-------
Results from Newport AAP, Indiana
(Continued)
RDX Concentration Estimate ftig/g)
Standard
Colorimetric RP-HPLC
Sample # Method Method
7
8
9
10
11
Otmtima Moan Corp.
17.4
45.4
674
2,430
7,690
38.6
258
1,800
3,170
12,200
Overall Advantages of
Field Methods
Fast
ซ Low cost
ป Selection of samples for lab
analysis
ซ Correlates with standard lab
methods
9 Low incidence of false negatives
* Low detection limits
Interferences
Acetone extracts must contain
water
TNT method
Humics
Other nitroaromatics - Tetryl, TNB
RDX method
Other nitramines - HMX, Tetryl
ซ Nitrate esters - NG, PETN, NC
-36-
-------
Field Screening for
Explosives and Propellants
Colors Observed
Compound TNT Method RDX Method
2,4-dinitrotoluene
TNT
1 ,3,5-trinitrobenzene
Tetryl
NG
PETN
RDX
HMX
NC
Blue
Red
Red
Orange
None
None
None
None
None
None
None
None
Pink
Pink
Pink
Pink
Pink
Pink
r
Sites Where Field Screening
Methods Have Been Used
Eagle River Flats, AK (CRREL)
Camp Shelby, MS
(CRREL, Mobile District)
Seneca Army Depot, NY
(C.T. Main, Aquatec)
Newport AAP, IN (Dames and Moore)
Savanna Army Depot, IL
(Dames and Moore)
Sites Where Field Screening
Methods Have Been Used
Umatilla Army Depot, OR
(CRREL, Weston)
Aberdeen Proving Ground, MD
(Argonne N.L.)
Bangor, WA (B&V Waste Science)
Cornhusker AAP, NE
(Watkins-Johnson, USAEC)
Kentucky Ordnance Works, KY
(TCT-St. Louis)
-37-
-------
Performance
Characteristics
Analysis time
Sample throughput
Estimated cost of
supplies
30 minutes
per sample
25 samples
per day
$20 per
sample
Current Status of TNT and
RPX Test Kits
Methods developed and field tested
Final reports completed
Draft SW846 Method 8510 in review
"How-to" videotape available
List of supplies available
TNT kit commercially available
Available Field Screening
Methods
TNT RDX
CRREL
Color/metric
ENSYS
Colorimetrlc
EM Science
Enzyme Immunoassay
-38-
-------
Acknowledgments
Capt. Craig Myler and Mr. Jim Arnold
U.S. Army Environmental Center
Dr. Richard Williams
Weston Corp.
Dr. Richard Coghlan and Mr. Wayne Dixon
Dames and Moore Corp.
Mr. Brad Chirgwin
Aquatec, Inc.
Dr. Murray Brown
USAEHA
Mr. Robbin Blackman and Mr. Terry Williams
Mobile District, COE
Funding Provided by
U.S. Army
Environmental Center
Aberdeen Proving Ground, MD
Project Monitor: M.H. Stutz
-39-
-------
-------
Search for a White Phosphorus
Munitions Disposal Site in
Chesapeake Bay
Harry Compton
-41-
-------
-------
Search for a White
Phosphorus Munitions
Disposal Site in
Chesapeake Bay
Gary A. Buchanan, IT Corp.
Harry R. Compton, us EPA/ERT
John Wrobel, APG
Introduction
History
Alleged disposal of WWI munitions
barge might have occurred between
1922-1925
Waterfowl kill reported after hurricane
in 1933
Proclamation issued in 1944 under
Migratory Bird Act of 1918-Delineating
a WP Zone
Proclamation 2383
Closed Area Under the
Migratory Bird Treaty Act
Maryland Phosphorus
Area Unit
Signed into law January 24,1940, by
President Franklin D. Roosevelt
-43-
-------
Important Species Using Aquatic
Habitats at Aberdeen Proving Ground
Fish/invertebrates
Striped Bass
White Perch
Yellow Perch
Herring
Shad
Blue Crab
Important Species Using Aquatic
Habitats at Aberdeen Proving Ground
(Continued)
Waterfowl
Mallard
Black Duck
Wood Duck
Canvasback
Goldeneye
Canada Geese
Whistling Swan
Loon
Merganser
Gallinule
American Coot
Methods
-44-
-------
Two-Phase Approach
Phase I-
Geophysical investigation
Phase II-
Sampling and analysis
Black Point Transect 9
Magnetic Field (Gammas)
55,000.0
-200.0 0.0 200.0 400.0 600.0 800.0 1,000.0 1,200.0 1,400.0 1,6000 1,800.0 2,000.0
South Distance (Feet) North
Black Point Transect 12
ft
56,000.0
55,800.0
55,800.0
55,700.0
55,600.0
55,500.0
55,400.0
55,300.0
55,200.0
55,100.0
55,000.0
-2
So
Magnetic Reid (Gammas)
-
-
-
-
_
-Tie Line C
i i i
00.0 0.0 200.0 400.0
uth
_J||ป_-JU:-..J'. j..,,n-,, .-/A- -"IN
Tie Una B
l ll l l 1 l
600.0 800.0 1,000.0 1,200.0 1,400.0 1,600.0 1,800.0 2,000.0
Distance (Feet) North
-45-
-------
Phase II
Sampling and Analysis
Logistics
Remote coring operations
Sample preparation
Remote Coring Operations
Coring operations-safety
procedures
Surety monitoring
Independent chemical agent detector
(ICAD)
UXO Screening
Aluminum core barrel
Acetate core sleeve
U.S. Army Technical Escort Unit
Six Explosives Detected
(Cannot Differentiate)
SconXJfBMponta
Blank
C-4 (Source I)
Dynamite
Prima-Cord (PETN)
TNT
C-4 (Source I)
2.4 DNT
Nclt: Mtrogtyctrin* doltimlnod by Itself under different parameters.
-46-
-------
White Phosphorus EC50 and LC50
Toxicity Values for Freshwater and
Marine Organisms
Invertebrate Species
Common
Name
EC50(ng/L)
Chironomus tentans
Daphnia magna
Gammarus oceanicus
Homarus americanus
Midge
Cladoceran
Amphipod
Lobster
140 (48-hr)
30 (48-hr)
6,500 (24-hr)
2-40 (168-hr)
souicw suflhwnrtal. (1976)
White Phosphorus EC50 and LC50
Toxicity Values for Freshwater and
Marine Organisms (Continued)
Fish Species
Common
Name
(H9/L, 96-hr)
Lepomis macrochirus
Pimephales promelas
Salmo salar
Gadus morhua
Bluegill 2
Fathead minnow 21
Atlantic salmon 2.3
Atlantic cod 2.5
SOUTOK Sufltvw ซt ml. (1070)
Sediment Toxicity Testing Results
White Phosphorus Munitions Burial Area
Aberdeen Proving Ground, MD
Core#
Pimephales
Promelas1
Menidia Chironomus
Beryllina1 Tentans2
02
16
17
34
35
37
42
45
49
50
52
58
NTO
NTO
54.83
NTO
>100
67.3
89.23
NTO
_
>100
NTO
NTO
93.9
NTO
NTO
NTO
NTO
NTO
NTO
NTO
NTO
NTO
NTO
NTO
NTO
Not tested
NTO No toxlclty
1 96-hr acute
elutrlate-phaso
tests
2 10-day acute
solid-phase
tests
'LCjo Lethal
concentration
(%)to50%of
test organisms
-47-
-------
Results of Elemental Phosphorus Analysis in Sediments
White Phosphorus Underwater Munitions Burial Area
AbardMn Proving Ground, MD-August1989
Location
Area I
Black Point
Black Point
Black Point
Black Point
Black Point
Channel
Area II
Area til
Area 111
Area IN
Core
3
11
17
18
20
25
31
40
54
55
58
Sample
#
4,356
4,427
4,433
4,434
4,436
4,441
4,448
4,457
4,475
4,476
4,480
Phosphorus
Dry Weight
fttg/kg)
0.78
2.22
0.72
0.62
2.22
1.16
0.74
2.41
4.64
3.38
3.84
Phosphorus
Wet Weight
0ป3*3)
0.42
1.00
0.30
0.28
0.71
0.94
0.34
1.04
1.90
1.55
1.80
Core
Length
(ft)
4.5
4
4.5
4.5
5.5
ซ.)
6
8.5
6
6
9
/ EM WHtf Fheipttmit Hunt ton* Buttl Jtrtf, January 1MO;
Conclusions
Remote coring
ii Vibracore system
Successful for sampling the estuarine
sediments
Difficulty in hard-packed sands
Emergency procedures were effective
Analyses
All holding times were met
Sediment toxicity implies toxic conditions do
not exist in the sediments sampled
History
1988-US EPA/ERT/REAC study
of underwater burial site
Sept. 1991-Record of decision
No risk for the underwater site
MDE recommends further study for a
possible land disposal site
Aug. 1991-Aeromagnetic survey
-48-
-------
Approach
Munitions impact area and active
range
Modeled magnetic response of
barge
Programmed positioning system
20-meter line spacing
Used a helium magnetometer
Flew at two altitudes
Requirements of Navigation
Stable platform (Sikorsky-61)
Computer control
Accurate positioning
GPS (Global Positioning System)
Microwave Positioning System
Requirements of Magnetometer
High sensitivity helium metastable
magnetometer
Dynamic Sensitivity of 0.01 nT
Operational Noise of < 0.1 nT
Nondirectional dependency
< 2 nT shift
Continuous sampling
1 Hz digital record
20 Hz analog record
-49-
-------
Magnetic Field Model of WWI Barge
10.00
a co
-10,00
000
-040
ToU! MignotSe FI.W (Glmmti)
r\
Dซplh(KUomttซri)
} O2 0.4 0.6 0.8 1
WsUnco (Kilometers)
Assume capacity
of WWI era barg#
Is 50 tons
Assume that 40%
of the cargo was
Iron
Assume the barge
Is loaded to 60%
capacity
Assume an
ox Water factor of
75%
50 tons- 0.8
(barge loaded to
60% capacity}*
0.4 (Iron) * 18
tons; and
16 tons -0.75
{oxidation factor
estimate) ซ 4 ton*
Black Point Magnetic Profiles
Total Magnetic Intensity (1GRF Romoved) Nanoteila
ฃ3,700.00
u,ซซaoo
S3.S8000
n,ซraoo
--O~Unซป154
1.10 1.16 1.22 1.28 1.34 1.40 1.40 1.52 1.58
South Distance (Kilometers) North
Results
Black Point
One anomaly detected that fit
the model
Two altitudes flown because of
tree cover
-50-
-------
Detection, Retrieval, and Disposal
of Buried Munitions
James Pastorick
-51-
-------
-------
Detection, Retrieval,
and Disposal of Buried
Munitions
James Pastorick
IT Corporation
Edison, NJ
Definitions
Ordnance and Explosive Waste
(OEW)
Unexploded Ordnance
(UXO)
Chemical Weapons Material
(CWM)
Definitions (continued)
Explosive Ordnance Disposal
(EOD) Technician
Unexploded Ordnance
(UXO) Specialist
-53-
-------
Detection
Low-Sensitivity Magnetometer
(LSM)
High-Sensitivity Magnetometer
(HSM)
Metal detector
Other (GPR, EM)
Retrieval (Access)
Hand excavation
Mechanized excavation
Disposal of UXO
-54-
-------
Potential Hazards and
Unpredictability of UXO
Complicate the Disposal Process
Unpredictability
UXO is often severely stressed
(i.e., fired down-range,
incompletely detonated or burned,
subjected to deterioration by
weather and time)
To Determine the Disposal Method, Each UXO
Must Be Subjected to a Strict Decision Process
UXO Is Located
Can UXO Be Positively Identified?
YES
I
Is UXO Safe to Move?
YES
NO
Move to Secure
Storage Area
for Later
Disposal
BIP or RSP
(RSP by
Military
EOD)
NO
Assume Not
Safe to Move.
BIP or RSP (RSP
by Military EOD)
Limiting Factors Make Onsite
Disposal of UXO Desirable
Limiting Factors
UXO specialists limited by lack of
EOD 60-Series pubs
o UXO specialists do not perform
RSP
Often, very few UXO meet the
strict criteria for transportation
-55-
-------
-------
Compressed Gas Cylinder/Reactive
Chemical Hazards Techniques
Irwin Kraut
-57-
-------
-------
Compressed
Cylinder/Reactive
Chemical Handling
Techniques
Irwin Kraut
Emergency Technical Services Corporation
Schaumburg, IL
What Does Evaluation Entail?
Integrity test of the body, valves, and
fittings
Leak tests
Mandatory for phosgene per 40 CFR 173.333-Level B
Ultrasonic depth gauge readings
Recording all pertinent data
Height, weight, diameter, etc.
. DOT and other markings (i.e., hydrostatic test dates)
ID number for future tracking
ETSC Protocols are based on CGS recommended guidelines
Evaluations
Why Are They Necessary?
Per 40 CFR 173.301-
Ail cylinders destined for
offsite recovery or disposal
must be positively identified
and in DOT shippable
condition
-59-
-------
Evaluations
What Will They Tell Us?
Is it known?
Unknown cylinders cannot be identified via color
and/or valve configuration-
CGA (Compressed Gas Association)
Is it shippable?
Can its contents be recovered?
Less expensive than disposal
Mora consistent with RCRA (waste minimization)
Exempt as hazardous waste per 40 CFR 261
High Hazard Chemicals
The environmental community
defines a High Hazard Chemical as
any liquid, solid, or gas that is:
Reactive
Explosive
Pressurized
Pyrophoric
Unstable
Extremely toxic
High Hazard Chemicals
(Continued)
A specific example of each High
Hazard category is:
Reactive:
Explosive:
Pressurized:
Pyrophoric:
Unstable:
Extremely toxic:
Alkali metals
Picric acid
Unknown gas cylinder
White Phosphorous
Peroxidized Ether
Phosgene
Some chemicals might fit into more
than one High Hazard category
-60-
-------
What Are You Likely to Find?
Drums containing unknown
materials-labeled "Explosive"
Cylinders in various states of
deterioration
Small containers of laboratory
chemicals labeled as nitro-based
compounds dating back 10 to 30
years
What Are You Likely to Find?
(Continued)
Cans, bottles, or drums of ethers
Vessels used for heat exchange
containing alkali metals such as
sodium metal and NaK
All of the above improperly stored
in bunkers, warehouses, closed
laboratories, or in buried drums
Peroxide Formers
Isopropyl Ether
Ethyl Ether
Dioxane
Tetrahydrofuran
-------
Nitro Compounds
Nitro compounds
Dinitro compounds
Trinitro compounds
Hexanitro compounds
Examples:
Nitroguantdine
Dlnitrobenzene
Trlnitrophenyl (Picric Acid)
Hexanitrodiphenylamine
Perchloric Acid (HCปO4)
A colorless, fuming, hygroscopic
oxidizing liquid. In the anhydrous state
and allowed to stand at room temperature,
it will decompose spontaneously
Commonly used are aqueous solutions of
perchloric acid with concentrations
ranging from 60 to 72% (by weight)
Perchloric acid should be stored away
from all flammable and combustible
chemicals
Perchloric Acid (HCIQ4)
t Fume hoods used for perchloric acid
should be constructed of impervious,
nonflammable materials
> Fume hoods not designed specifically for
perchloric acid usage and without a wash-
down system might develop metallic
perchlorates or perchloric salt deposits in
bends, elbows, and fan housings. Metallic
perchlorates and perchloric salts are
sensitive and considered explosive
hazards
-62-
-------
Open Burn/Open Detonation
Techniques for Unexploded
Ordnance Management
Steven Whited
-63-
-------
-------
Open Burn/Open
Detonation Techniques
for Unexploded Ordnance
Management
Steven Whited
Hercules Incorporated
Hazards Analysis Department
Rocket Center, WV
Definition of Terms
Open Burning
Is the disposal of explosives
of munitions by an external
ignition source
Definition of Terms
Open Detonation
Is the disposal of explosives
or munitions by propagating a
detonation from a disposal
charge to the explosives or
explosive contained in the
munition under destruction
-65-
-------
RCRA Permitting Survey
Facilities receiving permits
to date
H Schlumberger Well Services, located
in Coyanosa, Texas
5 tons of RDX per year
Air emissions were based on literature
research
RCRA Permitting Survey
Facilities receiving permits
to date (Continued)
m Nasa Yellow Creek Facility in
Mississippi
600 tons of propellant, including
contaminated Items
Air emissions were based on a NASA-
developed computer program simulating
propellant combustion
J
RCRA Permitting Survey
Facilities receiving permits
to date (Continued)
m U.S. Naval Weapons Industrial
Reserve Plant, in McGregor, Texas
246 tons of propellant and
miscellaneous contaminated waste
Air emissions were based on combining
U.S. EPA 42 factor and estimates for
propellents
-66-
-------
RCRA Permitting Survey
Determination of explosive waste
emissions
Laboratory results and studies are
difficult
Small sample size
Initiator and igniter emissions might
bias results
Vacuum or inert background does not
replicate real world situations
r \
RCRA Permitting Survey
Determination of explosive waste
emissions (Continued)
m Field studies are equally as hard
Plume usually disperses quickly
Concentrations of many key pollutants
become difficult to detect
Pollutants are necessarily distributed
evenly throughout the plume
RCRA Permitting Survey
BangBox study at Dugway
Proving Ground, Utah
Purpose:
Enclosed structure to analyze explosive
byproducts
Develop methodology needed for testing
emission for similar OB/OD treatments
-67-
-------
RCRA Permitting Survey
BangBox Study at Dugway
Proving Ground, Utah (Continued)
u Conclusion:
BangBox is the only study where a quantitative
measurement can be made close to field
conditions from detonation
Selection of target substance based upon health
risk considered the only way to proceed with
studies
Authors are not comfortable using computer
simulations with the success of BangBox and
field studies
Safety Measures and Precautions
Disposal area-2,400 Ib
Net Explosive Weight (NEW)
Minimum distances
H 1,200 feet radius for nonfragment
operations
2,500 feet radius for fragment producing
operations
M 4,000 feet radius for bombs and
projectiles with a caliber of 5 inches or
greater
Safety Measures and Precautions
Basic layout
At the center-pits for fragment
protection and pads for burning
200 feet radius-clear all combustible
mateials sufficient to spread fire
300 feet from destruction point-
minimum distance for personnel
shelter - fragment protected
-68-
-------
Safety Measures and Precautions
Basic layout (Continued)
m 1,200 feet from destruction point-
explosive holding area - fragment
protected
Perimeter-warning and informational
signs and road blocks
Safety Measures and Precautions
Weather
Site selection-prevailing winds away from
other facilities
No operations during:
B Electrical storm
Sand storm
Snow storm
Any storm strong enough to produce
static electricity
Operation should be conducted
between 4-15 MPH
Safety Measures and Precautions
Personnel
Supervised by experienced and
well-trained person
Each person should be trained on:
OB/OD procedures
Materials handled
Hazards involved
Precautions necessary
B Danger of deviating from standard
procedure
Minimum of two individuals
-69-
-------
Safety Measures and Precautions
Explosives Used in OB/OD
Ignition and initiation
Ensure explosive is powerful enough and in
sufficient quantity to ensure propagation
High brisance explosives are preferred in
OD operation
Shaped charges are very effective in case
opening and venting
Detonating cord is used to initiate buried
charges and multiple locations at once
OB/OD Procedures
Burning
Must be prepared for detonation
Do not burn primary explosives in
quantities greater than one ounce
Use burning trays or pads
OB/OD Procedures
Burning (Continued)
m Burning wet explosives-add nonexplosive
combustible material to ensure complete
burning
Burning trays designed without cracks
and corners-to prevent build up of
residue
Pit or trench burning used for munitions
or fragment producing explosives
-70-
-------
OB/OD Procedures
Detonation
Pit should be used to reduce fragmentation
hazards
The pit should be at least four feet deep
Munitions items should be covered with two
feet of earth or wire screening
Caution-items found outside the pit can be
very dangerous
Detonation can be used to open containers
and ignite explosives or propellents
New Series GP/750 Ib
Demolition (Demo) Bomb
Fuze
Fuze
CBU-24, -29, -49, -52, and -58
Charge Placement
20 Pounds of Comp C (4 Places)
Detonation Cord
-71-
-------
M15 HE Heavy Antitank
Mine Placement
-72-
-------
Recycle/Reuse Options for
Propellants and Explosives
William Munson
-73-
-------
-------
Recycle/Reuse Options
for Propellents and
Explosives
William Munson
Thiokol Corporation/Strategic Operations
Brigham City, UT
Overview
Why reuse?
Reuse applications/options
Removal methods/issues
Wash out
Cryofracture
Reuse of materials options/issues
Boosters
SBIR examples
Ingredient recovery
AP recovery
Critical fluids technology
Summary
Acknowledgments
r \
The EPA and Congress Have Provided
a Logical Hierarchy of Waste
Elimination, Treatment, and Disposal
Highest preference is substitution of
nonhazardous materials
m Substitute CO2 cleaners for degrease, acetic acid for
HNOs, etc.
Use of ultrasound favored over X-ray measurements
Next, reduce waste via operational change
m Refine mix size to reduce amount of "top-off" mix
discarded
Refrain from bringing materials into an area to be
contaminated
-75-
-------
The EPA and Congress Have Provided a
Logical Hierarchy of Waste Elimination,
Treatment, and Disposal (Continued)
Then recycle by direct use, cleanup, or
Ingredient recovery
m Ingredient recovery with AP and residue recycle/use
1.1 propeltant recovery/reuse for blast boosters
Finally, treatment and disposal by
appropriate means
u Incinerators with scrubbers
OB/OD
IMtraao*? F*dซrtin*g!ttปrPu%ac*!!aAofEPAi TTiWHilnr Hซte,DttcutUon on Pollution Prevention
KCnttU Am* 1,!HO.pป). XKa
Why Reuse?
Environmentally sound
(positive to neutral)
Recovery of valuable materials
Cost-effective
Minimum permitting required
Important- Safety must always be the
dominant concern
Reuse Opportunities
Manufacturing waste
Excess batch size
Out of specification
Demilitarization
Overage/obsolete
Treaty required
Cleanup
Concentrated sludges
Bunkered ordnance
-76-
-------
Potential Options
Removal of Energetic Material from Containers) Reuse Options
Rocket Motor
Wash Out
Machine Out
Cryocycle
Large Ordnance Melt Out
Wash Out
Machine Out
Saw/Cut
Cryofracture
Small Ordnance Saw/Cut
O O O O Cryofracture
O O O O Reverse Manufacture
Sludge
Liquid/Solid Extraction
Solvents
Supercritical Fluids
Removal Methods
Method
Facility
Status
Washout Thiokol Corporation Production
water Aerojet Propulsion Production
Division
University of Mo Rolla Prototype
Liquid ammonia U.S. Army MICOM
LNz
General Atomics
Prototype
under
development
Prototype
under
development
Removal Methods
(Continued)
Method
Facility
Status
Mechanical
Melt/Steam Out
Cryofracture
Cryocycle
Reverse
Manufacture
Numerous
U.S. Army Facilities
General Atomics
Sandia National Labs
U.S. Army Facilities
Production
Production
Pilot
production
Bench scale
Production
-77-
-------
Thiokol
Water Washout Facility
Water Wash Out
Schematic Diagram
Hyoromlfte
Operation
1
10,00 MI
nS
Holding
Tanks
High Pressure .
Pump*
> Water/PropelUnt
Vibrating
Screen
-
Wซt9r/Rnซ
SXHIOS
> Propdlant
Facility
Wato
Weir Tanks &
Filter Press
,
Water
NPDS
r<10%AP Discharge
Water |
>10%AP
Energetic
Waste Water
Treatment Plant
Nonreactive 1 ..
' Solids Y p
Landfill
Sale
Pyrotechnics |
M-115 Solid Propellent Motor
Washout Facility
-78-
-------
Hydromining Summary of Solid Rocket
Motors Reclaimed by Thiokol
Motor
Minuteman,
Stage 1
Genie
Poseidon,
First Stage
SRM Segment
Tomahawk
Warhead
Number
Reclaimed
330
2,321
1
2
4
Case
Material
Steel
Steel
Glass
Steel
Titanium
Case Size
21 ft x 65.5 in. dia.
54 in. x 14.9 in. dia.
14.75 ft x 84 in. dia.
25 fix 144 in. dia.
50 in. x 50 in. dia.
Propellent
Weight (Ib)
44,000
320
38,000
250,000
270
Cryofracture-
General Atomics
Cryofracture Process
Development at General Atomics
Cryofracture is the process of embrittling steel
parts in liquid nitrogen and then fracturing the
parts in a hydraulic press to access the contents
for destruction
1982 Concept identified for chemical munition disposal
1984 Prototype system demonstration and feasibility
established for explosive munitions
1987 Cryofracture chemical demilitarization plant
design
1988 Extended tests of Cryofracture plant components
-79-
-------
Cryofracture Process
Development at General Atomics
(Continued)
1991 Cryofracture feasibility for simulated nuclear
mixed waste drums and boxes demonstrated
1992 Design verification tests on Cryofracture plant
components
Initial Cryofracture tests for conventional
munition disposal (Germany)
1993 Demonstrate Cryofracture of more than 2,500
explosively configured simulant-filled chemical
munitions - projectiles, mortars in boxes, mines
in drums
Munition Cryofracture Data Base
All Explosives Fractured Without Explosion
Munition Typซ T*st*d Form
Explosive
Items
Explosive Elements Cryofracturod
M55 BoeKlts Rocket In firing tube
(,123 Land Mints Stool drum with threo
mines and packing
malarial
MM 105-iti m Wood box with two
Cartrldaei cartridges In fiber
tutus
Comp B burster 3.2 Ib 5
Double-base cast
propollant19.3lb
Comp B burster 0.8 Ib 126
1S5*mm
Prefect!)*!
Projectile
Totrytol burster 0.3 Ib 72
Totrytol booster 0.05 Ib
Single-base grain
propellent 2.8 Ib
M110andM21A1 1204
Reuse of
Propellents & Explosives
-80-
-------
Use Summary
Use
Major Issues/
Barriers
Candidate
Material(s)
Original
Application
Commercial
Explosives
Specifications
Requalification
costs
Consistency
Cost
Handling
TNT-based
explosives
Gun propellents
Above, PBX's
Rocket
propellents
Use Summary (continued)
Use
Major Issues/
Barriers
Candidate
Material(s)
New Mixtures Quality
DOD Cost
Commercial Required
solvents
Thermal
Energy
e Hazards
Consistency
Permitting
HMX, RDX, TNT
AP, Al
TNT, RDX, Gun
Propellant
Sludge extract
AI/Binder
Explosive Booster-2 Ib
0.003 InJln. T*pซr OpHorad
-81-
-------
Detonation Characterization of
Explosive Booster Class 1.1 Propellant*
Test No.
1
2
3
4
5
G
Initiation Temperature (ฐF) Results
No, 6 Cap
No. 6 Cap
No. 6 Cap
50 gr Primacord
50 gr Primacord
50 gr Primacord
-40
+70
+120
-40
+70
+120
Detonated
Detonated
Detonated
Detonated
Detonated
Detonated
POA-NG-HMX-AP-AI
Material Recovery/Reuse
Commercial Explosive Market Potential for 1.1 Propellant
25
Mlbjyr
10
m*
Xtefttft'liS
Booster Explotfva
Uinufซc*urod(1ซ9)
Bootter Expbuhra from 100
PoMldon Stage B and 200
MM Stag* RVYetr
Booster Btptottvo from 50
PoMkJon SUQซ II and 100
HU Stigi IB
SBIR Example(s)
TPL Inc.
-82-
-------
Industrial and Military Reuse of Surplus
Explosives and Propellants
Phase ISBIR
Phase II SBIR
Pilot Plant
Reclaimed PBX as
Blasting Agent
(NSWC/Crane)
v Explosive i
r\ Metal Bonding r\
FY94 Proposed
Activity &
Expansion
to A-3 & LX-14
Nitrocellulose
Propellants for
Agricultural Applications !_/
(NSWC/Crane)
Recommended
for Funding
Qualification of
Reclaimed HMX for
Reuse (NSWC/Crane)
Nitrocellulose
Propellants for
Industrial Applications
(CERL)
Blasting Agent for
Explosive Metal Bonding
Dissimilar metals - Bonded,
welded, cladded by explosives
2M Ib ANFO/diluent consumed
annually
Granular explosive product
developed from reclaimed PBX
Blasting Agent for
Explosive Metal Bonding (continued)
Velocity specifications met
Magnitude = 2.2 km/s
Variation = ฑ 50 m/s
Customer-manufactured bonded
metal product-exceptionally high
quality
Stainless steel clad carbon steel
plate
-83-
-------
Energetics Reuse in Slurry
Explosives/Blasting Agents
ป Use of surplus gun propellants, TNT,
others as filler demonstrated in
production several companies
i Present activity
t Thlokol Corp/
Ireco, Inc.
\lreco, Inc.
Demonstrate use of rocket
propellant (lab & field tests)
Development
demonstration with military
explosives
Energetics Fieuse in Slurry
Explosives/Blasting Agents (continued)
ปPresent activity (continued)
i Technology 100 Ib/day pilot plant in
operation, successful field
tests, military explosives &
propellants
Actively interested in
recycling and reuse of
demilled high explosives,
propellants & rocket
motor propellants
Development,
Inc.
i ICI Explosives
Nitrocellulose Propellants for
Agricultural Applications
Applications
Nitrogen feed supplements commonly
employed for ruminant animals (cattle,
sheep)
High nitrogen content, slow release rate
fertilizers have numerous applications
Feasibility experiments conducted in
conjunction with New Mexico State
University
-84-
-------
Nitrocellulose Propellants for
Agricultural Applications (continued)
Feed
NC & NQ digested by unadapted rumen
microbes
Preference over low quality feed shown
Fertilizer
Nitrogen release demonstrated from NC &
NQ through plant growth experiments
Feasibility demonstrated
Purification requirements established
Ingredient Recovery/Reuse
AP recovery plant
(THIOKOL)
Critical fluids technology
(MICOM)
Ingredient Reclamation
Process Schematic
Propellant
| Centrifuge [.
Residue (Wet)
Ammonium
Perchlorate
(Wet)
-85-
-------
Critical Fluid Demilitarization
by Extraction
Method is based on simple "liquid-to-gas"
and "gas-to-liquid" phase transitions
H High operating pressures (compression) produce
"liquefied fluids" which serve as extraction solvents
it Reduced operating pressures (volume expansion)
causa "liquefied fluids" to revert to gaseous state and
spontaneously release all extracted ingredients
n RecomproBslon of the expanded gas regenerates the
original extraction solvent (100% recovery) and
forms the basis of the continuous, nonpollutlng
extraction process
Rocket Motor Demilitarization
Using Liquefied Gases
_, High-Pressure Nozzles
for Propellant Removal
Rocket Motor
Propel lint
Slurry
Extractor^
Separator
Oxldlzer
Evaporator
for
Oxldlzer
Recovery
solvent
Vapor
Solvent
Liquefaction
and
Recycling
Condensed Supply
The 4-step, closed-loop, continuous process is
based on Ingredient recovery and reclamation
Measurements Show That NH3 is a
Super-Solvent for AP
AP Solubility
Sm/t00gm
O Liquid
Ammonia
Eotvtr.t
Q Wttor
Sotvint
300.00
200.00
110.00
100.00
50.00
0.00
-ซ
1 - A
0 <]
d
J \J '
i nL
[Era
1.00 0.00 60.CO 100.00
Temperature, ปC
-86-
-------
Critical Fluid Demilitarization
Technology Program
High purity HMX/RDX recovered from
class 1.1 solid rocket propellants
Independent analytical tests confirm recovery
of high purity HMX/RDX
Test samples representative of anticipated
pilot plant recovery products
Preliminary tests indicate that recovered
HMX/RDX ingredients can meet Mil spec
requirements
Critical Fluid Demilitarization
Technology Program
(Continued)
Bench and pilot-scale demonstrations at
Holston Army Ammunition Plant are
required to certify reclaimed HMX/RDX for
reuse purposes
The feasibility of recovering
HMX/RDX for reuse has been
successfully demonstrated
Holston Test Results for
Recovered HMX/RDX
Test
Method
Impact, CM.
(5 Kg. WL)
Microscopic
DSC, Onset
LC, Purity
FT-//? Scan
Standard
HMX
>26
Beta HMX
275-280
98+% HMX
Baseline
Chaparral
HMX
26
Same
278
100% HMX
Normal
Standard
RDX
>33
No Alpha
205-220
85% RDX
Baseline
Tow-2
RDX
35
Same
215
84.5% RDX
Normal
-87-
-------
Qualification of Reclaimed
HMX for Reuse
9 Recovery of HMX for class 1.1.
propellants of significant economic
value
o Military reuse might be viable
application
Upgrade performance - bulk explosives for
demolition charges (Pro)
Weapon systems might require extensive
requaliflcatlon (Con)
Qualification of Reclaimed
HMX for Reuse (continued)
Commercial reuse
Specialty applications, such as oil and gas well
perforating charges, use HMX; costs on the
order of $30/lb
Activities include extraction processes
(solvolysis and supercritical fluid) and
commercial application qualification
tests
Super Critical CO2
> SCF processing proven in commercial
applications-coffee decaffeination,
etc.
ป SC-CO2 extraction of nitrate esters,
TNT demonstrated
ป Current R&D being conducted for
demilitarization applications
Many advantages over other (organic)
solvents
-88-
-------
Summary
Recovery & reuse gaining momentum
Reduced permitting required
Environmentally positive to neutral
Removal/extraction method might dictate
end use
Specification/requalification costs largest
barrier to military reuse
Commercial reuse demonstrated
Variety of applications
Large market
Consistency required
Acknowledgements
Ireco Inc.
General Atomics
U.S. Army MICOM
TPL Inc.
TDI
ICI Explosives
USN Crane
USN Indian Head
Sandia National Labs
Clark Bonner
Lou Johnson
William Melvin
Hap Stoller
Terry Nixon
Neil Gehrig
Dan Burch
George Nauflett
Leroy Winnery
801-364-4800
619-455-2711
205-876-4096
505-345-5668
314-341-3614
214-387-2400
812-854-3505
301-743-4436
510-294-3022
-89-
-------
-------
Ordnance Recovery Operations in
the State of Kuwait
Richard Posey
-91-
-------
-------
Ordnance Recovery
Operations in the
State of Kuwait
Richard Posey
Environmental Health Research and Testing, Inc.
Lexington, KY
Introduction
> The more liberal rules and unusual
circumstances in Kuwait
Ordnance removal vs. land reclamation and
contaminant remediation
Final disposal
i The direct link between battlefield
clearance and all other clearance
operations
Similarities of procedures
Current in-use procedures
Logic for development of new procedures
Visual Inspection
Situation always dictates
procedures
Ordnance configuration only
one part of situation
Surface/sub-surface
inspection
-93-
-------
Electronic Detection
Types
ฉLimitations
Problems
Retrieval of
Buried Munitions
Practical concerns/safety
problems of:
Remote methods
Hand removal
Use of heavy equipment
Remote Methods
Types
Expense
Time factors
Safety
-94-
-------
Hand Removal
Access
Terrain
Amount
Ordnance items and condition
Protective equipment
Safety concerns
Use of Heavy Equipment
Bomb excavation
Small ordnance items
Protective measures
Operator safety
Item Categories
Type by function
Munition filler
Fuze by type and
condition
Final disposition
-95-
-------
-------
Incineration of Soils and Sludges
Contaminated with Explosives
Charles Lechner and Dianna Feireisel
-97-
-------
-------
INCINERATION
Charles A. Lechner, PhD
Dianna F. Feireisef
U.S. Army Environmental Center (AEC)
(formerly U.S. Army Toxic and Hazardous Materials Agency (USATHAMA))
Aberdeen Proving Ground, MD
Applications
Explosives-contaminated
soil and debris
Explosives with other
organ ics
Explosives with metals
Explosives with metals and
other organics
Applications (Continued)
> Explosives and initiators
> Bulk explosives
> Ordnance
> Bulky radioactive waste
> Pyrophoric waste
-99-
-------
Advantages
Low residual
contaminant levels
Organics to nondetect
Simpler handling of treated soil
Lower site cleanup goals
Media Insensltfva
Effective on variety of wastes and mixtures of wastes
Established/demonstrated
Known (B)wt(A)vปI!ab!o (T}echnology
Moderate coat
Onslte/no permits under CERCLA
Advantages
lowmtduilcontimlnintta/oli
Media insensitive
m Metals pieces, concrete, sand, clay,
water, sludge
Able to feed
Sufficient heatup
Stabilization/bio affected by media
Effective on var!ซty of waitas and mixtures of wastes
Ettปbl!ih*a7tf*motปlnM
Known (B)*it(A)vil(ab!< (T)*ehnotosy
Modซrataoost
Oniltcino pwmtts under CERCLA
Advantages
* LowntldualconUmlnanttevels
Mtdtaliuonaltlv*
' Effective on variety of wastes and
mixtures of wastes
m Mixtures common
Few technologies are general
Incineration will burn all the organics
Successful in presence of inerts
EatabHittcd'demonstrated
Known (B}ซat(A)val!ซb!o(0ซcnno!agy
On*!:*/no permits under CERCLA
-100-
-------
Advantages
Low residual contaminant levels
Media Insensitive
Effective on variety of wastes and mixtures of wastes
Established/demonstrated
* Well-known/literature available
Equipment/vendors available
Good competition/lower prices
Variety of equipment size to suit site/tower prices
Experienced contractors
Certainty that it will work
Known (BJest (Available (T)echnology
Moderate cost
Onslte/no permits under CERCLA
Advantages
Low residual contaminant levels
Media Insensitive
Effective on variety of wastes and mixtures of wastes
Established/demonstrated
Known (B)est (Available
(T)echnology
m Land disposal restrictions
Incineration required for some wastes
Basis for concentration-based standards
Moderate cost
Onslte/no permits under CERCLA
Advantages
Low residual contaminant levels
Media insensitive
Effective on variety of wastes and mixtures of wastes
Established/demonstrated
Known (B)est(A)vallable(T)echnology
Moderate cost
m Incineration
Stabilization
Composting
Solvent extraction
Onsite/no permits under CERCLA
-101-
-------
Advantages
Low residual contamlnan t levels
Medta In sensitive
Effective on variety of wastes and mixtures of wastes
Established/demonstrated
Known (B)est (Available (Technology
Moderate cost compared to other technologies
Onsite/non permits under
CERCLA
m Mobile incinerator, onsite
Air emissions are onsite
Section 121 CERCLA, no permits
Limitations/Disadvantages
Safety concerns
m Handling of reactive soil
Defense department approvals
M Industrial operations
Air em listens
Large capital/mobilization costs
Negative public perception
Required test bums
Ash product
Materials handling (small openings)
Many utilities
Limitations/Disadvantages
Safety concerns
Air emissions
m Might involve modeling for NOx
Metals emissions
Products of incomplete combustion
Large capital/mobilization costs
Negative public perception
Required tastbums
Ash product
Materials handling (small openings)
Many utilities
-102-
-------
Limitations/Disadvantages
Safety concerns
Air emissions
Large capital/
mobilization costs
m Mob/demob could be $1-2M
Incinerators are costly
Negative public perception
Required test bums
Ash product
Materials handling (small openings)
Many utilities
Limitations/Disadvantages
Safety concerns
Air emissions
Large capital/mobilization costs
Negative public perception
m Equates incineration with hazardous
waste
Usually considered a permanent unit
Required test burns
Ash product
Materials handling (small openings)
Many utilities
Limitations/Disadvantages
Safety concerns
Air emissions
Large capital/mobilization costs
Negative public perception
ป Required test burns
Required by RCRA if hazardous waste
Pressure to pass
Might require spiking
Might involve delays
Ash product
Materials handling (small openings)
Many utilities
-103-
-------
Limitations/Disadvantages
Safety concerns
Air emissions
Large capital'moblllz jtfon costs
Negative public percoptlon
Required test bums
Ash product
m Power plant ash problems
Ash might be special waste
Materials handling (small openings)
Many utilities
Limitations/Disadvantages
Safety concerns
Air emissions
Large capital/mobilization costs
Negative public perception
Required test bums
Ash product
Materials handling
m Small feed opening
Clayey soils are sticky
Feed preparation
Many utilities
Limitations/Disadvantages
Safety concerns
Air emissions
Large capital/mobilization costs
Negative public perception
Required test bums
Ash product
Materials handling (small openings)
Many utilities
m Needs substantial electric
Needs much fuel
-104-
-------
Effect of Site Size on
Incineration Costs
some* EPM4VHUI14
Very Small
30,000-
Costs
Explosives-Contaminated
Soil Incineration
CAAP 40,000 tons $260/ton
LAAP 102,000 tons $333/ton
SVADA 25,000 tons S370/ton
ALAAP 35,000 tons $220/ton
Cost Items
Incineration
Materials handling
Fixed costs (mobilization and
demobilization)
Planning
Other
i Analytical
i Surveying
i Water treatment
Utility connections
Site preparation
Taxes
-105-
-------
Case Histories
Cornhusker Army
Ammunition Plant, 1986-1988
Louisiana Army Ammunition Plant,
1987-1990
Savanna Army Depot Activity,
1991-1993
Alabama Army Ammunition Plant,
1992-1994
"x! .i.
Cornhusker
Army
Ammunition
Plant
Grand Island, NE
CAAP Cleanup Criteria (Ppm)
Analyto
EDK
2,4,6-TNT
1,3,5-TNB
2,4-DNT
2,6-DNT
HMX
1,3-DNB
NB
Totryl
2A.4.6-DNT
Excavation
Criteria
<10
<5
<15
<0.5
<0.4
NA
NA
NA
NA
NA
Incineration Criteria
(Method
Detection Limits)
<2.2
<1.3
<1.25
<0.24
<1.26
<2.9
<1.2
<1.26
<2.2
<1.25
-106-
-------
CAAP Problems
Feed system seals
Slagging
Winter weather
Rotary Kiln Incineration System
Air Pollution Control
Secondary
Combustion
Chamber
Stack
Air In
Ash Moisturizer
Case Histories
Cornhusker Army Ammunition
Plant, 1986-1988
Louisiana Army Ammunition
Plant, 1987-1990
Savanna Army Depot Activity,
1991-1993
Alabama Army Ammunition Plant,
1992-1994
-107-
-------
Distribution
of RDX (ug/1)
AreaP
Alluvium
Distribution
of TNT (ng/1)
Area P
Alluvium
Louisiana
Army
Ammunition
Plant
Shreveport, LA
LAAP Cleanup Criteria (Ppm)
Analyto
RDX
2,4,6-TNT
1,3,5-TNB
2,4-DNT
2,6-DNT
HMX
1,3-DNB
NB
Toby!
2A.4.6-DNT
Incineration Criteria
Excavation (Method
Criteria Detection Limits)
Sum of all less
than 100 ppm
after 1 foot
excavation of
lagoons
<2.2
<1.3
<1.25
<0.24
<1.26
<2.9
<1.2
<1.26
<2.2
<1.25
^s
LAAP Problems
ซ Feed system pluggage
o Slagging/carryover
ฎ Site conditions
(rain, metals degree)
-108-
-------
Rotary Kiln Incineration System
Air Pollution Control
Secondary
Combustion
Chamber
Stack
Air In
Ash Moisturizer
Case Histories
Cornhusker Army Ammunition
Plant, 1986-1988
Louisiana Army Ammunition Plant,
1987-1990
Savanna Army Depot Activity,
1991-1993
Alabama Army Ammunition Plant,
1992-1994
t-l blew Dtuclton Unit
""""
Savanna
Army
Depot
Activity
Savanna, IL
Concentration of
total explosives In
ground water at the
old TNT washout
lagoons and new
TNT leaching
lagoons
-109-
-------
SVADA Cleanup Criteria (Ppm)
Analyte
RDX
2,4,6-TNT
1,3,5-TNB
2,4-DNT
2,6-DNT
HMX
1,3-DNB
NB
Tetryl
2A.4.6-DNT
Excavation
Criteria
<5.75
<21.1
<3.7
<9.3
<4.3
<3,722
<7.4
<37.2
<112
Incineration Criteria
(Method
Detection Limits)
.-j
<1
<1
<1
<1
<1
<(
^j
<1
_^>
SVADA Problem Areas
Feed system clogging
Site conditions
(rain, cold)
SVADA Results to Date
New incinerator set and
operating
Trial burn completed
Lower lagoon
excavation completed
-no-
-------
Case Histories
ซ Cornhusker Army Ammunition
Plant, 1986-1988
Louisiana Army Ammunition Plant,
1987-1990
Savanna Army Depot Activity,
1991-1993
ฉ Alabama Army Ammunition
Plant, 1992-1994
Alabama Army Ammunition Plant
Childersburg, AL
Areas from which soil was removed for stockpiling
AAAP Cleanup Criteria (Ppm)
Analyte
RDX
2,4,6-TNT
1,3,5-TNB
2,4-DNT
2,6-DNT
HMX
1,3-DNB
NB
Tetryl
2A.4.6-DNT
Excavation
Criteria
None
<1.92
<5.5
<0.42
<.40
None
None
None
Incineration Criteria
(Method
Detection Limits)
I
-111-
-------
Potential Problem Areas
Chunks of explosives,
asbestos, and debris
o Lead levels in soil
0 Asbestos emissions
Deactivation Furnace
> Army peculiar equipment
(APE) 1236
' Deactivates small arms
cartridges, mines, grenades
Intended to burn reactive
materials/handle small
detonations
Deactivation Furnace (continued)
Thick-walled rotary kiln,
secondary containment
Air pollution control
(baghouse) for metals
emissions
No afterburner
-112-
-------
Contaminated Waste Processors
Stationary oven with or
without afterburner
Intended to accept
su rf ace-con tarn i nated
debris
No high levels of
explosives
Contaminated Waste Processors
(Continued)
Treat debris to
time/temperature requirements
to allow release of debris
under Army safety regulations
General time/temperature
requirements still being
developed
Open Containment Burning
ป Common Army practice
ป Formerly Army burned
explosives directly on the
ground, now metal trays are used
ป Associated with large quantities
of explosives/propellants and
need to remove reactive
characteristic
-113-
-------
Open Containment Burning
(Continued)
Likely requires exemption
from air emissions limits
Might not remove all traces
of explosive and might
require additional
verification sampling
-114-
-------
Biological Treatment Methods for
Soils and Sludges Contaminated
with Explosives
Kevin Keehan
-115-
-------
-------
Biological Treatment
Methods for Soils and
Sludges Contaminated
with Explosives
Kevin R. Keehan
U.S. Army Environmental Center
Technical Support Division
Aberdeen Proving Ground, MD
Biological Treatment
Biodegradation:
Organic &
compounds
Less toxic or
non-toxic
Potential product fates:
Mineralization
Biotransformation
Assimulation into biomass
Binding to organic matter
Volatilization
Advantages of
Bioremediation
Destruction technology
Lower treatment costs
Greater public acceptance
Regulatory encouragement
-117-
-------
Primary Contaminants of
Explosives-Contaminated Soils
Cyclo-1,3,5- Cyclo-1,3,5,7-
trlmtlliylin*- tatramathylene-
2,4,6-WnltrซmInซ (RDX) 2,4,6,8-t.ilronltramIno (HDX)
2,6-DlnItrotoluMB Tclnllro-2,4,6-
(DNT) phynylmelhylnllraralna
(Tebyl)
Biodegradation of Explosives
Explosives
Compound
Degradation
Products
Optimum
Conditions
TNT
RDX
HMX
Amtno-dinitrotoluenes
Dlamlno-nitrotoluenes
Hydroxylamino-
dinitrotoluenes
Tetranltro-
ozoxynitrotoluenes
Mineralization
Mineralization
[High organic]
Aerobic
Anaerobic
Anaerobic
Potential
Biological Methods for
Explosives-Contaminated Soils
Solid-phase biological
treatment
Fungal technologies
Landfarming
Composting
-118-
-------
Potential
Biological Methods for
Explosives-Contaminated Soils
(Continued)
Aqueous-phase biological
treatment
Above-ground slurry reactors
Lagoon slurry treatment
In-situ biological treatment
Fungal Technologies for
Explosives-Contaminated Soils
Applications/contaminants:
Low to medium contaminant
levels
Broad spectrum of
contaminants
Fungal Technologies for
Explosives-Contaminanted Soils
(Continued)
Advantages:
Simple procedure
Inexpensive
Mineralization of TNT and RDX
Disadvantages:
Laboratory studies only
-119-
-------
Landfarming for
Explosives-Contaminated Soils
Applications/contaminants:
Low to medium contaminant
levels
VOCs, PCP, PAHs
Landfarming for
Explosives-Contaminated Soils
(Continued)
Advantages:
Simple procedure
Inexpensive
Disadvantages:
Slow degradation rates
Long treatment periods
Unsuccessfully demonstrated for
explosives
Composting of
Explosives-Contaminated Soils
Applications/contaminants:
High contamination levels
Soils and sludges
TNT, RDX, HMX, Tetryi, DNT, NC
-120-
-------
Composting of
Explosives-Contaminated Soils
(Continued)
Advantages:
Demonstrated effective
Product is enriched
Various reactor configurations
Disadvantages:
Innovative
Composting Process Designs
Mechanical In-Vessel
Composting
Explosives Reduction
Explosives Concentration (jig/g)
,
5,000
Soil Volume = 25%
0 TNT
0 5 10 15 20 25 30 35 40
Days
-121-
-------
Windrow Composting
Demonstration at Umatilla Depot
Activity
Process design: Windrow
Turning frequency: 1 x Day
Temperature: 55ฐC
Soil content: 30% (by volume)
Windrow Composting
Demonstration at Umatilla Depot
Activity (Continued)
Amendments (by volume)
Manure (cow) - 24.4%
Vegetable waste -10.0%
Alfalfa/sawdust - 35.6%
Treatment time: 40 Days
Windrow Composting
Demonstration
Explosives Reduction
Expio
OTOT
QRDX
AHMX
-122-
-------
Windrow Composting
Explosives Reduction
TNT RDX HMX
% Reduction
Day
0
5
10
15
20
40
(ug/g)
1563
101
23
19
11
4
(ugfg)
953
1124
623
88
5
2
(ug/g)
156
158
119
118
2
5
TNT
0.0
93.5
98.5
98.8
99.3
99.7
RDX
0.0
0.0
34.6
90.7
99.5
99.8
HMX
0.0
0.0
23.7
24.4
98.7
96.8
Composting of Explosives
TNT Biotransformation
TNT Biotransformation Product
Products
o 2.4-DA-6-NT
D 2-A-2.6-NT
A2.6-DA-4-NT
V2-A-4.6-NT
15 20 25 30
Days
Windrow Composting Demonstration
Compost Toxicological and
Chemical Characterization
Toxicological study
90 to 98% reduction in aquatic toxicity
observed in CCLT leachates
No rat oral toxicity detected
No mutagenicity observed in CCLT
leachates
Biotransformation to less toxic
compounds
-123-
-------
Compost Toxicological and
Chemical Characterization
(Continued)
Radiolabeled TNT study
Chemical binding to the compost
Composting
Key Factor Costs
> Process selected
> Volume of contaminated soil
> Soil throughput
Amendment costs
Treatment time
UMDA
Composting and Incineration
Remediation Costs
CoitP.rTon(S)
em
400
200
o WlndrowComposUng
D MAIV Composting
A Incineration
0248 8 10 12 14 16 18 20 2,7 24 26 28 30
Thousands of Tom (K)
-124-
-------
UMDA Feasibility Study
Comparison of Alternatives
Overall protection?
Meets cleanup
requirements?
Effectiveness?
Reduces toxicity?
Long term protection?
Time
Incineration
Yes
Yes
99.99%
>90%
Yes
16 months
Composting
Yes
Yes
97 to 99%
>905
Yes
24 months
-**
Composting Treatability Study
Objectives
Indigenous microorganisms
Amendment mixtures/availability
Maximum quantity of soil
Percent reduction/levels achievable
Potential toxic degradation products
Potential degradation rate
Slurry Bioreactor Treatment for
Explosives-Contaminated Soils
Advantages:
Improved process control
Improved materials handling
Potential to achieve lower levels
Many configurations
Can be used in treatment train
-125-
-------
Slurry Bioreactor Treatment for
Explosives-Contaminated Soils
(Continued)
Disadvantages:
Laboratory scale only
Costs unknown
Laboratory Slurry Reactor
TNT Reduction
TNT Concentration (mg/L)
JAAP Consortium
o Aoroblc+Mnlato
n Anoxlc+Succlnate
AAnoxIc+Malato
0 2 4 E 8 10 12 14 16 18 20
Lagoon Slurry Reactor
Nutrients
1 Aeration
1 I Microorganisms
v HI Mixers _
< iri^ ^^l_ J
\T Y f "-i r*1 f^* ^
\
\^
1 Water 1 I /
*** Sludge *" /
-126-
-------
Above-Ground Slurry Reactor
Excavation
Soil Screening
Water Recycle
Dewatering
Nutrients
| Aeration
I Microorganisms
'
i
~
1
1
Slurry Bioreactors
In-Situ Treatment for
Explosives-Contaminated Soils
Advantages:
Potential for large cost savings
ซ Disadvantages:
Negative data for explosives
Mass transfer rates are slow
Completeness difficult to verify
Process control is difficult
-127-
-------
-------
UV Oxidation Treatment and
Activated Carbon Treatment of
Explosive-Contaminated Water
Wayne Sisk
-129-
-------
-------
UV Oxidation Treatment and
Activated Carbon Treatment
of Explosive-Contaminated
Water
Wayne E. Sisk
U.S. Army Environmental Center
Aberdeen Proving Ground, MD
Explosive-Contaminated
Water Sources
Process wastewater from
munitions production
Contaminated ground water
from past industrial
operations
Process Wastewater from
Munitions Production
(Pink Water)
> Load, assemble, and pack (LAP)
Army ammunition plants
> Munition demilitarization
Army ammunition plants
Depots
-131-
-------
Contaminants of Concern
2,4,6-Trinitrotoluene (TNT)
Cyclotrimethylenetrinitramine (RDX)
CyclotetramethylenetetranJtramine
(HMX)
Trinitrophenylmethylnitramine
(Tetryl)
Contaminants of Concern
(Continued)
2,4-Dinitrotoluene (2,4-DNT) ,
2,6-Dinitrotoiuene (2,6-DNT)
1,3-Dinitrobenzene (1,3-DNB)
1,3,5-Trinitrobenzene (1,3,5-TNB)
Nitrobenzene (NB)
Process Wastewater Treatment
Kansas AAP Pilot Study, 1981
Influent RDX concentration 0.8 to
21.0 mg/L
30 UV lamps 40 watts
Ozone generator
Treatment times-37 to 375 min
Flow rates-0.2 to 2.0 GPM
Effluent RDX concentration 0.1 to
1.7 mg/L
-132-
-------
Process Wastewater
Treatment
Crane AAP
Iowa AAP
Holston AAP
Picatinny Arsenal
Treatment Parameters
Residence times
Concentration and species of
explosives
Real vs. simulated pink water
Combinations of UV, O3, and H2O2
Different power wattage
Bench-Scale Ground Water
Treatability Studies
Determine general effectiveness
of electrochemical precipitation
and UV oxidation to treat metals
and explosives
Select design and operating
conditions for follow-on pilot test
program
-133-
-------
Electrochemical
Precipitation Tests
10 gal. of contaminated water
Metals and explosives analyzed
1,000 mL beaker tests
Electrodes to generate ferrous
ions, Andco anionic polymer
2600, NaOH, H2O2, and filter paper
Conclusions from
Precipitation Tests
MCLs for metals can be
achieved
Reinjection of treated water
would require no metals
treatment
Surface discharge would
require metals treatment
Conclusions from
Precipitation Tests (continued)
ซ Iron dosage of 25 mg/L and pH of
9 recommended
* Chemical oxidation with H2O2
recommended
Explosives not removed by this
process
-134-
-------
UV-Oxidatfon Tests
15 gal. contaminated water
12 tests conducted
Explosives analyzed
2.4 L reactor, 40 watt UV bulb,
magnetic stirrer, ozone gas
sparger, H2O2 port
UV-Oxidation Tests (continued)
Influent concentration 57,500
Ozone diffused at rate of 2.8 to
15.0 mg/L/min.
pH 4.0 to 8.5
UV exposure time 40 to 200 min.
H2O2 35% by volume
Conclusions for UV-
Oxidation Tests
UV radiation required to enhance
oxidation of explosives
H2O2 did not improve destruction rate
pH levels at or above 7 required
Longer UV exposure time yields better
results
1,3,5-TNB rate controlling compound
-135-
-------
Electrochemical
Precipitation Test
Andco Model 2B containing two
cells
13.5 to 15 GPM flow rate, 4 hr. per
day for 6 days, 17,725 gal. treated
90 min. retention time at 15 GPM
flow rate
Electrochemical
Precipitation Test (continued)
32 electrodes, H2O2, Andco
polymer, HCI, NaCI
24 metals analyzed
Effluent and influent 100% toxic
to ceriodaphnia dubia
Pilot-Scale Ground Water
Treatability Studies
Objectives
> Verify effectiveness, operability,
and implementability of
electrochemical precipitation
followed by UV oxidation with or
without secondary carbon
treatment
-136-
-------
Pilot-Scale Ground Water
Treatability Studies
Objectives (Continued)
Obtain design data for full-scale
(500 GPM) system
ป Obtain operating data and
material data to establish cost
estimate for full-scale system
UV-Oxidation Tests
650 gal. Ultrox P-650 system
6 reaction chambers twelve
65-watt UV lamps in each chamber
Recycle batch mode operation
Recycled 7-8 times during each test
Ten tests conducted
UV-Oxidation Tests (continued)
Influent 20,656 jig/L total explosives
pH range 7 to 11
Ozone dose 1.11 to 3.33 mg/L/min
Exposure time up to 210 min
Treatment goal 20 jig/L for TNT and
1,3,5-TNB
-137-
-------
Results
pH of 9 was best
Ozone dose of 3.33 mg/L/min
best
120 min with high-ozone dose
destroyed all explosives
60 min. with high-ozone dose
did not destroy all TNB
ReSUltS (Continued)
180 min with low-ozone dose
did not destroy TNB
Biotoxicity tests-effluent
biotoxic because of metals
leached from equipment
Contaminated Ground-Water
Treatment with Carbon
Isotherm tests
Continuous flow
column studies
-138-
-------
Isotherm Test Program
Purpose
Relative adsorbability of
explosives
Adsorption capacities and
exhaustion rates
Degree of removal
Preferential adsorption
Isotherm Test Procedures
Series of batch adsorption
experiments
Multiple aliquots of ground water
Varying dosages of different
carbons
Continuous agitation to achieve
equilibrium
Solution filtered and analyzed
Continuous-Flow Column
Studies
Badger AAP
Milan AAP
-139-
-------
Continuous Flow Procedures
4.25-inch ID columns
First column-test column
Second column-backup column
2 Series of test columns
Variable fill depths (2 to 4 ft)
Variable flow rates
Badger AAP
2,4-DNT and 2,6-DNT
2 different carbons
2 test trains of 2 columns each
3 flow rates-0.3, 0.5, and
0.7 GPM
Up to 20,000 gal. used in each test
Badger AAP Chemistry
200 p.g/L to 600 (ig/L influent
concentration
Detection limit 2,4-DNT 0.46
Detection limit 2,6-DNT 0.01 7
HPLC
Field lab and fixed lab
-140-
-------
Milan AAP
7 explosives
2 different carbons
2 test trains of 2 columns each
4 flow rates-0.2 to 1.0 GPM
Up to 56,000 gal. used in each
test
Milan AAP Chemistry
600 to 900 ng/L influent
concentration
Detection limit TNT 0.78 \ig/L
Detection limit RDX 0.63 jig/L
HPLC
Field lab and fixed lab
Results
Activated carbon successfully
removed explosives
2,4-DNT and 2,6-DNT can be
removed to below detection
Concurrent removal of 7
explosives is feasible
-141-
-------
-------
Unsuccessfully Demonstrated
Technologies for Explosive Waste
Kevin Keehan
-143-
-------
-------
Unsuccessfully
Demonstrated Technology
for the Remediation of
Explosives-Contaminated
Soils
Kevin R. Keehan
U.S. Army Environmental Center
Technical Support Division
Aberdeen Proving Ground, MD
Reasons for Not Developing
Technically infeasible
Low destruction and
removal efficiency
Production of potential
toxic products
Uneconomical
Engineering Evaluation of
Technologies for Lagoon
Sediments (1981)
Wet air oxidation
Incineration
Microwave plasma
Gamma irradiation
-145-
-------
Engineering Evaluation of
Technologies for Lagoon
Sediments (1981) (continued)
High energy electrons
Ultraviolet oxidation
Chemical degradation
Biological treatment
Laboratory Testing of
Technologies for Lagoon
Sediments (1982)
Gamma irradiation
Wet air oxidation
Solvent extraction
Water extraction
Composting
Evaluation of Technologies
for Removal of
Contaminants in Soil (1983)
57 treatment technologies
assessed
Two level assessment
process
-146-
-------
Evaluation of Technologies
for Removal of
Contaminants in Soil (1983)
First level
Technically feasible
Second level
Which were commercially available
Investment capital to develop
Could be implemented in 1987
Gamma Irradiation
Laboratory study
Lagoon samples
Irradiated with Cobalt-60
and Cesium-137
Effective at low
concentrations
30% ORE at 4.1 megarads
Gamma Irradiation (continued)
Advantages
Low operating costs
Disadvantages
High capital costs
Dilution of sediment
Safety aspects
Public reaction
Not recommended for further
development
-147-
-------
Liquid Sludge Gamma Irradiation
Facility at Guselbullach, West Germany
Sludge Inlet
Ground Level
,Vent
Sludge
Cobalt Rods
Concrete
Shielding
Sludge Outlet
Wet Air Oxidation
Laboratory study
10% lagoon slurries
Chemical catalysts added
RDX effectively destroyed
TNT daughter products
Wet Air Oxidiation (continued)
o Advantages
Proven technology for propellants
0 Disadvantages
High capital costs
Dilution of sediment
Post treatment required
o Not recommended for further
development
-148-
-------
Basic Wet-Air Oxidation Flow Scheme
-O Pressure Controller
Waste
Compressor
High
Pressure
Pump
Separator
N2( CO2, Steam
level Controller
Oxidized Liquid
Low-Temperature
Thermal Desorption
Originally designed for
volatile organic compounds
Laboratory study
Aqueous slurries
Heated to 200 to 300ฐC
Elevated pressure
95% ORE in 20 minutes
Low-Temperature
Thermal Desorption (Continued)
Laboratory study (Continued)
m Degradation products
3,5-dinitroanaline
3,5-dinitrophenol
Pilot-scale engineering design
and cost analysis delayed
-149-
-------
Od Heating
System
Air
Containing
Stripped
VOCs
Air to
Atmosphere
ฉ
Combustion
AlrPreheater Blower
After-
'Burner
Solvent Extraction
Laboratory study (1982)
Lagoon samples
Washed with 90% Acetone
>90% removal of explosives
Pilot-scale engineering analysis (1985)
Engineering concept design developed
# Solvent washes need to be reduced
Further laboratory work required
Solvent recovery required
Safety considerations-"Acetone Rocket"
High-Pressure Walter
Extraction
Laboratory study (1982)
Lagoon samples
Washed with water at 100,149, and 200ฐC
Efficient at 200ฐC
Laboratory study and engineering design
Several different lagoon samples
Washed with water at 200 and 250ฐC
Under pressure
-150-
-------
Reaction Apparatus
Liquid
Sampling
s=ฃ]HPLCPump
Temperature and
Pressure Recording
Temperature
Controller
Aqueous Thermal Decomposition
Process Flow Diagram 3
T=2SOฐC P=492psag
Reactor
Recycle
Water Pump Recycle
Water Tank
Vapor
Liquid to Carbon
Solids to Lagoon
High-Pressure Water
Extraction (Continued)
Advantages
Effective destruction of explosives
Reduction to 1 mg/kg
Disadvantages
Slow decomposition
Several different lagoon samples
Safety concerns-heat & pressure
Costs unknown
Recommended for further evaluation
-151-
-------
Chemical Treatment
Technologies
1990 Economic Analysis
Caustic/hydrolysis/peroxide
oxidation
Schock plasma
Microwave/hydrolysis/oxidation
Nitric acid/heat
Supercritical fluids
-152-
-------
Depleted Uranium Management
Operations
Donald Barbour
-153-
-------
-------
Depleted Uranium
Management
Operations
Donald Barbour
Nuclear Metals, Inc.
Concord, MA
Depleted Uranium
Applications
Counter weights
Catalyst in chemical reactions
Shielding
Anti-armor munitions
Depleted Uranium
Characteristics
> Byproduct of uranium fuel
fab and enrichment
production cycles
> Primarily U-238
> High density/tensile strength
-155-
-------
Depleted Uranium
Characteristics (continued)
Chemically toxic
Radioactive
Pyrophoric
DU Contamination
Issues
Oxidizes easily (U3O8; UO2)
Small particle size produced
Many environmental and
biological pathways
ซ Not easy to detect small
quantities
Characterize Contamination
ซ Direct radiation measurements
Surface
Airborne
> Radioanalytical/chemical analysis
Structures
Soils/air
Ground water/surface water
-156-
-------
Characterize Contamination
(Continued)
Isotopes/chemical
compounds
Particle size
Morphology
Solubility
Remediation/Waste
Treatment/Disposal
Excavation/burial
Soil washing/leaching agents
Solution ion
exchange/filtering
Vitrification
Hydrometallurgical
-157-
-------
-------
Guidance for Conducting a
Treatability Study for the Volume
Reduction of Radioactive Soils
Michael Eagle
-159-
-------
-------
Guidance for Conducting a
Treatability Study for the
Volume Reduction of
Radioactive Soils
Mike Eagle
U.S. Environmental Protection Agency
Office of Radiation and Indoor Air
Washington, DC
Introduction
In 1987, ORIA began a treatability
study for the Montclair and Glen
Ridge Superfund Sites in NJ
Montclair/Glen Ridge Sites
323,000 cubic yards of contaminated soil
Contaminated with Ra-226, about 50pCi/g
Transportation and burial cost:
$900/cubic yard
Volume Reduction/Chemical
Extraction Program
VORCE
Treatability studies for the volume
reduction of radioactive soils
Site characterization
Feasibility of volume reduction
Study application of technology that is
common to processing of minerals
and coal
-161-
-------
Volume Reduction/Chemical
Extraction Program
VORCE (Continued)
Treatability studies for the
volume reduction of
radioactive soils
n Study application of chemical
extraction
it Evaluate and recommend volume
reduction processes
Four Tiers of a
Treatability Study
Soil characterization
ii Determine if volume reduction is
feasible
Bench-scale testing
n Verifies whether volume reduction
technology can meet performance
goals for the site
Four Tiers of a
Treatability Study
Process Development Unit
(PDU)
Demonstrates volume reduction
on site at a small scale (150 IbJhr.)
Pilot plant
Provides detailed cost, design, and
performance data
-162-
-------
Tier 1, Soil Characterization
Determines if volume
reduction is feasible
Identifies exploitable physical
and chemical differences
Size Friability
Specific gravity Solubility
Particle shape Wettability
Magnetic property
Radionuclide Distribution
Ra-226 Activity
70
A 60
C 50
} 40
y ao
T 20
Y 10
0
A.A\
pci/g
\
^ \
\ \
*V \ ^
>s\ \
.038 .075 .16 .30 1.18 sTe
PARTICLE SIZE (mm)
V.R.Grace O-OMaywood *-*Ottawa D-OMontolalr
Tier 2, Bench-Scale Testing
Particle liberation unit
Operations
Particle separation unit
operations
Dewatering
-163-
-------
ORP Bench-Scale Testing Techniques
PiEJfc!* Serration Technique*
wtti lnปnw^hซ tar ARM
Bvtttfewi ซ*jra(ซ
Flotalonn
WEUCOUb-Fag
ORP Bench-Scale Testing Techniques
Bito'a
Principle
Gtnfrnl
Cqulpmmt
SjuJjpm*n*
Particle Liberation Tochnlquos
Surface
Scrubbing Da-Bonding Attrition
Water action
Particle/
particle
action
Surfactant
action
Vigorous
particle/
particle
action
Trommel, Trommel,
washer, screw screw
classifier classifier
Trommel, mill Trommel, mill
Stirring units, Trommel, Trommel, Trommel,
trommel, WEMCO WEMCO WEMCO
ehitrlatlon Lab-Fag Lab-Fag Lab-Fag
column
Radioactivity Distribution
Soil #2 (Montclair) 180 pCi/g
3
aw-;
c "H
I ซ*:
Y tป-
J^
Particle Slป (mm)
land gravel
-164-
-------
Monfclair, New Jersey
Ra-226 Distribution
350
300
250
200
150
100
50
0
140 f
pCi/g
\
\
\
\
V
\
.038 .075 .15 .30 1.18 5.6
tCi/g PARTICLE SIZE (mm)
"ซ* Ra-226 ACTIVITY
Radioactivity Distribution
Soil #2 (Montclair) 180 pCi/g
plcoCurioi Rซ226 ptr gram
Screen
ts!avo
t Slavanngoroua Wash
Particle Stze (mm)
sand flravaf
Prototype System Design
Grizzly
Plan & Frarn* FIHw Pint
-165-
-------
-------
Characterization of Radioactive
Contaminants in Airfields and
Military Installations for Removal
Assessments
James Neiheisel
-167-
-------
-------
Characterization of
Radioactive Contaminants in
Airfields and Military
Installations for Removal
Assessments
James Neiheisel, Ph.D.
U.S. Environmental Protection Agency
Office of Radiation and Indoor Air
Washington, DC 20460
Standard Versus Protocol Method
Standard RI/FS
on Bulk Sample
Protocol
Addition
Soil Fractions by Water
Separation
(Sieving and Sedimentation)
+
Petrographic &
Soil Fractions
*
Data Quality Parameters
Applicable to RI/FS Tasks
Protocol Parameters Applicable
to Feasibility of Volume
Reduction as a Remedial
Measure at Superf und Sites
Parameters
Grain size distribution curve
Radioactivity of soil fractions
Mineralogy and physical properties
of radioactive contaminants and host
media materials of soil fractions
-169-
-------
Potential Use of ORIA Soil
Characterization Protocol for the
Feasibility of Soil Washing as a
Cleanup Method at Military and
Federal Sites
Potential Situations
Identification of radium migration
from bunkers at airfields
Identification of natural radioactive
minerals as source of radiation
Other areas
Cost and Time Consideration for Tier I
Testing of Site by the Protocol Method
in Which Five Representative Soil
Samples Are Tested
Time and Cost Estimate
Petrographic analysis - one week
ป Radiochemical analysis and
soil separation into size
fractions - three weeks
i Preparation of report - one week
$5,000
$15,000
$500
Tiered Protocol Methodology
Developed from Investigations of
Radioactive Soils at Superfund Sites
Sites Investigated
Wayne/Maywood, New Jersey
Thorium-contaminated sites
Montclair/Glen Ridge, New Jersey
Radium-contaminated sites
Nevada Test Site, Nevada
Plutonium surrogate host soil
-170-
-------
Tier I - Feasibility Study
Methodology Steps
Soil fractions by sieving
Grain size distribution curve and
texture description
Radioactivity versus particle size
Petrographic analysis of fractions
Tier I - Feasibility Study
Methodology Steps
Soil fractions by sieving
Grain size distribution curve
and texture description
Radioactivity versus particle size
Petrographic analysis of fractions
Grain Size Distribution Curve and Histogram of
Area II Nevada Test Site Soil (Gravelly Silty Sand)
CUMULATIVE
WEIGHT 50
% RETAINED
0.01 0.1 1 10
GRAIN SIZE IN MILLIMETERS
-171-
-------
Tier I - Feasibility Study
Methodology Steps
9 Soil fractions by sieving
ซ Grain size distribution curve and
texture description
9 Radioactivity versus
particle size
ซ Petrographic analysis of fractions
ป
40
30
20
10
ฐ0
tCOCUfUES PER GRAM
\
\
4
p
UH , 0.1
Fla-228
Th-23Z
Ra-226
U-238
Th-230
, 1
Radioactivity
vs.
Particle Size
3
Silt ' Stnd Gravol
PARTICLE SEE (mm)
Tier I - Feasibility Study
Methodology Steps
Soil fractions by sieving
Grain size distribution curve and
texture description
Radioactivity versus particle size
Petrographic analysis of
fractions
-172-
-------
Stages of Petrographic
Examination
Stage
Coarse
Medium
Size Range
0.60 mm and
greater
0.038 to 0.60 mm
Instrumentation
Visual
Petrographic and
Binocular
Microscopes
Fine
Less than 0.038 mm X-Ray Diffraction
Petrographic Heavy Mineral
Separations
Essential Category
Minerals or materials greater than 3.0
specific gravity
Many natural and anthropogenic materials
found in this fraction
Sodium polytungstate recommended as
non-toxic heavy liquid for separation by
sink-float method
Performed on size fractions between
0.30 mm and 0.045 mm
Mineral and Material Composition-
Wayne
PERCENTAGE OF SIZE CLASS
CoarsoSand Pino Sand Silt and Clay
SIZE CLASS
Q Sandstone
Q Granitic Rock
Q Quartdte
0 Basalt
H Quartz
| Feldspar
| Heavy-Minerals
Q Clay Minerals
-173-
-------
Heavy Mineral Composition
PERCENTAGE OF SIZE CLASS
30
20
10
r
MI
I r
lA
I
V
1
n
i
n Opaque
D Amphlbols
Q Garnet
Q Epldoto
B Zircon
Monazlta
0 Other
WiyiM * WiyiwSI* ' Mayvrood 'MiywoodSItt
nrn&tnd FlntSind
SIZE CUSS
Tier II - Optimization Study
Methodology Steps
Additional size fractions than in
Tier I including sedimentation and
centrifugation separations of silt/clay
Additional instruments for analysis
such as SEM/EDX
Use of chemical assays to quantify
mineralogical analysis
Case Studies of
Radioactive Sites
Superfund Sites
Wayne and May wood,
New Jersey
Thorium-Contaminated Sites
Montclair and Glen Ridge,
New Jersey
Radium-Contaminated Sites
-174-
-------
Flow Chart of Wayne/May wood, NJ
Tier I Soil Characterization Study
| Sample Receipt and Preparation |
I
c
[
Screen for Radioactivity |
Vigorous Wash |
1 ,
Wet Sieving 1 Vertical Column
1
cz
ML
Petrographic Analysis |
Radiochemistry |
Report |
CUMULATIVE WEIGHT PERCENT
100
90
BO
70
60
50
40
30
20
10
Clay
0.001
r
May wood
Wayne
Cumulative
Weight
Percent
vs.
Particle
Size
Silt I Sand
PARTICLE SIZE (mm)
Mineral and Material Composition-
Wayne
PERCENTAGE OF SIZE CLASS
CoaraeSand Fine Sand Silt and Clay
SIZE CLASS
fj Sandstone
0 Granitic Rock
Q Quartzlte
Q Basalt
H Quartz
| Feldspar
Heavy Minerals
Q Other
-175-
-------
Heavy Mineral Composition
40
30
SO
10
0
PERCENTAGE OF SIZE CLASS
-,
r
HI
n n
Id
1
l
i
l
It
Oii
1
Q Opaque
Q Amphlbole
Q Garnet
Q Epldote
| Zircon
Monazlte
0 Other
Wiynt ' WiyrwSM ' Uiyxocd 'MaywoodSIH
FhwSiixi FliwSind
SIZE CLASS
Results of the Tier I Protocol Study at
the Wayne and Maywood, New Jersey
Thorium-Contaminated Sites
Basis for Feasibility of Soil Washing
55-65 percent of contaminated soil
reduced to target level of 5 pCi/g
Insoluble monazite and minor zircon
identified as the radioactive
contaminants
Wash water can be recycled
Case Studies of
Radioactive Sites
Superfund Sites
Wayne and Maywood,
New Jersey
Thorium-Contaminated Sites
Montclair and Glen Ridge,
New Jersey
Radium-Contaminated Sites
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Montclair and Glen Ridge, New Jersey
Radium Contaminated NPL Sites
Montclair Soil Sample
CUMULATIVE % RET AIMED
1001
Until
1/2 Inch
1/4 Inch
No. 4
No. 10
No. 19
No. so
No. 60
No. 100
No. 140
No. 200
-S -4 -3 -2 -1 0 1 2 3 4 5 6 7 8 9 10
0 SCALE
PICOCUHIES Ra-226 PER GRAM
Clay
Silt I Sand
PARTICLE SIZE (mm)
Activity
vs.
Grain
Size
Gravel
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Types of Radium Contaminants
at Montclair Site
15% - Carnotite and Uraninite
85% - Anthropogenic Radium
Materials
50% Radiobarite
23% Amorphous silica
6% Furnace fired cinders/slag
6% Aclsorbate on illite, etc.
Linear Density Gradient Analysis
of Radium Activity in the Glen Ridge, NJ, Soil
10-20 Micron Size
Density Weight %
Ught
2.10-2.25 32.20
Medium
2^5-2.71 55.69
Heavy
>2.71 12.01
Ra-226 Activity
1,640 pCi/g
1,040pCI/g
8,270 pCVg
%Ra
25.21
27.55
47.24
_^*
Results:
Montclair/Glen Ridge
Radium-Contaminated Soils
Vigorous water wash/wet sieving
in laboratory scale tests reduced
30-40% of Montclair and Glen
Ridge soil to a target level of
12-15 pCi/g (Ra-226)
The wash water can be recycled
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Summary Soil Characterization Protocol
Additions to RI/FS Process
Identifies the physical form and
mineral/material composition of
radioactive contaminants and
activity levels on the various size
fractions
Data applicable to prediction of
retention or transport of
contaminant and impact on ground
water
Summary Soil Characterization Protocol
Additions to RI/FS Process (continued)
Provides explicit site specific data
to key parameters in risk
assessment evaluations
Provides data to evaluate
feasibility of Volume Reduction
technologies
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.Treatment of Radioactive
Compounds in Water
Thomas Sorg
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Treatment of Radioactive
Compounds in Water
Radium Uranium Radon
Thomas Sorg
U.S. Environmental Protection Agency
Risk Reduction Engineering Laboratory
Cincinnati, OH
Treatment Methods
Precipitation
Ion exchange
Adsorption
Membrane
Aeration
Treatment Methods
i Precipitation
Coagulation/filtration
Lime softening
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Treatment Methods
Ion exchange
Cation exchange
Anion exchange
Treatment Methods
Adsorption
Granular Activated
Carbon (GAC)
Activated alumina
Selective complexers
Treatment Methods
Membrane processes
Reverse osmosis
Electrodialysis
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Treatment Methods
> Aeration
Packed tower
Diffused bubble
Spray
Slat or cascade tray
r \
Treatment Selection Factors
Removal requirements
Best Available Technology (BAT)
Source water
Water quality
Cost of treatment
Disposal of residuals (waste)
Safe Drinking Water Act
Maximum Contaminant Level
Goal (MCLG)
Health criteria
Non-enforceable
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Safe Drinking Water Act
(Continued)
Maximum Contaminant Level
(MCL)
Health criteria
Available technology
Cost
Enforceable
Safe Drinking Water Act
(Continued)
Secondary Maximum
Contaminant Level (SMCL)
Public welfare
Odor
Appearance
Drinking water regulations
(Radionuclides)
Maximum contaminant
level goal
(MCLG)
"0" concentration for all
Radionuclides
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Drinking Water Regulations
(Radionuclides)
Current and Proposed MCLs
Radionuclide
Current Proposed Limit
Limit (July 1991)
Combined Ra-226
and RA-228
Ra-226
Ra-228
Rn-222
U (Total)
5 pCi/L -
20 pCi/L
20 pCi/L
300 pCi/L
20 ug/L(30pCi/L)
Drinking Water Regulations
(Radionuclides)
Current and Proposed MCLs
Radionuclide
Gross Alpha
Beta particle and
photon emitters
(man-made radio-
nuclides)
Current
15pCi/L
(including
Ra-226, but not
U, nor Rn-222)
4 mrem/year
(dose to body
or any internal
organ)
Proposed Limit
(July 1991)
15pCi/L
(excluding
Ra-226, U,
and Rn-222)
4 mrem/year
(dose to body
or any internal
organ)
Best Available Technology
SDWA
Radionuclide(s) BAT
Ra-226/Ra-228
Rn-222
U
Cation exchange
Lime softening
Reverse osmosis
Aeration
Coagulation/filtration
Ion exchange (anion/cation)
Lime softening
Reverse osmosis
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Annual Average Concentration
Yielding 4 Mrem/Year for a Two Liter Daily Intake
Radlonuclldes
Tritium
C-14
Co-60
Sr-90
Cs-137
Ba-131
Ba-140
^-
Conc.-pCi/L
20,000
2,000
100
8
200
600
90
Best Available Technology
SDWA
Radionuclide(s) BAT
Alpha emitters Reverse osmosis
Beta and photon Ion exchange
emitters Reverse osmosis
BAT - Percent Removal
Contaminant-% Removal
Treatment Method Radium Uranium Radon
Coag/fiit 85-95
Lime softening 75-97 85-99
Ion ex 65-97 65-99
RO 87-98 98-99
Aeration up to
99
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BAT - Percent Removal
Beta Emitters - % Removal
Treatment Method Cs -137 I- 131
Sr89
Reverse osmosis 90-99
Ion exchange 95-99
90-99
90-99
95-99
Treatment - Source Water
Method
Source Water
Coag/filtration
Lime softening
Ion exchange
RO/ED
GAC/AA
Surface
Surface & ground
Ground
Ground
Ground
Uranium Technology
o Coagulation/filtration 80-95
Lime softening 85-99
Ion exchange 90-99
Reverse osmosis 90-99
Eiectrodialysis 90-99
Activated alumina 90-99
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Mote
Percent 60
Dissolved
Species
Racllonuclides
Chemical Form in Water
Radium
Rn(Gas)
Uranium
fc-
Cation-Ra+2
Gas-RNฐ
pH < 2.5 Cation
pH 2.5-7 Neutral
pH7~10Anion
-UO2+
-U02(C03)ฐ
-U02(C03)2-*
-U02(C03)3-ซ
_^
Effect of pH Removal of
Uranium by Iron Coagulation
Ferric Chloride
30mg/L
U 450 ug/L
678
pH - Units
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Uranium Removal-Lime Softening
Percent Removal
MgCG3 LIME DOSE - Ca(OH)2 - mg/L
mg/L 50 150 250
10
40
80
120
32
9
24
15
90
95
93
99
89
94
98
99
ซ
Uranium Removal-Anion Exchange
Field Influent
Bed Volume
Percent
Site
1(0
2(0
3(0
4(C)
5(C)
6(C)
U-vg/L
22
30
104
52
35
28
SOf-mg/L
<5
320
9
390
400
3
Treated (xK)
9.4
25
7.9
34.5
11.9
62.9
Uranium
99.8
99.8
99.8
72.1
29.8
99.6
Radium Technology
Method
Percent
Removal
Lime softening 80-95
Ion exchange 65-95
Reverse osmosis 90-99
Electrodiaiysis 90-99
Selective complexers 97+
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Radium
Ion Exchange Treatment
Selectivity Sequence
Ra+2> Ba+2 > Ca+2 > Mg+2 > Na+ > H*
Radium Treatment Methods
Experimental methods
Specific adsorbents
RSC (Dow Chemical)
CYC (Isoclear)
OT11000 (Omni Tech)
Activated alumina (modifications)
Manganese dioxide
Absorbants-Radium Removal
(Lament, IL Ra 226 12pci/L, Ra 228 6pCi/L)
Radium
Breakthrough -BV Total Ra
Absorbent
RSC
CYC{*1)
Radt-Sorb
OTl-1000
Activated
Alumina
Aetlvntod
Alumina
(Treated)
Company
Dow Chem.
Isoclear
Grlndle
Omnl-Tech
ALCOA
ALCOA/UH
at5pCi/L
38,000
1,800
<10
0
3,350
27,500
Total
90,000
5,700
51,000
Loading - mCi/L
3.9
0.49
0.77
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Radon Technologies
Aeration 90-99.9%
GAC 80-99%
Ion Exchange Treatment
Radium + Uranium
Radium Cation (Na+Ex) 100-1500 BV
Uranium Anion(ChEx) 10K-100K BV
Disposal Options
ป Stream
i Sewer
> Land
ปSanitary landfill
ปRadioactive waste
disposal site
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Residuals for Disposal
Treatment Method Residual (Waste)
Coag/filtration
Lime softening
Ion exchange
Backwash water
sludge - alum/iron
Backwash water
sludge - lime
Brine
Caustic solution
Acid solution
Resin
Residuals for Disposal
Treatment Method Residual (Waste)
Adsorption
(GAC/AA)
Membrane processes Reject water
(RO/ED)
Aeration Air/adsorption
media
GAC
Activated alumina
Uranium Treatment
Waste Production
Waste Production
Treatment gal/mg Ib/mg U cone.
Coag/filt
Lime
softening
Anlon ex 340
RO 333,000
2,100 1,800
5,000 800
925 pCi/gm
2,077 pCi/gm
6x105pCi/L
600 pCi/L
*U.S.COVERNMENTPIUNTINGOmCE:199'3 -750 -002,60195
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