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Natural source zone depletion (NSZD) is a term used to describe the collective, naturally occurring processes of dissolution, volatilization, and biodegradation that result in mass losses of light non-aqueous phase liquid (LNAPL) petroleum hydrocarbon constituents from the subsurface. NSZD is coming to the forefront of decision making at petroleum hydrocarbon remediation sites because much higher source attenuation rates are now being measured compared to previous rates based on incomplete conceptual models<ref>Lundegard, P.D. and Johnson, P.C., 2006. Source zone natural attenuation at petroleum hydrocarbon spill sites-II: application to a former oil field. Groundwater Monitoring & Remediation, 26(4), pp.93-106.[http://dx.doi.org/10.1111/j.1745-6592.2006.00115.x doi:10.1111/j.1745-6592.2006.00115.x]</ref><ref name="McCoy2015">McCoy, K., Zimbron, J., Sale, T. and Lyverse, M., 2015. Measurement of natural losses of LNAPL using CO2 traps. Groundwater, 53(4), pp.658-667. [http://dx.doi.org/10.1111/gwat.12240 doi: 10.1111/gwat.12240]</ref><ref>Palaia, T. 2016. Natural Source Zone Depletion Rate Assessment. Applied NAPL Science Review (ANSR), Volume 6, Issue 1, May</ref>. NSZD processes occur at most petroleum release sites and quantifying NSZD rates is an important part of an overall site remediation strategy.
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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>
  
'''Related Articles:'''
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'''Related Article(s)''':
  
  
'''CONTRIBUTOR(S):''' [[Tom Palaia]] and [[Jeff Fitzgibbons]]
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'''CONTRIBUTOR(S):''' [[Dr. Samuel Beal]]
  
  
'''Key Resource(s):'''  
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'''Key Resource(s)''':
*American Petroleum Institute (API). Pending. Quantification of Vapor Phase-Related NSZD Processes. In draft, pending publication in 2016/17.
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*[[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>
*[http://www.environmentalrestoration.wiki/images/b/bd/ITRC-2009-Nat_Zone_Depletion.pdf Evaluating Natural Source Zone Depletion at Sites with LNAPL. LNAPL-1. Washington, D.C.: Interstate Technology & Regulatory Council, LNAPLs Team.]<ref name="ITRC2009">Interstate Technology & Regulatory Council (ITRC). 2009. Evaluating Natural Source Zone Depletion at Sites with LNAPL. LNAPL-1. Washington, D.C.: Interstate Technology & Regulatory Council, LNAPLs Team. [http://www.environmentalrestoration.wiki/images/b/bd/ITRC-2009-Nat_Zone_Depletion.pdf Report pdf]</ref>  
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*[[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>
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*[[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==
 +
[[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>]]
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[[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)]]
  
After a release into the environment, petroleum hydrocarbon constituents in LNAPL undergo various different degradation processes including dissolution, volatilization, and biodegradation<ref>Kostecki, P.T. and E.J. Calabrese. 1989. Petroleum Contaminated Soils, Volumes 1 through 3. Lewis Publishers, Inc., Chelsea, MI.</ref><ref>National Research Council (NRC). 1993. In Situ Bioremediation - When Does It Work? Committee on In Situ Bioremediation, Water Science and Technology Board, Commission on Engineering and Technical Systems, National Academy Press, Washington D.C. [https://doi.org/10.17226/2131 doi: 10.17226/2131]</ref><ref name="NRC2000">National Research Council (NRC). 2000. Natural Attenuation for Groundwater Remediation. Washington, DC: The National Academies Press. [https://doi.org/10.17226/9792 doi: 10.17226/9792]</ref><ref name="Johnson2006">Johnson, P., Lundegard, P. and Liu, Z., 2006. Source Zone Natural Attenuation at Petroleum Hydrocarbon Spill Sites-I: Site‐Specific Assessment Approach. Groundwater Monitoring & Remediation, 26(4), pp.82-92.[http://dx.doi.org/10.1111/j.1745-6592.2006.00114.x doi: 10.1111/j.1745-6592.2006.00114.x]</ref>. NSZD is a term used to describe these collective processes that result in mass losses of LNAPL petroleum hydrocarbon constituents from the subsurface. NSZD processes occur naturally within LNAPL-impacted zones in the subsurface. These processes physically degrade the LNAPL by mass transfer of chemical components to the aqueous and gaseous phases where they are biologically broken down via anaerobic and aerobic biodegradation.
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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>.
 
 
Traditional methods of NSZD monitoring have focused on the aqueous phase biodegradation and groundwater transport of the solubilized LNAPL constituents that occur through various terminal electron acceptor processes. Aerobic respiration, denitrification, sulfate reduction, iron and manganese reduction, and methanogenesis each support hydrocarbon degradation as the supply of each electron acceptor (e.g., dissolved oxygen, nitrate, sulfate), oxidation-reduction state, and the microbiological conditions allow. These processes manifest themselves as changes in dissolved electron acceptor concentrations and production of soluble byproducts such as ferrous iron, dissolved methane (CH<sub>4</sub>), and carbon dioxide (CO<sub>2</sub>). Through stoichiometric conversion of the mass of electron acceptor loss and byproduct formation, the soluble or aqueous contribution to NSZD can be estimated<ref name="Wiedemeier1995">Wiedemeier, T.H., Wilson, J.T., Kampbell, D.H., Miller, R.N. and Hansen, J.E., 1995. Technical Protocol for Implementing Intrinsic Remediation with Long-Term Monitoring for Natural Attenuation of Fuel Contamination Dissolved in Groundwater. U.S. Air Force Center for Environmental Excellence, Technology Transfer Division, Brooks Air Force Base, San Antonio, Texas.]</ref><ref name="Newell1996">Newell, C.J., Gonzales, J., and McLeod, R., 1996.  BIOSCREEN natural attenuation decision support system, U.S. Environmental Protection Agency. EPA/600/R-96/087. [http://www.environmentalrestoration.wiki/images/3/3e/Newell-1996-Bioscreen_Natural_Attenuation_Decision_Support_System.pdf Report pdf]</ref><ref name="NRC2000"/>).
 
 
 
[[File:Palaia-Article 1-Figure 1.PNG|500 px|thumbnail|right]]
 
Understanding of the gaseous expression of NSZD processes has recently improved via emerging research<ref name="Amos2005">Amos, R.T., Mayer, K.U., Bekins, B.A., Delin, G.N. and Williams, R.L., 2005. Use of dissolved and vapor‐phase gases to investigate methanogenic degradation of petroleum hydrocarbon contamination in the subsurface. Water Resources Research, 41(2). [http://dx.doi.org/10.1029/2004wr003433 doi: 10.1029/2004WR003433]</ref><ref name="Johnson2006"/><ref name="Sihota2011">Sihota, N.J., Singurindy, O. and Mayer, K.U., 2010. CO2-efflux measurements for evaluating source zone natural attenuation rates in a petroleum hydrocarbon contaminated aquifer. Environmental Science & Technology, 45(2), pp.482-488. [https://doi.org/10.1021/es1032585 doi: 10.1021/es1032585]</ref><ref name="McCoy2015"/>. A large advance occurred with respect to the significant amount of gases that can be produced because of anaerobic petroleum hydrocarbon biodegradation processes, predominantly methanogenesis<ref name="Amos2005"/>. Within the highly reduced saturated zone and overlying capillary fringe, methanogenesis occurs and generates CH<sub>4</sub> and CO<sub>2</sub>. Because of the relatively low solubility of CH<sub>4</sub>, it is subsequently transported up to the vadose zone along with smaller amounts of CO<sub>2</sub> and volatile organic compounds (VOCs). Within the vadose zone, LNAPL, CH<sub>4</sub>, and volatile hydrocarbons are anaerobically and aerobically biodegraded removing CH<sub>4</sub> and O<sub>2</sub> from the soil gas and adding CO<sub>2</sub>. We can conceptualize these vapor transport-related NSZD processes that are occurring at petroleum release sites (Fig. 1). In response to this improved understanding of NSZD, new monitoring methods have evolved to use stoichiometric conversion of the gaseous signatures left by NSZD.
 
 
 
In summary, NSZD processes occurring within the subsurface manifest themselves as changes to both the aqueous and gaseous phases. The NSZD rate can be best quantified by incorporating their petroleum hydrocarbon stoichiometric mass loss equivalents<ref name="ITRC2009"/>. The methods and procedures to do this are described below.
 
 
 
==Significance==
 
Quantifying site-specific NSZD rates is important for various reasons. First, NSZD forms an important part of the LNAPL conceptual site model (LCSM), the written and/or illustrative representation of the physical, chemical and biological processes that control the transport, migration and actual/potential impacts of contamination. Within the LCSM, NSZD establishes a remediation baseline and supports interpretation of contaminant delineation and concentration trends. NSZD measurements can be used to:
 
*Refine the LCSM with quantification of LNAPL loss rates
 
*Delineate the LNAPL footprint using vadose zone indicators of biodegradation
 
*Support estimates of remedial timeframes
 
*Assess LNAPL stability through application of a mass balance of losses and measured mobile LNAPL flux<ref>Mahler, N., Sale, T. and Lyverse, M., 2012. A mass balance approach to resolving LNAPL stability. Groundwater, 50(6), pp.861-871.[http://dx.doi.org/10.1111/j.1745-6584.2012.00949.x doi: 10.1111/j.1745-6584.2012.00949.x]</ref>
 
Measured NSZD rates can also form the basis for remediation technology selection, design, and optimization. For example:
 
*Comparing LNAPL mass removal rates from NSZD to other future potential remedial actions
 
*Supporting a cost/benefit analysis of future remediation by evaluating the value of additional remediation compared to NSZD
 
*Evaluating remedial progress via periodic NSZD measurements during static, re-equilibration periods in areas of residual hydrocarbons during an active remediation program
 
*Using NSZD rates as an endpoint for active remediation
 
  
Throughout the remediation life cycle, measured NSZD rates can be used for a variety of decision-making purposes, ranging from technology selection to system shutdown or site closure.
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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>
  
==Measuring the NSZD Aqueous Expression==
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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).
NSZD is quantified by summing the petroleum hydrocarbon stoichiometric equivalent of biodegradation that expresses itself by changes in both the aqueous (soluble) and gaseous (vapor) phases<ref name="ITRC2009"/>. This section covers the aqueous component.
 
Within the saturated zone, aerobic respiration, denitrification, sulfate reduction, iron and manganese reduction, and methanogenesis each support hydrocarbon degradation and LNAPL mass loss. For example, nitrate, iron, sulfate, and manganese reduction are some of the representative reactions for each process (Table 1). These processes manifest themselves as decreases in dissolved electron acceptor concentrations and production of soluble byproducts such as ferrous iron and dissolved CH<sub>4</sub> and carbon dioxide (CO<sub>2</sub>). The soluble or aqueous contribution to NSZD can be estimated through stoichiometric conversion of the mass of electron acceptor loss and byproduct formation<ref name="Wiedemeier1995"/><ref name="NRC2000"/>). Because these estimates can be made using conventional groundwater sampling and analytical methods, the saturated zone component of NSZD is relatively well understood and well-established procedures have been in place for over 20 years to monitor the NSZD process.
 
[[File:Palaia-Article 1-Table 1.PNG|900px|thumbnail|center|Table 1. Terminal Electron Accepting Processes Associated with the Aqueous Expression of NSZD (for decane, excerpt from Johnson et al., 2006<ref name="Johnson2006"/>)]]
 
  
The aqueous contribution to NSZD, historically known as the microbiological natural attenuation rate or assimilative capacity, is typically calculated using a mass budgeting approach<ref name="NRC2000"/>. The mass budgeting approach estimates dissolved hydrocarbon constituent losses within the saturated zone based on changes in the aforementioned electron acceptors and byproducts across transects through the hydrocarbon plume that spans upgradient and downgradient areas. Changes in concentrations for each process are stoichiometrically converted to hydrocarbon losses using the coefficients in Table 1. Groundwater models such as BIOSCREEN combine this mass budgeting approach with an advection dispersion model<ref name="Newell1996"/>.  
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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"/>.
  
==Measuring the NSZD Gaseous Expression==
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{| class="wikitable" style="float: right; text-align: center; margin-left: auto; margin-right: auto;"
Current NSZD practice is to evaluate the petroleum hydrocarbon stoichiometric equivalent of biodegradation in both the aqueous phase and gaseous (vapor) phase<ref name="ITRC2009"/>. This section covers the gaseous component.
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|+ 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
 +
|-
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| Mortar || RDX || <0.04 – 2,400 || 1.7 || 441
 +
|-
 +
| Artillery || RDX || <0.04 – 170 || <0.04 || 454
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|-
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| colspan="5" style="text-align: left;" | '''Incremental Samples*'''
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|-
 +
| Artillery FP || 2,4-DNT || 0.60 – 1.4 || 0.92 || 26
 +
|-
 +
| Bombing || TNT || 13 – 17 || 14 || 17
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|-
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| Artillery/Bombing || RDX || 3.9 – 9.4 || 4.8 || 38
 +
|-
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| Thermal Treatment || HMX || 3.96 – 4.26 || 4.16 || 4
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|-
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| colspan="5" style="text-align: left; background-color: white;" | * For incremental samples, 30-100 increments and 3-10 replicate samples were collected.
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|}
  
At one site, the gaseous expression of NSZD has been shown to account for >70% of the hydrocarbon biodegradation that occurs in the subsurface<ref>Molins, S., Mayer, K.U., Amos, R.T. and Bekins, B.A., 2010. Vadose zone attenuation of organic compounds at a crude oil spill site - Interactions between biogeochemical reactions and multicomponent gas transport. Journal of Contaminant Hydrology, 112(1), pp.15-29. [http://dx.doi.org/10.1016/j.jconhyd.2009.09.002 doi: 10.1016/j.jconhyd.2009.09.002]</ref>; <ref>Crystal Ng, G.H., Bekins, B.A., Cozzarelli, I.M., Baedecker, M.J., Bennett, P.C., Amos, R.T. and Herkelrath, W.N., 2015. Reactive transport modeling of geochemical controls on secondary water quality impacts at a crude oil spill site near Bemidji, MN. Water Resources Research. [http://dx.doi.org/10.1002/2015wr016964 doi:10.1002/2015WR016964]</ref>. Three methods to monitor the vapor transport-related portion of NSZD are currently available and widely used. These are the gradient, passive flux trap, and dynamic closed chamber (DCC) methods elaborated on below. Method choice for a particular project is a site-specific judgment based on data quality, objectives, and site conditions.  
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==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<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.
 +
[[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]]
  
New NSZD monitoring methods continue to emerge, including an approach that uses thermal gradients <ref>Sweeney, R.E. and Ririe, G.T., 2014. Temperature as a tool to evaluate aerobic biodegradation in hydrocarbon contaminated soil. Groundwater Monitoring & Remediation, 34(3), pp.41-50. [http://onlinelibrary.wiley.com/wol1/doi/10.1111/gwmr.12064/abstract doi:10.1111/gwmr.12064]</ref><ref>Warren, E. and Bekins, B.A., 2015. Relating subsurface temperature changes to microbial activity at a crude oil-contaminated site. Journal of Contaminant Hydrology, 182, pp.183-193. [http://dx.doi.org/10.1016/j.jconhyd.2015.09.007 doi:10.1016/j.jconhyd.2015.09.007]</ref>. Due to their limited applications, however, these emerging methods are not discussed herein.
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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.
  
===Gradient Method===
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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)]]
The gradient method uses oxygen or CO<sub>2</sub> concentration profiles in soil gas and select soil properties (e.g., effective soil gas diffusion coefficients) to estimate the flux of gases through the vadose zone using Fick’s First Law. The change in concentration of these gases with depth within un-impacted soil above the petroleum hydrocarbons is used as a basis for estimating the flux using Equation 1.  
 
  
<div align="center">[[File:Palaia-Article 1-Equation 1.PNG]]</div>
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==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<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.
  
Where '''fraction here''' is the effective diffusion coefficient of the gas of interest in the vadose zone soils and '''fraction here''' is the vertical concentration gradient of the gas being used to estimate NSZD rates. The gas flux is then stoichiometrically converted to an NSZD rate. The gradient method was the first published method to estimate NSZD<ref name="Johnson2006"/>.
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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>]]
  
A typical gradient method NSZD monitoring setup primarily includes a nested set of soil vapor probes installed above the LNAPL-impacted soils (Fig. 2). Soil gas samples are collected from the probes using industry-standard procedures and analyzed using a field landfill gas meter (e.g., LANDTEC GEM 2000). The data can then be analyzed using existing software such as Microsoft Excel.  
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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.
  
===Passive Flux Trap===
+
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>.
A passive flux trap is a flow-through, static chamber fitted with a chemical trap that has historically been used to measure soil-surface CO<sub>2</sub> efflux<ref>Humfeld, H. 1930. A Method for Measuring Carbon Dioxide Evolution from Soil. Soil Science, Vol. 30(1), pp: 1-12.</ref>. The passive flux trap method was recently adapted for NSZD monitoring<ref name="McCoy2015"/> and subsequently commercialized and further refined by E-Flux, LLC in Fort Collins, Colorado. The E-Flux CO<sub>2</sub> trap employs the use of a dual-sorbent design to collect CO<sub>2</sub> leaving the subsurface (Fig. 3). The traps are installed in the shallow ground surface (i.e., 1–3 inches deep) and left in place for a 1–2 week timeframe. Over this time, CO<sub>2</sub> derived from LNAPL degradation (i.e., fossil fuel-derived CO<sub>2</sub>) migrating upward from the subsurface to the atmosphere is collected inside the receiver pipe by a bottom caustic sorbent element. An upper sorbent element captures atmospheric CO<sub>2</sub> (i.e., modern CO<sub>2</sub>) to avoid cross-contamination of the lower sorbent element, which is solely used for the NSZD estimate. The trap is deployed for a period of time that does not allow for either the top or bottom elements to become saturated with CO<sub>2</sub>. After the deployment period, the trap is retrieved and shipped to a laboratory for analysis of CO<sub>2</sub>. The CO<sub>2</sub> efflux is estimated by dividing the trip blank-corrected mass of CO<sub>2</sub> sorbed on the lower element by the deployment duration and the cross sectional area of the received pipe.  
 
[[File:Palaia-Article 1-Figure 2.PNG|450px|thumbnail|left|Figure 2. Schematic of a Typical Gradient Method Monitoring Setup (excerpt from Johnson et al., 2006<ref name="Johnson2006"/>).]]
 
[[File:Palaia-Article 1-Figure 3.PNG|550px|thumbnail|center|Figure 3. Schematic (left) and Photo (right) of a Passive CO2 Flux Trap (Used with permission from E-Flux, LLC. [http://www.soilgasflux.com Soil Gas Flux])]]
 
  
 +
==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.
  
===Dynamic Closed Chamber (DCC) Method===
+
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.
[[File:Palaia-Article 1-Figure 4.PNG|500px|thumbnail|right]]
 
A DCC system is an active, specially adapted, direct measurement approach to estimate soil gas efflux at the ground surface. It pumps a small, closed loop circulation of air between a chamber set on a soil collar shallowly embedded in the ground surface and an external non-destructive gas analyzer that monitors the increase in CO<sub>2</sub> concentration. To minimize errors associated with pressure differential inside and outside of the chamber, it is fitted with an engineered vent. DCC has been demonstrated to be a consistent efflux measurement method and used as reference for comparison to others<ref>Norman, J.M., Kucharik, C.J., Gower, S.T., Baldocchi, D.D., Crill, P.M., Rayment, M., Savage, K. and Strieglfi, R.G., 1997. A comparison of six methods for measuring soil-surface carbon dioxide fluxes. Journal of Geophysical Research, 102(D24), pp.28-771. [http://dx.doi.org/10.1029/97jd01440 doi: 10.1029/97JD01440]</ref>. The DCC has been used primarily for ecological carbon monitoring purposes and was recently was adapted for NSZD monitoring<ref name="Sihota2011"/>. Figure 4 shows an example DCC system, the LI-COR® 8100A automated soil flux system (LI-COR® BioSciences, Inc., Lincoln, Nebraska), and its typical setup for NSZD monitoring.
 
  
Using an internal pump, the DCC system circulates vapor that has accumulated within the chamber through a closed loop. Through continuous circulation and in-line measurement of the CO<sub>2</sub> concentration by the non-destructive IRGA, the temporal increase in CO<sub>2</sub> is recorded. The CO<sub>2</sub> efflux is estimated using a curve fitting routine on the time series CO<sub>2</sub> concentration data and dividing the results by the cross sectional area of the soil collar. The DCC collects rapid CO<sub>2</sub> efflux measurements over a period of approximately 2 minutes. A series of multiple measurements are typically recorded during each field event. A long-term DCC system is also commercially available for automated repeated measurement programs<ref>Sihota, N.J., Trost, J.J., Bekins, B.A., Berg, A., Delin, G.N., Mason, B., Warren, E. and Mayer, K.U., 2016. Seasonal Variability in Vadose Zone Biodegradation at a Crude Oil Pipeline Rupture Site. Vadose Zone Journal,15(5). [https://doi.org/10.2136/vzj2015.09.0125 doi:10.2136/vzj2015.09.0125]</ref><ref>LI-COR Chambers. 2016. Accessed by https://www.licor.com/env/products/soil_flux/chambers.html. October 2016.[http://www.environmentalrestoration.wiki/images/e/e7/LI-COR-2016_Webpage.pdf Report pdf]</ref>).  
+
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).
  
==Gaseous Flux Background Correction==
+
<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>
The gaseous expression of NSZD is complicated by concurrent, non-petroleum related processes that also consume O<sub>2</sub> and create CO<sub>2</sub><ref>Rochette, P. and Hutchinson, G.L., 2005. Measurement of soil respiration in situ: chamber techniques. Publications from USDA-ARS / UNL Faculty. Paper 1379 [http://www.environmentalrestoration.wiki/images/6/6d/Rochette-2005-Soil_Respiration.pdf Report pdf]</ref>. These “background” processes include contributions from plant roots and microbes present in surficial and deeper soils containing natural organic matter. Therefore, correction is needed to subtract these effects prior to using the data from the gradient method and the two CO<sub>2</sub> efflux methods (i.e., trap and DCC) for NSZD estimates. Options to eliminate the gaseous contributions of non-petroleum related sources include:
+
<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>
*Install measurement locations in a nearby uncontaminated setting with similar surface and subsurface conditions. Calculation of NSZD rates using this approach involves subtracting the gaseous flux measured at the background location from the total flux at each survey location atop the LNAPL footprint.
+
<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>
*Use radiocarbon-14 (<sup>14</sup>C) analysis on the CO<sub>2</sub> collected from either the soil gas probes (gradient method) or the passive flux traps. The use of <sup>14</sup>C provides an alternative, more accurate means to isolate the NSZD-derived CO<sub>2</sub> efflux without the need to monitor outside areas. Background correction using <sup>14</sup>C is detailed in Sihota and Mayer (2012)<ref>Sihota, N.J. and Mayer, K.U., 2012. Characterizing vadose zone hydrocarbon biodegradation using carbon dioxide effluxes, isotopes, and reactive transport modeling. Vadose Zone Journal, 11(4). [https://doi.org/10.2136/vzj2011.0204 doi:10.2136/vzj2011.0204]</ref> and McCoy et al. (2014)<ref name="McCoy2015"/>.
+
<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>
  
==Converting Gaseous Flux to an NSZD Rate==
+
==Analysis==
After elimination of gaseous effects due to non-petroleum processes, the corrected flux results can then be used to estimate a NSZD rate. A NSZD rate is typically expressed as a hydrocarbon degradation rate per unit area in a unit such as grams per square meter per day (g/m<sup>2</sup>/d). Using O<sub>2</sub> or CO<sub>2</sub> flux input, the NSZD rate is calculated by multiplying the background corrected gas flux, typically expressed as micromoles per square meter per second (mol/m<sup>2</sup>/s), by the molar ratio of hydrocarbon degraded in a representative mineralization reaction as shown for octane on Equation 2;
+
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.
  
<div align="center">[[File:Palaia-Article 1-Equation 2.PNG]]</div>  
+
{| class="wikitable" style="float: center; text-align: center; margin-left: auto; margin-right: auto;"
Stoichiometry is used to determine a mass-based NSZD rate from gaseous flux data. The mass-based unit can be converted to a volume-based unit, for example gallons per acre per year (gal/acre/yr), using the density of the predominant hydrocarbon at the site.
+
|+ 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>)
 
+
|-
If enough representative measurements are made across the lateral extent of the LNAPL footprint, then a site-wide estimate of NSZD can be made. Stated simply, a site-wide NSZD rate (in units of mass per time) can be estimated by multiplying a unit area NSZD rate by an estimated lateral area of the LNAPL source zone. If unit area NSZD rates have been estimated at multiple locations, each can be apportioned to a representative area and totaled to arrive at a site-wide value. Figure 5 shows an example of mapping of NSZD rates from multiple DCC measurements at a site from which the site-wide NSZD rate was estimated to be 500 gallons per year (gal/yr).
+
! rowspan="2" | Compound
 
+
! colspan="2" | Soil Reporting Limit (mg/kg)
==Limitations and Challenges==
+
|-
NSZD is occurring at most petroleum release sites, however, site-specific conditions will drive the magnitude of rates. For example, the presence of a “typical” gaseous expression of NSZD (Fig. 1) is contingent upon the presence of LNAPL and free exchange of atmospheric oxygen with the subsurface. If the site contains predominantly impervious ground cover, then NSZD processes will deviate from that described herein and procedures to measure it must be adapted accordingly. Many other site conditions such as low permeability soil layers, perching water or wet vadose zones, shallow water tables, and cold climates can also affect NSZD processes that must also be taken into account during the design of any NSZD monitoring plan.
+
! HPLC (8330)
[[File:Palaia-Article 1-Figure 5.PNG|thumbnail|center|600 px]]
+
! GC (8095)
 
+
|-
NSZD rates measured using the methods described above quantify total hydrocarbon mass loss and do not speciate loss or degradation rates of individual chemicals such as benzene or naphthalene from soil or LNAPL phases. Therefore, the use of NSZD data for assessment of remedial timeframe, if based on time to achieve cleanup criteria in groundwater for example, is limited. Current research is focused on correlating NSZD rates to better established remediation metrics such as LNAPL transmissivity and chemical-specific degradation rates. For example, '''Ng et al. (2016)''' developed a mass balance model that provides some insights on the contributions of various hydrocarbon constituent classes to the overall NSZD rate at a crude oil research site.
+
| HMX || 0.04 || 0.01
 
+
|-
Lastly, NSZD rates are variable. They can fluctuate daily with day/night and changes in weather conditions, seasonally in temperate and cold climates, and anthropogenically with surrounding land use. Additionally, each method has its own unique procedure and inherent assumptions, which make its measurement results difficult to compare with others.  
+
| RDX || 0.04 || 0.006
 
+
|-
Due to these limitations and challenges, NSZD monitoring must be performed with a firm understanding of the data objectives and use and a sound LCSM.
+
| [[Wikipedia: 1,3,5-Trinitrobenzene | TNB]] || 0.04 || 0.003
 
+
|-
==Summary==
+
| TNT || 0.04 || 0.002
NSZD is an important process that is occurring at most petroleum release sites. Measuring the rate of NSZD can be very helpful in implementing an effective remediation strategy at these sites. Several approaches to measuring and quantifying NSZD rates are now available. However, as with most environmental remediation techniques, it is equally important to be cognizant of and account for the limitations and challenges with the approach and its associated measurements.
+
|-
 +
| [[Wikipedia: 2,6-Dinitrotoluene | 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
 +
|-
 +
| [[Wikipedia: Dinitrobenzene | DNB ]] || 0.04 || 0.002
 +
|-
 +
| [[Wikipedia: Tetryl | Tetryl ]]  || 0.04 || 0.01
 +
|-
 +
| [[Wikipedia: Pentaerythritol tetranitrate | PETN ]] || 0.2 || 0.016
 +
|}
  
 
==References==
 
==References==
 
 
<references/>
 
<references/>
  
 
==See Also==
 
==See Also==
 +
*[https://itrcweb.org/ Interstate Technology and Regulatory Council]
 +
*[http://www.hawaiidoh.org/tgm.aspx Hawaii Department of Health]
 +
*[http://envirostat.org/ Envirostat]

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