbances of the standards were measured. The yg
of nitrocellulose in each sample was determined from the standard curve.
The yg/g of nitrocellulose in the soil-were calculated from the following
formula:
U g Nitrocellulose = y g Nitrocellulose x dilution factor
g soil dry weight of soil, g
This method differs from the USATHAMA standard method using acidifed
sulfanilamide in that solutions are acidified to pH 2.2 with H2S04- This
acidification allows better control of the pH for the color reaction than
the neutralization which depends on the acid in the reagent. If the color
reaction is carried out immediately after neutralization, addition of Cd
to reduce nitrate to nitrite is not necessary. Dilution before the
addition of the color reagent is preferable. However, equally good results
can be obtained if dilution is made after the addition of the color reagent
using a blank to which no color reagent has been added. This method
eliminates the problems of dilution that were experienced with the acidic
sulfanilamide color reagent.
124
-------
Appendix G
Analysis of Trichloroethylene (TCE) in Soil
Approximately 5 g of contaminated soil were weighed into 20 mL screw-
cap vials and extracted with 2 x 10 mL portions of methanol. The combined
extracts were brought to 25 mL with methanol. The samples were then
analyzed by gas chromatography-mass spectrometry.
The HP 5992 GC-MS system was set up using a packed column and a
molecular jet separator between the column effluent and MS ionization
source. The GC parameters were as follows:
Column: 8 ft x 2 mm I.D. glass packed with 1% SP-
1000 on 60/80 mesh Carbopack B with the
first 4 in packed with 10% SP-1000 on 80/100
mesh Supelcoport.
Oven: Initial temperature 70°C. Hold for 2 min-
utes, then 10°C/min to 220°C and hold.
Injection Port Temp: 230°C
Solvent Time Out: 3.5 minutes
Carrier Gas: Helium at 30 mL/min
The sample injection size was 8pl. The mass spectrometer was scanned from
29 to 400 amu in the electron impact mode. Quantitation was accomplished
by comparing peak height of the total ion-currnt chromatogram vs stand-
ards .
125
-------
Appendix H
Analysis of TNT, RDX, HMX, 2A-DNT and 4A-DNT in Compost
The composts (either hay-horse feed, hay-manure, or sewage sludge-
wood chips) were extracted by placing 280 mL of acetonitrile in the Mason
jar with the preweighed, wet compost materials. The mixture was carefully
stirred and placed in an ultrasonic bath (maintained at 35°C) at full
intensity for 30 minutes. The solvent was then decanted from the solids
and filtered using Whatman #2 filter paper on a Buchner funnel and vacuum.
The compost solids were then extracted three additional times using this
same procedure except that only 200 mL of acetonitrile were used in the
second, third and fourth extractions. The extracts were combined in a one
liter volumetric and brought up to volume with acetonitrile.
Clean-up of the extract for HPLC analysis was accomplsihed in the
following manner. Thirty mL of the extract were placed in a 50 mL (25 mm
x 150 mm) culture tube. The extract was then blown to dryness under a
stream of nitrogen while maintaining the temperature at 35-40°C using a
water bath. The residue was then sonicated for 30 minutes with 4 mL of
acetonitrile. The liquid was withdrawn from the tube and run through a
Pasteur pipet packed with 50 mm x 6 mm of activated florisil. The eluate
was collected in a 10 mL volumetric flask. The culture tube was rinsed with
1 mL of acetonitrile and this liquid was run through the florisil column.
The florisil column was rinsed with an additional 10 mL of acetonitrile.
The volume of the eluate was brought up to 10 mL with high purity water.
The solution turns cloudy at this point and is clarified by running through
a 0.2 u nylon 66 disposable filter which fits a 10 mL syringe. The
clarified solution was placed in a 16 mm x 125 mm culture tube. The hay-
horse feed and hay-manure extracts were analyzed by HPLC at this point.
The sewage sludge-wood chip extracts required further cleansing to
remove interferences. The sample was run through a C-18 sep pak under 5
inches Hg vacuum and the C-18 cartridge was then rinse with 1 mL of 65/35
acetonitrile/water.
126
-------
All samples were analyzed by HPLC using a LKB 2150 HPLC Pump, a
Perkin-Elmer LC55 UV detector and a Vista CDS 402 computer controller and
integrator. Separation was accomplished on a 4.6 mm I.D. x 25 cm Alltech
Econosphere 5 C-18 column using a mobile phase which consisted of 51%
methanol, 2% dioxane, 0.5% acetonitrile and 46.5% high purity water which
was 0.004 M in n-hexylamine and 0.004 M in the tetramethylammomium
hydroxide buffered to pH 7.5 with phosphoric acid. The mobile phase flow
rate was 1.3 mL/min. UV detection was at 232 nm. Under these conditions,
the explosives had the following retention times and detection limits:
Detection Limit
Retention Time (ppm in Compost)
Explosive (min) H/HF or H/M SS/WC
HMX
RDX
TNT
2A-DNT
4A-DNT
3.5
4.7
7.8
8.5
9.2
4.8
4.0
3.7
9.3
3.3
7.1
8.0
8.2
7.7
7.7
The explosives were quantitated by comparing the HPLC peak areas of
the extracts to those of standard explosive solutions. The ppm of the
explosives in the composts were calculated as follows:
H/HF or H/M Cone, in compost (dry wt. basis) yg/g =
# ng explosive x 1000 mL extraction volume x DF
3 (cone.factor) x dry wt of compost*
SS/WC Cone, in compost (dry wt. basis) ug/g -
# ng explosive x 1000 mL extraction volume x DF
2.727(cone.factor) x dry wt of compost*
* Dry wt. determined from % moisture calculations.
127
-------
Appendix I
Analysis of Tetryl in Compost
The composts (either hay-horse feed, hay-manure, or sewage sludge-
wood chip) were extracted four time with 200 mL of benzene. The
extractions were accomplished by placing the preweighed, wet compost
materials in a Mason jar with 200 mL of benzene. The mixture was carefully
stirred and placed in an ultrasonic bath (maintained at 35°C) at full
intensity for 30 minutes. The solvent was then decanted from the solids
and filtered using a Whatman #2 filter paper on a Buchner funnel with
vacuum. The procedure was repeated three additional times and the extracts
combined and brought up to 800 mL.
Tetryl was quantitated on a HP-5880 gas chromatograph using a
nitrogen-phosphorus detector. A 4 ft x 22 mm I.D. column packed with 3%
OV17 on 80/100 ANAKROM was used to affect separation with a nitrogen
carrier gas at a flow rate of 30 mL/min. A 4 yL injection volume was used.
The oven was programmed as follows: initial temperature was 190°C, held
for 1 minute then 5°C/min to 210°C and hold for 0.5 min then 10°C/min to
240°C and hold. The injection port was maintained at 215°C and the
detector at 310°C. Retention time for tetryl was 8.1 min with a detection
limit of 128 ppm in the compost.
Tetryl was quantitated by comparing the GC peak areas of these
extracts to those of standard explosive solutions. The ppm of the
explosives in the compost were calculated as follows:
Tetryl Cone, in compost (dry wt basis*) Ug/g = # Ug explosive x 800 mL extractior
dry wt of compost
* Dry wt determined from % moisture calculations
128
-------
Appendix J
Analysis of Nitrocellulose in Compost
Dried samples were weighed into quart Mason jars and then extracted
with acetone. For this extraction, 250 mL of acetone were added to each
Mason jar and the jars placed in an ultrasonic bath at 35°C for 30 minutes.
The mixture was then filtered through a Whatman No. 1 filter paper with a
Buchner vacuum filter apparatus and the filtrate saved. The compost
material was then extracted three more times with 250 mL of acetone. All
the extracts were combined and the final volume brought to 1000 mL.
Twenty mL of each extract were placed in a 50 mL graduated centrifuge
tube and were blown to dryness under a steam of nitrogen at 35°C. Two mL
of a 90:10 methanol-water mixture were added to each tube, shaken, and
centrifuged. The liquid was then carefully withdrawn with a Pasteur pipet
and the procedure repeated. This washing procedure removed nitrate and
nitrite from the sample which interfere with the analysis.
The washed sample, containing the nitrocellulose, was then reacted
with base to hydrolyze the nitrocellulose to cellulose and nitrite. To
perform this reaction, 9 mL of acetone and 3 mL of 1 N_ sodium hydroxide were
added to each tube. The tubes were placed in a water bath at 30°C under a
stream of nitrogen. The reaction was allowed to proceed until the volume
was less than three mL (but not less than 2 mL). A blank (containing
reagents only) and standards ranging from 20 yg to 100 yg of nitrocellulose
were also reacted in the same manner at this time.
Two to three mL of nitrite/nitrate free distilled water were added to
each tube. The solutions were then acidified to pH approximately 2.2 with
3 N H2S04- After acidification, the volume was brought to 25 mL with
nitrate/nitrite free distilled water. If the mixture was cloudy, it was
filtered through a nylon 66 0.45 |jm filter using a 25 mL leuer-lock syringe.
If high levels of nitrocellulose were expected, appropriate dilutions were
made at this point using nitrate/nitrite free distilled water. The
remainder of the analysis proceeded immediately after the acidification.
129
-------
The nitrite from the nitrocellulose hydrolysis was determined colori-
metrically using Hach Nitraver 3 powder pillows. One powder pillow was
added to each 25 mL standard or blank sample. The colo'r was allowed to
develop for 10 minutes (but no longer than 15 minutes). The Hach DR2
spectrophotometer was set to 540 nm and the 100% T set with the blank. The
standards were then run and the absorbance of the standards determined. A
standard curve of yg nitrocellulose vs absorbance was then constructed.
Powder pillows were then added to the samples (no more than 6 at a time).
After the appropriate reaction time, the absorbance of the samples were
determined. The number of y ;* of nitrocellulose in the samples was then
determined from the standard curve. The y g/g of nitrocellulose in the
compost was determined by the following formula:
y g NC x 1000 mL extraction volume x dilution factor
yg NC/g in compost = dry weight of compost in g
130
-------
Appendix K
Analysis of Trichloroethylene (TCE) in Methanol
Methanol samples from cold trap washings were analyzed using a Varian
6000 gas-chromatograph and a Hall Electrolytic Conductivity Detector
(HECD) operated in the halogen mode. The GC and HECD operating parameters
are given below:
Column:
Column Oven:
Injection Port:
Detector Base:
HECD Reaction Tube:
Reaction Gas:
Carrier Gas:
Solvent:
Injection Size:
8 ft x 2 mm I.D. I.D. glass pack with 1%
SP-1000 on 60/80 mesh Carbopack B with the
first 4 in packed with 10% SP-1000 on 80/100
mesh Supelcoport.
150°C Isothermal
230°C
300°C
800°C
Hydrogen at 35 mL/min
Helium at 32 mL/min
n-propanol at .5 mL/min
131
-------
Appendix L
Temperature Records for Laboratory Compos-ts
132
-------
14c-TNT Compost Temperatures (°C)
u>
u>
Hay-Horsefeed Compost
Sewage Sludge Compost
DATE
11/28/84
11/29/84
11/30/84
12/02/84
12/03/84
12/04/84
12/05/84
12/06/84
12/07/84
12/08/84
12/10/84
12/12/84
12/13/84
12/14/84
12/18/84
12/19/84
12/20/84
12/21/84
12/22/84
12/23/84
12/24/84
12/25/84
12/26/84
12/27/84
12/28/84
12/29/84
12/30/84
12/31/84
01/01/85
10 A*
60
60
61
60
60
61
62
63
62
62
63
62
61
62
62
62
62
61
59
59
61
61
61
61
61
61
61
61
61
10B
60
60
60
60
60
61
62
63
62
62
63
62
61
62
62
61
62
62
60
61
61
61
61
61
61
61
61
61
61
18A
60
60
60
60
60
61
61
62
62
62
62
61
61
61
61
61
62
61
60
60
60
60
60
61
60
60
60
60
60
18B
60
60
60
59
59
61
61
62
62
62
62
61
61
61
61
60
61
61
60
60
60
60
60
60
60
60
60
60
60
25A 25B
59
59
60
59
59
60
61
62
61
62
62
61
60
61
61
60
61
61
60
60
60
60
60
60
60
60
60
60
60
10A
59
60
60
60
60
61
61
62
62
62
62
62
61
61
62
61
62
61
61
61
60
61
60
61
60
61
61
61
61
10B
59
59
60
59
59
60
61
62
61
62
62
61
60
61
61
61
62
60
60
60
60
60
60
61
60
60
60
60
60
18A
59
59
59
58
58
59
60
60
60
61
61
60
59
60
60
60
60
60
59
59
59
59
59
59
59
59
59
59
59
18B
59
59
60
58
58
59
60
61
61
61
62
61
60
60
60
59
61
60
59
59
59
59
59
60
59
59
59
59
59
25A
59
59
60
59
59
60
61
61
61
62
62
61
60
61
61
60
61
61
60
60
60
60
60
60
60
60
60
60
60
25B
59
59
60
59
59
60
61
61
61
62
62
61
60
61
61
60
61
61
60
60
60
60
60
60
60
60
60
60
60
INCUBATOR
59
59
60
59
59
60
61
61
61
61
62
61
59
61
61
60
61
61
59
59
59
60
59
60
59
59
59
59
60
"' 10A = first replicate of compost with 10% sediment addition
- = thermocouple malfunction
-------
RDX Compost Temperature (°C)
Hay-Horsefeed Compost
Sewage Sludge Compost
DATE
12/22/84
12/23/84
12/24/84
12/25/84
12/26/84
12/27/84
12/28/84
12/29/84
12/30/84
12/31/84
01/01/85
01/02/85
01/03/85
01/04/85
01/05/85
01/07/85
01/08/85
01/09/85
01/10/85
01/11/85
01/14/85
01/15/85
01/16/85
01/17/85
01/18/85
01/21/85
01/22/85
01/23/85
01/24/85
01/25/85
01/28/85
01/29/85
01/30/85
10A*
67
67
67
67
66
66
58
59
58
60
59
59
59
58
58
59
59
58
59
59
59
59
59
59
59
60
58
59
59
61
61
59
61
10B
70
70
70
70
70
70
60
61
60
61
61
61
61
61
61
61
61
60
61
61
61
61
62
62
61
63
61
62
61
64
63
61
63
18A
_
72
72
72
72
72
61
61
61
61
61
62
62
62
61
62
61
61
61
62
61
62
62
62
61
63
61
62
62
64
64
62
64
18B
64
70
72
71
71
72
62
62
61
62
62
62
61
61
61
61
61
60
60
61
60
61
61
61
60
62
60
61
60
62
62
60
62
25A
72
72
72
72
72
72
64
64
64
64
64
64
65
65
66
65
65
65
65
65
65
65
65
65
65
66
64
65
65
67
67
64
66
25B
68
67
68
67
68
67
59
59
59
61
59
60
60
59
59
59
59
58
58
59
59
59
59
59
59
60
58
59
59
61
61
59
61
10A
71
71
71
71
71
72
61
61
61
61
61
61
61
60
61
61
61
60
60
61
61
60
61
61
60
62
60
61
61
63
63
61
63
10B
70
70
70
70
70
70
61
61
61
61
61
62
62
61
62
62
61
61
61
62
61
61
62
62
61
62
61
62
62
63
64
62
64
18A
70
70
70
70
70
70
61
61
61
62
62
62
62
62
62
62
62
62
62
62
62
62
63
63
62
63
62
62
62
64
64
62
64
18B
74
74
74
75
74
74
63
63
63
63
63
64
64
64
64
64
64
63
63
64
63
63
64
64
63
64
63
64
64
65
66
63
66
25A
63
63
63
64
63
63
58
58
58
58
58
58
58
59
58
58
58
58
58
59
58
58
59
59
58
58
58
58
58
59
60
58
60
25B
68
68
68
68
67
68
59
59
59
59
59
59
60
60
60
59
59
59
59
60
59
59
60
60
59
59
59
60
59
61
61
59
61
INCUBATOR
59
59
59
60
59
60
59
59
59
59
60
60
60
60
60
60
60 '
59
60
61
60
60
60
60
60
61
60
61 ,
62
64
64
61
64
-------
CJ
Ol
RDX Compost Temperature (°C) (continued)
02/01/85 59 62 62 61 64 59 61 62 62 64 58 60 62
02/04/85 56 58 58 57 61 56 57 58 59 60 54 56 59
02/05/85 55 57 57 56 59 55 57 57 58 59 54 56 60
02/06/85 57 58 59 58 61 57 58 59 59 61 55 57 60
02/07/85 57 58 59 58 61 57 58 59 59 61 55 57 60
02/08/85 57 58 59 58 61 57 58 59 59 61 56 57 61
02/11/85 55 57 58 56 60 55 57 58 58 60 54 56 60
02/12/85 57 59 59 58 62 57 58 59 59 61 56 56 60
02/13/85 55 57 58 56 60 55 57 58 58 60 54 56 60
02/14/85 55 57 57 56 60 55 57 57 58 60 54 . 56 59
02/15/85 56 58 59 57 61 56 58 59 59 61 55 57 61
02/18/85 56 58 59 58 61 56 58 58 59 61 55 57 59
02/19/85 57 58 59 58 61 57 58 59 59 61 55 57 59
02/20/85 57 58 59 58 61 57 58 59 59 61 56 57 61
02/21/85 56 58 59 58 61 57 58 58 59 60 55 57 59
02/22/85 57 59 59 58 62 57 59 59 59 61 56 57
02/25/85 58 59 60 59 63 58 56 60 61 62 57 58 61
02/26/85 58 60 61 60 63 59 60 61 61 63 57 59 62
02/27/85 57 59 60 59 62 57 58 60 60 62 56 58 61
02/28/85 57 58 59 58 62 57 57 59 60 61 55 58 61.
03/01/85 57 58 59 59 62 57 58 59 60 61 56 58 61
*10A = first replicate of compost with 10% sediment addition
-------
Hay-Horsefeed Compost
HMX-Compost Temperature (°C)
Sewage Sludge Compost
U)
DATE
12/18/84
12/19/84
12/20/84
12/21/84
12/22/84
12/23/84
12/24/84
12/25/84
12/26/84
12/27/84
12/28/84
12/29/84
12/30/84
12/31/84
01/01/85
01/02/85
01/03/85
01/04/85
01/05/85
01/07/85
01/08/85
01/09/85
01/10/85
01/11/85
01/14/85
01/15/85
01/16/85
01/17/85
01/18/85
01/21/85
01/22/85
01/23/85
01/24/85
01/25/85
01/28/85
01/29/85
01/30/85
10A*
59
59
60
59
58
58
58
59
58
58
59
57
57
57
58
58
58
57
57
57
57
57
57
58
57
57
57
57
57
57
57
57
57
58
59
57
58
10B
60
58
60
60
59
59
59
59
59
59
59
57
57
57
58
58
58
58
58
57
57
56
57
57
57
57
58
57
58
57
57
57
57
58
59
57
59
ISA
61
59
62
61
60
60
60
60
60
60
58
58
58
58
59
59
59
59
59
59
58
58
59
59
59
59
59
59
59
59
59
59
59
60
60
59
60
18B
62
60
61
60
61
62
61
62
61
61
59
58
58
59
60
61
60
59
59
59
59
58
59
59
59
60
59
59
59
59
58
59
58
61
60
59
60
25A
63
61
62
60
62
63
63
63
63
63
61
60
59
61
61
61
61
60
59
60
59
59
59
59
59
60
60
60
60
60
58
59
59
63
61
59
61
25B
60
57
59
56
58
59
59
59
59
59
58
57
56
58
58
58
58
57
56
57
56
53
54
52
56
57
57
57
57
58
55
56
56
59
58
57
58
10A
61
57
60
57
60
60
60
60
60
60
58
58
57
59
59
59
59
58
58
59
58
57
58
57
57
59
58
59
58
60
56
58
57
61
59
58
60
10B
62
59
61
59
61
61
61
61
61
61
59
59
58
60
60
60
60
59
59
60
59
58
59
59
59
60
59
59
59
61
58
59
59 .
62
61
59
61
ISA
63
61
63
60
62
62
62
62
62
62
60
60
59
60
61
61
60
60
60
60
60
59
60
60
59
60
60
60
59
61
58
59
59
62
62
60
62
18B
65
63
65
62
64
64
64
64
64
64
62
62
61
62
62
62
62
62
61
6!
60
60
61
61
61
61
61
62
61
63
60
61
61
64
63
61
62
25A
60
59
60
58
60
60
60
60
60
60
58
59
58
59
59
59
59
59
58
58
58
58
59
58
58
59
59
60
58
60
57
59
58
61
60
59
60
25B
61
60
61
59
61
60
60
61
60
60
59
59
58
60
60
60
59
59
59
60
60
59
60
60
59
60
60
60
59
60
58
59
59
62
62
60
61
INCUBATOR
61
60
61
61
59
59
59
60
59
59
59
59
59
59
60
60
60
60'
60
60
59
59
60
61
60
60
60
60
61
61
60
61
62
64
64
61
64
-------
HMX-Compost Temperature (°c) (continued)
02/01/85
02/04/85
02/05/85
02/06/85
02/07/85
02/08/85
02/11/85
02/12/85
02/13/85
02/14/85
02/15/85
02/18/85
02/19/85
02/20/85
02/21/85
02/22/85
58
55
54
55
55
55
55
55
55
55
55
55
55
55
55
56
58
55
55
55
55
56
55
55
55
55
56
55
55
56
56
56
59
56
56
56
57
57
57
56
56
56
57
56
57
57
57
57
59
56
56
57
56
56
57
57
56
57
58
57
57
57
56
57
59
57
57
57
56
57
57
57
56
56
58
56
57
57
56
57
58
55
54
56
54
54
55
55
54
55
56
52
52
53
54
55
59
60
61
61
59
60
62
56
55
57
55
55
56
57
55
55
57
56
56
57
55
56
57
56
58
57
56
57
57
56
56
57
57
57
58
56
57
58
57
58
58
57
57
58
57
57
58
58
58
58
58
58
59
56
58
57
55
58
59
57
57
58
59
59
59
59
59
56
55
56
56
56
56
57
55
55
56
56
57
57
56
57
57
56
57
57
57
56
57
56
56
57
57
57
57
57
57
59
60
60
60
61
60
60
60
59
61
59
59
61
59
-
* 10A = first replicate of compost with 10% sediment addition
-------
Tetryl Compost Temperatures (°C)
Hay-Horsefeed Compost
Sewage Sludge Compost
OJ
oo
DATE
4/18/85
4/19/85
4/21/85
4/22/85
4/23/85
4/24/85
4/25/85
ft/26/85
4/28/85
4/29/85
4/30/85
5/01/85
5/02/85
5/03/85
5/05/85
5/06/85
5/07/85
5/08/85
5/09/85
5/10/85
5/13/85
5/14/85
5/15/85
5/16/85
5/17/85
5/20/85
5/21/85
5/22/85
5/23/85
5/24/85
5/28/85
5/29/85
5/30/85
5/31/85
10A*
56
56
57
57
57
57
57
56
57
57
57
57
57
57
58
57
57
58
58
57
56
55
56
56
55
58
56
57
57
57
57
57
57
57
10B
56
57
58
57
58
58
57
57
58
58
58
58
58
58
58
58
57
58
58
57
57
56
57
57
56
58
57
57
57
57
57
57
57
58
18A
58
58
59
59
59
59
58
59
59
58
59
59
59
59
59
58
58
58
58
58
58
58
58
58
58
60
59
59
58
58
58
58
58
59
18B
58
59
59
59
60
59
59
59
59
59
59
59
59
59
59
58
58
58
58
58
59
58
58
59
58
60
59
59
58
58
58
59
59
59
25A
60
60
61
61
61
61
60
60
60
60
60
60
60
60
60
60
60
60
60
59
60
59
59
59
59
61
60
60
60
59
60
60
60
60
25B
56
56
57
57
57
57
56
56
56
56
56
57
57
57
57
56
56
56
56
56
57
55
56
56
55
57
56
56
57
56
57
57
56
57
10A
57
57
53
50
57
57
57
57
57
57
57
57
57
58
58
57
57
57
57
57
57
56
56
57
56
58
57
57
57
57
57
57
57
57
10B
58
58
58
58
59
58
58
58
58
58
58
58
58
58
58
57
57
58
57
57
57
57
57
57
57
59
57
58
58
58
58
58
58
58
18A
59
59
60
60
60
60
60
59
60
59
59
59
60
59
59
59
59
59
59
58
59
59
59
59
59
61
59
60
60
59
60
59
59
60
18B
59
59
59
59
59
59
59
59
59
59
59
59
59
59
59
59
58
59
58
58
59
58
58
58
58
60
58
59
59
59
59
59
59
59
25A
56
56
57
57
57
57
57
56
57
56
57
57
57
57
57
56
57
57
57
56
57
56
56
56
56
58
56
57
57
57
57
57
56
56
25B
57
57
57
57
58
57
57
57
57
57
57
57
57
57
58
57
57
57
57
57
57
57
57
57
57
58
57
57
58
58
57
57
57
57
INCUBATOR
60
60
61
61
61
60
60
60
61
60
60
60
60
60
60
60
60
60
62
59
59
59
59
60
60
61
60
60
60
60
60
60
60
61
•'•' 10A = first replicate of compost with 10% sediment addition
-------
Control Compost Temperatures
Hay-Horsefeed Compost
Sewage Sludge Compost
DATE
12/29/84
12/30/84
01/01/85
01/04/85
01/05/85
01/06/85
01/07/85
01/08/85
01/11/85
01/12/85
01/13/85
01/14/85
01/15/85
01/18/85
01/19/85
01/20/85
01/21/85
01/22/85
01/25/85
01/26/85
01/27/85
01/28/85
0
59
61
60
58
57
57
58
57
57
57
57
57
58
57
58
58
58
58
59
59
59
59
10
59
61
59
57
58
57
57
58
58
58
58
57
58
57
57
57
57
58
58
58
58
57
18
59
61
60
57
58
57
58
57
57
58
58
58
59
57
58
58
58
58
58
59
58
57
25
60
62
60
58
58
58
58
58
58
58
58
58
59
57
58
58
58
59
59
59
59
58
0
59
61
60
57
57
57
58
58
58
58
57
57
58
58
58
58
58
59
59
59
59
59
10
59
61
59
57
57
57
57
57
57
57
57
57
58
57
58
58
58
58
59
59
59
59
18
59
61
59
57
57
56
57
57
57
57
57
57
58
58
57
57
57
58
58
58
58
57
25
59
61
60
57
57
57
57
57
57
57
57
57
58
58
57
58
57
58
58
58
58
58
INCUBATOR
61
64
62
59
60
60
60
61
60
60
60
59
61
59
59
61.
59
-
61
62
61
61
-------
Hay-Horsefeed Compost
Nitrocellulose Compost Temperatures
Sewage Sludge Compost
DATE
A/01/85
4/02/85
4/03/85
A/04/85
4/05/85
4/06/85
4/07/85
4/08/85
4/09/85
4/10/85
4/11/85
4/12/85
4/13/85
4/14/85
4/15/85
4/16/85
4/17/85
£ 4/18/85
o 4/19/85
4/21/85
4/22/85
4/23/85
4/24/85
4/25/85
4/26/85
4/28/85
4/29/85
4/30/85
5/01/85
5/02/85
5/03/85
5/05/85
5/06/85
5/07/85
5/08/85
5/09/85
5/10/85
10A*
68
71
67
74
67
68
66
68
69
67
70
69
65
66
68
68
68
64
69
67
69
65
67
68
67
66
67
66
68
71
68
66
66
69
69
65
66
10B
68
71
68
75
67
67
66
68
69
68
71
69
65
66
68
69
67
65
70
67
69
66
67
68
68
67
67
66
68
72
69
66
67
69
67
66
66
18A
69
73
68
75
67
68
66
68
69
68
72
69
66
66
68
68
68
65
70
67
69
67
67
69
69
67
67
66
68
72
69
66
67
69
67
66
66
18B
71
73
69
75
67
67
66
67
69
68
71
70
66
67
68
68
68
65
70
67
69
66
68
69
69
67
68
67
68
72
69
66
67
69
67
66
66
25A
70
70
69
76
67
67
66
67
69
69
71
69
66
67
68
68
68
65
70
67
69
67
68
69
69
67
68
67
68
72
69
66
67
70
67
66
67
25B
70
70
67
74
68
66
65
67
69
68
71
70
66
66
68
68
67
65
70
67
68
66
67
68
68
67
67
66
68
72
69
66
67
69
67
66
66
10A
70
70
67
74
66
66
65
67
68
68
71
69
66
66
68
68
67
65
70
67
69
66
67
68
68
67
67
66
68
72
69
66
67
69
67
66
66
10B
70
70
67
74
66
66
65
67
68
68
71
69
66
66
68
68
68
65
71
67
69
66
68
68
68
67
67
66
68
72
69
66
67
69
67
66
66
18A
70
70
68
74
66
66
66
67
69
69
71
70
66
67
68
68
68
65
71
67
70
67
68
69
69
67
68
66
68
72
69
67
68
70
67
66
67
18B
70
70
67
74
66
66
66
68
69
68
71
70
66
67
68
68
68
66
72
68
70
67
68
69
69
68
68
67
68
73
69
67
68
70
68
67
67
25A
69
69
67
74
66
66
66
68
68
68
71
69
66
66
68
68
67
64
71
67
69
66
67
68
69
67
67
66
68
72
69
66
67
69
67
66
66
25B
69
69
67
74
65
66
66
68
68
69
71
69
66
66
68
68
68
64
71
68
70
67
68
68
68
67
68
66
68
72
69
67
67
69
67
66
66
INCUBATOR
60
60
60
65
60
60
60
60
60
60
59
59
59
60
60
60
60
60
60
61
61
61
60
60
60
60
60
60
60
60
60
60
60
60
60
62
59
"•'•' 10A = first replicate of compost with 10% sediment addition
-------
Appendix M
RCRA R.D&D Permit Public Announcement and Fact.Sheet
141
-------
, Vkgna 22313. EFA Menaneaaon Numoer VAO
0> 113 S156. The nmew MM conducted pureuent to
vie HI ao urea rinaanami end naaa ary Act {RCMA)
ea amended By me Haxarooua and SOIM Waate
Aiie»iUiia»a« of 10S4 (H8WA). Alienee Beeeeren Cor-
mentonat
lue fer mavnant of naz*
aracua Mem EPA nee mane e tame*
to leeue e oermit IMBT mi aunorny of aOU.
H8WAI
I end enforced Oy EPA inn me Com-
form:
m. area Vlrgna la currently not
i HO & O uermiav EPA MI aae»mme
wnettter to leaue a permit to Atlantic Reeeeren
at r» naailrmarieia and
Alexandria. Wgna.
• e wane treevnent
piaduet • mixed Mm e DuMng agent to form a conv
ooat "pee" and Ho»ni3 to deoampoaa eermmaay for a
panodof Ome.
EPA pruBoaaa to laaue a oermit for an BO * 0 pro-
tect. The aeUMienia Ma Be ucnaaiau from wane la-
goana Bcatadaeua ArmyAmrruvaon PMraa in LouMt-
ena and ^Arteoonaex The eeolmont in oleadc aned aeaet
orunej MI oe atored in a concreei tank at Aoanac «e-
L Compoadng «»Denr»e.na MI Be conducted n
i located m a aa-
oured gnerrajaa. The majamum amount of
to Mua me oermrt Mffi me foaoMng
1) The oermit inoudee ••oeHerpiete" reouremanta
MUcn era in al EPA ooeieBng permmj per regua-
Bona 40 C.' a Section 270.30.
2) The perrm MI expire one year teaoMng data of
to toeow m conducflng vie
Perepna Marenq to cumieu on EPA'a draft parmn
anouM auBnut meir oommenei m Mieng ex
1M
ATTNiNeny
oononona of M Ofefl pevtnit te tfiavoroonata or mat
a mart oermit •
, muet raiaa al laeuiiarti aacemnaaie
.by We
> of ma pupae com-
h M and may not be incorporated By iencAjdmg an oata
cnme «• be orovioeo for cxoic uee al a cnaroe oar
pege. Any pereen deamng furmerjrtformanon. cooiaa of
poroona of ffie edmmieWBWw 'ecoru or an IIUKOU-
mem n tewew me record enema contact joen Henry al
me eeove edoreae or can (21 i) 907.
A/ty relevem cufI'mientB ^eceA
deya of me date of ma OUDNC noece w« oe coneoereo
In me formuiaiMn of nnai oetermnaoona •vaaramg
EPA'a oermt. After ooneoeraoon of u «nnen conv
menta and me reauremema ana ooiiciee n acn> and
HSWA. EPA wM maMa a final oeoann to *mr aaue.
modtfy or deny met cermet. At mat nme. £PA «wi -onty
me applicant and eecn oeraon wno naa aucmmed «"t-
ten commenia on reoueeted nonce of Tie "n* aermit
decteion. The nnel oermit oecawn win Become «ffec-
one mrty I3OI aaya aner ma axvice a' -one* gf me
aeoaion uneea a later aata >a toeciflea or -wvi*w ,a
ranuaaiau inder reguailon 40 CFP Secoon '24 19 if
no conmieiiia mqueatea a cnange m ma arart se»mit.
me final permit wu become affecflve mvnemateiy opon
May 30. -9M
!R3O01OOO
142
-------
- FACT SHEET -
FOR DRAFT RESEARCH, DEVELOPMENT AND DEMONSTRATION PERMIT
Atlantic Research Corporation, Alexandria, Virginia
This fact sheet has been developed for the draft permit under Section 3005(g)
of the Resource Conservation and Recovery Act (RCRA) (42 U.S.C. §6925(g))
for research, development and demonstration (RD & D) of a hazardous waste
treatment process which EPA intends to issue to Atlantic Research Corporation,
Alexandria, Virginia (Permittee). This fact sheet was prepared in accordance
with the general permitting requirements of Section 124.8 of Title 40 of the
Code of Federal Regfulations (40 CFR).
A. PURPOSE OF THE PERMITTING PROCESS
The purpose of the permitting process is to afford the Environmental Pro-
tection Agency (EPA), interested citizens and other governmental agencies
the opportunity to evaluate the ability of the Permittee to comply with
the relevant and applicable hazardous waste research requirements
promulgated under the Solid Waste Disposal Act (commonly referred to as
the Resource Conservation and Recovery Act or "RCRA"). EPA is required to
prepare a draft permit which sets forth in one concise document all the
relevant and applicable requirements the Agency has established for the
Permittee during the one-year duration of the permit. The public is given
forty-five days to review the application and comment on the draft permit
conditions prior to EPA taking any final action on the application for a
hazardous waste research permit.
143
-------
B. PROCEDURES FOR REACHING A FINAL DECISION
Section 7004(b) of RCRA and 40 CFR §124.10 require that the public be given
forty-five (45) days to comment on each draft permit prepared under the
Resource Conservation and Recovery Act. The comment period for this draft
permit will begin on May 30, 1985 and will end on July 15, 1985. Any
person interested in commenting on the application or draft permit must do
so within this forty-five (45) day comment period.
All persons wishing to comment on any of the permit conditions or the per-
mit application should submit the comments in writing to the Environmental
Protection Agency (EPA), Region III, 841 Chestnut Street, Philadelphia,
Pennsylvania 19107, Attention: Mr. Roland Schrecongost, Acting Director,
Hazardous Waste Management Division (3HWOO). Comments should include all
reasonably available references, factual grounds and supporting material.
EPA has scheduled a public hearing on the draft permit for July 1, 1985 at
the following location:
Atlantic Research Corporation
5390 Cherokee Avenue
Alexandria, Virginia 22312
Time: 7:00 p.m.
Any written comments should be addressed to Mr. Roland Schrecongost, Acting
Director, Hazardous Waste Management Division, Environmental Protection
Agency, Region III, 841 Chestnut Street, Philadelphia, Pennsylvania 19107.
- 2 -
144
-------
When making a determination regarding the issuance of a hazardous waste
permit to Atlantic Research Corporation, EPA will consider all written
comments received during the comment.period, any oral or written statements
received during the public hearing, any relevant provisions of the
hazardous waste regulations of 40 CFR Parts 124, 260-264, and 270,
42 U.S.C. §6925(g) and the Agency's permitting policies.
When EPA makes a final permit decision to either issue, deny or modify the
permit, notice will be given to the applicant and each person who has sub-
mitted written comments or requested notice of the final decision. If no
comments requested a change in the draft permit, the final permit shall
become effective immediately upon issuance, in accordance with 40 CFR
§124.15(b)(3).
The contact person for the Atlantic Research Corporation draft permit is:
Mr. Harry Harbold
U.S. Environmental Protection Agency
Region III
841 Chestnut Street
Philadelphia, Pennsylvania 19107
(215) 597-9287
C. AUTHORITY FOR ISSUING RD&D PERMIT
On November 8, 1984, the President signed into law the Hazardous and Solid
Waste Amendments of 1984 (HSWA), which amended the Resource Conservation
and Recovery Act (RCRA). RCRA, as amended by HSWA, under Section 3005(g) ,
(42 U.S.C. §6925(g))authorizes the Agency to permit research, development,
and demonstration facilities for the treatment of hazardous waste without
- 3 -
145
-------
having substantive regulations in effect under 40 CFR Part 264. Many
requirements of 40 CFR §264 can be and are applied to the facility through
this permit, as they are necessary to protect human health and the environment.
The new Section 3005(g) provides that:
o EPA may issue RD&D permits, without promulgation of permitting
regulations under Part 264, for technologies or processes that
treat hazardous waste in an innovative and experimental manner.
o An RD&D permit shall provide for the receipt and treatment of only
those types and quantities of hazardous waste that are necessary
for determination of the efficacy and performance capabilities of
the technology or process being researched and tested and its
effects on human health and the environment.
o RD&D permits shall include any conditions that the Agency believes
are necessary for protection of human health and the environment.
o For RD&D permits, the Agency may modify or waive the permit
application and permit issuance requirements applicable to
hazardous waste management facilities, except that financial
responsibility requirements and the public participation
requirements may not be modified or waived.
o An RD&D permit shall provide for the construction of the RD&D
facility if necessary and for its operation for a period not
exceeding 365 operating days. Permits may be renewed up to three
times, with each renewal not to exceed 365 operating days..
o The Agency may terminate an RD&D permit at any time necessary for
protection of human health or the environment.
D. FACILITY DESCRIPTION
Atlantic Research Corporation, Inc. (ARC), proposes to conduct research on
composting techniques for degrading explosives, propellents and explosives
related compounds from lagoon sediments at two Army ammunition plants, the
Louisiana Army Ammunition Plant in Doyline, Louisiana and the Badger Armv
- 4 -
146
-------
Ammunition Plant in Baraboo, Wisconsin. The sediments from the Louisiana
plant contain TNT, RDX, HMX and tetryl as the main explosive contaminants;
the sediments from the Badger plant contain nitrocellulose as the main
explosive contaminant. Composting is an accelerated aerobic microbial
digestion of organic materials at elevated temperatures.
The purpose of this research is to develop a safe and economical process
for degradation of explosives, propellents and explosives related compounds
in sediments of waste water settling lagoons which pose environmental prob-
lems at various Army ammunition plants. The proposed research, to be
performed by ARC under contract with the U.S. Army Toxic and Hazardous
Materials Agency, would attempt to demonstrate the viability of two
composting techniques for reducing the explosives content of the actual
explosive contaminated sediments from the two above-mentioned Army
ammunition plants on a pilot-project scale.
In conducting the research, sediments from the two plants will be mixed
with bulking materials and nutrients required for efficient composting.
Six composts will be set up for each sediment, three using hay-horse feed
and three using sewage sludge—wood chips as bulking materials/nutrients.
The compost will be moistened Co approximately 60% moisture content.
The contaminated sediments and bulking materials/nutrients will be
manually loaded and mixed in four 488-gallon stainless steel tanks used as
composting vessels. To serve as a control, two additional 488-gallon
stainless steel tanks will be set up using uncontaminated soil from areas
near the two contaminated sites.
- 5 -
147
-------
The tanks will be maintained within two fully enclosed greenhouses located
within the ARC complex during the entire duration of the composting experi-
ment, with three tanks in each greenhouse. Each greenhouse is underlined
with a concrete lined pit filled with gravel. The gravel is covered with
a 3.5 mm polyethylene liner to contain any spilled wastes. At the end of
each compost experiment, all composted material, spilled material and
associated cleaning materials will be placed in polyethylene lined 55
gallon drums and hauled off-site by a licensed commercial hazardous waste
hauler for disposal in a qualifying RCRA hazardous waste landfill.
Removal of the composted material will occur within two weeks of the
completion of each experiment.
The duration of each composting experiment is expected to be approximately
six weeks. Since there will be two sets of experiments, the total
duration of the research, development and demonstration is expected to be
approximately twelve weeks.
Contaminated sediments from the two Army ammunition plants will be stored
in a fully enclosed building located within the ARC complex. The con-
taminated sediments will be contained within polyethylene-lined 55 gallon
drums which will remain closed and secured within the storage building at
all times during storage. The drums will be kept within a concrete pit
inside the shed for secondary containment of spilled or leaked wastes and
will be elevated at all times to minimize contact with any spilled or
leaked wastes contained within the pit. A maximum of seven drums with a
total of 385 gallons of contaminated soil will be stored at the facility
at any time during the permit period.
- 6 -
148
-------
ARC conducted tests on samples of wastes from both Army Ammunition Plants
to determine their reactivity at the maximum explosive concentrations to
be used in the RD&D project under this proposed permit. All tests were
negative, indicating that the wastes to be used in the research activity
are not reactive. This testing, along with sampling in the Waste Analysis
Plan, are considered adequate to ensure safe handling of the waste. These
tests were conducted under the direction of EPA and have been approved by
the Agency.
The total amount of wastes that the Permittee plans to receive and treat
under this permit are as follows:
Hazardous Waste No. Description Annual Amount
K044 Waste water treatment 500 gallons
sludges from the manu-
facturing and processing
of explosives
The application from Atlantic Research Corporation indicates the site is
located 25 feet above the 100-year flood plain.
The final project report will be public record and forwarded to EPA when
completed. The permittee shall provide EPA with experimental data upon
project completion after receiving approval by the U.S. Army. EPA will
notify the Army in writing of this requirement. This approval is
necessary to satisfy contractural requirements between Atlantic Research
and the U.S. Army. Records of data used to complete the permit
application will be retained by the permittee for a period of one year.
- 7 -
149
-------
E. PERMIT ORGANIZATION
The permit is divided into five sections as outlined below.
Section Topic
Part I Standard Conditions
Part II General Facility Conditions
Part III Storage In Containers
Part IV Storage And Treatment In Tanks
Part V Special Conditions
Parts I and II contain conditions which generally apply to all hazardous
waste facilities, although certain conditions, described in the following
summary, have been deleted, added or revised to fit the unique RD & D
project. Part(s) III and IV pertain specifically to the hazardous waste
RD&D facilities at the ARC facility in Alexandria, Virginia. Part V
identifies the total amount of sediment to be received and treated during
the project.
F. SUMMARY OF THE PERMIT CONDITIONS
This section of the fact sheet provides a summary of the standard
conditions in the draft permit. The column titled "Regulation" provides
the regulatory authority for the permit condition specified in the column
titled "Permit Condition." For convenience in reviewing the permit
application, the column headed "Location in Application" is provided. The
permit application cited in this section is the February 5, 1985 permit
application, as amended on April 19, 1985, April 25, 1985, and May 20,
1985.
- 8 -
.50
-------
PART I
STANDARD CONDITIONS
Part I of the permit sets forth the standard procedural conditions that are
applicable to the hazardous waste management facility. All citations of the
regulations refer to the regulations as codified in Title 40 of the Code of
Federal Regulations (40 CFR).
Permit
Condition
I.A
I.B
Subject
I.C
I.D
I.E
I.F
I.G
I.H
I.H.I
Effect of Permit
Permit Actions
Severability
Definitions
Reports, Notifications, and Submissions
to the Regional Administrator
Signatory Requirement
Documents to be Maintained at Facility
Site
Duties and Requirements
Duty to Comply
Regulation (40 CFR)
§270.4
§270.30(g),
§270.30(f)
§270.41
§270.42
§270.43
5124.16(a)
Part 264
Part 260
Part 270
§270.11
§270.30(k)
§264.13
§264.16(d)
§264.53(a)
§264.112(a)
§264.73
§264.15(b)
§264.142(d)
§270.30(a)
- 9 -
151
-------
Permit
Condition
I.H.2
I.H.3
I.H.4
I.H.5
I.H.6
I.H.7
I.H.S
I.H.9
I.H.10
I.H.ll
I.H.12
I.H.13
I.H.14
I.H.15
I.H.16
A. WAIVERS
Subject
Need to Halt or Reduce Activity
Not a Defense
Duty to Mitigate
Proper Operation and Maintenance
Property Rights
Duty to Provide Information
Inspection and Entry
Monitoring and Records
Planned Changes
Anticipated Non-compliance
Twenty-Four Hour Reporting
Manifest Discrepancy Report
Unmanifested Waste Report
Other Noncompliance
Other Information
Protection of Human Health
and the Environment
Regulation (40 CFR)*
§270.30(c)
§270.30(d)
§270.30(e)
§270.30(g)
§270.30(h)
§264.74(a)
§270.30(i)
§270.30(j)
S270.30(l)(l)
§270.30(1)(2)
§270.30(1)(6)
S264.56(d)(l)
and (j)
§264.72
§264.76
§270.30)0(10)
§270.30(0(11)
§42 U.S.C. §6925(g)
No waivers from the standard conditions applicable to all hazardous waste
management facilities have been given, except those related to requiring
Notice to Generators, permit renewal and transferability.
* Title 40 of the Code of Federal Regulations
- 10 -
152
-------
1. Required Notice to Generator:
The permittee will be responsible for collecting sediment samples and
shipping the waste to its facility in Alexandria, VA. Since the
permittee will be involved in preparing samples for shipment with the
Army (generator), the notice to generator requirements under C.F.R.
§264.12(b) have not been included in the permit.
2. Permit Renewal:
Pursuant to Section 3005(g)(4) of RCRA, an RD & D permit may be
renewed, for a period not to exceed one year, for a maximum of three
times. However, due to the anticipated short duration of the RD & D
activities under this proposed permit (approximately 12 weeks), EPA
has not included a standard condition providing for renewal. The time
provided in the proposed permit, one year from the date of issuance,
should be sufficient for completion of all RD & D activities and the
closure plan provided in this permit.
3. Transfer of Permit:
Due to the short period of RD & D activities under this proposed
permit, the requirements of Sections 270.40 and 270.30(1)(3), which
provide procedures for transfer of permits, are not incorporated in
the proposed permit. Therefore, this permit may not be transferred.
- 11 -
153
-------
B. ADDITIONAL CONDITIONS
1. Protection of Human Health and the Environment:
Under Section 3005(g) of RCRA, 42 U.S.C. §6925(g), EPA may order an
immediate termination of all operations at an RD & D facility at any
time it determines that termination is necessary to protect human
health and the environment. This provision is included in Section
I.H.14 of the standard conditions of the proposed permit.
- 12 -
J54
-------
PART II
GENERAL FACILITY CONDITIONS
Part II of the permit sets forth general conditions for this facility with
which the Permittee must comply. All citations of the regulations refer to
the regulations as codified in Title 40 of the Code of Federal Regulations
(40 CFR). NOTE: N. C. = NOT COVERED - the application is not required to
cover this topic.
Permit
Condition
II. A
II. B
II. C
II. D
Regulation
Subject ( 40 CFR)
Design and Operation of the S264.31
Facility
General
General
Waste Analysis S264.13
Inspection Requirements §264.15
Personnel Training S264.16
Location in
Application*
(1)
(3)
(3)
(4)
(3)
(4)
(3)
(4)
pp.
pp.
pp.
pp.
pp.
pp.
pp.
P-
7-22;
4-10.
1-11;
7-8.
12, 14, 15;
9-12.
13, 16, 17,
18;
16.
II.E 'Preparedness and Prevention
II.E.I Required Equipment S264.32
II. E. 2 Testing and Maintenance of S264.33
Equipment
II.E.3 Access to Communications or §264.34
Alarm System
II. E. 4 Required Aisle Space S264.35
II. E.5 Arrangements with Local Author- S264.37
ities
II. F Contingency Plan
(3): pp. 29, 32;
(4): p. 15.
(4): p. 13.
(3): pp. 29, 32.
(4): p. 14.
(3): pp. 36-39.
- 13 -
155
-------
Permit
Condition
II. F.I
II. F. 2
II. F. 3
II. F. 4
II. F. 5
II. G
II. G.I
n.^.22.
II.H
II. H.I
II.H.2
II.H. 3
II.H. 4
II.H. 5
II.H. 6
II. I
Subject
implementation of Contingency
Plan
Copies of Plan
Amendment of Contingency Plan
Emergency coordinator
Emergency Procedures
Recordkeeping and Reporting
Operating Record
J Required Reports
Closure
Closure performance standard
Amendment to Closure Plan
Notification of closure
Time Allowed for closure
Disposal or Decontamination of
Equipment
Certification of closure
Cost Estimate for Facility
Closure
Regulation
(40 CFR)
§264.51
§264.53
§264.54
§264.55
§264.56
§264.73
§264.113
§264.115
§264.143
§264.148
§264.56(d)
(1) & (J)
§264.111
§264.112
§264.113
§264.113
§264.114
§264.115
Location in
Application*
(3 ): p. 30.
N.C.
N.C.
(3): p. 30;
(4): p. 13.
(3): pp. 30, 34, 35.
N.C.
N.C.
I
(3): p. 41.
N.C.
(3): p. 42.
(3): p. 42.
(3): pp. 41-42;
(4): p. 17.
(3): p. 42.
(3): p. 42;
(4): p. 17.
11. I.I Adjustment for Changed condi-
tions
II.I.2 Availability
§264.142(c)
§264.142(d)
N.C.
N.C.
- 14 ~
156
-------
Permit Regulation Location in
Condition Subject (40 CFR) Application*
II.J Incapacity of Owners/Operators, §264.148 N.C.
Guarantors or Financial Insti-
tutions
II.K Manifest System §264.71 (3): p. 40.
§264.72
§264.76
ILL Financial Assurance for Facil- §264.143 (2): pp. 15, L6;
ity Closure §264.151 (3): pp. 46-48.
II.M Liability Requirements §264.147 (2): pp. 15-17;
(3): pp. 55-57.
II.N Security §264.14 (3): p. 12.
II.0 Experimental Procedures N.A. (1): pp. 7-22;
(3): pp. 4-10.
* Key to Application References:
(1) Application for a Research, Development and Demonstration Permit as
specified in "The Hazardous and Solid Waste Amendments of 1984," dated
February 5, 1985.
(2) Response to EPA's Questions on ARC Research, Development and Demonstration
Permit Application, undated, provided to EPA at April 19, 1985 site visit.
(3) Revision #2, Application for a Research, Development and Demonstration
permit as specified in "The Hazardous and Solid Waste Amendments of 1984,"
dated April 25, 1985.
(4) Revision #3, Application for a Research, Development and Demonstration
Permit as specified in "The Hazardous and Solid Waste Amendments of 1984,"
dated May 20, 1985.
- 15 -
'57
-------
A. WAIVERS
Due to the short period of experimental activities under this permit, the
requirements of §264.75 for biennial reports is waived.
B. ADDITIONAL CONDITIONS
An additional condition, II.P (Experimental Procedures), has been included
to assure that the scope of activities conducted under this permit are
limited to RD&D activities. This additional condition also requires that
all leachate produced during the experiment shall be analyzed, collected
and stored or recycled for use in the experiment and that the quantity of
leachate produced shall be measured and recorded.
- 16 -
158
-------
PART III
STORAGE IN CONTAINERS
Pact III of the permit sets forth conditions for storage in containers with
which the Permittee must comply. All citations of the regulations refer to
the regulations as codified in Title 40 of the Code of Federal Regulations
{40 CFR).
Permit
Condition
III. A
III.B
III.C
III.D
Subject
Waste identification
Condition of containers
Placement Requirements
Compatibility of wastes With
Regulation
(40 CFR)
S264.13
§264.171
§264.176
§264.177
§264.172
Location in
Application*
(4):
(4):
(3):
(4):
(3):
P.
P.
pp.
P.
P.
4.
2.
21, 26, 27;
3.
2.
containers
III.E Management of containers
II I. F containment
§264.173 (3): p. 2.
§264.175 (3): pp. 21, 26, 27;
(4): p. 3.
* See key to Application References in Part II of this fact sheet.
- 17 -
J59
-------
PART IV
STORAGE AND TREATMENT IN TANKS .
Part IV of the permit sets forth conditions for storage and treatment in tanks
with which the Permittee must comply. All citations of the regulations refer
to the regulations as codified in Title 40 of the Code of Federal Regulations
(40 CFR).
permit
Condition Subject
IV. A
IV. 3
IV. C
IV. D
Waste identification
Design and construction of Tanks
Protection from overfilling
Secondary containment
Regulation
(40 CPR)
S264.13
§264.191
S264.192(b)
N.A.
Location in
Application*
(4):
(3):
(1):
(3):
(4):
P-
PP
PP
P.
P.
4.
. 21-25,
43-44.
. 16-18.
21;
8.
* See key to Application References in Part n of this fact sheet.
A. WAIVERS
Given chat the tanks are new and made of corrosion resistant materials,
that the hazardous wastes are compatible with the tank materials, that Che
duration of the experiment is less than one year, and that the lined secondary
containment system is in place to contain any leaks or spills, EPA expects
that the minimum shell thickness that might result during the experiment
will ensure sufficient shell strength.
_ 18 .
.'.60
-------
B. ADDITIONAL CONDITIONS
Permit condition IV.D requires that the permittee maintain, at all times,
a liner beneath the tanks capable of containing all materials spilled or
leaked from tanks during loading, unloading or experimental operations.
- 19 -
161
-------
PART V
SPECIAL CONDITION
Part V of the permit limits the maximum amount of hazardous waste to be
received and treated by the facility during the term of this permit to no more
than 500 gallons.
- 20 -
162
-------
Appendix N
Analysis of TNT, RDX, Tetryl, HMX,
2A-DNT and 4A-DNT in Compost Leachates
The water leachate was filtered through a 0.45 millipore filter in
preparation for direct injection into the HPLC for quantitation. A LKB
2150 HPLC pump, a Perkin-Elmer LC55 UV detector and a Vista CDS 402
computer controller and integrator were used. Separation was accomplished
on a 4.6 mm I.D. x 25 cm Alltech Econosphere 5 MC-18 column using a mobile
phase consisting of 51% methanol, 2% dioxane, 0.5% acetonitrile and 46.5%
high purity water which was 0.004 M in n-hexylamine and 0.004 M in
tetramethylammonium hydroxide buffered to pH 7.5 with phosphoric acid.
The mobile phase flow rate was 1.3 mL/min. UV detection was at 232 nm.
Under these conditions, the explosives had the following retention times
and detection limits.
Retention Time Detection Limit
Explosive (min) (mg/L in Leachate)
HMX 3.5 0.248
RDX 4.7 0.303
Tetryl 6.9 0.267
TNT 7.8 0.285
2A-DNT 8.5 0.309
4A-DNT 9.2 0.263
163
-------
Appendix 0
Metal Analysis in Compost Materials and Soils
Barium, Cadmium, Chromium, Copper, Iron, Lead, and Zinc were analyzed
according to EPA Methodology using direct aspiration flame Atomic Absorp-
tion. Mercury was determine using the Cold Vapor technique according to
EPA Method #7471.
Samples were digested for Ba, Cd, Cr, Cu, Fe, Pb, and Zn analysis by
EPA Method #3050. Approximately 1 g of ground soil or compost material was
weighed into 125 mL Erlenmyer flask. Ten mL of 50:50 HN03-H20 were added
and each flask was covered with a small watch glass. The HN03-H20 digest
was then boiled on a hot plate for ten minutes. Then 10 mL of concentrated
HNC-3 were added and boiling was continued for another 30 minutes. At this
point, the flasks were cooled and 2 mL of H20 and 3 mL of 35% H2C-2 were
added. The flasks were then gently warmed until effervescence started.
Then more H202 was added in 2 mL aliquots until a total 10 mL of H202 had
been added. When the efferverscence subsided, 10 mL of H20 and 5 mL of
50:50 HC1-H20 were added. The mixture was refluxed for an additional 10
minutes and cooled. The digest was then filtered through a Whatman #42
ashless filter paper and brought to 100 mL with H20 in a volumetric flask.
A Varian AA-775 Atomic Absorption Spectrometer with a variable
uptake nubulizer and D2 Background Correction Lamp was used. Uptake rate
was set at approximately .7 mL/min. Operating parameters were taken from
EPA methods for the individual elements and summaried below:
Barium -X = 553.6 nm, slit width = .2 nm. A nitrous oxide-acetylene
flame in the reducing mode was used. A 10% potassium (as KN03) stock
was spiked into samples and standards such that all solutions
contained, 2000 ppm K. Lamp Current = 10 milliamps. Since a D2 lamp
has insufficient emmision at 553.6 nm wavelength to match the Hollow
Cathode lamp, no background correction was used. (EPA Method #7080).
164
-------
Cadmium - X = 228.8 nm, slit width = .5 nm. An air-acetylene flame was
used in the oxidizing mode. Background correction was used. Hollow
Cathode lamp current was 5 milliamps. (EPA Method #7130)
Chromium - X = 357.9 nm, slit width = .2 nm. A nitrous oxide -
acetylene flame was used in the reducing mode. 10% potassium (as
KN03) solution was spiked into all standards and samples such that all
solutions contained 2000 ppm K. Since the I>2 lamp emission was
insufficient, no background correction was used. (EPA Method #7190)
Copper - X = 324.7, slit width = .5 nm. Air-acetylene flame in the
oxidizing mode was used. Background correction was used. Hollow
Cathode lamp current =3.5 ma. (EPA Method #7380)
Lead - X = 283.3, slit width = .5 nm. Air-acetylene flame in the
oxidizing mode was used. Background correction was used. Hollow
cathode lamp current =5 ma. (EPA Method #7420)
Zinc - X= 213.9 nm, slit width =1.0 nm. Air-acetylene flame in the
oxidizing mode was used. Background correction was used. Hollow
cathode lamp current = 5 ma. 12% strontium (as Sr(N03)2) was spiked
into all standards and samples such that all solutions contained 1500
ppm Sr. (EPA Method #7950)
165
-------
Mercury Analysis
Compost samples were screened for mercury using the cold vapor
generation technique according to EPA-Method #7471. Samples (0.2 grams)
were weighed into BOD bottles. Five mL of Aqua Regia and 5 mL of distilled
water were added to the bottle and it was placed on a boiling water bath for
2 minutes. The bottle was cooled and 15 mL of 5% potassium permanganate was
added before placing the bottle back in the boiling water bath for an
additional 30 minutes. After cooling, 55 mL of distilled water and 6 mL of
sodium chloride-hydroxylamine sulfate solution were added. This solution
contained 12% of each component dissolved in distilled water. At this
point, 5 mL of a 10% suspension of stannous sulfate in 0.5 N sulfuric acid
were added and the bottle attached to the aeration system.
The aeration system was assembled according to Figure 0-1 with the
absorption cell placed in the light path of a Varian AA-775 Atomic
Absorption Spectrometer. The desiccant used was magnesium perchlorate. A
Masterflex peristalltic pump was used and the flow rate was maintained at
1 liter per minute. The flow rate was monitored with a flowmeter inserted
between the desiccant tube and the absorption cell.
A mercury Hollow Cathode lamp was used with a 5 ma lamp current. The
wavelength was 253.7 nm with a band pass of .5 nm. Absorbance was read
directly from the spectrometer readout once it had reached a maximum value.
166
-------
Sample Solution
In HOI) Hot H.
Scrubber
Containing
• Mercury
Absorbing
Media
Figure 0-1. Apparatus for Flameless Mercury Determination
-------
Appendix P
Metal Analysis in Leachate Samples
Aqueous leachate samples were prepared for metal analysis by EPA
Method #3010. Three mL of cone HN03 were added to 20 mL of the leachate in
a beaker and the beaker covered. The solution was heated (without boiling)
to near dryness on a hot plate. The solution was cooled and an additional
3 mL of cone HN03 added. The sample was covered and refluxed until it
became clear and light colored after which it was evaporated to near
dryness. One mL of 1:1 HC1 was added to the beaker and warmed to dissolve
any precipitate. The solution was transferred to a 10 mL volumetric, and
the beaker rinsed with high purity water and added to the solution in the
volumetric. High purity water was added to bring the volume to 10 mL.
Analysis for the individual metals was as described in Appendix 0.
168
-------
Appendix Q
Pesticide Analysis
Compost samples were screened for pesticides using the EPA contract
laboratory procedure for soil samples. This method was taken from an RFP
released in January 1985. This procedure was used because EPA method #608
(Federal Register Vol. 48, #209, p. 43321) does not specifically address
the preparation of solid samples. Additionally, the method was scaled down
by a factor of three to accommodate the limited sample size.
Approximately 10 g of compost sample and 15 grams of anhydrous sodium
sulfate were shaken in a 50 mL test tube. The sample was then extracted
with 3 x 30 mL portions of 1:1 acetone-methylene chloride using an
ultrasonic bath and occasional shaking. The extracts were collected in a
125 mL Erlynmyer flask and the volume reduced to approximately 1 mL under
a gentle stream of nitrogen. The flask was washed with 10 mL of hexane and
the solution transferred to a 15 mL test tube. The volume was again reduced
to 1 mL using nitrogen blowdown. The sample was then quantitatively
transferred and brought to volume in a 10 mL volumetric flask.
At this point, an alumina sample clean-up was used. Activity III
alumina was prepared baking 100 g of neutral alumina (Fisher) at 400°C for
24 hours in a muffle furnace and, after cooling, adding 7 mL of distilled
water. The alumina was then tumbled overnight using a laboratory shaker.
Three grams of activity III alumina were placed in a 5 mL serological
pipet, fitted with a glass wool plug. 1.9 mL of the hexane extract was then
added to the top of the dry column and hexane was used to elute 10 mL in a
volumetric flask. This solution was analyzed using gas chromatography and
an electron capture detector. The analytical parameters were as follows:
Column: 10 ft x 2 mm I.D. packed with 1.5% 0V-
17/1.95% OV-210 of 80/100 mesh ANAKROM
Q
Column Oven Temperature: 190°C initial hold 2 minutes, then
5°C/minute to 210°C and hold
169
-------
Injection Port Temperature: 230°C
Detector Temperature: 300°C
Carrier Gas Flow: 24-mL/min Nitrogen
Injection Volumn: 4p 1 manual
170
-------
Appendix R
Gas Sample Analysis
Air samples from the compost piles were collected using Pressure-Lok
push-button gas syringes. Two 100 pi aliquots were collected for each
sample. Analysis was accomplished using a Varian 3700 Gas Chromatograph
with thermal conductivity detection. These analyses were performed in two
parts using two different columns to detect oxygen, nitrogen, carbon
monoxide, carbon dioxide and ammonia.
02, N2, and CO were separated and detected using a 6ft x l/8in O.D.
nickel column packed with 60-80 mesh, acid-washed molecular seives 5A. The
GC was operated under the following conditions:
Column Oven Temperature = 60°C Isothermal
Injection Port = 200°C
c
Thermal Conductivity Oven = 210°C
Filament Temperature = 310°C
Helium Carrier Gas Flow = 35 mL/min
Output Sensitivity = 2 x .05 mL full scale
Recording and integration were provided using Hewlett-Packard 5880 A GC
computer.
C02 and NH3 were separated and detected using a 5ft x l/8in O.D.
teflon-lined stainless steel column packed with Porpak N 80-100 mesh. The
operating conditions were the same as for 02, N2, and CO analysis except
the column oven was operated in a temperature programmed mode with the
following parameters: Initial temperature was 85°C for the first two
minutes, then 5°C per minute to 110°C final temperature and hold for 3
minutes. Sensitivity, recording, and integration were the same as for 02
and N2 analysis.
171
-------
Appendix S
Daily Composting Facility Inspection Sheets
172
-------
"N s.i A
"N "A
"N "A
(•N SHA
"N ''•"•A
"N "A
"N "A
ON BOA
ON s ,IA
ON SHA
"N snA
"N <=OA
ON snjk
ON S3A
"N S^A
ON S3 A
"N S3A
<>N saA
i).i|ilinof) uol]r>v n. )>)!>! n<| )!•;<) pon3
3ui,,r3, Poo3
SIM^U;,, poo3
3iilHr,->] poo3
Sui^i...!! pn.,3
3ui)(p3| poo3
3u l >|PO| poo3
Suiirni Poo3
3,,,>,r.M -'- p,,o3
Sinnr.)) piM.3
3ui>|pn| poii'.l
3ll 1 ^l?n | poo3
3uinrn| 7 pooH
3llli|p.)| p
'J
I
•-
1
"
',
''
<
r
i
ii'M •- , i" I >.»l--ii|
NO I. I.37HH SN I A.I.TIIOV.H ONI J.SO.IWO3
-------
PACE 2
I nspi'i tor's N.iiiu- :
Inspection Date:
Integrity
t .>»i|M..si ,-j Links
1 inei lor leaks or d.un.igc
St in nl W.iste Drums
Krni i ug ,11 ul gates
Kri-ciiliiinsr/sl iirugi* ,iru.i
1 . i .• Kxl iiif.ui -,1,1-rb
1 good
2 good
3 good
It good
5 good
6 good
1 good
2 good
1 good
2 good
J good
s good
5 good
6 good
1 closed
2 closed
1 good
2 K"'"'
leaking
leaking
leaking
leaking
leaking
leaking
moisture or dam.ige
mositure or damage
leaking
leaking
leak ing
leak ing
leak ing
leaking
open or damage
open or damage
low or empty
1 ow or cuip( y
Remedial Action Date Remedial
Response Required to be taken Action Cnimil.
-------
COMI'OSTING FACILITY INSPECTION
Response Required
Quality & Dispositon at
of Spilled Hatler
Date Remedial
Action Completed
'1 I JI1.*>|H>I t A I ea
Yes
No
l.itluld Levels, tut.
1 volume ml.
2 volume ml.
3 volume ml.
I* volume nil.
5 volume ml.
b volume ml.
1
2
3
A
5
6
vu 1 nine
vo In me
volume
vo 1 ume
volume
volume
ml.
ml.
ml.
ml.
ml.
ml.
-------
Appendix T
Louisiana AAP Sediment Pilot-Scale Composting
176
-------
T-l
Daily Temperatures (°C) - Louisiana AAP Pilot Scale Composts
Sewage Sludge-
Hay-Horse Feed ' Wood Chips
DATE
8/22/85
8/23/85
8/24/85
8/25/85
8/26/85
8/27/85
8/28/85
8/29/85
8/30/85
8/31/85
9/01/85
9/02/85
9/03/85
9/04/85
9/05/85
9/06/85
9/07/85
9/08/85
9/09/85
9/10/85
9/11/85
9/12/85
9/13/85
9/14/85
9/16/85
9/17/85
9/18/85
9/19/85
9/20/85
9/21/85
9/22/85
9/23/85
9/24/85
9/25/85
9/26/85
9/27/85
9/28/85
9/29/85
9/30/85
10/1/85
10/2/85
10/3/85
10/4/85
10/5/85
10/7/85
1
44
53
42
43
44
39
45
44
47
47
49
47
48
45
48
50
52
51
51
49
50
50
48
66
65
65
61
67
61
58
54
54
54
56
62
66
63
55
54
52
53
62
59
56
45
2
39
38
41
44
44
44
44
45
45
50
49
48
47
47
45
53
55
54
52
50
61
59
59
65
61
60
60
64
62
58
58
54
58
61
67
65
62
54
54
54
67
63
57
60
50
3
23
33
35
41
38
38
43
48
52
58
58
50
51
53
55
55
53
53
52
49
52
47
53
71
65
65
66
65
67
58
55
52
53
50
59
62
52
50
51
48
48
55
58
56
46
4
40
45
48
45
42
42
45
46
46
45
43
42
45
45
47
46
46
46
46
45
55
50
49
50
49
46
43
45
47
51
52
47
45
48
46
51
49
51
47
47
53
52
47
51
47
5
44
42
47
46
47
47
43
43
46
50
52
51
51
50
50
50
50
50
50
49
50
51
50
51
52
49
51
49
50
51
52
48
47
48
48
52
48
50
51
48
52
51
51
51
48
6
47
51
45
31
45
47
44
41
47
48
50
49
52
52
50
48
47
49
48
49
48
38
32
59
60
56
53
48
48
49
48
49
53
51
47
47
50
53
52
49
50
50
52
52
49
177
-------
T-1A
Daily Temperatures (°C) - Louisiana AAP Pilot Scale Manure Composts
DATE
Tank 5
Tank 6
DATE
Tank 5
Tank 6
2/21/86
2/22/86
2/23/86
2/24/86
2/25/86
2/26/86
2/27/86
2/28/86
3/1/86
3/2/86
3/3/86
3/4/86
3/5/86
3/6/86
3/7/86
3/8/86
3/9/86
3/10/86
3/11/86
3/12/86
3/13/86
3/14/86
3/15/86
3/16/86
3/17/86
3/18/86
3/19/86
3/20/86
3/21/86
3/22/86
3/23/86
3/24/86
3/25/86
3/26/86
3/27/86
3/28/86
3/29/86
3/30/86
3/31/86
26
37
47
51
53
53
57
54
53
56
47
47
45
42
39
39
37
38
40
39
53
62
66
70
71
69
70
68
69
69
67
66
65
63
62
72
71
56
63
76
56
69
65
64
62
57
66
70
65
59
60
63
62
59
61
61
62
62
53
63
63
60
58
58
57
57
55
57
57
57
54
52
49
48
53
55
55
4/1/86
4/2/86
4/3/86
4/4/86
4/5/86
4/6/86
4/7/86
4/8/86
4/9/86
4/10/86
4/11/86
4/12/86
4/13/86
4/14/86
4/15/86
4/16/86
4/17/86
4/18/86
64
66
64
62
58
61
58
58
57
55
53
55
56
54
55
52
51
49
55
54
53
51
46
42
39
41
40
38
35
36
35
33
35
32
31
No readin
taken
178
-------
T-2
Metals Analysis of Louisiana AAP Compost Components
Component
Tank #1
Hay -
Horse Feed
LAAP Soil-B
Tank #2
Hay-
Horse Feed
LAAP Soil -A
Tank #4
SS-WC
LAAP Soil-B
Tank #5
SS-WC
LAAP Soil -A
NA
-
Dry
Weight
Ibs
225
222
54
214
211
59
410
155
441
163
- Not Analyzed
Not Detected
Detection Limits
Iron Copper Cadmium
U g/g yg/g ]jg/g
601.9 -
239.9
13,479 38.16
2,755
248.0 -
36,925 80.4
56,366 284.4 3.272
13,479 38.16
39,372 287.0 4.102
36,925 80.4
in Compost and Materials: Fe 33
Cu 13
Cr 27
Cd 3.3
Zn 33
Hg .2
Chromium Lead Zinc Barium
Ug/g U g/g pg/g pg/g
3.0
5U.O
423.7 2,430.9 - 65.4
23.9
60.1
240.4 1,673.3 - 85.7
171.77 151.3 285.38 430.5
423.7 2,430.9 - 65.4
171.61 149.1 205.45 428.03
240.4 1,673.3 - 85.7
ppm
ppm
ppm
ppm
ppm
yg
Mercury
Ug/g
M " *£
NA
NA
0.75
NA
NA
2.84
0.62
0.75
0.62
2.84
•
-------
T-3
Leachate Metals--
Tank I - Hay-Horse Feed Compost with Louisiana AAP-B Soil
ZINC
Leachate
PH
00
0
6
8
8
8
8
8
8
.55
.2
.9
.4
.7
.9
.9
Leachate
Vol. , L.
.503
.716
.780
8.056
14.85
9.30
5.10
ppm
10.096
2.85
.670
.679
-
.42
.61
Amount
Leached, g
.0051
.0020
.0005
.00547
-
.00391
.0031
ppm
3
1
2
2
1
-
.517
.02
.83
.22
.44
.984
Amount Amount
Leached, g ppm Leached,
_
.00037
.0024
.0147
.0330
.0227
.0101
Amount
g ppm Leached, g ppm
2.972 .0015 612.
2.817 .0020 13.
5.
- - 8.
- 8.
22.
9.
7
36
89
98
77
63
403
Amount
Leached, g
.308
.0096
.0046
.0723
.1302
.2105
.0480
.0201
*No Cadmium or Mercury detected in leachate
- Not detected
.0833
.0035
Detection Limits:
Fe .5 ppm
Cu .2 ppm
Cr .4 ppm
Hg .2 jig
Cd .05 ppm
Pb 1 ppm
Zn .5 ppm
.7832
-------
T-4
Leachate Metals*
Tank II - Hay-Horse Feed Compost with Louisiana AAP-A Soil
Leachate
pH
5.65
7.95
,- 8.85
00
"" 8.5
8.7
8.7
8.7
Leachate
Vol. L.
.670
1.033
1.106
8.588
12.935
1 1 . 300
7.25
IRON COPPER CHROMIUM LEAD
Amount Amount Amount Amount
ppm Leached, g ppm Leached, R ppm Leached, g ppm Leached, g
23.50
8.47
.578
.570
.825
1.319
.016 - - - - 1.971 .0013
.0088 - - - - -
.55 .0006 - - -
.0050 3.05 .0262 .51 .0044
.0074 2.71 .0351 - -
.0093 1.66 .0188 - -
.0096 1.963 .0142 - -
0561 .0949 .0044 .0013
ZINC
Amount
ppm Leached, g
1215.4
20.10
9.29
31.63
16.48
17.85
28.41
.8228
.0208
.0103
.2716
.2132
.2017
. 2060
1.746
* No Cadmium, Barium or Mercury detected in Leachate
- Not detected
Detection Limits: Fe .5 ppm Cd .05 ppm
Cu . 2 ppm Pb 1 ppm
Cr .4 ppm Zn .05 ppm
Hg .2 ug
-------
T-5
Leachate Mrtuls"
Tank III - Hay-Horse Feed Compost with Louisiana AAP Non-Contaminated Soil
CO
: j
Leach;
. 1'"
6.6
8.3
8.75
8.6
8.7
8.9
8.9
* No
ale Leachate
Vol. I,.
.583
1. 162
1.599
10.352
4.229
2.314
2.080
Cadmium, Chromium,
Amount Amount Amount Amount
ppm Leached, g ppm Leached, g ppm Leached, g ppm Leached, g.
9.151 .0053 - - - 607.67 .3543
5.775 .0067 10.54 .0123
.5 .0008 3.44 .0055 - - 19.26 .0308
.724 .0075 3.52 .0364 - - 49.06 .5079
1.52 .0064 2.24 .0095 - - 38.35 .1622
1.10 .0026 2.27 .0053 - - 31.63 .0732
2.195 .0045 2.139 .0045 - - 14.224 .0296
.0271 .0612 .0067 1.1703
Barium or Mercury detected in leachate.
- Not detected
Detection Limits: Fe
Cu
Cr
. 5 ppm Cd .05 ppm
. 2 ppm Pb 1 ppm
.4 ppm Zn .05 ppm
Hg .2 pg
-------
T-6
Leachate Metals*
Tank IV - Sewage Sludge-Wood Chips with Louisiana AAP-B Soil
I ejchate
Pll
8.
8.
8.
a 8,
1.0
8,
8,
8.
.4
.4
,85
.6
.9
.9
,9
Leachate
Vol. L.
.592
.930
3.118
3.262
1.143
3.160
2.995
Amount
ppm Leached,
4.009 .0024
1.410 .0013
-
.713 .0023
.690 .0008
.940 .0030
.834 .0025
.0123
g ppm
1.
3,
3,
3.
3
1
-
.511
.40
.21
.48
.36
.911
Amount
Leached ,
-
.0014
.0106
.0105
.0040
.0106
.0057
.0428
Amount
g pprn Leached, g ppm
13.
2.622 .0024 30.
13.
20.
34.
30 ,
18,
.0024
7
22
36
.66
.09
.78
.859
Amount
Leached, g.
.0081
.0281
. 04 1 7
.0674
.0390
. 1004
.0565
.3412
* No Cadmium,Chromium, Barium or Mercury detected in leachate,
- Not detected
Detection Limit: Fe .5 ppm Cd .05 ppm
Cu .2 ppm Pb 1 ppm
Cr .4 ppm Zn .05 ppm
Hg -2pg
-------
T-7
Leachate Metals'"
Tank V - Sewage Sludge-Wood Chips with Louisiana AAP-A Soil
Leachate Leachate
pH Vol, L.
8,
8.
8.
8.
8.
8.
8.
.3
3
75
8
8
,7
7
.724
1.054
.762
1.646
.244
2.545
4.00
ppm
9.
2.
9.
6,
7,
9.
.818
,69
-
,46
.71
.56
,056
Amount
Leached ,
.0071
.0028
-
.0156
.0016
.0192
.0362
g ppm
-
-
.35
1.08
1.05
.103
.065
Amount Amount
Leached, g ppm Leached,
- -
2.077 .0022
.0003
.0018
.0003
.0003
. 000 J
g ppm
8
8
33
68
25
27
.850
.644
1
.60
.53
.72
.80
Amount
Leached , g .
. 0064
.0091
?
.0553
.0167
.0655
.0655
.0825
.0030
.0022
.1092
No Cadmium, Chromium, Barium or Mercury detected in leachate
Not detected
Detection Limits: Fe .5 ppm Cd .05 ppm
Cu .2 ppm Pb 1 ppm
Cr .4 ppm Zn .05 ppm
HE .2 llR
-------
T-8
Leachate Metals--
Tank VI - Sewage Sludge-Wood Chips with Louisiana AAP Non-Contaminated Soil
I.eachate Leachate
pll Vol. L.
IRON COPPER
Amount Amount
pm Leached, g ppm Leached, g ppm
LEAD ZINC
Amount Amount
Leached, g ppm Leached, g.
8
8.
9
8
8
8.
8,
.7
.55
.0
.5
.8
.9
.9
.591
.909
.924
10.105
2.783
5.06
4.56
2
1
1.
2.
3
.822
-
-
.216
.66
.59
.00
.0017
-
-
.0123
.0046
.0130
.0137
-
2.505
1.62
2.51
1.93
.993
. 36b
-
.0023
.0015
.0254
.0054
.0050
. 00 1 7
18,
2.139 .0019 80.
92.
9
29
8
1
.50
.26
.06
.263
.21
.25
.521
.0109
.0730
.0851
.0936
.0813
.0418
.0069
.0453
. 04 1 3
.1)019
. 3926
"No Cadmium, Chromium, Barium or Mercury detected in leaih.ite
- Not detected
Detection Limits: Fe .5 ppm Cd .05 ppm
Cu .2 ppm Pb 1 ppm
Cr .4 ppm Zn .05 ppm
Hg .2 p g
-------
T-9
Explosives in Leachate
Tank I - Hay-Horse Feed Compost with Louisiana AAP-B Soil
l.cacliatc
Vol., L.
TNT
Amount
ppm Leached, g
PP1"
RDX
Amount
Leached, g
PP"1
HMX
Amount
Leached, g
2A-DNT
Amount
ppm Leached, g
4A-DNT
Amount
ppm Leached, g.
oo
.503
.716
.780
8.056
14.85
9.30
5.10
1.426
.377
.0096
.0016
.0112
1.462
1.631
.07
.0099
.0069
.0002
.0017
6.71
.16
.57
.0245
.0011
.0024
.028
Significant interference from compost materials
Not Detected
Detection Limits: TNT .285 ppm
RDX .303 ppm
HMX .248 ppm
2A-DNT .309 ppm
4A-DNT .263 ppm
-------
T-10
Explosives in Leachate
Tank II - Hay-Horse Feed Compost with Louisiana AAP-A Soil
Leachate
Vol.. 1..
TNT
Amount
pptn Leached, g
PP"'
RDX
Amount
Leached, g
PP'"
I1MX
Amount
Leached, g
2A-DNT
Amount
m Leacluid,
4A-DNT
Amou nt
|)|nn Leached, g.
CO
.670
1 .033
1.106
8.588
12.935
11.300
7.25
1.86
.889
.384
.0006
.0052
.0020
.0078
1.743 .0007
1.795 .0105
.404 .0021
.0133
.482
4.699
. 110
.0002
.0018
.0007
.423
.308
.162
.0027
. 001 7
.0018
.0008
.0043
.763
" Significant interference from compost nuteria Is
- Not Detected
Detection Limits: TNT .285 ppm
RDX .303 ppm
HMX .348 ppm
2A-DNT .309 ppm
4A-DNT .263 ppm
-------
T-ll
Explosives in Leachate
Tank IV - Sewage Sludge-Wood Chips Compost with Louisiana AAP-B Soil
Leachate
Vol., L.
3
oo 3
CO
1
3
2
.592
.930
.118
.262
.143
. 160
.995
TNT
Amount
ppm Leached, g
4.23 .0011
1.694 .0007
.440 .0006
-
.056 .00003
-
_ _
.00243
ppm
.672
.863
9.300
7.565
3.946
4.348
4.051
RDX
Amount
Leached, g
.0002
. 0004
.0132
.0112
.0021
.0062
.0055
.0388
HMX
Amount
ppm Leached, g
-
-
3.973 .0056
3.284 .0049
.517 .0003
.711 .0010
.317 .0004
.0122
2A-DNT
Amount
ppm Leached, g
.373
-
-
.779
.24
.815
1 . 969
.0001
-
-
. 00 1 2
.0001
.0012
.0027
.0053
4A-DNT
Amount
ppm Leached, g.
-
-
.861 .0012
.444 .0007
-
.206 .0003
1.296 .0018
.0040
Significant interference from compost materials
Not Detected
Detection Limits: TNT .285 ppm
RDX .303 ppm
HMX .248 ppm
2A-DNT .309 ppm
4A-DNT .263 ppm
-------
T-12
Explosives in Leachate
Tank V - Sewage Sludge-Wood Chips with Louisiana AAP-A Soil
00
Leachate
Vol., L.
1
1
2
4
.724
.054
.762
.646
.244
.545
.000
TNT RDX 1IMX 2A-DNT 4A-DNT
Amount Amount Amount Amount Amount
ppm Leached, g ppm Leached, g ppm Leached, g ppm Leached, g ppm Leached, g.
1.12 . 0004 -- -- -- --
.676 .0003 - - .316 .0002 - - -
.103 .00001 1.708 .0002 .552 .00006 .161 .00002
6.258 .0072 1.754 .0020 .933 .0011 .567 .0007
4.541 .0083 .886 .0016 .119 .0002
.00071
.0157
.00386
.00132
.0007
- Not Detected
Detection Limits:
TNT .285 ppm
RDX .303 ppm
HMX .248 ppm
2A-DNT .307 ppm
4A-DNT .263 ppm
-------
T-13
Explosives in Leachate
Tank V - Manure-Hay-Saw Dust with Louisiana AAP-C Soil
* Trace (unreliable integration)
** Masked by compost organics
TNT
KDX
IIMX
Time Period
Collected
3/1-3/7
3/8 -
3/16 -
3/22 -
3/29 -
4/5 -
3/15
3/21
3/28
4/4
4/18
Leachate
Vol., L.
.580
.200
1.845
10.950
19.650
4 . 1 00
Maximum Totals
Amount Amount
ppm Lcadx-d, g ppm Lcaclii'd,
-
.239 .00005 1.934 .000)9
*
-
-
-
.00005 .00019
'!. i 4A-DNT
Amount Amount
2 009 .00040
.00007
.00040
Telry1
Amount
ri Leached, g
-------
U. Badger AAP Sediment Pilot-Scale Composting
191
-------
U-l
Daily Temperatures (°C) - Badger AAP Pilot Scale Composts
DATE
10/30/85
10/31/85
11/01/85
11/02/85
11/03/85
11/04/85
11/05/85
11/06/85
11/07/85
11/08/85
11/09/85
11/11/85
11/12/85
11/13/85
11/14/85
11/15/85
11/16/85
11/17/85
11/18/85
11/19/85
11/20/85
11/21/85
11/22/85
11/23/85
11/24/85
1
34
65
72
78
75
68
76
83
78
73
75
69
82
80
66
65
70
71
74
65
72
50
65
71
55
2
35
73
80
73
72
77
69
86
75
69
70
62
86
71
52
71
83
62
63
63
77
65
70
75
60
TANKS
3 4
20
21
24
31
37
50
68
68
74
70
68
68
68
68
65
64
60
55
52
55
61
57
55
52
50
5 6
35
47
55
57
56
67
68
72
65
66
62
67
63
67
68
57
52
52
42
46
55
53
47
40
43
192
-------
U-2
Metal Analysis of Badger Time Zero Compost
Tank #
Weight Iron Copper Cadmium Chromium Lead Zinc Barium Mercury
lbs U8/g Mg/g M 8/g Ug/g Ug/g pg/g Ug/g Ug/g
1 Hay-Horse Feed
with BAAP-B
Sediment
2 Hay-Horse Feed
with BAAP-B
Sediment
4 Sewage Sludge-
Wood Chips with
3 BAAP-A Sediment
j
5 Sewage Sludge -
Wood Chips with
BAAP-A Sediment
508 3,837 25.2
523 2,966 21.6
702 44,820 214.5
742 45,023 234.8
166.8
163.9
740.0 - .68
2,058.9 - .675
106.6 3,389.6 400.2 .776
99.6 4,356.0 416.1 .715
- Not Detected
Detection Limits in Solids: Fe 33 ppm
Cu 13 ppm
Cr 27 ppm
Cd 3.3 ppm
Zn 33 ppm
Hg .2 ug
-------
U-3
Leachate Metals *
Tank I - Hay-Horse Feed Compost with Badger AAP-B Soil
Time Period
Collected
10/29 - 11/4
11/5 - 11/11
11/12 - 11/18
11/19 - 11/24
Leachate
PH
8.1
8.7
8.8
Leachate
Vol., L
None
.355
3.035
1.725
* No Cadmium, Chromium,
Detection
Limits: Fe
Cu
Cr
Hg
IRON
ppm
1.175
.711
2.843
Barium, Lead
. 5 ppm
. 2 ppm
. 4 ppm
•2 [J g
Amount
Leached, g
.00042
.00216
.00490
.00748
or Mercury
Cd .05 ppm
Pb 1 ppm
Zn . 5 ppm
ZINC COPPER
Amount Amount
ppm Leached, g ppm Leached, g
48.1 .01708 1.282 .00046
12.03 .03651 1.495 .00454
8.34 .01439 1.920 .00331
.06798 . .00831
detected in leachates
-------
U-4
Leachate Metals*
Tank II - Hay-Horse Feed Compost with Badger AAP-B Soil
IRON
ZINC
COPPER
Time Period Leachate Leachate
Collected PH Vol., L ppm
10/29 - 11/4 None
11/5 - 11/11 9.0 .845 .924
11/12 - 11/18 8.5 3.600 .284
11/19 - 11/24 8.8 4.825 2.592
" No Cadmium, Chromium, Barium,
Detection Limits: Fe .5 ppm
Cu . 2 ppm
Cr .4 ppm
Hg -2 Mg
Amount Amount
Leached, g ppm Leached, g
.00078 17.70 .01496
.00102 10.21 .03676
.001251 4.87 .02350
.00305 .07522
Lead or Mercury detected in leachates
Cd .05 ppm
Pb 1 ppm
Zn . 5 ppm
Amount
ppm Leached, g
1.718 .00146
1.473 .00531
2.334 .01126
.01803
•
-------
U-5
Leachate Metals*
Tank III - Sewage Sludge-Wood Chips Compost with Badger AAP-A Soil
ON
Time Period
Collected
10/29 - 11/4
H/5 - 11/11
11/12 - 11/18
11/19 - 11/24
Leachate
PH
8.7
8.7
8.6
Leachate
Vol. , L
None
3.71
9.63
3.075
* No Cadmium, Chromium,
Detection
Limits: Fe
Cu
Cr
Hg
ppm
.460
.535
1.764
Barium
. 5 ppm
. 2 ppm
.4 ppm
•2 ug
IRON
Amount
Leached, g
.00171
.00515
.00542
.01228
, Lead or Mercury
Cd .05 ppm
Pb 1 ppm
Zn . 5 ppm
ZINC
Amount
ppm Leached, g
44.15 .1638
42.40 .40831
40.50 .12454
.69665
detected in leachates
COPPER
Amount
ppm Leached p
.336 .00125
1.930 .01859
2,982 .00917
.02901
.
-------
U-6
Leachate Metals*
Tank IV - Sewage Sludge-Wood Chips Compost with Badger AAP-A Soil
Time Period
Collected
10/29 - 11/4
11/5 - 11/H
11/12 - 11/18
11/19 - 11/24
IRON ZINC
Leachate Leachate Amount Amount
pH Vol., L ppm Leached, g ppm Leached, g
None
9.1 .997 1.576
8.9 7.326 2.442
8.6 2.965 1.037
•'• No Cadmium, Chromium, Barium,
Detection Limits: Fe .5 ppm
Cu . 2 ppm
Cr .4 ppm
Hg -2 ug
.00157 1290.0 1.2861
.01789 343.0 2.51282
.00307 15.5 .04611
.02253 3.84503
Lead or Mercury detected in leachates
Cd .05 ppm
Pb 1 ppm
Zn .5 ppm
COPPER
Amount
ppm Leached, g
8.46 .00843
1.526 .01118
1.792 .00531
.02492
-------
DISTRIBUTION LIST
Defense Technical Information Center " 12
Cameron Station
Alexandria, VA 22314
Commander 2
U.S. Army Toxic and Hazardous Materials Agency
ATTN: AMXTH-CO-P
Aberdeen Proving Ground, MD 21010-5401
Commander 2
U.S. Army Toxic and Hazardous Materials Agency
ATTN: AMXTH-TE-D
Aberdeen Proving Ground, MD 21010-5401
Defense Logistics Studies Information Exchange 5
U.S. Army Logistics Management Center
Fort Lee, VA 23801
198
------- |