Session D Range Management/Outreach Grenade Range Management Using Lime to Transform Explosives

Transcription

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,

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 2

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 Lime Addition Soil Receiving Grenade Residue Contamination Dissolved Hydroxide Hydroxide Induced Transformation of Explosives And Immobilization of Heavy Metals Clean pore water to groundwater ph = 12.5 T 1/2 = 7 hrs Soluble Lime Moving Downward Dissolved Water Hydroxide Water Movement Surface Water Transport Soluble Explosives Moving With Time (min) 3

4 Experimental Design 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. 4

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 RDX in groundwater and surface water Impact Area Throwing Pit Remagen HGR Throwing Bay #4 (limed) 5

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 6

7 Lysimeter Cell Fort Jackson Control Treatability Study Results: Total RDX Leaving Lysimeter Shading indicates project goal was achieved. RDX leaving cell as Leachate (mg/l) % Reducti on compared to Control Cell n.a. RDX leaving cell as Runoff (mg/l) 4.61 % Reducti on compared to Control Cell n.a. Fort Jackson 0.5% Lime % <3.42 * >26% Fort Jackson 1%Lime Fort Jackson 2% Lime % 4.91 n.a % <3.53 >23% * Calculations based on the report limit where < present 7

8 TECHNICAL APROACH: Bio-mineralization of RDX base-hydrolysis products Carbonate Aqueous Solid RDX without alkaline hydrolysis RDX following alkaline hydrolysis The degradation of RDX base-induced transformation products continues via both anaerobic and aerobic RDX concentration below detection limit. >75% aerobic mineralization obtained in [ 14 C]-labeled study 8

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 m 2 9

10 Field Demonstration: Sampling and Data Collection Pore Water suction lysimeter at Fort Jackson 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 25 pt composite sampling at Fort Jackson 10

11 Fort Jackson Remagen HGR 1 ton of lime to elevate ph > % lime per 6 inch depth for Bay 4 Field Demonstration: Lime Application Mixing lime into range at Fort Jackson Lime application at Fort Jackson Application Cost ~ $ / ton This range is limed quarterly Spread bags by hand or with drop spreader Disc into soil Required less than 2 hours 11 labor

12 Sampling Date Field Demonstration Results: RDX in Soil Pre Lime Bay 4 (Limed) Avg RDX Conc. (ppm) Post Lime % Change Rain Between Sample Events (inches) Apr < >58% 0.12 Post Lime % Soil Moisture 2.21 Oct <0.08 >59% Jan 07 <0.09 <0.10 No Change 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. 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 12

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 RDX lost in the pore water (mg) Mass balance for RDX in Pore Water L1 L2 L3 L4 L5 L6 L7 L8 L9 L10 Limed- Bay 4 Control- Bay 2 16-M ar-07 6-Jan-07 Dec-06 Nov Oct Sep Aug-06 9-Jul-06 6-Jun Apr-06 9-Apr M ar F eb-06 6-Jan D ec Dec-05 13

14 Field Demonstration Results: Soil ph at Surface Average (n=8) Soil ph During Field Study Bay 4 (Limed) Bay 2 (Control) Limed Goal Soil ph Dec Dec (PL) Jan M ar Apr Apr (PL) Jul Oct (PL) Jan Jan (PL) M ar 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 14

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 Bay 4 (Limed) Soil ph by depth (April 21, 2007) Dissolved Hydroxide ph Area #5 Area #8 0 to 2 2 to 6 6 to to to to 30 Depth (inches bgs) 15

16 Field Demonstration Results: RDX in Leachate Five pore water lysimeters per bay Observed similar results from treatability study RDX Lysimeter Conc. (mg/l) Average Pore Water Lysimeter Concentration Average Bay 4 (limed) Average Bay 2 (control) 7-Dec Dec-05 6-Jan Feb Mar Apr Apr-06 6-Jun-06 9-Jul Aug Sep Oct-06 6-Jan Mar-07

17 Field Demonstration: Lessons Learned Lime is an effective option for range management Controls munitions constituents mobility Doesn t contribute to water or air issues Cost of application Lime is inexpensive and readily available. Necessary equipment to deliver and mix lime into the soil is readily available. Lime application rate is dependent on Soil particle size Range use and maintenance (e.g. divot repair, application of top soil) Number of grenades detonated per year Annual rain fall 17

18 Peer Review Articles Concerning 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: 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: 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: 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: Hwang, S., Bouwer, E., Larson, S., Davis, J.L. (2004), Decolorization of alkaline TNT hydrolysis effluents using UV/H2O2, Journal of Hazardous Materials, B108:

19 A Special Thanks to All Involved! ESTCP Beth-Anee Johnson Fort Jackson ITAM Fort Jackson Remagen HGR Cadre USMA HGR Cadre and Environmental Office EQT Dr. Steven Larson ERDC Andy Martin ERDC Dr. Jeff Davis ERDC Gene Fabian ATC Cathy Nestler ARA Michelle Thompson ARA Chris Griggs ARA Greg Zynda ATC Chris Compton ENSR Milton Beverly ER&D John Niles ARDEC Greg O Connor ARDEC Deborah Ragan SpecPro Kerry Taylor Jackson State University Kym Powell Jackson State University Casey Trest Mississippi State University 19 Tarmiko Graham Alcorn State University

20 QUESTIONS? 20

21 BACKUP MATERIAL 21

22 Bay 4 (limed) 22

23 TECHNICAL APROACH: Active Grenade Range Management RDX Unknown TNT RDX Concentration (mg/l) Detector Response Time RDX TNT Concentration (mg/l) Detector Response Time Unknown Time TNT Time (min) 1 0 C=7.93e -0.18t, r 2 = C=5.66e t,r 2 = Reaction Time (hr) Reaction Time (hr) O 2 N NO N 2 RDX N Aqueous N ph=12 Half Life ~ 5 hrs NO 2 O TNT 2 N Aqueous ph=11.5 Half Life < 2 hrs CH 3 NO 2 NO 2 23

24 TECHNICAL PROGRESS: Lysimeter Cell: Total Metals Leaving Cell Lysimeter Cell Fort Jackson Control Leachate total based on volume and concentrations from 16 rain events (mg) TSS Zinc Iron Manganes e Calcium <27 1,899 Fort Jackson 0.5% Lime <30 2 <498 <27 23,449 Fort Jackson 1.0 % Lime Fort Jackson 2.0 % Lime 264 <20 <420 <29 28, <22 <309 <27 52, % 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 <. 24

25 TECHNICAL PROGRESS: Lysimeter Cell: Total Metals Leaving Cell Lysimeter Cell Fort Jackson Control Fort Jackson 0.5 % lime Fort Jackson 1.0 % Lime Fort Jackson 2.0 % Lime Runoff total based on volume and concentrations from 16 rain events (mg) TSS Zinc Iron Manganes e Calcium <1,746 2 <17 < ,303 <16 < ,458 <17 2, <17 2, % lime = amount of lime required to elevate soil ph to 11.5 for this soil. 2 Report limit values used in calculations where < present. 25

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 26

27 Field Demonstration Results: Air Monitoring Air Monitoring MET Station Calcium Concentration (mg/m3) Bay 2 (Control) Bay 4 (Limed) Nov 10-Jan 27-Jan 2-Mar 16-Mar 15-Feb Average Date Sample Taken 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 27

28 Field Demonstration: Leachate and Surface Water ph 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 Average Leachate ph Bay 4 Avg Bay 2 Avg Average Surface Water ph Sample ID Avg ph Std Dev ph Jan Feb Mar Apr Jul Oct Jan Bay 4 (Limed) Bay 2 (Control) SW SW SW SW

29 Technical Reports: TECHNOLOGY TRANSFER Larson, S.L., Davis, J.L., Martin, W.A., Felt, D.R., Nestler, C. C., Brandon, D.L., Fabian, G., O Connor, G 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 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 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) 29