Munitions Constituents - Alkaline Degradation - Revision history

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Jhurley: /* Principal of Operation */

2019-05-16T20:09:19Z

‎Principal of Operation

Jhurley: /* Aqueous Kinetics */

2019-05-16T19:55:32Z

‎Aqueous Kinetics

Jhurley: /* Performance in Soil Systems */

2019-05-16T19:45:45Z

‎Performance in Soil Systems

Jhurley: /* Performance in Soil Systems */

2019-05-16T19:42:50Z

‎Performance in Soil Systems

Jhurley: /* Principal of Operation */

2019-05-16T19:39:25Z

‎Principal of Operation

Jhurley: /* Ammunition Plant */

2019-05-16T19:32:18Z

‎Ammunition Plant

Jhurley at 19:27, 16 May 2019

2019-05-16T19:27:50Z

Show changes

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 *[[Munitions Constituents - Abiotic Reduction]]
 *[[Munitions Constituents - Composting]]
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 '''Key Resource(s)''':
-*[//www.enviro.wiki/images/e/e2/2011_-_Johnson_-_Management_of_Munitions_Constituents_in_Soil.pdf  Management of Munitions Constituents in Soil Using Alkaline Hydrolysis: A Guide for Practitioners]<ref name="Johnson2011">Johnson, J.L., Felt, D.R., Martin, W.A., Britto, R., Nestler, C.C. and Larson, S.L., 2011. Management of munitions constituents in soil using alkaline hydrolysis: A guide for practitioners (No. ERDC/EL-TR-11-16). Vicksburg, MS: U.S. Army Engineer Research and Development Center.[//www.enviro.wiki/images/e/e2/2011_-_Johnson_-_Management_of_Munitions_Constituents_in_Soil.pdf  Report.pdf]</ref>
+*[//www.enviro.wiki/images/e/e2/2011_-_Johnson_-_Management_of_Munitions_Constituents_in_Soil.pdf Management of Munitions Constituents in Soil Using Alkaline Hydrolysis: A Guide for Practitioners]<ref name="Johnson2011">Johnson, J.L., Felt, D.R., Martin, W.A., Britto, R., Nestler, C.C. and Larson, S.L., 2011. Management of munitions constituents in soil using alkaline hydrolysis: A guide for practitioners (No. ERDC/EL-TR-11-16). Vicksburg, MS: U.S. Army Engineer Research and Development Center.[//www.enviro.wiki/images/e/e2/2011_-_Johnson_-_Management_of_Munitions_Constituents_in_Soil.pdf Report.pdf]</ref>
 ==Principal of Operation==
 [[wikipedia: Alkaline hydrolysis | Alkaline hydrolysis]] reactions involve the aqueous interaction of added OH<sup>-</sup> ions with dissolved organic compounds. Degradation of nitroaromatics (i.e., TNT and DNT) is hypothesized to occur through formation of a Meisenheimer complex or TNT anion<ref>Saupe, A., Garvens, H.J. and Heinze, L., 1998. Alkaline hydrolysis of TNT and TNT in soil followed by thermal treatment of the hydrolysates. Chemosphere, 36(8), pp.1725-1744. [https://doi.org/10.1016/S0045-6535(97)10063-7 doi: 10.1016/S0045-6535(97)10063-7]</ref><ref>Salter-Blanc, A.J., Bylaska, E.J., Ritchie, J.J. and Tratnyek, P.G., 2013. Mechanisms and kinetics of alkaline hydrolysis of the energetic nitroaromatic compounds 2, 4, 6-trinitrotoluene (TNT) and 2, 4-dinitroanisole (DNAN). Environmental science & technology, 47(13), pp.6790-6798. [https://doi.org/10.1021/es304461t doi:10.1021/es304461t]</ref>. Initial denitration of nitroamines (i.e., RDX, HMX, and CL-20) by OH<sup>-</sup> is thought to cause molecular instability leading to ring cleavage, followed by spontaneous decomposition <ref>Jones, W.H., 1954. Mechanism of the Homogeneous Alkaline Decomposition of Cyclotrimethylenetrinitramine: Kinetics of Consecutive Second-and First-order Reactions. A Polarographic Analysis for Cyclotrimethylenetrinitramine1. Journal of the American Chemical Society, 76(3), pp.829-835. [https://doi.org/10.1021/ja01632a058 doi: 10.1021/ja01632a058]</ref><ref name="Balakrishnan2003">Balakrishnan, V.K., Halasz, A. and Hawari, J., 2003. Alkaline hydrolysis of the cyclic nitramine explosives RDX, HMX, and CL-20: New insights into degradation pathways obtained by the observation of novel intermediates. Environmental Science & Technology, 37(9), pp.1838-1843. [https://doi.org/10.1021/es020959h doi: 10.1021/es020959h]</ref>. This degradation pathway is supported by observations of nitrite and formate production during the alkaline decomposition of nitramines<ref name="Hwang2006">Hwang, S., Felt, D.R., Bouwer, E.J., Brooks, M.C., Larson, S.L. and Davis, J.L., 2006. Remediation of RDX-contaminated water using alkaline hydrolysis. Journal of Environmental Engineering, 132(2), pp.256-262. [https://doi.org/10.1061/(ASCE)0733-9372(2006)132:2(256) doi: 10.1061/(ASCE)0733-9372(2006)132:2(256)]</ref><ref name="heilmann1996">Heilmann, H.M., Wiesmann, U. and Stenstrom, M.K., 1996. Kinetics of the alkaline hydrolysis of high explosives RDX and HMX in aqueous solution and adsorbed to activated carbon. Environmental Science & Technology, 30(5), pp.1485-1492. [https://doi.org/10.1021/es9504101 doi: 10.1021/es9504101]</ref>.
-The terminal degradation products of alkaline hydrolysis are commonly formate, formaldehyde, nitrate, nitrite, and nitrous oxide. At pH greater than 11, TNT degrades readily to formate and nitrate, but at lower pH it tends to polymerize<ref>Felt, D.R., Nestler, C.C., Davis, J.L. and Larson, S.L., 2007. Potential for biodegradation of the alkaline hydrolysis end products of TNT and RDX (No. ERDC/EL-TR-07-25). Engineer Research and Development Center Vicksburg, MS. [//www.enviro.wiki/images/5/5b/2001-Felt-_Potential_for_biodegradatio_of_the_alkaline_hydrolysis.pdf  Report.pdf]</ref>.
+The terminal degradation products of alkaline hydrolysis are commonly formate, formaldehyde, nitrate, nitrite, and nitrous oxide. At pH greater than 11, TNT degrades readily to formate and nitrate, but at lower pH it tends to polymerize<ref>Felt, D.R., Nestler, C.C., Davis, J.L. and Larson, S.L., 2007. Potential for biodegradation of the alkaline hydrolysis end products of TNT and RDX (No. ERDC/EL-TR-07-25). Engineer Research and Development Center Vicksburg, MS. [//www.enviro.wiki/images/5/5b/2001-Felt-_Potential_for_biodegradatio_of_the_alkaline_hydrolysis.pdf Report.pdf]</ref>.
-Propellant residues have been studied less than secondary explosives, but studies have shown the insoluble [[wikipedia: Nitrocellulose | nitrocellulose]] matrix in some propellants to be rendered biodegradable under alkaline conditions<ref>Kenyon, W.O. and Gray, H.L., 1936. The Alkaline Decomposition of Cellulose Nitrate. I. Quantitative Studies1. Journal of The American Chemical Society, 58(8), pp.1422-1427. [https://doi.org/10.1021/ja01299a034 doi: 10.1021/ja01299a034]</ref><ref>Kim, B.J., Alleman, J.E. and Quivey, D.M., 1998. Alkaline hydrolysis/biodegradation of nitrocellulose fines (No. CERL-TR-98/65). Consstruction Engineering Researcg Lab (ARMY) Champaign, IL.[//www.enviro.wiki/images/9/95/1998-Kim-Alkline_Hydrolysis_Biodegradation_of_Nitrocellulose_Fines.pdf  Report.pdf]</ref>. Ultimately, alkaline material is neutralized over time by the natural buffering capacity of soil.
+Propellant residues have been studied less than secondary explosives, but studies have shown the insoluble [[wikipedia: Nitrocellulose | nitrocellulose]] matrix in some propellants to be rendered biodegradable under alkaline conditions<ref>Kenyon, W.O. and Gray, H.L., 1936. The Alkaline Decomposition of Cellulose Nitrate. I. Quantitative Studies1. Journal of The American Chemical Society, 58(8), pp.1422-1427. [https://doi.org/10.1021/ja01299a034 doi: 10.1021/ja01299a034]</ref><ref>Kim, B.J., Alleman, J.E. and Quivey, D.M., 1998. Alkaline hydrolysis/biodegradation of nitrocellulose fines (No. CERL-TR-98/65). Consstruction Engineering Researcg Lab (ARMY) Champaign, IL.[//www.enviro.wiki/images/9/95/1998-Kim-Alkline_Hydrolysis_Biodegradation_of_Nitrocellulose_Fines.pdf Report.pdf]</ref>. Ultimately, alkaline material is neutralized over time by the natural buffering capacity of soil.
 ==Aqueous Kinetics==
@@ Line 69: / Line 70: @@
 |13||25||27.7||25||Hwang, et al., 2006<ref name="Hwang2006" />
 |-
-|12||25||2.7||260||Gent, et al., 2010<ref name="gent2010">Gent, D.B., Johnson, J.L., Felt, D.R., O'Connor, G., Holland, E., May, S. and Larson, S.L., 2010. Laboratory demonstration of abiotic technologies for removal of RDX from a process waste stream (No. ERDC/EL-TR-10-8). Engineer Research and Development Center Vicksburg MS Environmental Lab. [[media:2010-Gent-laboratory_Demostration_of_abiotic_tech_for_removal_of_RDX.pdf| Report.pdf]]</ref>
+|12||25||2.7||260||Gent, et al., 2010<ref name="gent2010">Gent, D.B., Johnson, J.L., Felt, D.R., O'Connor, G., Holland, E., May, S. and Larson, S.L., 2010. Laboratory demonstration of abiotic technologies for removal of RDX from a process waste stream (No. ERDC/EL-TR-10-8). Engineer Research and Development Center Vicksburg MS Environmental Lab. [[Special:FilePath/2010-Gent-laboratory Demostration of abiotic tech for removal of RDX.pdf| Report.pdf]]</ref>
 |-
 |12.5||25||8.3||83||Gent, et al., 2010<ref name="gent2010" />
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 |-
 ! rowspan="4" |CL-20
-|10||25||8||87||Santiago, et al., 2007<ref name="Santigo2007">Santiago, L., Felt, D.R. and Davis, J.L., 2007. Chemical Remediation of an Ordnance-Related Compound: The Alkaline Hydrolysis of CL-20. Environmental Quality Technology Program (No. ERDC/EL-TR-07-18). Engineer Research and Development Center, Vicksburg, MS Environmental Lab. [//www.enviro.wiki/images/e/ef/2007-Santiago-chemical_remediation_of_an_ordnance_related_compound.pdf  Report.pdf]</ref>
+|10||25||8||87||Santiago, et al., 2007<ref name="Santigo2007">Santiago, L., Felt, D.R. and Davis, J.L., 2007. Chemical Remediation of an Ordnance-Related Compound: The Alkaline Hydrolysis of CL-20. Environmental Quality Technology Program (No. ERDC/EL-TR-07-18). Engineer Research and Development Center, Vicksburg, MS Environmental Lab. [//www.enviro.wiki/images/e/ef/2007-Santiago-chemical_remediation_of_an_ordnance_related_compound.pdf Report.pdf]</ref>
 |-
 |11||25||50.3||14||Santiago, et al., 2007<ref name="Santigo2007" />
@@ Line 102: / Line 103: @@
 Soil microcosm studies with 5% w/w calcium hydroxide and 50% w/w water observed half-lives for TNT, RDX, and HMX on the order of a day to a week, with degradation rates following the sequence of TNT > RDX > HMX, similar to the aqueous studies. Soil slurries using 2,4-DNT and the single amino substituted TNT degradation products (4A-2,6-DNT and 2A-4,6-DNT) also exhibited day to week-long half-lives at pH 11 and 12<ref name="emmrich1999" /><ref>Emmrich, M., 2001. Kinetics of the alkaline hydrolysis of important nitroaromatic co-contaminants of 2, 4, 6-trinitrotoluene in highly contaminated soils. Environmental Science & Technology, 35(5), pp.874-877. [https://doi.org/10.1021/es0014990 doi: 10.1021/es0014990 doi: 10.1021/es0014990]</ref>.
-A meso-scale soil treatability study was conducted using soils collected from two different hand grenade ranges<ref name="Larson2007">Larson, S.L., Davis, J.L., Martin, W.A., Felt, D.R., Nestler, C.C., Brandon, D.L., Fabian, G. and O'Connor, G., 2007. Grenade Range Management Using Lime for Metals Immobilization and Explosives Transformation Treatability Study (No. ERDC/EL-TR-07-5). Vicksburg, MS: U.S. Army Engineer Research and Development Center. [//www.enviro.wiki/images/a/a2/2007-Larson-grenade_Range_Management_Using_Lime_for_Metals_Immobilization.pdf  Report.pdf]</ref>. These soils were treated with a well-mixed application of hydrated lime, and migration of RDX was monitored by analyzing porewater concentrations in installed lysimeters over time (Figure 1). Overall, the reduction in RDX leaving the mesocosms as both leachate and runoff was greater than 90% with application of hydrated lime. The study authors also observed that alkaline amendments were able to fix metals contamination in place on hand grenade range soils.
+A meso-scale soil treatability study was conducted using soils collected from two different hand grenade ranges<ref name="Larson2007">Larson, S.L., Davis, J.L., Martin, W.A., Felt, D.R., Nestler, C.C., Brandon, D.L., Fabian, G. and O'Connor, G., 2007. Grenade Range Management Using Lime for Metals Immobilization and Explosives Transformation Treatability Study (No. ERDC/EL-TR-07-5). Vicksburg, MS: U.S. Army Engineer Research and Development Center. [//www.enviro.wiki/images/a/a2/2007-Larson-grenade_Range_Management_Using_Lime_for_Metals_Immobilization.pdf Report.pdf]</ref>. These soils were treated with a well-mixed application of hydrated lime, and migration of RDX was monitored by analyzing porewater concentrations in installed lysimeters over time (Figure 1). Overall, the reduction in RDX leaving the mesocosms as both leachate and runoff was greater than 90% with application of hydrated lime. The study authors also observed that alkaline amendments were able to fix metals contamination in place on hand grenade range soils.
 ==Field-Scale Performance Examples==
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 After one week, soil sampling was performed per site specific sampling protocol and analyzed for contaminants of concern, daughter products, and breakdown products.  If needed for soil with higher concentrations of explosives, caustic reagent was supplemented to maintain the pH at the 13.0 unit level.  Soil continued to be treated until TNT and DNT concentrations were below cleanup levels (57 mg/kg for TNT and 25.4 mg/kg for total DNTs).  Metals were also analyzed periodically and [[wikipedia: Toxicity characteristic leaching procedure | TCLP]] tests were performed per site treatment goals.  When needed on a small percentage of batches, denitrification of soil was performed to lower the nitrite end-product using citric acid as the pH reducer and carbon substrate. After complete treatment, the soil was transported back to the excavation.  ''In-situ'' treatment is performed in a similar way to ''ex-situ'' treatment using conventional equipment and prescribed quantities of chemical reagents.
-Some general heuristic guidelines are summarized in Figure 4. An active firing range requires treatment technologies that have minimal soil disturbance, requiring topical application of hydrated lime for most range applications. Therefore the fate of hydroxide (OH<sup>-</sup>) ions during transport through the soil is an important aspect of this proposed remediation technology. Studies performed by the agricultural and oil industries provide evidence of the transport limitations of hydroxide ions in soils, particularly in those soils with significant clay content <ref>Breit, V.S., Mayer, E.H. and Carmichael, J.D., 1979, January. An easily applied black oil model of caustic waterflooding. In SPE California Regional Meeting. Society of Petroleum Engineers. [https://doi.org/10.2118/7999-MS doi: 10.2118/7999-MS]</ref><ref>DeZabala, E.F., Vislocky, J.M., Rubin, E. and Radke, C.J., 1982. A chemical theory for linear alkaline flooding. Society of Petroleum Engineers Journal, 22(02), pp.245-258. [https://doi.org/10.2118/8997-PA [https://doi.org/10.2118/8997-PA doi: 10.2118/8997-PA]</ref><ref>Somerton, W. H., and C. J. Radke. 1980. Roles of clays in the enhanced recovery of petroleum. Proceedings of the first joint SPE/DOE symposium on enhance oil recovery. Society of Petroleum Engineers.[//www.enviro.wiki/images/9/98/1980-_Somerton-_Role_of_Clays_in_the_enhanced_reovery_of_petroleum.pdf  Report.pdf]</ref><ref>Smith, C.J., Peoples, M.B., Keerthisinghe, G., James, T.R., Garden, D.L. and Tuomi, S.S., 1994. Effect of surface applications of lime, gypsum and phosphogypsum on the alleviating of surface and subsurface acidity in a soil under pasture. Soil Research, 32(5), pp.995-1008. [https://doi.org/10.1071/SR9940995 doi: 10.1071/SR9940995]</ref>.
+Some general heuristic guidelines are summarized in Figure 4. An active firing range requires treatment technologies that have minimal soil disturbance, requiring topical application of hydrated lime for most range applications. Therefore the fate of hydroxide (OH<sup>-</sup>) ions during transport through the soil is an important aspect of this proposed remediation technology. Studies performed by the agricultural and oil industries provide evidence of the transport limitations of hydroxide ions in soils, particularly in those soils with significant clay content <ref>Breit, V.S., Mayer, E.H. and Carmichael, J.D., 1979, January. An easily applied black oil model of caustic waterflooding. In SPE California Regional Meeting. Society of Petroleum Engineers. [https://doi.org/10.2118/7999-MS doi: 10.2118/7999-MS]</ref><ref>DeZabala, E.F., Vislocky, J.M., Rubin, E. and Radke, C.J., 1982. A chemical theory for linear alkaline flooding. Society of Petroleum Engineers Journal, 22(02), pp.245-258. [https://doi.org/10.2118/8997-PA [https://doi.org/10.2118/8997-PA doi: 10.2118/8997-PA]</ref><ref>Somerton, W. H., and C. J. Radke. 1980. Roles of clays in the enhanced recovery of petroleum. Proceedings of the first joint SPE/DOE symposium on enhance oil recovery. Society of Petroleum Engineers.[//www.enviro.wiki/images/9/98/1980-_Somerton-_Role_of_Clays_in_the_enhanced_reovery_of_petroleum.pdf Report.pdf]</ref><ref>Smith, C.J., Peoples, M.B., Keerthisinghe, G., James, T.R., Garden, D.L. and Tuomi, S.S., 1994. Effect of surface applications of lime, gypsum and phosphogypsum on the alleviating of surface and subsurface acidity in a soil under pasture. Soil Research, 32(5), pp.995-1008. [https://doi.org/10.1071/SR9940995 doi: 10.1071/SR9940995]</ref>.
 ==References==

@@ Line 9: / Line 9: @@
 *[[Munitions Constituents - Composting]]
-'''CONTRIBUTOR(S):''' [[Jared Johnson]]
 '''Key Resource(s)''':

← Older revision		Revision as of 03:08, 26 April 2022
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	*[[Munitions Constituents]]		*[[Munitions Constituents]]
		+	*[[Munitions Constituents - Abiotic Reduction]]
	*[[Munitions Constituents - Composting]]		*[[Munitions Constituents - Composting]]

@@ Line 15: / Line 15: @@
 ==Principal of Operation==
-Alkaline hydrolysis reactions involve the aqueous interaction of added OH<sup>-</sup> ions with dissolved organic compounds. Degradation of nitroaromatics (i.e., TNT and DNT) is hypothesized to occur through formation of a Meisenheimer complex or TNT anion<ref>Saupe, A., Garvens, H.J. and Heinze, L., 1998. Alkaline hydrolysis of TNT and TNT in soil followed by thermal treatment of the hydrolysates. Chemosphere, 36(8), pp.1725-1744. [https://doi.org/10.1016/S0045-6535(97)10063-7 doi: 10.1016/S0045-6535(97)10063-7]</ref><ref>Salter-Blanc, A.J., Bylaska, E.J., Ritchie, J.J. and Tratnyek, P.G., 2013. Mechanisms and kinetics of alkaline hydrolysis of the energetic nitroaromatic compounds 2, 4, 6-trinitrotoluene (TNT) and 2, 4-dinitroanisole (DNAN). Environmental science & technology, 47(13), pp.6790-6798. [https://doi.org/10.1021/es304461t doi:10.1021/es304461t]</ref>. Initial denitration of nitroamines (i.e., RDX, HMX, and CL-20) by OH<sup>-</sup> is thought to cause molecular instability leading to ring cleavage, followed by spontaneous decomposition <ref>Jones, W.H., 1954. Mechanism of the Homogeneous Alkaline Decomposition of Cyclotrimethylenetrinitramine: Kinetics of Consecutive Second-and First-order Reactions. A Polarographic Analysis for Cyclotrimethylenetrinitramine1. Journal of the American Chemical Society, 76(3), pp.829-835. [https://doi.org/10.1021/ja01632a058 doi: 10.1021/ja01632a058]</ref><ref name="Balakrishnan2003">Balakrishnan, V.K., Halasz, A. and Hawari, J., 2003. Alkaline hydrolysis of the cyclic nitramine explosives RDX, HMX, and CL-20: New insights into degradation pathways obtained by the observation of novel intermediates. Environmental Science & Technology, 37(9), pp.1838-1843. [https://doi.org/10.1021/es020959h doi: 10.1021/es020959h]</ref>. This degradation pathway is supported by observations of nitrite and formate production during the alkaline decomposition of nitramines<ref name="Hwang2006">Hwang, S., Felt, D.R., Bouwer, E.J., Brooks, M.C., Larson, S.L. and Davis, J.L., 2006. Remediation of RDX-contaminated water using alkaline hydrolysis. Journal of Environmental Engineering, 132(2), pp.256-262. [https://doi.org/10.1061/(ASCE)0733-9372(2006)132:2(256) doi: 10.1061/(ASCE)0733-9372(2006)132:2(256)]</ref><ref name="heilmann1996">Heilmann, H.M., Wiesmann, U. and Stenstrom, M.K., 1996. Kinetics of the alkaline hydrolysis of high explosives RDX and HMX in aqueous solution and adsorbed to activated carbon. Environmental Science & Technology, 30(5), pp.1485-1492. [https://doi.org/10.1021/es9504101 doi: 10.1021/es9504101]</ref>.
+[[wikipedia: Alkaline hydrolysis | Alkaline hydrolysis]] reactions involve the aqueous interaction of added OH<sup>-</sup> ions with dissolved organic compounds. Degradation of nitroaromatics (i.e., TNT and DNT) is hypothesized to occur through formation of a Meisenheimer complex or TNT anion<ref>Saupe, A., Garvens, H.J. and Heinze, L., 1998. Alkaline hydrolysis of TNT and TNT in soil followed by thermal treatment of the hydrolysates. Chemosphere, 36(8), pp.1725-1744. [https://doi.org/10.1016/S0045-6535(97)10063-7 doi: 10.1016/S0045-6535(97)10063-7]</ref><ref>Salter-Blanc, A.J., Bylaska, E.J., Ritchie, J.J. and Tratnyek, P.G., 2013. Mechanisms and kinetics of alkaline hydrolysis of the energetic nitroaromatic compounds 2, 4, 6-trinitrotoluene (TNT) and 2, 4-dinitroanisole (DNAN). Environmental science & technology, 47(13), pp.6790-6798. [https://doi.org/10.1021/es304461t doi:10.1021/es304461t]</ref>. Initial denitration of nitroamines (i.e., RDX, HMX, and CL-20) by OH<sup>-</sup> is thought to cause molecular instability leading to ring cleavage, followed by spontaneous decomposition <ref>Jones, W.H., 1954. Mechanism of the Homogeneous Alkaline Decomposition of Cyclotrimethylenetrinitramine: Kinetics of Consecutive Second-and First-order Reactions. A Polarographic Analysis for Cyclotrimethylenetrinitramine1. Journal of the American Chemical Society, 76(3), pp.829-835. [https://doi.org/10.1021/ja01632a058 doi: 10.1021/ja01632a058]</ref><ref name="Balakrishnan2003">Balakrishnan, V.K., Halasz, A. and Hawari, J., 2003. Alkaline hydrolysis of the cyclic nitramine explosives RDX, HMX, and CL-20: New insights into degradation pathways obtained by the observation of novel intermediates. Environmental Science & Technology, 37(9), pp.1838-1843. [https://doi.org/10.1021/es020959h doi: 10.1021/es020959h]</ref>. This degradation pathway is supported by observations of nitrite and formate production during the alkaline decomposition of nitramines<ref name="Hwang2006">Hwang, S., Felt, D.R., Bouwer, E.J., Brooks, M.C., Larson, S.L. and Davis, J.L., 2006. Remediation of RDX-contaminated water using alkaline hydrolysis. Journal of Environmental Engineering, 132(2), pp.256-262. [https://doi.org/10.1061/(ASCE)0733-9372(2006)132:2(256) doi: 10.1061/(ASCE)0733-9372(2006)132:2(256)]</ref><ref name="heilmann1996">Heilmann, H.M., Wiesmann, U. and Stenstrom, M.K., 1996. Kinetics of the alkaline hydrolysis of high explosives RDX and HMX in aqueous solution and adsorbed to activated carbon. Environmental Science & Technology, 30(5), pp.1485-1492. [https://doi.org/10.1021/es9504101 doi: 10.1021/es9504101]</ref>.
 The terminal degradation products of alkaline hydrolysis are commonly formate, formaldehyde, nitrate, nitrite, and nitrous oxide. At pH greater than 11, TNT degrades readily to formate and nitrate, but at lower pH it tends to polymerize<ref>Felt, D.R., Nestler, C.C., Davis, J.L. and Larson, S.L., 2007. Potential for biodegradation of the alkaline hydrolysis end products of TNT and RDX (No. ERDC/EL-TR-07-25). Engineer Research and Development Center Vicksburg, MS. [//www.enviro.wiki/images/5/5b/2001-Felt-_Potential_for_biodegradatio_of_the_alkaline_hydrolysis.pdf  Report.pdf]</ref>.
-Propellant residues have been studied less than secondary explosives, but studies have shown the insoluble nitrocellulose matrix in some propellants to be rendered biodegradable under alkaline conditions<ref>Kenyon, W.O. and Gray, H.L., 1936. The Alkaline Decomposition of Cellulose Nitrate. I. Quantitative Studies1. Journal of The American Chemical Society, 58(8), pp.1422-1427. [https://doi.org/10.1021/ja01299a034 doi: 10.1021/ja01299a034]</ref><ref>Kim, B.J., Alleman, J.E. and Quivey, D.M., 1998. Alkaline hydrolysis/biodegradation of nitrocellulose fines (No. CERL-TR-98/65). Consstruction Engineering Researcg Lab (ARMY) Champaign, IL.[//www.enviro.wiki/images/9/95/1998-Kim-Alkline_Hydrolysis_Biodegradation_of_Nitrocellulose_Fines.pdf  Report.pdf]</ref>. Ultimately, alkaline material is neutralized over time by the natural buffering capacity of soil.
+Propellant residues have been studied less than secondary explosives, but studies have shown the insoluble [[wikipedia: Nitrocellulose | nitrocellulose]] matrix in some propellants to be rendered biodegradable under alkaline conditions<ref>Kenyon, W.O. and Gray, H.L., 1936. The Alkaline Decomposition of Cellulose Nitrate. I. Quantitative Studies1. Journal of The American Chemical Society, 58(8), pp.1422-1427. [https://doi.org/10.1021/ja01299a034 doi: 10.1021/ja01299a034]</ref><ref>Kim, B.J., Alleman, J.E. and Quivey, D.M., 1998. Alkaline hydrolysis/biodegradation of nitrocellulose fines (No. CERL-TR-98/65). Consstruction Engineering Researcg Lab (ARMY) Champaign, IL.[//www.enviro.wiki/images/9/95/1998-Kim-Alkline_Hydrolysis_Biodegradation_of_Nitrocellulose_Fines.pdf  Report.pdf]</ref>. Ultimately, alkaline material is neutralized over time by the natural buffering capacity of soil.
 ==Aqueous Kinetics==

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 |-
 ! rowspan="6" |TNT
-|10||20||0.0||n/a||Emmrich, 1999<ref name="" emmrich1999''="" />
+|10||20||0.0||n/a||Emmrich, 1999<ref name="emmrich1999" />
 |-
-|11||20||0.43||1,600||Emmrich, 1999<ref name="" emmrich1999''="" />
+|11||20||0.43||1,600||Emmrich, 1999<ref name="emmrich1999" />
 |-
-|12||20||6.1||115||Emmrich, 1999<ref name="" emmrich1999''="" />
+|12||20||6.1||115||Emmrich, 1999<ref name="emmrich1999" />
 |-
 |11||25||0.15||4,621||Hwang, et al., 2005<ref name="Hwang2005" />
@@ Line 46: / Line 46: @@
 |-
 ! rowspan="14" |RDX
-|11.18||50||9.3||75||Heilmann, et al., 1996<ref name="" heilmann1996''="" />
+|11.18||50||9.3||75||Heilmann, et al., 1996<ref name="heilmann1996" />
 |-
-|11.32||50||13||53||Heilmann, et al., 1996<ref name="" heilmann1996''="" />
+|11.32||50||13||53||Heilmann, et al., 1996<ref name="heilmann1996" />
 |-
-|12||50||58.2||12||Heilmann, et al., 1996<ref name="" heilmann1996''="" />
+|12||50||58.2||12||Heilmann, et al., 1996<ref name="heilmann1996" />
 |-
-|12.3||50||127.2||5.5||Heilmann, et al., 1996<ref name="" heilmann1996''="" />
+|12.3||50||127.2||5.5||Heilmann, et al., 1996<ref name="heilmann1996" />
 |-
 |11||25||0.8||866||Hwang, et al., 2006<ref name="Hwang2006" />
@@ Line 66: / Line 66: @@
 |13||25||27.7||25||Hwang, et al., 2006<ref name="Hwang2006" />
 |-
-|12||25||2.7||260||Gent, et al., 2010<ref name="" gent2010''="">Gent, D.B., Johnson, J.L., Felt, D.R., O'Connor, G., Holland, E., May, S. and Larson, S.L., 2010. Laboratory demonstration of abiotic technologies for removal of RDX from a process waste stream (No. ERDC/EL-TR-10-8). Engineer Research and Development Center Vicksburg MS Environmental Lab. [[media:2010-Gent-laboratory_Demostration_of_abiotic_tech_for_removal_of_RDX.pdf| Report.pdf]]</ref>
+|12||25||2.7||260||Gent, et al., 2010<ref name="gent2010">Gent, D.B., Johnson, J.L., Felt, D.R., O'Connor, G., Holland, E., May, S. and Larson, S.L., 2010. Laboratory demonstration of abiotic technologies for removal of RDX from a process waste stream (No. ERDC/EL-TR-10-8). Engineer Research and Development Center Vicksburg MS Environmental Lab. [[media:2010-Gent-laboratory_Demostration_of_abiotic_tech_for_removal_of_RDX.pdf| Report.pdf]]</ref>
 |-
-|12.5||25||8.3||83||Gent, et al., 2010<ref name="" gent2010''="" />
+|12.5||25||8.3||83||Gent, et al., 2010<ref name="gent2010" />
 |-
-|13||25||26.8||26||Gent, et al., 2010<ref name="" gent2010''="" />
+|13||25||26.8||26||Gent, et al., 2010<ref name="gent2010" />
 |-
-|13.3||25||52.3||13||Gent, et al., 2010<ref name="" gent2010''="" />
+|13.3||25||52.3||13||Gent, et al., 2010<ref name="gent2010" />
 |-
 ! rowspan="3" |HMX
-|10.34||50||0.09||7,788||Heilmann, et al., 1996<ref name="" heilmann1996''="" />
+|10.34||50||0.09||7,788||Heilmann, et al., 1996<ref name="heilmann1996" />
 |-
-|11.32||50||0.99||700||Heilmann, et al., 1996<ref name="" heilmann1996''="" />
+|11.32||50||0.99||700||Heilmann, et al., 1996<ref name="heilmann1996" />
 |-
-|12.36||50||1.1||641||Heilmann, et al., 1996<ref name="" heilmann1996''="" />
+|12.36||50||1.1||641||Heilmann, et al., 1996<ref name="heilmann1996" />
 |-
 ! rowspan="4" |CL-20
@@ Line 90: / Line 90: @@
 |12||25||858||0.8||Santiago, et al., 2007<ref name="Santigo2007" />
 |}
-Degradation rates by alkaline hydrolysis for major secondary explosive compounds in aqueous systems have been measured under a range of pHs and temperatures (Table 1). Reported half-lives of TNT ranged from about 2-6 hours at pH 12 to up to six days at pH 11 in stirred aqueous reactors<ref name="" emmrich1999''="">Emmrich, M., 1999. Kinetics of the alkaline hydrolysis of 2, 4, 6-trinitrotoluene in aqueous solution and highly contaminated soils. Environmental Science & Technology, 33(21), pp.3802-3805. [https://doi.org/10.1021/es9903227 doi: 10.1021/es9903227]</ref><ref name="Hwang2005">Hwang, S., Ruff, T.J., Bouwer, E.J., Larson, S.L. and Davis, J.L., 2005. Applicability of alkaline hydrolysis for remediation of TNT-contaminated water. Water research, 39(18), pp.4503-4511. [https://doi.org/10.1016/j.watres.2005.09.008 doi: 10.1016/j.watres.2005.09.008]</ref>. Hydrolysis of RDX is reported to also occur with half-lives on the order of hours, with a strong dependence on temperature<ref name="" heilmann1996''="" /><ref name="Hwang2006" />. HMX reacted more slowly with a reaction rate two orders of magnitude slower than that observed for RDX<ref name="" heilmann1996''="" />. Alkaline hydrolysis of the caged nitroamine CL-20 had an observed half-life of roughly one hour in pH 10 solution and on the order of minutes at higher pH<ref name="Balakrishnan2003" />.
+Degradation rates by alkaline hydrolysis for major secondary explosive compounds in aqueous systems have been measured under a range of pHs and temperatures (Table 1). Reported half-lives of TNT ranged from about 2-6 hours at pH 12 to up to six days at pH 11 in stirred aqueous reactors<ref name="emmrich1999">Emmrich, M., 1999. Kinetics of the alkaline hydrolysis of 2, 4, 6-trinitrotoluene in aqueous solution and highly contaminated soils. Environmental Science & Technology, 33(21), pp.3802-3805. [https://doi.org/10.1021/es9903227 doi: 10.1021/es9903227]</ref><ref name="Hwang2005">Hwang, S., Ruff, T.J., Bouwer, E.J., Larson, S.L. and Davis, J.L., 2005. Applicability of alkaline hydrolysis for remediation of TNT-contaminated water. Water research, 39(18), pp.4503-4511. [https://doi.org/10.1016/j.watres.2005.09.008 doi: 10.1016/j.watres.2005.09.008]</ref>. Hydrolysis of RDX is reported to also occur with half-lives on the order of hours, with a strong dependence on temperature<ref name="heilmann1996" /><ref name="Hwang2006" />. HMX reacted more slowly with a reaction rate two orders of magnitude slower than that observed for RDX<ref name="heilmann1996" />. Alkaline hydrolysis of the caged nitroamine CL-20 had an observed half-life of roughly one hour in pH 10 solution and on the order of minutes at higher pH<ref name="Balakrishnan2003" />.
 ==Performance in Soil Systems==

@@ Line 97: / Line 97: @@
 Alkaline material is neutralized over time by the natural buffering capacity of the soil. Protons (H<sup>+</sup>) exchanged from low pH soils and metal cations interact with hydroxide (OH<sup>-</sup>) ions to mitigate the alkaline degradation of munitions constituents. Furthermore, hydrogen ions associated with various functional groups in humic matter may also dissociate under elevated pH conditions and likewise inhibit alkaline hydrolysis of the explosive contaminants. Soil chemistry therefore plays an important role in energetics remediation through alkaline hydrolysis.
-Soil microcosm studies with 5% w/w calcium hydroxide and 50% w/w water observed half-lives for TNT, RDX, and HMX on the order of a day to a week, with degradation rates following the sequence of TNT > RDX > HMX, similar to the aqueous studies. Soil slurries using 2,4-DNT and the single amino substituted TNT degradation products (4A-2,6-DNT and 2A-4,6-DNT) also exhibited day to week-long half-lives at pH 11 and 12<ref name="emmrich1999"><ref>Emmrich, M., 2001. Kinetics of the alkaline hydrolysis of important nitroaromatic co-contaminants of 2, 4, 6-trinitrotoluene in highly contaminated soils. Environmental Science & Technology, 35(5), pp.874-877. [https://doi.org/10.1021/es0014990 doi: 10.1021/es0014990 doi: 10.1021/es0014990]</ref>.
+Soil microcosm studies with 5% w/w calcium hydroxide and 50% w/w water observed half-lives for TNT, RDX, and HMX on the order of a day to a week, with degradation rates following the sequence of TNT > RDX > HMX, similar to the aqueous studies. Soil slurries using 2,4-DNT and the single amino substituted TNT degradation products (4A-2,6-DNT and 2A-4,6-DNT) also exhibited day to week-long half-lives at pH 11 and 12<ref name="emmrich1999" /><ref>Emmrich, M., 2001. Kinetics of the alkaline hydrolysis of important nitroaromatic co-contaminants of 2, 4, 6-trinitrotoluene in highly contaminated soils. Environmental Science & Technology, 35(5), pp.874-877. [https://doi.org/10.1021/es0014990 doi: 10.1021/es0014990 doi: 10.1021/es0014990]</ref>.
 A meso-scale soil treatability study was conducted using soils collected from two different hand grenade ranges<ref name="Larson2007">Larson, S.L., Davis, J.L., Martin, W.A., Felt, D.R., Nestler, C.C., Brandon, D.L., Fabian, G. and O'Connor, G., 2007. Grenade Range Management Using Lime for Metals Immobilization and Explosives Transformation Treatability Study (No. ERDC/EL-TR-07-5). Vicksburg, MS: U.S. Army Engineer Research and Development Center. [//www.enviro.wiki/images/a/a2/2007-Larson-grenade_Range_Management_Using_Lime_for_Metals_Immobilization.pdf  Report.pdf]</ref>. These soils were treated with a well-mixed application of hydrated lime, and migration of RDX was monitored by analyzing porewater concentrations in installed lysimeters over time (Figure 1). Overall, the reduction in RDX leaving the mesocosms as both leachate and runoff was greater than 90% with application of hydrated lime. The study authors also observed that alkaline amendments were able to fix metals contamination in place on hand grenade range soils.

@@ Line 115: / Line 115: @@
 The basic ''ex-situ'' treatment process involved the excavation of contaminated soil to a lined basin onsite. A typical excavation is shown in Figure 3. Caustic reagents in pellet form were added at a one to two percent weight by weight basis (depending on the starting concentrations, starting pH, and the buffering capacity) along with small quantities of metal catalyst, if needed. The soil was treated in 300 cubic yard batches, with amended chemicals thoroughly mixed into the soil using conventional equipment.  Water was added as needed to increase the moisture content to near saturation. Mixing was repeated two to three times a week and samples were collected for moisture content and pH, which are critical field monitoring and effectiveness parameters.
-After one week, soil sampling was performed per site specific sampling protocol and analyzed for contaminants of concern, daughter products, and breakdown products.  If needed for soil with higher concentrations of explosives, caustic reagent was supplemented to maintain the pH at the 13.0 unit level.  Soil continued to be treated until TNT and DNT concentrations were below cleanup levels (57 mg/kg for TNT and 25.4 mg/kg for total DNTs).  Metals were also analyzed periodically and TCLP tests were performed per site treatment goals.  When needed on a small percentage of batches, denitrification of soil was performed to lower the nitrite end-product using citric acid as the pH reducer and carbon substrate. After complete treatment, the soil was transported back to the excavation.  ''In-situ'' treatment is performed in a similar way to ''ex-situ'' treatment using conventional equipment and prescribed quantities of chemical reagents.
+After one week, soil sampling was performed per site specific sampling protocol and analyzed for contaminants of concern, daughter products, and breakdown products.  If needed for soil with higher concentrations of explosives, caustic reagent was supplemented to maintain the pH at the 13.0 unit level.  Soil continued to be treated until TNT and DNT concentrations were below cleanup levels (57 mg/kg for TNT and 25.4 mg/kg for total DNTs).  Metals were also analyzed periodically and [[wikipedia: Toxicity characteristic leaching procedure | TCLP]] tests were performed per site treatment goals.  When needed on a small percentage of batches, denitrification of soil was performed to lower the nitrite end-product using citric acid as the pH reducer and carbon substrate. After complete treatment, the soil was transported back to the excavation.  ''In-situ'' treatment is performed in a similar way to ''ex-situ'' treatment using conventional equipment and prescribed quantities of chemical reagents.
 ==References==