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Landfarming is a well proven ex-situ bioremediation technology that has been successfully used since the 1980s for treating petroleum impacted soils/sediments, drill cuttings, low brine drilling fluids, oily sludges, tank bottoms and pit sludges. The material to be treated is incorporated into surface soil.  Naturally occurring microbes in the soil and waste material transform the organic contaminants to carbon dioxide, water and biomass (<ref name= "USEPA1993Bio">U.S. Environmental Protection Agency (USEPA), 1993. Bioremediation using the land treatment concept. US Environmental Protection Agency. Office of Research and Development, Washington, D.C. [[media:USEPA-1993._bio_using_land_treatment.pdf| Report.pdf]]</ref><ref name= "USEPA2003LF">U.S. Environmental Protection Agency (USEPA), 2003. Aerobic Biodegradation of Oily Wastes: A Field Guidance Book for Federal On-scene Coordinators, Version 1.0, October 2003. Region 6 South Central Response and Prevention Branch. [[media:USEPA-2003-Landfarming-OSC-Aerobic_Biodegradation_of_Oily_Wastes.pdf| Report.pdf]]</ref><ref>U.S. Environmental Protection Agency (USEPA), 2017. How to Evaluate Alternative Cleanup Technologies for Underground Storage Tank Sites: A Guide for Corrective Action Plan Reviewers, Chapter V: Landfarming , Land and Emergency Management 5401R, EPA 510-B-17-003. [[media:USEPA-2017._How_to_Evaluate_Alternative_Cleanup_tech_for_UST_Sites.pdf| Report.pdf]]</ref>). Maintaining optimum soil conditions for rapid biodegradation of organic contaminants can help meet cleanup goals within a reasonable timeframe.
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The heterogeneous distribution of munitions constituents, released as particles from munitions firing and detonations on military training ranges, presents challenges for representative soil sample collection and for defensible decision making. Military range characterization studies and the development of the incremental sampling methodology (ISM) have enabled the development of recommended methods for soil sampling that produce representative and reproducible concentration data for munitions constituents. This article provides a broad overview of recommended soil sampling and processing practices for analysis of munitions constituents on military ranges.  
 
 
 
<div style="float:right;margin:0 0 2em 2em;">__TOC__</div>
 
<div style="float:right;margin:0 0 2em 2em;">__TOC__</div>
  
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'''Related Article(s)''':
  
'''Related Article(s):'''
 
*[[Bioremediation_-_Anaerobic | Anaerobic Bioremediation]]
 
  
 
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'''CONTRIBUTOR(S):''' [[Dr. Samuel Beal]]
'''CONTRIBUTOR(S):''' [[Roopa Kamath]], [[Sara McMillen]], [[Rene Bernier]], and [[Deyuan Kong]]
 
 
 
 
 
'''Key Resource(s):'''
 
*[[media:USEPA-1993._bio_using_land_treatment.pdf| Bioremediation using the land treatment concept.]]<ref name= "USEPA1993Bio"/>
 
*[[media: USEPA-2003-Landfarming-OSC-Aerobic_Biodegradation_of_Oily_Wastes.pdf| Biotreating E&P Wastes: Lessons Learned from 1992-2003]]<ref name= "USEPA2003LF"/>.
 
  
  
 +
'''Key Resource(s)''':
 +
*[[media:Taylor-2011 ERDC-CRREL TR-11-15.pdf| Guidance for Soil Sampling of Energetics and Metals]]<ref name= "Taylor2011">Taylor, S., Jenkins, T.F., Bigl, S., Hewitt, A.D., Walsh, M.E. and Walsh, M.R., 2011. Guidance for Soil Sampling for Energetics and Metals (No. ERDC/CRREL-TR-11-15). [[media:Taylor-2011 ERDC-CRREL TR-11-15.pdf| Report.pdf]]</ref>
 +
*[[Media:Hewitt-2009 ERDC-CRREL TR-09-6.pdf| Report.pdf | Validation of Sampling Protocol and the Promulgation of Method Modifications for the Characterization of Energetic Residues on Military Testing and Training Ranges]]<ref name= "Hewitt2009">Hewitt, A.D., Jenkins, T.F., Walsh, M.E., Bigl, S.R. and Brochu, S., 2009. Validation of sampling protocol and the promulgation of method modifications for the characterization of energetic residues on military testing and training ranges (No. ERDC/CRREL-TR-09-6). Engineer Research and Development Center / Cold Regions Research and Engineering Lab (ERDC/CRREL) TR-09-6, Hanover, NH, USA. [[Media:Hewitt-2009 ERDC-CRREL TR-09-6.pdf | Report.pdf]]</ref>
 +
*[[media:Epa-2006-method-8330b.pdf| U.S. EPA SW-846 Method 8330B: Nitroaromatics, Nitramines, and Nitrate Esters by High Performance Liquid Chromatography (HPLC)]]<ref name= "USEPA2006M">U.S. Environmental Protection Agency (USEPA), 2006. Method 8330B (SW-846): Nitroaromatics, Nitramines, and Nitrate Esters by High Performance Liquid Chromatography (HPLC), Rev. 2. Washington, D.C. [[media:Epa-2006-method-8330b.pdf | Report.pdf]]</ref>
 +
*[[media:Epa-2007-method-8095.pdf | U.S. EPA SW-846 Method 8095: Explosives by Gas Chromatography.]]<ref name= "USEPA2007M">U.S. Environmental Protection Agency (US EPA), 2007. Method 8095 (SW-846): Explosives by Gas Chromatography. Washington, D.C. [[media:Epa-2007-method-8095.pdf| Report.pdf]]</ref>
  
 
==Introduction==
 
==Introduction==
During landfarming, the waste materials are typically placed as a layer on the ground surface with variable thickness. The waste is then tilled and amended with nutrients to enhance biodegradation by naturally occurring bacteria (Figure 1). Fertilizers such as urea and triple superphosphate (TSP) are used to provide nitrogen and phosphate necessary for biodegradation. Reduction in hydrocarbon concentrations can be expected within a span of weeks to months, depending on the initial concentration and composition of hydrocarbons, and whether the soil conditions are optimized for biodegradation. Once cleanup goals have been achieved, the treated material can be i) re-used in construction activity such as berms, landfill cover, backfill, regrading, or for agricultural purposes, ii) disposed at a landfill and/or iii) left in place and revegetated, depending on local regulations or site-specific considerations.
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[[File:Beal1w2 Fig1.png|thumb|200 px|left|Figure 1: Downrange distance of visible propellant plume on snow from the firing of different munitions. Note deposition behind firing line for the 84-mm rocket. Data from: Walsh et al.<ref>Walsh, M.R., Walsh, M.E., Ampleman, G., Thiboutot, S., Brochu, S. and Jenkins, T.F., 2012. Munitions propellants residue deposition rates on military training ranges. Propellants, Explosives, Pyrotechnics, 37(4), pp.393-406. [http://dx.doi.org/10.1002/prep.201100105 doi: 10.1002/prep.201100105]</ref><ref>Walsh, M.R., Walsh, M.E., Hewitt, A.D., Collins, C.M., Bigl, S.R., Gagnon, K., Ampleman, G., Thiboutot, S., Poulin, I. and Brochu, S., 2010. Characterization and Fate of Gun and Rocket Propellant Residues on Testing and Training Ranges: Interim Report 2. (ERDC/CRREL TR-10-13.  Also: ESTCP Project ER-1481) [[media:Walsh-2010 ERDC-CRREL TR-11-15 ESTCP ER-1481.pdf| Report]]</ref>]]
 +
[[File:Beal1w2 Fig2.png|thumb|left|200 px|Figure 2: A low-order detonation mortar round (top) with surrounding discrete soil samples produced concentrations spanning six orders of magnitude within a 10m by 10m area (bottom). (Photo and data: A.D. Hewitt)]]
  
Landfarming is a low-cost technology. Facilities are simple to construct and easy to operate. Standard construction and farming equipment can be used to move soils to the land treatment facility, to amend the soils with fertilizer, to apply water to the soils and to till the soils (e.g. excavator, plow, rotovator, water truck). Figures 2 through 4 show examples of equipment used at a typical landfarming facility.  
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Munitions constituents are released on military testing and training ranges through several common mechanisms. Some are locally dispersed as solid particles from incomplete combustion during firing and detonation. Also, small residual particles containing propellant compounds (e.g., [[Wikipedia: Nitroglycerin | nitroglycerin [NG]]] and [[Wikipedia: 2,4-Dinitrotoluene | 2,4-dinitrotoluene [2,4-DNT]]]) are distributed in front of and surrounding target practice firing lines (Figure 1). At impact areas and demolition areas, high order detonations typically yield very small amounts (<1 to 10 mg/round) of residual high explosive compounds (e.g., [[Wikipedia: TNT | TNT ]], [[Wikipedia: RDX | RDX ]] and [[Wikipedia: HMX | HMX ]]) that are distributed up to and sometimes greater than) 24 m from the site of detonation<ref name= "Walsh2017">Walsh, M.R., Temple, T., Bigl, M.F., Tshabalala, S.F., Mai, N. and Ladyman, M., 2017. Investigation of Energetic Particle Distribution from High‐Order Detonations of Munitions. Propellants, Explosives, Pyrotechnics, 42(8), pp.932-941. [https://doi.org/10.1002/prep.201700089 doi: 10.1002/prep.201700089] [[media: Walsh-2017-High-Order-Detonation-Residues-Particle-Distribution-PEP.pdf| Report.pdf]]</ref>.
  
 +
Low-order detonations and duds are thought to be the primary source of munitions constituents on ranges<ref>Hewitt, A.D., Jenkins, T.F., Walsh, M.E., Walsh, M.R. and Taylor, S., 2005. RDX and TNT residues from live-fire and blow-in-place detonations. Chemosphere, 61(6), pp.888-894. [https://doi.org/10.1016/j.chemosphere.2005.04.058 doi: 10.1016/j.chemosphere.2005.04.058]</ref><ref>Walsh, M.R., Walsh, M.E., Poulin, I., Taylor, S. and Douglas, T.A., 2011. Energetic residues from the detonation of common US ordnance. International Journal of Energetic Materials and Chemical Propulsion, 10(2). [https://doi.org/10.1615/intjenergeticmaterialschemprop.2012004956 doi: 10.1615/IntJEnergeticMaterialsChemProp.2012004956] [[media:Walsh-2011-Energetic-Residues-Common-US-Ordnance.pdf| Report.pdf]]</ref>. Duds are initially intact but may become perforated or fragmented into micrometer to centimeter;o0i0k-sized particles by nearby detonations<ref>Walsh, M.R., Thiboutot, S., Walsh, M.E., Ampleman, G., Martel, R., Poulin, I. and Taylor, S., 2011. Characterization and fate of gun and rocket propellant residues on testing and training ranges (No. ERDC/CRREL-TR-11-13). Engineer Research and Development Center / Cold Regions Research and Engineering Lab (ERDC/CRREL) TR-11-13, Hanover, NH, USA. [[media:Epa-2006-method-8330b.pdf| Report.pdf]]</ref>. Low-order detonations can scatter micrometer to centimeter-sized particles up to 20 m from the site of detonation<ref name= "Taylor2004">Taylor, S., Hewitt, A., Lever, J., Hayes, C., Perovich, L., Thorne, P. and Daghlian, C., 2004. TNT particle size distributions from detonated 155-mm howitzer rounds. Chemosphere, 55(3), pp.357-367.[[media:Taylor-2004 TNT PSDs.pdf| Report.pdf]]</ref>
  
<div><ul>
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The particulate nature of munitions constituents in the environment presents a distinct challenge to representative soil sampling. Figure 2 shows an array of discrete soil samples collected around the site of a low-order detonation – resultant soil concentrations vary by orders of magnitude within centimeters of each other. The inadequacy of discrete sampling is apparent in characterization studies from actual ranges which show wide-ranging concentrations and poor precision (Table 1).
<li style="display: inline-block;"> [[File:Kamath1w2 Fig1.png|thumbnail|500 px| Figure 1. Soils undergoing treatment at a Landfarming Facility]]</li>
 
<li style="display: inline-block;"> [[File:Kamath1w2 Fig2.png|thumbnail|500 px| Figure 2. Excavator to move soils]]</li>
 
<li style="display: inline-block;"> [[File:Kamath1w2 Fig3.png|thumbnail|500 px| Figure 3. Water truck to ensure optimal moisture content for microbial degradation in soils.]]</li>
 
</ul></div>
 
  
 +
In comparison to discrete sampling, incremental sampling tends to yield reproducible concentrations (low relative standard deviation [RSD]) that statistically better represent an area of interest<ref name= "Hewitt2009"/>.
  
[[File:Kamath1w2 Fig4.png|thumbnail|center|700 px| Figure 4. Rotovator and Plows to till soils]]
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{| class="wikitable" style="float: right; text-align: center; margin-left: auto; margin-right: auto;"
 +
|+ Table 1. Soil Sample Concentrations and Precision from Military Ranges Using Discrete and Incremental Sampling. (Data from Taylor et al. <ref name= "Taylor2011"/> and references therein.)
 +
|-
 +
! Military Range Type !! Analyte !! Range<br/>(mg/kg) !! Median<br/>(mg/kg) !! RSD<br/>(%)
 +
|-
 +
| colspan="5" style="text-align: left;" | '''Discrete Samples'''
 +
|-
 +
| Artillery FP || 2,4-DNT || <0.04 – 6.4 || 0.65 || 110
 +
|-
 +
| Antitank Rocket || HMX || 5.8 – 1,200 || 200 || 99
 +
|-
 +
| Bombing || TNT || 0.15 – 780 || 6.4 || 274
 +
|-
 +
| Mortar || RDX || <0.04 – 2,400 || 1.7 || 441
 +
|-
 +
| Artillery || RDX || <0.04 – 170 || <0.04 || 454
 +
|-
 +
| colspan="5" style="text-align: left;" | '''Incremental Samples*'''
 +
|-
 +
| Artillery FP || 2,4-DNT || 0.60 – 1.4 || 0.92 || 26
 +
|-
 +
| Bombing || TNT || 13 – 17 || 14 || 17
 +
|-
 +
| Artillery/Bombing || RDX || 3.9 – 9.4 || 4.8 || 38
 +
|-
 +
| Thermal Treatment || HMX || 3.96 – 4.26 || 4.16 || 4
 +
|-
 +
| colspan="5" style="text-align: left; background-color: white;" | * For incremental samples, 30-100 increments and 3-10 replicate samples were collected.
 +
|}
  
Some of the disadvantages of the technology are:
+
==Incremental Sampling Approach==
*It requires a large land area for treatment.
+
ISM is a requisite for representative and reproducible sampling of training ranges, but it is an involved process that is detailed thoroughly elsewhere<ref name= "Hewitt2009"/><ref name= "Taylor2011"/><ref name= "USEPA2006M"/>. In short, ISM involves the collection of many (30 to >100) increments in a systematic pattern within a decision unit (DU). The DU may cover an area where releases are thought to have occurred or may represent an area relevant to ecological receptors (e.g., sensitive species). Figure 3 shows the ISM sampling pattern in a simplified (5x5 square) DU. Increments are collected at a random starting point with systematic distances between increments. Replicate samples can be collected by starting at a different random starting point, often at a different corner of the DU. Practically, this grid pattern can often be followed with flagging or lathe marking DU boundaries and/or sampling lanes and with individual pacing keeping systematic distances between increments. As an example, an artillery firing point might include a 100x100 m DU with 81 increments.
*There may be regulatory limitations on wastes that can be treated by landfarming. For example, U.S. regulations prevent landfarming soil impacted with hazardous wastes such as motor oil, hydraulic oil, and solvents.
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[[File:Beal1w2 Fig3.png|thumb|200 px|left|Figure 3. Example ISM sampling pattern on a square decision unit. Replicates are collected in a systematic pattern from a random starting point at a corner of the DU. Typically more than the 25 increments shown are collected]]
*It may not be effective for highly impacted soils or soils impacted with severely degraded hydrocarbons (e.g. if soils contain >8% w/w petroleum hydrocarbons after spreading).  
 
*Although landfarming is effective for reducing hydrocarbon concentrations, it is not effective for reducing concentrations of other oil field waste components, such as elevated concentrations of metals, salt or wastes containing naturally occurring radioactive materials (NORM).
 
*Concentration reductions >95% or final concentrations <0.1% may not be successfully obtained based on the extent impacted and nature of the hydrocarbons.
 
*Dust and vapor emissions may pose air quality concerns.
 
  
==Suitability of Wastes for Landfarming==
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DUs can vary in shape (Figure 4), size, number of increments, and number of replicates according to a project’s data quality objectives.
Landfarming has been successfully used to reduce hydrocarbon concentrations in soils impacted with kerosene, diesel, jet fuel, and crude oil. It has also been successfully used to treat oil-based drilling wastes (drill cutting, low brine drilling), oily sludge, tank bottoms and pit sludges.  
 
  
Wastes may not be suitable for landfarming for a number of reasons:
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[[File:Beal1w2 Fig4.png|thumb|right|250 px|Figure 4: Incremental sampling of a circular DU on snow shows sampling lanes with a two-person team in process of collecting the second replicate in a perpendicular path to the first replicate. (Photo: Matthew Bigl)]]
  
*There may be regulatory or permit limitations. For instance, in the United States, wastes that are not exempted under RCRA <ref>U.S. Environmental Protection Agency (USEPA), 2002. Exemption of Oil and Gas Exploration and Production Wastes from Federal Hazardous Waste Regulations. Office of Solid Waste, EPA530-K-01-004. [[Media:USEPA-2002._Exemption_of_Oil_and_Gas_exploration_and_Production_Wastes....pdf| Report.pdf]]</ref> such as motor oil, hydraulic oil, and solvents cannot be treated by landfarming by law.
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==Sampling Tools==
*Wastes unsuitable by their composition such as solid, non-spreadable paraffins from pig trap scrapings from the maintenance of pipelines, or highly weathered wastes, or asphaltic wastes
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In many cases, energetic compounds are expected to reside within the soil surface. Figure 5 shows soil depth profiles on some studied impact areas and firing points. Overall, the energetic compound concentrations below 5-cm soil depth are negligible relative to overlying soil concentrations. For conventional munitions, this is to be expected as the energetic particles are relatively insoluble, and any dissolved compounds readily adsorb to most soils<ref>Pennington, J.C., Jenkins, T.F., Ampleman, G., Thiboutot, S., Brannon, J.M., Hewitt, A.D., Lewis, J., Brochu, S., 2006. Distribution and fate of energetics on DoD test and training ranges: Final Report. ERDC TR-06-13, Vicksburg, MS, USA. Also: SERDP/ESTCP Project ER-1155. [[media:Pennington-2006_ERDC-TR-06-13_ESTCP-ER-1155-FR.pdf| Report.pdf]]</ref>. Physical disturbance, as on hand grenade ranges, may require deeper sampling either with a soil profile or a corer/auger.
*Wastes containing contaminants that do not biodegrade: e.g., NORM, metals or salt.  
 
  
==Biodegradation Potential==
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[[File:Beal1w2 Fig5.png|thumb|left|200 px|Figure 5. Depth profiles of high explosive compounds at impact areas (bottom) and of propellant compounds at firing points (top). Data from: Hewitt et al. <ref>Hewitt, A.D., Jenkins, T.F., Ramsey, C.A., Bjella, K.L., Ranney, T.A. and Perron, N.M., 2005. Estimating energetic residue loading on military artillery ranges: Large decision units (No. ERDC/CRREL-TR-05-7). [[media:Hewitt-2005 ERDC-CRREL TR-05-7.pdf| Report.pdf]]</ref> and Jenkins et al. <ref>Jenkins, T.F., Ampleman, G., Thiboutot, S., Bigl, S.R., Taylor, S., Walsh, M.R., Faucher, D., Mantel, R., Poulin, I., Dontsova, K.M. and Walsh, M.E., 2008. Characterization and fate of gun and rocket propellant residues on testing and training ranges (No. ERDC-TR-08-1). [[media:Jenkins-2008 ERDC TR-08-1.pdf| Report.pdf]]</ref>]]
The initial concentration and composition of hydrocarbons strongly influences the biodegradation potential of a waste. [[File:Kamath1w2 Fig5.png|thumbnail|right| Figure 5. Correlation between API gravity (specific weight of the crude) and the predicted extent of biodegradation as measured by oil and grease (O&G)<ref name= "McMillen2004"/>]]
 
  
*Wastes with >5% (w/w) of hydrocarbons may have physical and chemical characteristics that hinder biodegradation. For example, oily wastes tend to repel water, and can be poorly aerated. This can hinder or inhibit biodegradation.  
+
Soil sampling with the Cold Regions Research and Engineering Laboratory (CRREL) Multi-Increment Sampling Tool (CMIST) or similar device is an easy way to collect ISM samples rapidly and reproducibly. This tool has an adjustable diameter size corer and adjustable depth to collect surface soil plugs (Figure 6). The CMIST can be used at almost a walking pace (Figure 7) using a two-person sampling team, with one person operating the CMIST and the other carrying the sample container and recording the number of increments collected. The CMIST with a small diameter tip works best in soils with low cohesion, otherwise conventional scoops may be used. Maintaining consistent soil increment dimensions is critical.
  
*The molecular structure and molecular weight of hydrocarbons in the waste may make them either more or less susceptible to attack by microorganisms. Typically, aliphatic hydrocarbons are more readily biodegraded than aromatic hydrocarbons.  Structurally more complex molecules such as isoprenoids and steranes are relatively recalcitrant to biodegradation. For crude oils, the API gravity is a reliable indicator of the composition of a crude oil and by extension, a good predictor of the biodegradation potential of a crude oil (see Figure 5)<ref name= "McMillen2004">McMillen, S.J., Smart, R., Bernier, R. and Hoffmann, R.E., 2004, January. Biotreating E&P wastes: lessons learned from 1992-2003. In SPE International Conference on Health, Safety, and Environment in Oil and Gas Exploration and Production. Society of Petroleum Engineers. [https://doi.org/10.2118/86794-ms  doi: 10.2118/86794-ms]</ref>. For example, a crude oil with API gravity of 40 (by virtue of its composition) may degrade by 75% within 4 weeks. A crude oil with API gravity of 25 may only degrade by 55%, and a crude oil with API gravity of 10 may not degrade more than 10% within that same timeframe.  
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The sampling tool should be cleaned between replicates and between DUs to minimize potential for cross-contamination<ref>Walsh, M.R., 2009. User’s manual for the CRREL Multi-Increment Sampling Tool. Engineer Research and Development Center / Cold Regions Research and Engineering Lab (ERDC/CRREL) SR-09-1, Hanover, NH, USA. [[media:Walsh-2009 ERDC-CRREL SR-09-1.pdf | Report.pdf]]</ref>.
  
This same correlation can be used to determine the maximum initial hydrocarbon concentration that can be treated using conventional landfarming within 4 weeks and/or the maximum endpoint achievable for a given waste material.  
+
==Sample Processing==
 +
While only 10 g of soil is typically used for chemical analysis, incremental sampling generates a sample weighing on the order of 1 kg. Splitting of a sample, either in the field or laboratory, seems like an easy way to reduce sample mass; however this approach has been found to produce high uncertainty for explosives and propellants, with a median RSD of 43.1%<ref name= "Hewitt2009"/>. Even greater error is associated with removing a discrete sub-sample from an unground sample. Appendix A in [https://www.epa.gov/sites/production/files/2015-07/documents/epa-8330b.pdf U.S. EPA Method 8330B]<ref name= "USEPA2006M"/> provides details on recommended ISM sample processing procedures.
  
Using analytical methods such as gas chromatography to determine the quantity and composition of organic contaminants in a waste may be useful in determining biodegradation potential. Lighter ends (lower boiling point components that elute earlier in the chromatogram) will typically degrade faster than heavier end components.
+
Incremental soil samples are typically air dried over the course of a few days. Oven drying thermally degrades some energetic compounds and should be avoided<ref>Cragin, J.H., Leggett, D.C., Foley, B.T., and Schumacher, P.W., 1985. TNT, RDX and HMX explosives in soils and sediments: Analysis techniques and drying losses. (CRREL Report 85-15) Hanover, NH, USA. [[media:Cragin-1985 CRREL 85-15.pdf| Report.pdf]]</ref>. Once dry, the samples are sieved with a 2-mm screen, with only the less than 2-mm fraction processed further. This size fraction represents the USDA definition of soil. Aggregate soil particles should be broken up and vegetation shredded to pass through the sieve. Samples from impact or demolition areas may contain explosive particles from low order detonations that are greater than 2 mm and should be identified, given appropriate caution, and potentially weighed.
  
*The extent of weathering (volatilization and biodegradation) may influence the rate and extent of biodegradation. Fresh crude oils with API gravity >30 are generally readily biodegradable; however, after extensive weathering as might be encountered at an old spill site, the oil may not be very biodegradable as most of the more volatile and biodegradable fractions of hydrocarbon have already disappeared. It is recommended that feasibility evaluations include hydrocarbon analysis of wastes using gas chromatography (GC) to assess the extent of weathering. (Figures 6a and 6b)
+
The <2-mm soil fraction is typically still ≥1 kg and impractical to extract in full for analysis. However, subsampling at this stage is not possible due to compositional heterogeneity, with the energetic compounds generally present as <0.5 mm particles<ref name= "Walsh2017"/><ref name= "Taylor2004"/>. Particle size reduction is required to achieve a representative and precise measure of the sample concentration. Grinding in a puck mill to a soil particle size <75 µm has been found to be required for representative/reproducible sub-sampling (Figure 8). For samples thought to contain propellant particles, a prolonged milling time is required to break down these polymerized particles and achieve acceptable precision (Figure 9). Due to the multi-use nature of some ranges, a 5-minute puck milling period can be used for all soils. Cooling periods between 1-minute milling intervals are recommended to avoid thermal degradation. Similar to field sampling, sub-sampling is done incrementally by spreading the sample out to a thin layer and collecting systematic random increments of consistent volume to a total mass for extraction of 10 g (Figure 10).
  
 +
<li style="display: inline-block;">[[File:Beal1w2 Fig6.png|thumb|200 px|Figure 6: CMIST soil sampling tool (top) and with ejected increment core using a large diameter tip (bottom).]]</li>
 +
<li style="display: inline-block;">[[File:Beal1w2 Fig7.png|thumb|200 px|Figure 7: Two person sampling team using CMIST, bag-lined bucket, and increment counter. (Photos: Matthew Bigl)]]</li>
 +
<li style="display: inline-block;">[[File:Beal1w2 Fig8.png|thumb|200 px|Figure 8: Effect of machine grinding on RDX and TNT concentration and precision in soil from a hand grenade range. Data from Walsh et al.<ref>Walsh, M.E., Ramsey, C.A. and Jenkins, T.F., 2002. The effect of particle size reduction by grinding on subsampling variance for explosives residues in soil. Chemosphere, 49(10), pp.1267-1273. [https://doi.org/10.1016/S0045-6535(02)00528-3 doi: 10.1016/S0045-6535(02)00528-3]</ref> ]]</li>
 +
<li style="display: inline-block;">[[File:Beal1w2 Fig9.png|thumb|200 px|Figure 9: Effect of puck milling time on 2,4-DNT concentration and precision in soil from a firing point. Data from Walsh et al.<ref>Walsh, M.E., Ramsey, C.A., Collins, C.M., Hewitt, A.D., Walsh, M.R., Bjella, K.L., Lambert, D.J. and Perron, N.M., 2005. Collection methods and laboratory processing of samples from Donnelly Training Area Firing Points, Alaska, 2003 (No. ERDC/CRREL-TR-05-6). [[media:Walsh-2005 ERDC-CRREL TR-05-6.pdf| Report.pdf]]</ref>.]]</li>
 +
<li style="display: inline-block;">[[File:Beal1w2 Fig10.png|thumb|200 px|center|Figure 10: Incremental sub-sampling of a milled soil sample spread out on aluminum foil.]]</li>
  
[[File:Kamath1w2 Fig6a.png|thumbnail| center| 600 px| Figure 6a. Chromatogram of fresh crude oil]]
+
==Analysis==
 +
Soil sub-samples are extracted and analyzed following [[Media: epa-2006-method-8330b.pdf | EPA Method 8330B]]<ref name= "USEPA2006M"/> and [[Media:epa-2007-method-8095.pdf | Method 8095]]<ref name= "USEPA2007M"/> using [[Wikipedia: High-performance liquid chromatography | High Performance Liquid Chromatography (HPLC)]] and [[Wikipedia: Gas chromatography | Gas Chromatography (GC)]], respectively. Common estimated reporting limits for these analysis methods are listed in Table 2.
  
[[File:Kamath1w2 Fig6b.png|thumbnail| center| 600 px| Figure 6b. Chromatogram of weathered crude oil]]
+
{| class="wikitable" style="float: center; text-align: center; margin-left: auto; margin-right: auto;"
 
+
|+ Table 2. Typical Method Reporting Limits for Energetic Compounds in Soil. (Data from Hewitt et al.<ref>Hewitt, A., Bigl, S., Walsh, M., Brochu, S., Bjella, K. and Lambert, D., 2007. Processing of training range soils for the analysis of energetic compounds (No. ERDC/CRREL-TR-07-15). Hanover, NH, USA. [[media:Hewitt-2007 ERDC-CRREL TR-07-15.pdf| Report.pdf]]</ref>)
*Light refined products, such as diesel and jet fuels, are highly biodegradable, similar to crude oils with API gravity >40. Heavy refined products like Bunker C or heavy fuel oils will biodegrade at rates similar to low API-gravity crude oils.
+
|-
 
+
! rowspan="2" | Compound
 
+
! colspan="2" | Soil Reporting Limit (mg/kg)
==Facility Design and Operation==
+
|-
Landfarming facilities are designed to prevent impacts to groundwater and surface water. The facilities typically include an impermeable or low permeability liner for the treatment pad to prevent leaching of chemical constituents from the treatment waste to the groundwater, and berms/dikes to prevent storm water runoff. (See Figure 7.)
+
! HPLC (8330)  
 
+
! GC (8095)
[[File:Kamath1w2 Fig7.PNG|thumbnail| center| 600 px| Figure 7. Typical Landfarming Operation]]
+
|-
 
+
| HMX || 0.04 || 0.01
Successful landfarm operation requires maintaining optimum conditions in the soil/waste materials (moisture, oxygen, pH and nutrient levels) to enhance biodegradation of petroleum hydrocarbons (see Table 1). Before beginning landfarm operations, the waste and the soil at the landfarm site should be characterized to establish the soil baseline characteristics and the need for soil additives such as agricultural lime for pH correction.
+
|-
 
+
| RDX || 0.04 || 0.006
{| class="wikitable" style="text-align: left;"
+
|-
|+ colspan="2" | Table 1. Optimum Conditions for Landfarming
+
| [[Wikipedia: 1,3,5-Trinitrobenzene | TNB]] || 0.04 || 0.003
 +
|-
 +
| TNT || 0.04 || 0.002
 +
|-
 +
| [[Wikipedia: 2,6-Dinitrotoluene | 2,6-DNT]] || 0.08 || 0.002
 
|-
 
|-
! Parameter
+
| 2,4-DNT || 0.04 || 0.002
! Optimum Condition
 
 
|-
 
|-
| Initial&nbsp;HC&nbsp;Concentration || 1% - 5% by weight in dry soil
+
| 2-ADNT || 0.08 || 0.002
 
|-
 
|-
| pH || 6 – 8.5. Agricultural lime can be added to increase soil pH.
+
| 4-ADNT || 0.08 || 0.002
 
|-
 
|-
| Aeration/Tilling || Initially and every 2 – 4 weeks.
+
| NG || 0.1 || 0.01
 
|-
 
|-
| Moisture Content || 60% – 80% of water holding capacity (field capacity).
+
| [[Wikipedia: Dinitrobenzene | DNB ]] || 0.04 || 0.002
 
|-
 
|-
| Salt Content || Electrical conductance of leachate <30 mS/cm (mhos/cm). Preferably <4 mS/cm for maximum reuse potential after cleanup.  Ocean water has an electrical conductance of ~50 mS/cm.
+
| [[Wikipedia: Tetryl | Tetryl ]]  || 0.04 || 0.01
 
|-
 
|-
| Nutrients ||  
+
| [[Wikipedia: Pentaerythritol tetranitrate | PETN ]] || 0.2 || 0.016
* Total Nitrogen: 250 – 500 ppm. Action Level: 50 ppm. Nitrogen source should be added if nutrient concentration falls below action level (e.g. urea).
 
* Available phosphate: 125 – 250 ppm. Action Level: 25 ppm. Phosphate source should be added if nutrient concentration falls below action level (e.g. triple superphosphate).
 
 
|}
 
|}
 
Maintaining optimum conditions for biodegradation is the key to achieving target cleanup goals within a reasonable timeframe. Figure 8 is an illustration of the effect of tilling and adding fertilizer on the rate of degradation of petroleum hydrocarbons.
 
 
[[File:Kamath1w2 Fig8.png|thumbnail|right|400 px| Figure 8. Typical results for total petroleum hydrocarbon (TPH) reduction without tilling/fertilizer addition (natural attenuation, shown in blue), with tilling only (orange), or with periodic tilling and fertilizer addition (grey).]]
 
 
*Fertilizer: Fertilizers can be added either manually or with mechanical spreaders. During landfarming, the nutrient conditions should be monitored, and additional fertilizer should be added if the concentration falls below action levels. Care should be taken not to add excess nutrients as it can result in fertilizer runoff and/or inhibit biodegradation.
 
*Moisture: Moisture should be maintained in the landfarm between 60 and 80% of the water holding capacity (field capacity) of the soil (roughly 15%-24% moisture by weight for most soils). For soils with less than 20% water holding capacity, some form of irrigation will likely be required.  For water saturated soils, no tilling should be performed while the water content is high since this can impair soil texture. Irrigation water should be fresh.  Low quality water may result in concentration of salt and subsequent inhibition of biotreatment.
 
*Aeration: Locally available agricultural equipment is most often used for tilling soils to break up clumps of clay and uniformly mix in amendments such as fertilizers, soil conditioners and water. 
 
*Monitoring Needs: Commonly monitored parameters include hydrocarbon concentration, moisture content, nutrients, and pH. Parameters are monitored on a biweekly or monthly basis as needed to confirm that the biodegradation process is progressing smoothly.
 
 
==Cleanup levels that can be attained==
 
Landfarming has been successful in meeting cleanup goals for a variety of hydrocarbon impacted wastes within a reasonable timeframe (see Figure 9). It is important to note that reductions in concentrations of total petroleum hydrocarbons (TPH) that are greater than 95% of the original concentrations are difficult to achieve.  It is also difficult to achieve a final concentration of TPH that is <0.1% of the dry weight of the soil. Cleanup goals for soils impacted with refined products such as gasoline may be lower than cleanup goals for crude oil based on risk to receptors and mobility of those products in the environment.
 
 
 
[[File:Kamath1w2 Fig9.png|thumbnail|center|600 px| Figure 9. Chromatogram Change illustrating a crude oil degradation with initial API gravity > 30 (week 0, 3, 7, and 15)]]
 
  
 
==References==
 
==References==
<references />
+
<references/>
  
 
==See Also==
 
==See Also==
*[https://doi.org/10.2118/126982-MS Hoffmann, R., Bernier, R., Smith, S. and McMillen, S., 2010, January. A Four-Step Biotreatability Protocol for Crude Oil Impacted Soil. In SPE International Conference on Health, Safety and Environment in Oil and Gas Exploration and Production. Society of Petroleum Engineers.]
+
*[https://itrcweb.org/ Interstate Technology and Regulatory Council]
*[https://doi.org/10.1080/15320389409383471 Huesemann, M.H., 1994. Guidelines for land‐treating petroleum hydrocarbon‐contaminated soils. Soil and Sediment Contamination, 3(3), pp.299-318.]
+
*[http://www.hawaiidoh.org/tgm.aspx Hawaii Department of Health]
*[https://doi.org/10.1080/21622515.2017.1310310 Lukić, B., Panico, A., Huguenot, D., Fabbricino, M., van Hullebusch, E.D. and Esposito, G., 2017. A review on the efficiency of landfarming integrated with composting as a soil remediation treatment. Environmental Technology Reviews, 6(1), pp.94-116.]
+
*[http://envirostat.org/ Envirostat]
*[https://link.springer.com/journal/11157 Maila, M.P. and Cloete, T.E., 2004. Bioremediation of petroleum hydrocarbons through landfarming: Are simplicity and cost-effectiveness the only advantages?. Reviews in Environmental science and bio/Technology, 3(4), pp.349-360.]
 

Latest revision as of 18:58, 29 April 2020

The heterogeneous distribution of munitions constituents, released as particles from munitions firing and detonations on military training ranges, presents challenges for representative soil sample collection and for defensible decision making. Military range characterization studies and the development of the incremental sampling methodology (ISM) have enabled the development of recommended methods for soil sampling that produce representative and reproducible concentration data for munitions constituents. This article provides a broad overview of recommended soil sampling and processing practices for analysis of munitions constituents on military ranges.

Related Article(s):


CONTRIBUTOR(S): Dr. Samuel Beal


Key Resource(s):

Introduction

Figure 1: Downrange distance of visible propellant plume on snow from the firing of different munitions. Note deposition behind firing line for the 84-mm rocket. Data from: Walsh et al.[5][6]
Figure 2: A low-order detonation mortar round (top) with surrounding discrete soil samples produced concentrations spanning six orders of magnitude within a 10m by 10m area (bottom). (Photo and data: A.D. Hewitt)

Munitions constituents are released on military testing and training ranges through several common mechanisms. Some are locally dispersed as solid particles from incomplete combustion during firing and detonation. Also, small residual particles containing propellant compounds (e.g., nitroglycerin [NG] and 2,4-dinitrotoluene [2,4-DNT]) are distributed in front of and surrounding target practice firing lines (Figure 1). At impact areas and demolition areas, high order detonations typically yield very small amounts (<1 to 10 mg/round) of residual high explosive compounds (e.g., TNT , RDX and HMX ) that are distributed up to and sometimes greater than) 24 m from the site of detonation[7].

Low-order detonations and duds are thought to be the primary source of munitions constituents on ranges[8][9]. Duds are initially intact but may become perforated or fragmented into micrometer to centimeter;o0i0k-sized particles by nearby detonations[10]. Low-order detonations can scatter micrometer to centimeter-sized particles up to 20 m from the site of detonation[11]

The particulate nature of munitions constituents in the environment presents a distinct challenge to representative soil sampling. Figure 2 shows an array of discrete soil samples collected around the site of a low-order detonation – resultant soil concentrations vary by orders of magnitude within centimeters of each other. The inadequacy of discrete sampling is apparent in characterization studies from actual ranges which show wide-ranging concentrations and poor precision (Table 1).

In comparison to discrete sampling, incremental sampling tends to yield reproducible concentrations (low relative standard deviation [RSD]) that statistically better represent an area of interest[2].

Table 1. Soil Sample Concentrations and Precision from Military Ranges Using Discrete and Incremental Sampling. (Data from Taylor et al. [1] and references therein.)
Military Range Type Analyte Range
(mg/kg)
Median
(mg/kg)
RSD
(%)
Discrete Samples
Artillery FP 2,4-DNT <0.04 – 6.4 0.65 110
Antitank Rocket HMX 5.8 – 1,200 200 99
Bombing TNT 0.15 – 780 6.4 274
Mortar RDX <0.04 – 2,400 1.7 441
Artillery RDX <0.04 – 170 <0.04 454
Incremental Samples*
Artillery FP 2,4-DNT 0.60 – 1.4 0.92 26
Bombing TNT 13 – 17 14 17
Artillery/Bombing RDX 3.9 – 9.4 4.8 38
Thermal Treatment HMX 3.96 – 4.26 4.16 4
* For incremental samples, 30-100 increments and 3-10 replicate samples were collected.

Incremental Sampling Approach

ISM is a requisite for representative and reproducible sampling of training ranges, but it is an involved process that is detailed thoroughly elsewhere[2][1][3]. In short, ISM involves the collection of many (30 to >100) increments in a systematic pattern within a decision unit (DU). The DU may cover an area where releases are thought to have occurred or may represent an area relevant to ecological receptors (e.g., sensitive species). Figure 3 shows the ISM sampling pattern in a simplified (5x5 square) DU. Increments are collected at a random starting point with systematic distances between increments. Replicate samples can be collected by starting at a different random starting point, often at a different corner of the DU. Practically, this grid pattern can often be followed with flagging or lathe marking DU boundaries and/or sampling lanes and with individual pacing keeping systematic distances between increments. As an example, an artillery firing point might include a 100x100 m DU with 81 increments.

Figure 3. Example ISM sampling pattern on a square decision unit. Replicates are collected in a systematic pattern from a random starting point at a corner of the DU. Typically more than the 25 increments shown are collected

DUs can vary in shape (Figure 4), size, number of increments, and number of replicates according to a project’s data quality objectives.

Figure 4: Incremental sampling of a circular DU on snow shows sampling lanes with a two-person team in process of collecting the second replicate in a perpendicular path to the first replicate. (Photo: Matthew Bigl)

Sampling Tools

In many cases, energetic compounds are expected to reside within the soil surface. Figure 5 shows soil depth profiles on some studied impact areas and firing points. Overall, the energetic compound concentrations below 5-cm soil depth are negligible relative to overlying soil concentrations. For conventional munitions, this is to be expected as the energetic particles are relatively insoluble, and any dissolved compounds readily adsorb to most soils[12]. Physical disturbance, as on hand grenade ranges, may require deeper sampling either with a soil profile or a corer/auger.

Figure 5. Depth profiles of high explosive compounds at impact areas (bottom) and of propellant compounds at firing points (top). Data from: Hewitt et al. [13] and Jenkins et al. [14]

Soil sampling with the Cold Regions Research and Engineering Laboratory (CRREL) Multi-Increment Sampling Tool (CMIST) or similar device is an easy way to collect ISM samples rapidly and reproducibly. This tool has an adjustable diameter size corer and adjustable depth to collect surface soil plugs (Figure 6). The CMIST can be used at almost a walking pace (Figure 7) using a two-person sampling team, with one person operating the CMIST and the other carrying the sample container and recording the number of increments collected. The CMIST with a small diameter tip works best in soils with low cohesion, otherwise conventional scoops may be used. Maintaining consistent soil increment dimensions is critical.

The sampling tool should be cleaned between replicates and between DUs to minimize potential for cross-contamination[15].

Sample Processing

While only 10 g of soil is typically used for chemical analysis, incremental sampling generates a sample weighing on the order of 1 kg. Splitting of a sample, either in the field or laboratory, seems like an easy way to reduce sample mass; however this approach has been found to produce high uncertainty for explosives and propellants, with a median RSD of 43.1%[2]. Even greater error is associated with removing a discrete sub-sample from an unground sample. Appendix A in U.S. EPA Method 8330B[3] provides details on recommended ISM sample processing procedures.

Incremental soil samples are typically air dried over the course of a few days. Oven drying thermally degrades some energetic compounds and should be avoided[16]. Once dry, the samples are sieved with a 2-mm screen, with only the less than 2-mm fraction processed further. This size fraction represents the USDA definition of soil. Aggregate soil particles should be broken up and vegetation shredded to pass through the sieve. Samples from impact or demolition areas may contain explosive particles from low order detonations that are greater than 2 mm and should be identified, given appropriate caution, and potentially weighed.

The <2-mm soil fraction is typically still ≥1 kg and impractical to extract in full for analysis. However, subsampling at this stage is not possible due to compositional heterogeneity, with the energetic compounds generally present as <0.5 mm particles[7][11]. Particle size reduction is required to achieve a representative and precise measure of the sample concentration. Grinding in a puck mill to a soil particle size <75 µm has been found to be required for representative/reproducible sub-sampling (Figure 8). For samples thought to contain propellant particles, a prolonged milling time is required to break down these polymerized particles and achieve acceptable precision (Figure 9). Due to the multi-use nature of some ranges, a 5-minute puck milling period can be used for all soils. Cooling periods between 1-minute milling intervals are recommended to avoid thermal degradation. Similar to field sampling, sub-sampling is done incrementally by spreading the sample out to a thin layer and collecting systematic random increments of consistent volume to a total mass for extraction of 10 g (Figure 10).

  • Figure 6: CMIST soil sampling tool (top) and with ejected increment core using a large diameter tip (bottom).
  • Figure 7: Two person sampling team using CMIST, bag-lined bucket, and increment counter. (Photos: Matthew Bigl)
  • Figure 8: Effect of machine grinding on RDX and TNT concentration and precision in soil from a hand grenade range. Data from Walsh et al.[17]
  • Figure 9: Effect of puck milling time on 2,4-DNT concentration and precision in soil from a firing point. Data from Walsh et al.[18].
  • Figure 10: Incremental sub-sampling of a milled soil sample spread out on aluminum foil.
  • Analysis

    Soil sub-samples are extracted and analyzed following EPA Method 8330B[3] and Method 8095[4] using High Performance Liquid Chromatography (HPLC) and Gas Chromatography (GC), respectively. Common estimated reporting limits for these analysis methods are listed in Table 2.

    Table 2. Typical Method Reporting Limits for Energetic Compounds in Soil. (Data from Hewitt et al.[19])
    Compound Soil Reporting Limit (mg/kg)
    HPLC (8330) GC (8095)
    HMX 0.04 0.01
    RDX 0.04 0.006
    TNB 0.04 0.003
    TNT 0.04 0.002
    2,6-DNT 0.08 0.002
    2,4-DNT 0.04 0.002
    2-ADNT 0.08 0.002
    4-ADNT 0.08 0.002
    NG 0.1 0.01
    DNB 0.04 0.002
    Tetryl 0.04 0.01
    PETN 0.2 0.016

    References

    1. ^ 1.0 1.1 1.2 Taylor, S., Jenkins, T.F., Bigl, S., Hewitt, A.D., Walsh, M.E. and Walsh, M.R., 2011. Guidance for Soil Sampling for Energetics and Metals (No. ERDC/CRREL-TR-11-15). Report.pdf
    2. ^ 2.0 2.1 2.2 2.3 Hewitt, A.D., Jenkins, T.F., Walsh, M.E., Bigl, S.R. and Brochu, S., 2009. Validation of sampling protocol and the promulgation of method modifications for the characterization of energetic residues on military testing and training ranges (No. ERDC/CRREL-TR-09-6). Engineer Research and Development Center / Cold Regions Research and Engineering Lab (ERDC/CRREL) TR-09-6, Hanover, NH, USA. Report.pdf
    3. ^ 3.0 3.1 3.2 3.3 U.S. Environmental Protection Agency (USEPA), 2006. Method 8330B (SW-846): Nitroaromatics, Nitramines, and Nitrate Esters by High Performance Liquid Chromatography (HPLC), Rev. 2. Washington, D.C. Report.pdf
    4. ^ 4.0 4.1 U.S. Environmental Protection Agency (US EPA), 2007. Method 8095 (SW-846): Explosives by Gas Chromatography. Washington, D.C. Report.pdf
    5. ^ Walsh, M.R., Walsh, M.E., Ampleman, G., Thiboutot, S., Brochu, S. and Jenkins, T.F., 2012. Munitions propellants residue deposition rates on military training ranges. Propellants, Explosives, Pyrotechnics, 37(4), pp.393-406. doi: 10.1002/prep.201100105
    6. ^ Walsh, M.R., Walsh, M.E., Hewitt, A.D., Collins, C.M., Bigl, S.R., Gagnon, K., Ampleman, G., Thiboutot, S., Poulin, I. and Brochu, S., 2010. Characterization and Fate of Gun and Rocket Propellant Residues on Testing and Training Ranges: Interim Report 2. (ERDC/CRREL TR-10-13. Also: ESTCP Project ER-1481) Report
    7. ^ 7.0 7.1 Walsh, M.R., Temple, T., Bigl, M.F., Tshabalala, S.F., Mai, N. and Ladyman, M., 2017. Investigation of Energetic Particle Distribution from High‐Order Detonations of Munitions. Propellants, Explosives, Pyrotechnics, 42(8), pp.932-941. doi: 10.1002/prep.201700089 Report.pdf
    8. ^ Hewitt, A.D., Jenkins, T.F., Walsh, M.E., Walsh, M.R. and Taylor, S., 2005. RDX and TNT residues from live-fire and blow-in-place detonations. Chemosphere, 61(6), pp.888-894. doi: 10.1016/j.chemosphere.2005.04.058
    9. ^ Walsh, M.R., Walsh, M.E., Poulin, I., Taylor, S. and Douglas, T.A., 2011. Energetic residues from the detonation of common US ordnance. International Journal of Energetic Materials and Chemical Propulsion, 10(2). doi: 10.1615/IntJEnergeticMaterialsChemProp.2012004956 Report.pdf
    10. ^ Walsh, M.R., Thiboutot, S., Walsh, M.E., Ampleman, G., Martel, R., Poulin, I. and Taylor, S., 2011. Characterization and fate of gun and rocket propellant residues on testing and training ranges (No. ERDC/CRREL-TR-11-13). Engineer Research and Development Center / Cold Regions Research and Engineering Lab (ERDC/CRREL) TR-11-13, Hanover, NH, USA. Report.pdf
    11. ^ 11.0 11.1 Taylor, S., Hewitt, A., Lever, J., Hayes, C., Perovich, L., Thorne, P. and Daghlian, C., 2004. TNT particle size distributions from detonated 155-mm howitzer rounds. Chemosphere, 55(3), pp.357-367. Report.pdf
    12. ^ Pennington, J.C., Jenkins, T.F., Ampleman, G., Thiboutot, S., Brannon, J.M., Hewitt, A.D., Lewis, J., Brochu, S., 2006. Distribution and fate of energetics on DoD test and training ranges: Final Report. ERDC TR-06-13, Vicksburg, MS, USA. Also: SERDP/ESTCP Project ER-1155. Report.pdf
    13. ^ Hewitt, A.D., Jenkins, T.F., Ramsey, C.A., Bjella, K.L., Ranney, T.A. and Perron, N.M., 2005. Estimating energetic residue loading on military artillery ranges: Large decision units (No. ERDC/CRREL-TR-05-7). Report.pdf
    14. ^ Jenkins, T.F., Ampleman, G., Thiboutot, S., Bigl, S.R., Taylor, S., Walsh, M.R., Faucher, D., Mantel, R., Poulin, I., Dontsova, K.M. and Walsh, M.E., 2008. Characterization and fate of gun and rocket propellant residues on testing and training ranges (No. ERDC-TR-08-1). Report.pdf
    15. ^ Walsh, M.R., 2009. User’s manual for the CRREL Multi-Increment Sampling Tool. Engineer Research and Development Center / Cold Regions Research and Engineering Lab (ERDC/CRREL) SR-09-1, Hanover, NH, USA. Report.pdf
    16. ^ Cragin, J.H., Leggett, D.C., Foley, B.T., and Schumacher, P.W., 1985. TNT, RDX and HMX explosives in soils and sediments: Analysis techniques and drying losses. (CRREL Report 85-15) Hanover, NH, USA. Report.pdf
    17. ^ Walsh, M.E., Ramsey, C.A. and Jenkins, T.F., 2002. The effect of particle size reduction by grinding on subsampling variance for explosives residues in soil. Chemosphere, 49(10), pp.1267-1273. doi: 10.1016/S0045-6535(02)00528-3
    18. ^ Walsh, M.E., Ramsey, C.A., Collins, C.M., Hewitt, A.D., Walsh, M.R., Bjella, K.L., Lambert, D.J. and Perron, N.M., 2005. Collection methods and laboratory processing of samples from Donnelly Training Area Firing Points, Alaska, 2003 (No. ERDC/CRREL-TR-05-6). Report.pdf
    19. ^ Hewitt, A., Bigl, S., Walsh, M., Brochu, S., Bjella, K. and Lambert, D., 2007. Processing of training range soils for the analysis of energetic compounds (No. ERDC/CRREL-TR-07-15). Hanover, NH, USA. Report.pdf

    See Also