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      Explosive detonation causes an increase in soil porosity leading to increased TNT transformation

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          Abstract

          Explosives are a common soil contaminant at a range of sites, including explosives manufacturing plants and areas associated with landmine detonations. As many explosives are toxic and may cause adverse environmental effects, a large body of research has targeted the remediation of explosives residues in soil. Studies in this area have largely involved spiking ‘pristine’ soils using explosives solutions. Here we investigate the fate of explosives present in soils following an actual detonation process and compare this to the fate of explosives spiked into ‘pristine’ undetonated soils. We also assess the effects of the detonations on the physical properties of the soils. Our scanning electron microscopy analyses reveal that detonations result in newly-fractured planes within the soil aggregates, and novel micro Computed Tomography analyses of the soils reveal, for the first time, the effect of the detonations on the internal architecture of the soils. We demonstrate that detonations cause an increase in soil porosity, and this correlates to an increased rate of TNT transformation and loss within the detonated soils, compared to spiked pristine soils. We propose that this increased TNT transformation is due to an increased bioavailability of the TNT within the now more porous post-detonation soils, making the TNT more easily accessible by soil-borne bacteria for potential biodegradation. This new discovery potentially exposes novel remediation methods for explosive contaminated soils where actual detonation of the soil significantly promotes subsequent TNT degradation. This work also suggests previously unexplored ramifications associated with high energy soil disruption.

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          Most cited references39

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          Three-Dimensional Quantification of Intra-Aggregate Pore-Space Features using Synchrotron-Radiation-Based Microtomography

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            Determination of nitroaromatic, nitramine, and nitrate ester explosives in soil by gas chromatography and an electron capture detector.

            M Walsh (2001)
            Hazardous waste site characterization, forensic investigations, and land mine detection are scenarios where soils may be collected and analyzed for traces of nitroaromatic, nitramine, and nitrate ester explosives. These thermally labile analytes are traditionally determined by high-performance liquid chromatography (HPLC); however, commercially available deactivated injection port liners and wide-bore capillary columns have made routine analysis by gas chromatography (GC) possible. The electron-withdrawing nitro group common to each of these explosives makes the electron capture detector (ECD) suitable for determination of low concentrations of explosives in soil, water, and air. GC-ECD and HPLC-UV concentration estimates of explosives residues in field-contaminated soils from hazardous waste sites were compared, and correlation (r>0.97) was excellent between the two methods of analysis for each of the compounds most frequently detected: 2,4,6-trinitrotoluene (TNT), hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX), 2,4-dinitrotoluene (2,4-DNT), 1,3-dinitrobenzene (1,3-DNB), 1,3,5-trinitrobenzene (TNB), and octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX). The analytes were extracted from soils with acetonitrile by 18 h of sonication in a cooled ultrasonic bath. Two soil-to-solvent ratios were evaluated: 2.00 g:10.00 ml and 25.0 g:50.0 ml. GC-ECD method detection limits were similar for the two soil-to-solvent ratios and were about 1 mug kg(-1) for the di- and trinitroaromatics, about 10 mug kg(-1) for the mono-nitroaromatics, 3 mug kg(-1) for RDX, 25 mug kg(-1) for HMX, and between 10 and 40 mug kg(-1) for the nitrate esters (nitroglycerine [NG] and pentaerythritol tetranitrate [PETN]). Spike recovery studies revealed artifacts introduced by the spiking procedure. Recoveries were low in some soils if the amount of soil spiked was large (25.0 g) compared to the volume of spike solution added (1.00 ml). Recoveries were close to 100% when 2.00-g soil samples were spiked with 1.00 ml of solution. Analytes most frequently found in soils collected near buried land mines were the microbial transformation products of TNT (2-amino-4,6-dinitrotoluene [2-Am-DNT] and 4-amino-2,6-dinitrotoluene [4-Am-DNT]), manufacturing impurities of TNT (2,4-DNT, 2,6-DNT, and 1,3-DNB), and TNT. The microbial reduction products of the isomers of DNT and of 1,3-DNB were also detected, but the ECD response to these compounds is poor.
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              Distribution and Fate of Military Explosives and Propellants in Soil: A Review

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                Author and article information

                Contributors
                Role: ConceptualizationRole: Formal analysisRole: InvestigationRole: MethodologyRole: Writing – original draftRole: Writing – review & editing
                Role: ConceptualizationRole: Formal analysisRole: InvestigationRole: MethodologyRole: SupervisionRole: Writing – review & editing
                Role: Formal analysisRole: MethodologyRole: Writing – review & editing
                Role: Formal analysisRole: ResourcesRole: SupervisionRole: Writing – review & editing
                Role: ConceptualizationRole: Funding acquisitionRole: InvestigationRole: MethodologyRole: SupervisionRole: Writing – review & editing
                Role: Editor
                Journal
                PLoS One
                PLoS ONE
                plos
                plosone
                PLoS ONE
                Public Library of Science (San Francisco, CA USA )
                1932-6203
                27 December 2017
                2017
                : 12
                : 12
                : e0189177
                Affiliations
                [1 ] Department of Chemistry, Curtin University, Perth, WA, Australia
                [2 ] Curtin Institute of Functional Molecules and Interfaces, Curtin University, Perth, WA, Australia
                [3 ] Centre for Anatomy and Human Identification, School of Science and Engineering, University of Dundee, Dundee, United Kingdom
                [4 ] The James Hutton Institute, Aberdeen, Scotland, United Kingdom
                [5 ] Forensic Science Laboratory, ChemCentre, Perth, WA, Australia
                The University of Sydney, AUSTRALIA
                Author notes

                Competing Interests: The authors have declared that no competing interests exist.

                Article
                PONE-D-17-00675
                10.1371/journal.pone.0189177
                5744939
                29281650
                b6822a47-d688-424d-a82e-2c1c0aac9b09
                © 2017 Yu et al

                This is an open access article distributed under the terms of the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original author and source are credited.

                History
                : 8 January 2017
                : 17 November 2017
                Page count
                Figures: 9, Tables: 0, Pages: 18
                Funding
                The author(s) received no specific funding for this work.
                Categories
                Research Article
                Physical Sciences
                Materials Science
                Materials by Attribute
                Explosives
                Tnt
                Physical Sciences
                Materials Science
                Materials by Attribute
                Explosives
                Research and Analysis Methods
                Microscopy
                Electron Microscopy
                Scanning Electron Microscopy
                Physical Sciences
                Materials Science
                Material Properties
                Porosity
                Biology and Life Sciences
                Ecology
                Community Ecology
                Ecological Remediation
                Ecology and Environmental Sciences
                Ecology
                Community Ecology
                Ecological Remediation
                Research and Analysis Methods
                Imaging Techniques
                Neuroimaging
                Computed Axial Tomography
                Biology and Life Sciences
                Neuroscience
                Neuroimaging
                Computed Axial Tomography
                Medicine and Health Sciences
                Diagnostic Medicine
                Diagnostic Radiology
                Tomography
                Computed Axial Tomography
                Research and Analysis Methods
                Imaging Techniques
                Diagnostic Radiology
                Tomography
                Computed Axial Tomography
                Medicine and Health Sciences
                Radiology and Imaging
                Diagnostic Radiology
                Tomography
                Computed Axial Tomography
                Engineering and Technology
                Equipment
                Laboratory Equipment
                Pipettes
                Biology and Life Sciences
                Biotechnology
                Applied Microbiology
                Biodegradation
                Biology and Life Sciences
                Microbiology
                Applied Microbiology
                Biodegradation
                Biology and Life Sciences
                Biotechnology
                Environmental Biotechnology
                Biodegradation
                Custom metadata
                Our data set is available at http://dx.doi.org/10.4225/06/59e6fba80564a.

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