1

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

• Analyzed for– Explosives (primarily RDX)– pH, TSS, Metals

7

Lysimeter Cell

RDX leaving cell as

Leachate(mg/L)

% Reducti

oncompared

toControl Cell

RDX leaving

cell asRunoff(mg/L)

% Reducti

oncompared

toControl Cell

Fort JacksonControl 63.14 n.a.

90%

Fort Jackson 1%Lime 6.05 90% 4.91 n.a.

Fort Jackson 2% Lime 4.79 92% <3.53 >23%

* 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

11

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

12

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

13

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

14

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

16

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

17

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

18

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

19

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

•• Cathy Cathy NestlerNestler –– ARAARA•• Michelle Thompson Michelle Thompson –– ARAARA

•• 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

20

QUESTIONS?

21

BACKUP MATERIAL

22

Bay 4 (limed)

23

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

24

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 ‘<‘.

25

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.

26

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

27

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

28

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

29

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)