1 Session D Range Management/Outreach Grenade Range Management Using Lime to Transform Explosives Deborah R. Felt Research Chemist Environmental Laboratory U.S. Army Engineer Research and Development Center (ERDC-EL) JSEM Conference- Platform 3829 Wednesday May 23, 2007
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Session DRange Management/Outreach
Grenade Range Management UsingLime to Transform Explosives
Deborah R. FeltResearch Chemist
Environmental LaboratoryU.S. Army Engineer Research and Development Center (ERDC-EL)
JSEM Conference- Platform 3829
Wednesday May 23, 2007
2
TECHNICAL OBJECTIVES
• Develop sustainable hand grenade training ranges by:– Controlling mobility of active grenade range munitions
constituents – Promoting explosives degradation that is low-cost and
minimally resource intensive
• This demonstrated technology provides range managers with an effective tool to– Reduce migration of constituents off of the range– Reduce future range cleanup time and costs
3
TECHNICAL APROACH
•Apply lime to active hand grenade range to elevate soil pH above 10.5
Transform explosives via alkaline hydrolysis
•Tool for sustainability of active ranges
•Range management that includes lime application allows range closure with minimal residual explosives on site
DissolvedHydroxide
Soil Receiving Grenade Residue Contamination
Hydroxide Induced Transformation of
ExplosivesAnd Immobilization of
Heavy Metals
Dissolved Hydroxide
Clean pore water to groundwater
Lime Addition
Wat
er M
ovem
ent
SolubleExplosivesMoving WithWater
Soluble LimeMoving Downward
Surface WaterTransport
Time (min)
0 200 400 600 800 1000 1200 1400
0
1
2
3
4
5
6
7
pH = 12.5T1/2 = 7 hrs
4
• Perform treatability study using actual site soil in mesoscale lysimeters to determine required lime dose, other parameters- 16 week duration.
• Collect site soil for initial characterization
• Perform Field Demonstration study at active training range-Fort Jackson, S.C.
Experimental Design
5
Demonstration Site:Fort Jackson, S.C.
• Active Hand Grenade Range~ 55,000 grenades per year
• Four throwing Bays• Permeable soil
• Sand / clay mixture• Scattered clay lenses
• Potential source zone for RDXin groundwater and surface water
Throwing Bay #4 (limed)Remagen HGR
Throwing Pit
Impact Area
6
Treatability Study:Experimental Design
• ~200 kg of Fort Jackson HGR soil into lysimeter cells– Four lysimeter cells– Control and 3 lime doses
• Simulated rainfall on cells for 16 weeks:– Equivalent to 2.94 in/ week (47 in/yr)
• Sampling schedule– Runoff and Leachate weekly– Soil Initial, mid-point, and final
* Calculations based on the report limit where ‘<‘ present
n.a.
Fort Jackson 0.5% Lime 6.57
4.61
>26%<3.42*
Treatability Study Results:Total RDX Leaving Lysimeter
Shading indicates project goal was achieved.
8
TECHNICAL APROACH:Bio-mineralization of RDX base-hydrolysis products
RDX following alkaline hydrolysis
RDX without alkaline hydrolysis
CarbonateAqueousSolid
The degradation of RDX base-induced transformation products continues via both anaerobic and aerobic
RDX concentration below detection limit. >75% aerobic mineralization obtained in [14C]-labeled study
9
Field Demonstration:Soil Sampling at Fort Jackson Site
• Limited time on range• Quick and consistent field sampling protocols• Lysimeters placed with range cadre input• Sample areas 1 to 8 range from 42 to 150 m2
10
Field Demonstration:Sampling and Data Collection
Collecting from Fort Jackson HGR• Air samples• Pore water• Surface water runoff• Soil samples (25 pt composites)• MET data (rainfall, temp, wind…)• Maintenance records (fill of divots)• Hand grenade “boom count” by Bay
Pore Water suction lysimeter at Fort Jackson
25 pt composite sampling at Fort Jackson
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Field Demonstration:Lime Application
Fort Jackson Remagen HGR• 1 ton of lime to elevate pH > 11.5• 1% lime per 6 inch depth for Bay 4
Application• Cost ~ $400.00 / ton• This range is limed quarterly• Spread bags by hand or
with drop spreader• Disc into soil • Required less than 2 hours
labor
Lime application at Fort Jackson
Mixing lime into range at Fort Jackson
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Field Demonstration Results: RDX in Soil
• Lag time between Apr and Jan pre / post liming samples approx. 24 hrs• Lag time before Oct post liming samples taken was approx. 30 days,
due to HGR training
Bay 4 (Limed) Avg RDX Conc. (ppm)Sampling
Date Pre Lime
Post Lime % Change
Rain Between Sample Events (inches)
Post Lime % Soil
Moisture
Apr 06 4.21 <1.751 >58% 0.12
3.2
Jan 07 <0.09 <0.10 No Change 0 6.831 Report limit (0.02 ppm) used in calculations where ‘<‘ present.2 Pre-lime samples taken in Jul; approximately 30 days between liming and post liming samples.
2.21
Oct 062 0.42 <0.08 >59% 6.36
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Field Demonstration Results: RDX in Pore Water
• Mass balance – more RDX leaving in pore water from control vs. treated bay
• Observed similar reduction in the lysimeter treatability study
Mass balance for RDX in Pore Water
0.00.20.40.60.81.01.21.41.61.82.02.2
L1 L2 L3 L4 L5 L6 L7 L8 L9 L10
Limed- Bay 4 Control- Bay 2
RDX
lost
in th
e po
re w
ater
(mg)
16-M ar-07
6-Jan-07
Dec-06
Nov-06
15-Oct-06
27-Sep-06
27-Aug-06
9-Jul-06
6-Jun-06
30-Apr-06
9-Apr-06
12-M ar-06
10-Feb-06
6-Jan-06
18-Dec-05
7-Dec-05
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Field Demonstration Results:Soil pH at Surface
Soil pH varied due to:• Range maintenance (divots) – addition of top soil to HGR• Hydroxide consumption via:
– Transformation of RDX & TNT; Metals Stabilization– Weathering Conditions (i.e. rain events)– Natural buffering of soil
Average (n=8) Soil pH During Field Study
0
2
4
6
8
10
12
14
Dec Dec (PL) Jan M ar Apr Apr (PL) Jul Oct (PL) Jan Jan (PL) M ar
2005 2006 2007
Soil
pHBay 4 (Limed)Bay 2 (Contro l)Limed Goal
15
Field Demonstration Results:Soil pH by Depth
• Apply lime to first 6 inches of soil• Over time hydroxide migrates
deeper into soil• Treatment becomes more effective
after continued applications
DissolvedHydroxide
Bay 4 (Limed) Soil pH by depth (April 21, 2007)
10
12
14
0
2
4
6
8
0 to 2 2 to 6 6 to 12 12 to 18 18 to 24 24 to 30
Depth (inches bgs)
pH
Area #5
Area #8
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Field Demonstration Results:RDX in Leachate
• Five pore water lysimeters per bay • Observed similar results from treatability study
Average Pore Water Lysimeter Concentration
0.0
0.5
1.0
1.5
2.0
2.5
Average Bay 4 (limed) Average Bay 2 (control)
RD
X Ly
sim
eter
Con
c. (m
g/L)
7-Dec-05
18-Dec-05
6-Jan-06
10-Feb-06
12-Mar-06
17-Apr-06
30-Apr-06
6-Jun-06
9-Jul-06
27-Aug-06
27-Sep-06
15-Oct-06
6-Jan-07
16-Mar-07
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Field Demonstration:Lessons Learned
Lime is an effective option for range managementControls munitions constituents mobility Doesn’t contribute to water or air issues
Cost of applicationLime is inexpensive and readily available.Necessary equipment to deliver and mix lime into the soil is readily available.
Lime application rate is dependent onSoil particle size Range use and maintenance (e.g. divot repair, application of top soil)Number of grenades detonated per yearAnnual rain fall
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Peer Review ArticlesConcerning Lime Treatment
•Hwang S., Ruff T.J., Bouwer E.J., Larson S.L., Davis J.L. (2005) Applicability of alkaline hydrolysis for remediation of TNT-contaminated water. Water Research, 39: 4503-4511
•Davis, J.L., Brooks, M.C., Larson, S.L., Nestler, C.C., Felt, D.R. (2007). Lime Treatment for Containment of Source Zone Energetics Contamination: Mesocosm Study. Practice Periodical Hazardous, Toxic and Radioactive Waste Management,11:11-19
•Davis, J.L., Brooks, M.C., Larson, S.L., Nestler, C.C., Felt, D.R. (2006) Lime Treatment of Explosives-Contaminated Soil from Munitions Plants and Firing Ranges. Soil and Sediment Contamination: an International Journal, 15: 565-580
•Hwang S., Ruff T.J., Bouwer E.J., Larson S.L., Davis J.L. (2005) Applicability of alkaline hydrolysis for remediation of TNT-contaminated water. Water Research, 39: 4503-451
•Hwang S., Felt D.R., Bouwer E.J., Brooks M.C., Larson S.L., Davis J.L. (2006) Remediation of RDX-contaminated water using alkaline hydrolysis. Journal of Environmental Engineering, 132:256-262
•Hwang, S., Bouwer, E., Larson, S., Davis, J.L. (2004), Decolorization of alkaline TNT hydrolysis effluents using UV/H2O2, Journal of Hazardous Materials, B108:61-67
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A Special Thanks to All Involved!A Special Thanks to All Involved!•• ESTCPESTCP
•• BethBeth--AneeAnee Johnson Johnson –– Fort Jackson ITAMFort Jackson ITAM•• Fort Jackson Fort Jackson RemagenRemagen HGR CadreHGR Cadre
•• USMA HGR Cadre and Environmental OfficeUSMA HGR Cadre and Environmental Office•• EQTEQT
•• Dr. Steven Larson Dr. Steven Larson –– ERDCERDC•• Andy MartinAndy Martin–– ERDCERDC
•• Dr. Jeff DavisDr. Jeff Davis–– ERDCERDC•• Gene Fabian Gene Fabian –– ATCATC
•• Chris Griggs Chris Griggs –– ARAARA•• Greg Zynda Greg Zynda –– ATCATC
•• Chris Compton Chris Compton –– ENSRENSR•• Milton Beverly Milton Beverly –– ER&DER&D
•• John Niles John Niles –– ARDECARDEC•• Greg O’Connor Greg O’Connor –– ARDECARDEC
•• Deborah Ragan Deborah Ragan –– SpecProSpecPro•• Kerry Taylor Kerry Taylor –– Jackson State UniversityJackson State University•• Kym Powell Kym Powell –– Jackson State UniversityJackson State University
•• Casey Trest Casey Trest –– Mississippi State UniversityMississippi State University•• Tarmiko Graham Tarmiko Graham –– Alcorn State UniversityAlcorn State University
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QUESTIONS?
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BACKUP MATERIAL
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Bay 4 (limed)
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TECHNICAL APROACH:Active Grenade Range Management
• RDX• Aqueous• pH=12• Half Life ~ 5 hrs
• TNT• Aqueous• pH=11.5• Half Life < 2 hrs
Reaction Time (hr)
0 5 10 15 20 25 30
RD
X C
once
ntra
tion
(mg/
L)
0
2
4
6
8
10
Time (min)
0 2 4 6 8 10 12 14
Det
ecto
r Res
pons
e
0
2
4
6
RDX
Unknown
C=7.93e-0.18t, r2=0.995
Tim
e
Reaction Time (hr)
0 5 10 15 20 25
TNT
Con
cent
ratio
n (m
g/L)
0
1
2
3
4
5
6
7
Time
0 2 4 6 8 10 12 14 16
Det
ecto
r Res
pons
e
0
2
4
6
8
10
12
14
16
Unknown
TNT
C=5.66e-0.233t,r2=0.971
Time
N
N
NO2N NO2
NO2
CH3
NO2O2N
NO2
RDX TNT
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TECHNICAL PROGRESS: Lysimeter Cell: Total Metals Leaving Cell
Leachate total based on volume and concentrationsfrom 16 rain events (mg)Lysimeter
Cell
TSS Zinc Iron Manganese Calcium
Fort JacksonControl 283 115 539 <27 1,899
Fort Jackson 0.5% Lime1 215 <302 <498 <27 23,449
Fort Jackson 1.0 % Lime 264 <20 <420 <29 28,410
Fort Jackson 2.0 % Lime 249 <22 <309 <27 52,641
1 1% lime = amount of lime required to elevate soil pH to 11.5 for this soil.2 Report limit values used in calculations where total has ‘<‘.
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TECHNICAL PROGRESS: Lysimeter Cell: Total Metals Leaving Cell
Runoff total based on volume and concentrationsfrom 16 rain events (mg)Lysimeter
Cell
TSS Zinc Iron Manganese Calcium
Fort JacksonControl 945 571 <1,7462 <17 <107
Fort Jackson 0.5 % lime 644 376 1,303 <16 <789
Fort Jackson 1.0 % Lime 715 393 1,458 <17 2,403
Fort Jackson 2.0 % Lime 373 196 610 <17 2,879
1 1% lime = amount of lime required to elevate soil pH to 11.5 for this soil.2 Report limit values used in calculations where ‘<‘ present.
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Treatability Study Results:TSS values
• Indication of metals loss in particulate form or of metals bound to suspended solids. May also include MC particles.
• TSS concentrations in leachate and surface water were lower than control for all limed lysimeters. Indicates decreased mobility.
Surface Water Samplers
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Field Demonstration Results:Air Monitoring
Air Monitoring
0.02
90.
019
0
0.02
0.04
0.06
0.08
0.1
2-Nov 10-Jan 27-Jan 2-Mar 16-Mar 15-Feb Average
Date Sample Taken
Cal
cium
Con
cent
ratio
n (m
g/m
3)
Bay 2 (Control)Bay 4 (Limed)
IDL = 0.01
• Concern over spread of lime in dust plumes generated by detonation on all bays
• Looked at calcium in air monitoring as signature for lime in dust generated by grenades
• No significant difference between limed and un-limed bays
MET Station
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Field Demonstration:Leachate and Surface Water pH
Average Leachate pH
02468
101214
Jan Feb Mar Apr Jul Oct Jan
2006 2007
pH
Bay 4 Avg
Bay 2 Avg
•No elevated pH values noted for leachate or surface water.•Limed Bay #4 leachate pH slightly lower than control Bay #2• Highest surface water pH from limed bay was 7.79
Average Surface Water pH
Sample ID Avg pH Std Dev
Bay 4 (Limed)
Bay 2 (Control)
SW 1 6.16 0.56
SW2 6.46 0.77
SW 3 6.24 0.45
SW 4 6.57 0.10
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TECHNOLOGY TRANSFERTechnical Reports:• Larson, S.L., Davis, J.L., Martin, W.A., Felt, D.R., Nestler, C. C., Brandon, D.L., Fabian, G., O’Connor, G. 2006. “Grenade Range Management Using Lime for Metals Immobilization and Explosives Transformation”, ERDC/EL TR-07-X (in press), U.S. Army Engineer Research and Development Center, Vicksburg, MS. • Larson, S.L., Davis, J.L., Martin, W.A., Felt, D.R., Nestler, C. C., Fabian, G.L., O’Connor, G. 2007. “Hand Grenade Residuals”, ERDC/EL TR-07-X (in press), U.S. Army Engineer Research and Development Center, Vicksburg, MS.• Larson, S.L., Davis, J.L., Martin, W.A., Felt, D.R., Nestler, C. C., Fabian, G., Zynda, G., O’Connor, G., Johnson, B-A. 2007. “Grenade Range Management Using Lime for The Dual Role of Metals Immobilization and Explosives Field Demonstration”, ERDC/EL TR-07-X (in draft form), U.S. Army Engineer Research and Development Center, Vicksburg, MS.• ESTCP Final Report: Grenade Range Management Using Lime for Dual Role of Metals Immobilization and Explosives Transformation (ESTCP Project ER 0216) (In draft)• ESTCP Cost and Performance Report: Grenade Range Management Using Lime for Dual Role of Metals Immobilization and Explosives Transformation (ESTCP Project ER 0216) (In draft)• ESTCP Guidance Document: Grenade Range Management Using Lime for Dual Role of Metals Immobilization and Explosives Transformation (ESTCP Project ER 0216) (In draft)