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7574-Wang-ch11_R2_030806 11 Explosive Waste Treatment J. Paul Chen, Shuaiwen Zou, and Simo Olavi Pehkonen National University of Singapore, Singapore Yung-Tse Hung Cleveland State University, Cleveland, Ohio, U.S.A. Lawrence K. Wang Zorex Corporation, Newtonville, New York, U.S.A., and Lenox Institute of Water Technology, Lenox, Massachusetts, U.S.A. 11.1 INTRODUCTION In the early 20th century, more than 60 highly explosive compounds were developed. Testing and use of high explosives has extensively contaminated soil, sediments, and water with toxic explosive residues at a large number of government installations. The end of the Cold War resulted in a significant surplus of both conventional and nuclear weapons. The United States and the former Soviet Union, together with their allies and the People’s Republic of China are destroying large quantities of weapons. As a result, a great many high explosives are being released directly and indirectly to the environment. These are highly toxic and mutagenic and classified as environmental hazards and priority pollutants by the U.S. Environmental Protection Agency (USEPA) [1–3]. Large amounts of highly explosive wastes (HEWs) need to be treated. The United States, Europe, and the former Soviet Union have produced more than 360,000 tons of HEW per year. It is estimated that 2,4,6-trinitrotoluene (TNT) alone is produced in amounts close to 1,000,000 kg a year. It has been well documented that the toxicity of these energetic chemicals can be accumulated in bodies of aquatic organisms and terrestrial species such as earthworms and mammals. Under the Intermediate-Range Nuclear Forces Treaty (INF) and Strategic Arms Reduction Treaties, the U.S. Department of Defense demilitarization program destroys a significant amount of weapons, which generates large amounts of high explosive contaminated wastewaters that needs to be treated [4–6]. In this chapter, we will discuss the generation of HEWs, and the respective treatment technologies. 429 © 2007 by Taylor & Francis Group, LLC 7574-Wang-ch11_R2_030806 11.2 CHARACTERIZATION OF EXPLOSIVE WASTEWATER 11.2.1 General Aspect “Explosive waste” normally refers to propellants, explosives, and pyrotechnics (PEP), which belong to the more general category of energetic materials. These materials are susceptible to initiation, or self-sustained energy release, when they are present in sufficient quantities and exposed to stimuli (e.g., heat, shock, and friction). Each reacts differently; all will burn, but explosives and propellants can detonate under certain conditions (e.g., confinement). Figure 1 outlines the various categories of energetic materials. Wastewaters containing explosives are produced at military installations carrying out manufacturing, and loading, assembly, and packing (LAP) of munitions, as well as washout or deactivation/demilitarization operations. The LAP generates wastewater from cleanup and washdown operations. Deactivation is accomplished by washing out or steaming out the explosives from bombs and shells. Explosives contaminated waters are normally subdivided into two categories based on the color of the wastewater: . Red water, which comes strictly from the manufacture of 2,4,6-trinitrotoluene (TNT); and . Pink water, which includes any washwater associated with LAP operations or with the deactivation of munitions involving contact with finished TNT. A list of explosive compounds is given in Table 1. The explosives-associated compounds (XACs) enter the natural subsurfaces from several types of sources: . Production facilities, e.g., wastewater lagoons and filtration pits; . Solid waste destruction facilities, e.g., burn pits and incineration wastes; . Packing or warehouse facilities; and . Dispersed, unexploded ordnance, e.g., from firing ranges. The wastewater from manufacturing and packing operations has posed the greatest threat to groundwater. In the United States, royal demolition explosives (RDX) is presently the most important military high explosive because TNT is no longer manufactured, although it is a Figure 1 Categories of energetic materials. 430 Chen et al. © 2007 by Taylor & Francis Group, LLC 7574-Wang-ch11_R2_030806 widely used military explosive. Energetic materials are classified into propellants, explosives, and PEP as shown in Figure 1. Characterization and environmental impact of PEP are summarized below. 11.2.2 Explosives Explosives are commonly classified as primary and secondary based on their susceptibility to initiation. Primary explosives such as lead azide and lead styphenate are highly susceptible to initiation; as they are used to ignite secondary explosives, they are referred to as initiating explosives. Secondary explosives include TNT, cyclotrimethylenetrinitroamine or cyclo-1,3,5- trimethylene-2,4,6-trinitramine or royal demolition explosives (RDX or cyclonite), cyclote- tramethylenetetranitramine (cyclo-1,3,5,7-tetramethylene-2,4,6,8-tetranitramine or high melting explosives (HMX), and tetryl. They are much more prevalent at military sites than primary explosives. As they are formulated to detonate only under specific circumstances, they are used as main charge or bolstering explosives. Secondary explosives can be loosely categorized into melt–pour explosives, which are based on TNT, and plastic-bonded explosives (PBX), which are based on a binder and crystalline explosive such as RDX. They can also be classified according to their chemical structure as nitroaromatics such as TNT, and nitramines such as RDX. Trinitrotoluene can have three structural isomers: 2,3,5-TNT, 2,4,6-TNT and 2,4,5-TNT. The symmetrical 2,4,6-trinitrotoluene is the most commonly found form and thus in most publications that discuss munitions compounds, the simple name TNT refers to this isomer. TNT is still the most widely used military explosive due to its low melting point of 80.18C, stability, low sensitivity to impact, and relatively safe methods of manufacture. RDX, or cyclonite as it is commonly referred to, is an explosive used extensively as a propellant for propelling artillery shells and in projectiles. It is used in the above applications because it offers higher energy, higher density, and lower flame temperatures. It is often used in binary mixtures with TNT. It finds its way into the munition wastewaters during manufacturing and blending operations [3]. The general chemical and physical properties of TNT, RDX, and HMX are illustrated in Table 2. The nitro-organics found in the waste streams from army ammunition plants (AAPs), are resistant to aerobic biodegradation and are toxic in nature in addition to being suspected carcinogens. These waste streams, if released untreated, would cause serious contamination in natural surface and subsurface systems, thereby affecting the health of humans and may have a detrimental effect on the environment. For example, HMX has adverse effects on the central nervous system (CNS) in mammals and has also been classified as a class D carcinogen by the USEPA. Therefore, army installations are prohibited from discharging wastewater into the environment prior to meeting a low interim discharge limit of 1 ppm of total nitrobodies. The USEPA has ambient criteria of 0.06 mg/L for TNT and 0.3 mg/L for RDX/HMX, and drinking water criteria of 0.049 mg/L for TNT and 0.035 mg/L for RDX/HMX [4–7]. Table 1 List of High Explosives TNT (2,4,6-Trinitrotoluene) Picrates RDX (Cyclo-1,3,5-trimethylene-2,4,6-trinitramine) TNB (Trinitrobenzenes) Tetryl (N-Methyl-N,2,4,6-tetranitrobenzeneamine) DNB (Dintrobenzenes) 2,4-DNT (2,4-Dinitrotoluene) Nitroglycerine 2,6-DNT (2,6-Dinitrotoluene) Nitrocellulose HMX (1,3,5,7-Tetranitro-1,3,5,7-tetraazocyclooctane) AP (Ammonium perchlorate) Nitroaromatics Nitroglycerine Explosive Waste Treatment 431 © 2007 by Taylor & Francis Group, LLC 7574-Wang-ch11_R2_030806 Table 2 Properties of Important Explosive Wastes Munitions TNT RDX HMX Chemical name 2,4,6-Trinitrotoluene Hexahydro-1,3,5-trinitro-s-triazine, cyclotrimethylenetrinitramine, 1,3,5-trinitro-1,3,5-triazocyclohexane, Hexogen, cyclonite, and T4 Octahydro-1,3,5,7-tetranitro-1,3, 5,7-tetrazocine, cyclotetramethylene-tetramine, and octogen Chemical formula C 7 H 5 N 3 O 6 C 3 H 6 N 6 O 6 C 4 H 8 N 8 O 8 Molecular weight 227.15 222.26 296.16 Physical property Light yellow or buff crystalline solid; soluble in alcohol, ether and hot water; detonates at around 2408C Colorless polycrystalline material; soluble in acetone; insoluble in water, alcohol, carbon tetrachloride, and carbon disulfide; slightly soluble in methanol and ether Colorless polycrystalline material; similar to replaced RDX but has a higher density and much higher melting point; highly soluble in dimethylsulfoxide Usage TNT is the most common military explosive because of its ease of manufacture and its suitability for melt loading, either as the pure explosive or as binary mixtures with RDX or HMX RDX is used extensively as the base charge in detonators. Its most common uses are as an ingredient in castable TNT-based binary explosives and as the primary ingredient in plastic-bonded explosives. Mixtures are used as the explosives fill in almost all types of munitions Because of its high density, HMX has replaced RDX in explosive applications for which energy and volume are important. It is used in castable TNT-based binary explosives, as the main ingredient in high-performance plastic-bonded explosives, and in high-performance solid propellants Hazard Flammable, dangerous fire risk, moderate explosion risk. Toxic by ingestion, inhalation, and skin absorption High explosive, easily initiated by mercury fulminate. Toxic by inhalation and skin contact. 1.5 times as powerful as TNT High explosive; toxic inhalation and skin contact 432 Chen et al. © 2007 by Taylor & Francis Group, LLC 7574-Wang-ch11_R2_030806 11.2.3 Propellants Propellants include both rocket and gun propellants. Most rocket propellants are either based on: (a) a rubber binder, ammonium perchlorate (AP) oxidizer, and a powdered aluminum (Al) fuel; or (b) a nitrate ester, usually nitroglycerine (NG), nitrocellulose (NC), HMX, AP, or polymer-bound low NC. If a binder is used, it is normally an isocyanate-cured polyester or polyether. Some propellants contain combustion modifiers, such as lead oxide. Gun propellants are usually single base (NC), double base (NC and NG), or triple base [NC, NG, and nitroguanidine (NQ)]. Some of the newer, lower vulnerability gun propellants contain binders and crystalline explosives and are similar to PBX. 11.2.4 Pyrotechnics Pyrotechnics include illuminating flares, signaling flares, colored and white smoke generators, tracers, incendiary delays, fuses, and photo-flash compounds. Pyrotechnics are composed of an inorganic oxidizer and metal powder in a binder. Illuminating flares contain sodium nitrate, magnesium, and a binder. Signaling flares contain barium, strontium, or other metal nitrates. 11.2.5 Safety Aspects Owing to the nature of explosive wastes, strict safety precautions must be taken at sites contaminated with explosive wastes to avoid initiation. The U.S. Army Environmental Center (USAEC) has developed protocols for identifying sites that require explosives safety precautions and for handling explosives wastes at these sites. With the protocol, people can determine quickly and inexpensively whether materials are susceptible to initiation and propagation by analyzing the composition of samples from the site. According to the deflagration-to-detonation test, soils containing more than 12% secondary explosives by weight are susceptible to initiation by flame; according to the shock gap test, soils containing more than 15% secondary explosives by weight are susceptible to initiation by shock. As a conservative limit, USAEC considers all soils containing more than 10% secondary explosives by weight to be susceptible to initiation and propagation and exercises a number of safety precautions when sampling and treating these soils. Sampling and treatment precautions are exercised when handling soils that contain even minute quantities of primary explosives. Work, sampling, and health and safety plans for explosives waste sites should incorporate safety provisions that normally would not be included in work and sampling plans for other sites. The most important safety precaution is to minimize exposure, which involves minimizing the number of workers exposed to hazardous situations, the duration of exposure, and the degree of hazard. 11.3 OVERVIEW OF TREATMENT TECHNOLOGIES 11.3.1 Basic Mechanisms of Remediation Based on treatment location, there are in situ and ex situ treatments. Each treatment includes physical, chemical, and biological processes, which are discussed in Sections 11.4 and 11.5. There are many technologies available in the market for remediation of contaminated sites. We can classify them into three categories. They can be used separately and in most of cases in conjunction to remediate explosive waste contaminated sites. They are: (a) alteration of contaminants; (b) separation of contaminants from environmental media; and (c) immobilization Explosive Waste Treatment 433 © 2007 by Taylor & Francis Group, LLC 7574-Wang-ch11_R2_030806 of contaminants. As no single technology can remediate an entire site, several treatment technologies must usually be combined for cost-effective treatment. Alteration of contaminant is usually referred to as destruction of the contaminant in most environmental engineering text books. Strictly speaking, the term alteration is more suitable, because treatment technologies in most cases are not able to eliminate the contaminants. There is always a question of treatment efficiency. In addition, a series of byproducts may be produced during the treatment. Destruction of contaminant can be fulfilled by altering the chemical structures of the contaminants by physical, biological, and chemical treatment approaches. These destruction technologies can be applied in situ or ex situ to contaminated media. Separation of contaminants from environmental media includes physical and chemical processes. The separated pollutants are eventually transported to treatment stations for their final destruction. This process is applied to contaminated sites. Typical examples are soil washing and pump-and-treat technologies. The technologies and the possible integration must be carefully selected based on the natural characteristics of water, soil, and sediment in order to achieve the most cost-effective treatment. For example, more air than water can be moved through soil. Therefore, for a volatile contaminant in soil that is relatively insoluble in water, soil vapor extraction would be more efficient than soil flushing or washing. Immobilization of contaminants includes stabilization, solidification, and containment technologies, such as placement in a secure landfill or construction of slurry walls. As no immobilization technology is permanently effective, monitoring and maintenance are important to prevent secondary pollution, such as leaching. 11.3.2 In Situ Treatment In in situ treatment or disposal, contaminated surface water, groundwater, soil, and sediment are treated directly in contaminated sites. This method does not require movement of contaminated materials. The main advantage is significant cost savings; however, it generally requires longer time periods. In addition, there is less certainty about the uniformity of treatment because of the variability in water and soil characteristics and because the efficacy of the process is more difficult to verify. Like treatment technologies for other contaminants, physical, physico- chemical, and biological processes are available. In Situ Physical and Physicochemical Treatment Physical and physicochemical treatments use the physical and chemical properties of the contaminants or the contaminated medium to destroy and separate the contamination. For con- taminated surface and subsurface waters, and leachate, the following technologies can be used: adsorption, membrane separation, air sparging, bioslurping, chemical oxidation, directional wells, dual phase extraction, thermal treatment, hydrofracturing enhancements, in-well air stripping, and passive/reactive treatment walls. For contaminated soil, sediment, bedrock, and sludge, the available technologies include: chemical oxidation, electrokinetic separation, fracturing, soil flushing, soil vapor extraction, solidification/stabilization, and thermal treatment [3,8–13]. Physical and physicochemical treatment technologies are normally costly even though removal of contaminants can be completed in short time periods in comparison with biological treatment. Residuals after treatment will require further disposal, which will add to the total project costs. In Situ Biological Treatment In in situ bioremediation processes, microorganisms are stimulated to grow and use the organic contaminants (e.g., TNT) as a food and energy source. In order to facilitate the processes, a 434 Chen et al. © 2007 by Taylor & Francis Group, LLC 7574-Wang-ch11_R2_030806 favorable environment for the microorganisms must be provided and maintained. This can be done by providing sufficient oxygen, nutrients, and moisture, and controlling the temperature and pH. Sometimes, microorganisms adapted for degradation of the specific contaminants are added to enhance the process. Bioventing, enhanced bioremediation, and phytoremediation are commonly used to treat contaminants in soil, sediment, bedrock, and sludge, while enhanced bioremediation, monitored natural attenuation, and phytoremediation are employed to remediate contaminated surface and subsurface waters [3]. These bioremediation techniques have been successfully used in the remediation of various contaminated sites; they have very limited effect on inorganic contaminants. Compared to physicochemical treatments, the operating costs for biological treatments are typically lower. The residuals after biological treatments are normally less harmful and thus no further treatment or disposal is required. However, in a few cases, the biological residuals could be more toxic and may be mobilized in natural subsurface waters if no careful control is performed. If it occurs, in situ bioremediation must be performed above a low permeability soil layer in order to avoid further groundwater pollution. In addition, a good groundwater monitoring system must be installed in the treatment site. 11.3.3 Ex Situ Treatment In ex situ treatment or disposal, contaminated surface water, groundwater, soil, and sediment are first transported from the contaminated sites and subsequently treated by various processes. Unlike in situ treatment, ex situ treatment requires shorter time periods. Ex situ remediation can be easily monitored and controlled, which is much better than in situ treatment. However, it requires transportation of contaminated substances, such as pumping of groundwater, which can lead to significantly higher operating costs. Like treatment technologies for other contaminants, physical, physico-chemical, and biological processes are available. Ex Situ Physical and Physicochemical Treatment Ex situ physical and physicochemical treatment processes destroy, separate, or concentrate contaminants based on the physical properties of the contaminants or the contaminated medium. For contaminated soil, sediment, bedrock, and sludge, chemical extraction, chemical reduction/oxidation, dehalogenation, soil washing, solidification/stabilization, hot-gas decon- tamination, incineration, open burn/open detonation, pyrolysis, thermal desorption, and landfill cap can be used. Contaminated groundwater, surface water, and leachate can be remediated by adsorption, advanced oxidation processes, air stripping, coagulation, and flocculation. Among the above technologies, advanced oxidation processes (e.g., UV oxidation) and thermal treatment processes (e.g., incineration) are destruction technologies; all other technologies are separation technologies, which either separate or concentrate pollutants. Ex situ physical and physicochemical remediation can be completed in shorter time periods than biological treatment. Treatment residuals from separation techniques will require treatment or disposal, which will add to the total project costs and may require permits. For example, adsorption can remove TNT species from aqueous solutions. The water after treatment becomes less contaminated; however, further disposal of TNT adsorbed chemically onto activated carbons is problematic. Ex Situ Biological Treatment In ex situ biological treatment, wastewater, soil, and sediment are first moved to treatment stations and treated biologically. For soil, sediment, bedrock, and sludge, biopiles, composting, Explosive Waste Treatment 435 © 2007 by Taylor & Francis Group, LLC 7574-Wang-ch11_R2_030806 landfarming, slurry phase biological treatment can be used; natural subsurface and surface waters can be remediated by bioreactors and constructed wetlands. A series of bioreactors have been widely studied and applied [12]. If based on oxygen environments, there are aerobic and anaerobic treatments; if based on reactor configuration, there are continuously stirred tank reactors (CSTR), plug-flow reactors (PFR), fixed-bed reactors (FBR), and fluidized-bed reactors. Ex situ biological remediation generally requires shorter time periods than in situ remediation. There is more certainty about the uniformity of treatment because of the ability to monitor and manage the treatment. However, ex situ treatment requires transportation of contaminated water, soil, and sediment (e.g., pumping of groundwater), leading to increased costs and inconvenience in management. Other properties of ex situ biological remediation are similar to those of in situ treatment as discussed previously. 11.4 PHYSICAL AND PHYSICOCHEMICAL TREATMENT The most common method for transformation of nitro-aromatics at present is incineration. However, while incineration has been demonstrated to be an effective technology, issues such as safety, noise, air emissions, costs, regulatory requirements, etc., have motivated research in physical and physico-chemical treatment technologies. Several commonly used technologies are summarized below. 11.4.1 Advanced Oxidation Treatment Oxidative processes have been used for the treatment of wastewater contaminated with organic compounds. Direct oxidation of aqueous solutions containing organic contaminants can be carried out under a variety of conditions. Catalytic oxidation of aromatics contaminated waste- water has shown that the ring cleavage step is very fast at moderate pressures and temperatures. Oxidation may also be carried out by enervation of hydroxyl radicals in sufficient quantities by ultraviolet radiation alone or in the presence of an oxidant chemical such as ozone (O 3 ) and hydrogen peroxide (H 2 O 2 ). These types of oxidation processes are referred as advanced oxidation processes (AOP). Hydrogen peroxide is a relatively inexpensive and readily available chemical. Photolysis of H 2 O 2 is the most direct method for the generation of hydroxyl radicals (HO † ) according to the following reaction: H 2 O 2 þ hv ! 2HO † (1) The excited hydrogen peroxide molecule is cleaved into two hydroxyl radicals, which initiate the chain decomposition: HO † þ H 2 O 2 ! † OOH þH 2 O 2 (2) † OOH þH 2 O 2 ! HO † þ H 2 O þ O 2 (3) 2 † OOH ! H 2 O þ O 2 (4) At the same time, these radicals initiate the degradation process by abstracting a hydrogen atom from a high explosives molecule: RH þHO † ! R † þ H 2 O (5) Direct ultraviolet photolysis and a combination of ultraviolet photolysis with hydrogen peroxide oxidation have been used to treat TNT, RDX, and HMX wastewater [13]. With a 436 Chen et al. © 2007 by Taylor & Francis Group, LLC 7574-Wang-ch11_R2_030806 low-pressure mercury UV lamp, more than 70% of RDX/HMX can be oxidized in about 10 min. Complete oxidation is achieved in 25 min. When ultraviolet oxidation is applied, 70% degradation of TNT is achieved; however, the process takes a rather long period due to the complicated structure of TNT. Hydrogen peroxide in combination with UV radiation does not significantly enhance degradation of RDX/HMX. However, it greatly improves the photolytic degradation of TNT. When the H 2 O 2 /TNT ratio is increased to a higher level, hydrogen peroxide has a negative effect on the UV photolytic process [13]. 11.4.2 Adsorption by Activated Carbon The adsorption of TNT and other explosive wastes on activated carbon has been one of the most common treatment technologies used by military ammunition plants. This technology is effective at removing a wide variety of explosive contaminants from water, but is nondestructive and expensive to operate. Moreover, after the carbon is exhausted, it has to be incinerated or disposed of into a hazardous waste disposal site. The disposal of used carbon is very costly. Batch reactors and fixed-bed reactors can be used for the remediation. The batch reactor is flexible to operate; the fixed-bed reactor is more convenient to use. The adsorption capacity and treatment efficiency are dependent on physical and chemical properties of carbon, solution chemistry, as well as operating conditions [3,8,9,12,14,15]. A successful example was illustrated in McAlester Army Ammunition Plant (McAAP) [7]. A process for pink water treatment includes storage tanks, coagulation/flocculation, settling tanks, sand filters, and activated carbon adsorption columns. When the concentration approaches the pretreatment discharge limit of 1 mg/L TNT, the carbon columns are replaced [7]. Heilmann and coworkers [5] used a combination of adsorption and alkaline hydrolysis to treat HMX and other explosive waste. The waste first enters the adsorption reactor, where the contaminants are adsorbed. The spent carbons are then sent to alkaline hydrolysis reactors for desorption. This system provides a better treatment result and can provide a higher degree of flexibility in operation. 11.5 BIOLOGICAL TREATMENT 11.5.1 Mechanisms Biological remediation of explosive wastes mainly occurs via compound oxidation and reduction. Oxidation takes place when oxygen is the reactant and oxygenase or peroxidase enzymes act as catalysts to cleave the aromatic ring. Reduction is the more common mechanism for nitroaromatics and occurs when the nitroaromatic compound is reduced to arylamines via hydrolytic deamination, acetylation, reductive deamination, and finally cyclization. It was found that the Pseudomonas species degraded both DNT and TNT aerobically with supplemental glucose as a carbon source [16,17]. Reduction of the nitro groups took place only at the para position and proceeded through hydroxylamino-nitrotoluene to aminonitrotoluene. Haidour and Ramos [18] observed 2-hydroxylamino-4,6-dinitrotoluene,4-hydroxylamino-2,6- dinitrotoluene, 4-amino-2,6-dinitrotoluene, 2-amino-4,6-dinitrotoluene, and 2,4-diamino-nitro- toluene as the products of TNT degradation with Pseudomonas sp. Boopathy et al. [19] reported the anaerobic degradation of TNT under different electron accepting conditions by a soil bacterial consortium. Hughes et al. [20] demonstrated the ability of Clostridium acetobutylicum to reduce TNT to 2,4-dihydroxylamino-6-nitrotoluene and then to phenol products via the Bamberger rearrangement. The transformation pathway is shown in Figure 2 [20]. Explosive Waste Treatment 437 © 2007 by Taylor & Francis Group, LLC 7574-Wang-ch11_R2_030806 Biotransformation of RDX has been observed by a number of researchers. Young et al. [21] found a bacterial consortium in horse manure capable of degrading RDX at the rate of 0.022 L/g cells per hour. Most of the research in the biological degradation of RDX has been carried out under anaerobic conditions. Kitts et al. [22] isolated three different genera of bacteria, which were able to degrade RDX. The most effective degrader of these three isolates was identified as Morganella morganii. One pathway for the biotransformation of RDX is a stepwise reduction of each of three nitro groups in RDX to form nitroso groups, as shown in Figure 3 [22,23]. Detail of site remediation and ground water decontamination technologies are presented in another chapter by Wang [27]. 11.5.2 Operation Conditions As with other organics, biodegradation of explosive wastes is influenced by temperature, oxygen supply, nutrient supply, pH, the availability of the contaminant to the microorganism, the concentration of the wastes, and the presence of substances toxic to the microorganisms (e.g., Figure 2 Pathway of TNT transformation observed in Clostridium acetobutylicum crude cell extracts. Figure 3 Stepwise reduction of RDX through reduction of nitroso groups. 438 Chen et al. © 2007 by Taylor & Francis Group, LLC [...]... three hexahydro-1,3,5-trinitro-1,3,5triazine-degrading species of the family Enterobacteriaceae from nitramine explosive contaminated soil Appl Environ Microbiol 1994, 60, 4608– 4 611 McCormick, N.G.; Cornell, J.H.; Kaplan, A.M Biodegradation of hexahydro-1,3,5-trinitro-1,3,5triazine Appl Environ Microbiol 1981, 42, 817 – 823 Maloney, S.W.; Adrian, N.R.; Hickey, R.F.; Heine, R.L Anaerobic treatment of... control and waste minimization in military facilities In Professional Engineering for Pollution Control and Waste Minimization; Wise, D.L., Trantolo D., Ed.; Marcel Dekker, New York, 1994 Noyes, R Chemical Weapons Destruction and Explosive Waste/ Unexploded Ordnance Remediation; Noyes Publications: New Jersey, 1996 U.S Army Environmental Center FY 2000– Annual Report, SFIM-AEC-ET-TR-20 0116 ; Pollution...7574-Wang-ch11_R2_030806 Explosive Waste Treatment 439 mercury) [3,12] Therefore, operation conditions must be carefully controlled in order to reach optimal treatment results for explosive wastes Nutrients required for cell growth are nitrogen, phosphorus, potassium, sulfur, magnesium, calcium, manganese,... metals Chemosphere 2002, 49 (4), 363– 370 Metcalf and Eddy Wastewater Engineering: Treatment Disposal Reuse, 4th ed.; McGraw-Hill, 2003 Alnaizy, R.; Akgerman, A Oxidative treatment of high explosives contaminated wastewater Water Res 1999, (33), 2021– 2030 Chen, J.P.; Lin, M.S Equilibrium and kinetics of metal ion adsorption onto a commercial H-type granular activated carbon: experimental and modeling... C.; Kapoor, J.C Development of adsorptive removal process for treatment of explosives contaminated wastewater using activated carbon J Hazardous Mater 2001, B87, 73 – 98 Parrish, F.W Fungal transformation of 2,4-dinitrotoluene and 2,4,6-trinitrotoluene Appl Environ Microbiol 1997, 47, 1295– 1298 Schackmann, A.; Muller, R Reduction of nitro-aromatic compounds by different species under aerobic conditions... explosive 1,3,5,7-tetraaza-1,3,5,7-tetranitrocyclooctane (HMX) Water Sci Technol 1994, 30, 53 – 61 Zoh, K.D.; Stenstrom, M.K Application of a membrane bioreactor for treating explosives process wastewater Water Res 2002, 36, 1018– 1024 U.S Department of Defense, Environmental Security Technology Certification Program Mineralization of TNT, RDX and by-products in an anaerobic granular activated carbon-fluidized... Meenakshisundaram, D.; Mehta, M.; Pehkonen, S.O Electrochemical reduction of nitro-aromatic compounds, product studies and mathematical modeling, technical report; U.S Army, Corps of Engineers, CERL: Champaign, IL; 1999, Report Number 99/85, ADANumber 371059, 01 Oct 1999 © 2007 by Taylor & Francis Group, LLC 7574-Wang-ch11_R2_030806 440 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 Chen et al Heilmann,... Hickey, R.F.; Heine, R.L Anaerobic treatment of pinkwater in a fluidized bed reactor containing GAC J Hazardous Mater 2002, 92, 77 –88 Bennett, J.W Prospects for fungal bioremediation of TNT munition waste Int Biodeter Biodegrad 1994, 34 (1), 21– 34 Lorin, R Constructed wetlands: passive system for wastewater treatment, Technology status report prepared for the USEPA Technology Innovation Office under a national... USEPA Technology Innovation Office under a national network of environmental management studies fellowship, 2001 Wang, L.K Site remediation and groundwater decontamination In: Handbook of Industrial and Hazardous Wastes Treatment Wang, L.K.; Hung, Y.T.; Lo, H.H.; Yapijakis C (eds.) Marcel Dekker: New York, 2004, 923–969 © 2007 by Taylor & Francis Group, LLC ... Department of Defense, 2003; CP-0004 Chen, J.P.; Yiacoumi, S Transport modeling of depleted uranium (DU) in subsurface systems Water, Air, Soil Pollut 2002 140 (1 – 4), 173– 201 Chen, J.P.; Wang, L Characterization of metal adsorption kinetic properties in batch and fixed-bed reactors., Chemosphere 2004, 54 (3), 397–404 Chen, J.P.; Lie, D.; Wang, L.; Wu, S.N.; Zhang, B.P Dried waste activated sludge as biosorbents . hydroxylamino-nitrotoluene to aminonitrotoluene. Haidour and Ramos [18] observed 2-hydroxylamino-4,6-dinitrotoluene,4-hydroxylamino-2, 6- dinitrotoluene, 4-amino-2,6-dinitrotoluene, 2-amino-4,6-dinitrotoluene,. (2,4,6-Trinitrotoluene) Picrates RDX (Cyclo-1,3,5-trimethylene-2,4,6-trinitramine) TNB (Trinitrobenzenes) Tetryl (N-Methyl-N,2,4,6-tetranitrobenzeneamine) DNB (Dintrobenzenes) 2,4-DNT (2,4-Dinitrotoluene). Francis Group, LLC 7574-Wang-ch11_R2_030806 Table 2 Properties of Important Explosive Wastes Munitions TNT RDX HMX Chemical name 2,4,6-Trinitrotoluene Hexahydro-1,3,5-trinitro-s-triazine, cyclotrimethylenetrinitramine, 1,3,5-trinitro-1,3,5-triazocyclohexane, Hexogen,

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  • Table of Contents

  • Chapter 11: Explosive Waste Treatment

    • 11.1 INTRODUCTION

    • 11.2 CHARACTERIZATION OF EXPLOSIVE WASTEWATER

      • 11.2.1 General Aspect

      • 11.2.2 Explosives

      • 11.2.3 Propellants

      • 11.2.4 Pyrotechnics

      • 11.2.5 Safety Aspects

      • 11.3 OVERVIEW OF TREATMENT TECHNOLOGIES

        • 11.3.1 Basic Mechanisms of Remediation

        • 11.3.2 In Situ Treatment

          • In Situ Physical and Physicochemical Treatment

          • In Situ Biological Treatment

          • 11.3.3 Ex Situ Treatment

            • Ex Situ Physical and Physicochemical Treatment

            • Ex Situ Biological Treatment

            • 11.4 PHYSICAL AND PHYSICOCHEMICAL TREATMENT

              • 11.4.1 Advanced Oxidation Treatment

              • 11.4.2 Adsorption by Activated Carbon

              • 11.5 BIOLOGICAL TREATMENT

                • 11.5.1 Mechanisms

                • 11.5.2 Operation Conditions

                • 11.5.3 Bioreactors

                • REFERENCES

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