Environmental behavior of explosives in groundwater from the Milan Army Ammunition Plant in aquatic and wetland plant treatments. Removal, mass balances and fate in groundwater of TNT and RDX.

Phytoremediation of 2,4,6-trinitrotoluene (TNT) and hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) in groundwater using constructed wetlands is a potentially economical remediation alternative. To evaluate Explosives removal and fate was evaluated using hydroponic batch incubations of plant and substrate treatments with explosives-contaminated groundwater amended with [U-14C]-TNT or [U-14C]-RDX. Plants and substrates were collected from a small-scale wetland constructed for explosives removal, and groundwater originated from a local aquifer at the Milan Army Ammunition Plant. The study surveyed three aquatic, four wetland plant species and two substrates in independent incubations of 7 days with TNT and 13 days with RDX. Parent compounds and transformation products were followed using 14C and chemical (HPLC) analyses. Mass balance of water, plants, substrates and air was determined. It was demonstrated that TNT disappeared completely from groundwater incubated with plants, although growth of most plants except parrot-feather was low in groundwater amended to contain 1.6 to 3.4 mg TNT L-1. Highest specific removal rates were found in submersed plants in water star-grass and in all emergent plants except wool-grass. TNT declined less with substrates, and least in controls without plants. Radiolabel was present in all plants after incubation. Mineralization to 14CO2 was very low, and evolution into 14C-volatile organics negligible. RDX disappeared less rapidly than TNT from groundwater. Growth of submersed plants was normal, but that of emergent plants reduced in groundwater amended to contain 1.5 mg RDX L-1. Highest specific RDX removal rates were found in submersed plants in elodea, and in emergent plants in reed canary grass. RDX failed to disappear with substrates. Mineralization to 14CO2 was low, but relatively higher than in the TNT experiment. Evolution into 14C-volatile organics was negligible. Important considerations for using certain aquatic and wetland plants in constructed wetlands aimed at removing explosives from water are: (1) plant persistence at the explosives level to which it is exposed, (2) specific plant-mass based explosives removal rates, (3) plant productivity, and (4) fate of parent compounds and transformation products in water, plants, and sediments.     

Dissolution and sorption of hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) and 2,4,6-trinitrotoluene (TNT) residues from detonated mineral surfaces

Composition B (Comp B) is a commonly used military formulation composed of the toxic explosive compounds 2,4,6-trinitrotoluene (TNT), and hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX). Numerous studies of the temporal fate of explosive compounds in soils, surface water and laboratory batch reactors have been conducted. However, most of these investigations relied on the application of explosive compounds to the media via aqueous addition and thus these studies do not provide information on the real world loading of explosive residues during detonation events. To address this we investigated the dissolution and sorption of TNT and RDX from Comp B residues loaded to pure mineral phases through controlled detonation. Mineral phases included nontronite, vermiculite, biotite and Ottawa sand (quartz with minor calcite). High Performance Liquid Chromatography and Attenuated Total Reflectance Fourier Transform Infrared spectroscopy were used to investigate the dissolution and sorption of TNT and RDX residues loaded onto the mineral surfaces. Detonation resulted in heterogeneous loading of TNT and RDX onto the mineral surfaces. Explosive compound residues dissolved rapidly (within 9 h) in all samples but maximum concentrations for TNT and RDX were not consistent over time due to precipitation from solution, sorption onto mineral surfaces, and/or chemical reactions between explosive compounds and mineral surfaces. We provide a conceptual model of the physical and chemical processes governing the fate of explosive compound residues in soil minerals controlled by sorption-desorption processes.     

Degradation of explosives-related compounds using nickel catalysts

We report the ability of nickel-based catalysts to degrade explosives compounds in aqueous solution. Several nickel catalysts completely degraded the explosives, although rates varied. Nearly all of the organic explosive compounds tested, including 2,4,6-trinitrotoluene (TNT), hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX), and octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX), were rapidly degraded to below detection limits by a powdered nickel on an alumina-silicate support (Aldrich nickel catalyst). Perchlorate degradation was minimal (<25%). Degradation of TNT by Aldrich nickel catalyst resulted in apparent first-order kinetics. Significant gaseous 14C was released and collected in an alkaline solution (most likely carbon dioxide) from [14C]RDX and [14C]HMX, indicating heterocyclic ring cleavage. Significant gaseous 14C was not produced from [14C]TNT, but spectrophotometric evidence indicated loss of aromaticity. Degradation occurred in low ionic strength solutions, groundwater, and from pH 3 to pH 9. Degradation of TNT, RDX, and HMX was maintained in flow-through columns of Aldrich nickel catalyst mixed with sand down to a hydraulic retention time of 4h. These data indicate that nickel-based catalysts may be an effective means for remediation of energetics-contaminated groundwater.     

Dissolution rates of three high explosive compounds: TNT,RDX, and HMX

Incidental exposure to high explosive compounds can cause subtle health effects to which a population could be more susceptible than injury by detonation. Proper source characterization is a key requirement in the conduct of risk assessments. For nonvolatile solid explosives, dissolution is one of the primary mechanisms that controls fate and transport, resulting in exposure to these compounds remote from their source. To date, information describing dissolution rates of high explosives has been sparse. The objective of this study was to determine the dissolution rates of three high explosive compounds, 2,4,6-trinitrotoluene (TNT), hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX), and octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX), in dilute aqueous solutions as a function of temperature, surface area, and energy input. To determine each variable's impact on dissolution rate, experiments were performed where one variable was changed while the other two were held constant. TNT demonstrated the fastest dissolution rate followed by HMX and then RDX. Dissolution rate correlation equations were developed for each explosive compound incorporating the three aforementioned variables, independently, and collectively in one correlation equation.     

Removal of TNT and RDX from water and soil using iron metal

Contaminated water and soil at active or abandoned munitions plants is a serious problem since these compounds pose risks to human health and can be toxic to aquatic and terrestrial life. Our objective was to determine if zero-valent iron (Fe(0)) could be used to promote remediation of water and soil contaminated with 2,4,6-trinitrotoluene (TNT) and hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX). As little as 1% Fe(0) (w/v) removed 70 mg TNT litre(-1) from aqueous solution within 8 h and removed 32 mg RDX litre(-1) within 96 h. Treating slurries (1:5 soil:water) of highly contaminated soil (5200 mg TNT and 6400 mg RDX kg(-1) soil) from the former Nebraska Ordnance Plant (NOP) with 10% Fe(0) (w/w soil) reduced CH(3)CN-extractable TNT and RDX concentrations below USEPA remediation goals (17.2 mg TNT and 5.8 mg RDX kg(-1)). Sequential treatment of a TNT-contaminated solution (70 mg TNT litre(-1) spiked with (14)C-TNT) with Fe(0) (5% w/v) followed by H(2)O(2) (1% v/v) completely destroyed TNT and removed about 94% of the (14)C from solution, 48% of which was mineralized to (14)CO(2) within 8 h. Fe(0)-treated TNT also was more susceptible to biological mineralization. Our observations indicate that Fe(0) alone, Fe(0) followed by H(2)O(2), or Fe(0) in combination with biotic treatment can be used for effective remediation of munitions-contaminated water and soil.     

Treatment of trinitrotoluene by crude plant extracts

Crude plant extract solutions (spinach and parrotfeather) were prepared and spiked with 2,4,6-trinitrotoluene (TNT) (20 mgl(-1)). 90-h TNT removal by these solutions was compared to controls. Spinach and parrotfeather extract solutions removed 99% and 50% of the initial TNT, respectively; TNT was not eliminated in the controls or in extract solutions where removal activity was deactivated by boiling. A first-order removal constant of 0.052 h(-1) was estimated for spinach extract solutions treating 20 mgl(-1) TNT concentrations, which compared favorably to intact plant removal. Concentration variation was described by Michaelis-Menton kinetics. Detectable TNT degradation products represented only a fraction of the total TNT transformed, and the transformation favored the formation of 4-aminodinitrotoluene. The results indicated that crude plant extracts transform TNT, without the presence of the live plant.     

Fate of RDX and TNT in agronomic plants

Phytoremediation is of great interest to remediate soil contaminated with hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) and 2,4,6-trinitrotoluene (TNT). The ability of 4 agronomic plants (maize, soybean, wheat and rice) to take up these explosives and their fate in plants were investigated. Plants were grown for 42 days on soil contaminated with [(14)C]RDX or [(14)C]TNT. Then, each part was analyzed for its radioactivity content and the percentage of bound and soluble residues was determined following extractions. Extracts were analyzed by radio-HPLC. More than 80% of uptaken RDX was translocated to aerial tissues, up to 64.5 mgg(-1) of RDX. By contrast, TNT was little translocated to leaves since less than 25% of uptaken TNT was accumulated in aerial parts. Concentrations of TNT residues were 20 times lower than for RDX uptake. TNT was highly metabolized to bound residues (more than 50% of radioactivity) whereas RDX was mainly found in its parent form in aerial parts.     

Biodegradation pathways of hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) by Clostridium acetobutylicum cell-free extract

Hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX), a military high explosive, is becoming an increasingly important pollutant in the US. The cleanup of RDX-contaminated soil and groundwater has been a serious challenge due to its recalcitrance in the environment. This study was conducted to determine the biodegradation kinetics of RDX by crude cell extract of Clostridium acetobutylicum (ATCC 824), and to examine whether this bacterium will carry out reductive transformation pathways similar to the transformation of 2,4,6-trinitrotoluene (TNT), 2,4- and 2,6-dinitrotoluenes (DNTs) we have reported previously. Batch studies on the anaerobic transformation of RDX were conducted in serum bottles with U-ring-14C-RDX. RDX and its transformation products were quantified by HPLC and qualified by LC/ MS interfaced to two soft ionization techniques--an atmospheric pressure ionization and an electron spray ionization (API-ES). Results demonstrated that C. acetobutylicum is capable of transforming RDX with H2 as the electron donor. The transformation followed a zero-order kinetics and the rates increased with increasing H2. RDX was transformed into several polar intermediates that could not be separated by reverse-phase HPLC and its molecular ions were unstable under the condition of commonly used electron impact detector. Using a polar and water immiscible solvent (ethyl acetate) and the softer MS ionization techniques, mass spectroscopy detected the presence of several RDX derivatives including mononitroso-, monohydroxylamino-, mononitrosomonohydroxylamino-, monoamino-, diamino-, and triamino-compounds. The presence of hydroxylamino compounds is analogous to the transformation of TNT and DNTs we elucidated previously.     

Localization of hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) and 2,4,6-trinitrotoluene (TNT) in poplar and switchgrass plants using phosphor imager autoradiography

Phosphor imager autoradiography is a technique for rapid, sensitive analysis of the localization of xenobiotics in plant tissues. Use of this technique is relatively new to research in the field of plant science, and the potential for enhancing visualization and understanding of plant uptake and transport of xenobiotics remains largely untapped. Phosphor imager autoradiography is used to investigate the uptake and translocation of the explosives 1,3,5-trinitro-1,3,5-triazine (RDX) and 2,4,6-trinitrotoluene within Populus deltoides × nigra DN34 (poplar) and Panicum vigratum Alamo (switchgrass). In both plant types, TNT and/or TNT-metabolites remain predominantly in root tissues while RDX and/or RDX-metabolites are readily translocated to leaf tissues. Phosphor imager autoradiography is further investigated for use in semi-quantitative analysis of uptake of TNT by switchgrass.     

The use of Microtox to assess toxicity removal of industrial effluents from the industrial district of Camaçari (BA, Brazil)

The treatment efficiency, as toxicity removal, of complex effluents from the Industrial District of Cama?ari (BA, Brazil), after biological treatment with activated sludge was evaluated using Microtox. Samples of the equalised effluent (EE) were collected prior to treatment together with samples of the treated effluent (TE), which remained 24 h in the treatment plant. Rehydrated colonies of Vibrio fischeri were exposed to sequential dilutions of EE and TE to assess luminosity interference. Values for EC50 were calculated, together with the respective toxicity units. In all, twenty assays of each effluent type were carried out and the mean toxicity removal was 92.71%, while the chemical oxygen demand (COD) presented mean reduction of 83.04%. There was a variability of an order of magnitude between the Microtox results for the two types of effluents. The mean EC50 values were 2.12 for EE and 47.78% for TE. In spite of its weakness in some conditions, the Microtox system demonstrated to work adequately in assessing effluent toxicity removal in this treatment plant and therefore can be used for further toxicity removal programs.     

Environmental behavior of explosives in groundwater from the Milan Army Ammunition Plant in aquatic and wetland plant treatments. Uptake and fate of TNT and RDX in plants

Uptake and fate of TNT and RDX by three aquatic and four wetland plants were studied using hydroponic, batch, incubations in explosives-contaminated groundwater amended with [U-14C]-TNT or [U-14C]-RDX in the laboratory. Substrates in which the plants were rooted were also tested. Plants and substrates were collected from a small-scale wetland constructed for explosives removal, and groundwater originated from a local aquifer at the Milan Army Ammunition Plant. This study demonstrated rapid uptake of [U-14C]-TNT derived 14C, concentration at the uptake sites and limited transport in all plants. Per unit of mass, uptake was higher in submersed than in emergent species. Biotransformation of TNT had occurred in all plant treatments after 7-day incubation in 1.6 to 3.4 mg TNT L-i, with labeled amino-dinitrotoluenes (ADNTs), three unidentified compounds unique for plants, and mostly polar products as results. Biotransformation occurred also in the substrates, yielding labeled ADNT, one unidentified compound unique for substrates, and polar products. TNT was not recovered by HPLC in plants and substrates after incubation. Uptake of [U-14C]-RDX derived 14C in plants was slower than that of TNT, transport was substantial, and concentration occurred at sites where new plant material was synthesized. As for TNT, uptake per unit of mass was higher in submersed than in emergent species. Biotransformation of RDX had occurred in all plant treatments after 13-day incubation in 1.5 mg RDX L-1, with one unidentified compound unique for plants, and mostly polar products as results. Biotransformation had occurred also in the substrates, but to a far lower extent than in plants. Substrates and plants had one unidentified 14C-RDX metabolite in common. HPLC analysis confirmed the presence of RDX in most plants and in three out of four substrates at the end of the incubation period.     

Sequential biodegradation of TNT,RDX and HMX in a mixture

We describe TNT's inhibition of RDX and HMX anaerobic degradation in contaminated soil containing indigenous microbial populations. Biodegradation of RDX or HMX alone was markedly faster than their degradation in a mixture with TNT, implying biodegradation inhibition by the latter. The delay caused by the presence of TNT continued even after its disappearance and was linked to the presence of its intermediate, tetranitroazoxytoluene. PCR–DGGE analysis of cultures derived from the soil indicated a clear reduction in microbial biomass and diversity with increasing TNT concentration. At high-TNT concentrations (30 and 90 mg/L), only a single band, related to Clostridium nitrophenolicum, was observed after 3 days of incubation. We propose that the mechanism of TNT inhibition involves a cytotoxic effect on the RDX- and HMX-degrading microbial population. TNT inhibition in the top active soil can therefore initiate rapid transport of RDX and HMX to the less active subsurface and groundwater.     

Photo-Fenton treatment of TNT contaminated soil extract solutions obtained by soil flushing with cyclodextrin

The technical feasibility and performances of coupling flushing abilities of cyclodextrin solutions for 2,4,6-trinitrotoluene (TNT) removal from contaminated soil and the ability of Photo-Fenton treatment for final disposal of soil extract solutions containing high TNT loads have been investigated at laboratory scale. Methylated-beta-cyclodextrin (MCD) has shown better ability than hydroxypropyl-beta-cyclodextrin (HPCD) to complex TNT. The MCD solution increased the aqueous concentration of TNT in soil extract effluents as much as 2.1 times the concentrations obtained during the water flush of the soil. TNT in soil extract solution has been treated by Photo-Fenton. Our results indicate that MCD has a beneficial effect on the degradation rates of TNT. This relative improvement of TNT degradation rate (1.3 time) in presence of high amounts of hydroxyl radical scavengers can be ascribed to the formation of a ternary complex (TNT-cyclodextrin-iron) which can direct hydroxyl radical reaction toward TNT. Complete mineralization of soil extraction solutions was not achieved and TNT degradation pathway has been elucidated in order to ensure that no potential toxic intermediate is left at the end of the treatment time. After successive TNT hydroxylations, oxidative opening of the TNT aromatic ring quickly occurred, leading to the accumulation of short chain carboxylic acids such as oxalic acid and formic acid.     

Dissolution kinetics of sub-millimeter Composition B detonation residues: role of particle size and particle wetting

The dissolution of the 2,4,6-trinitrotoluene (TNT), hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX), and octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) from microscale particles (<250 μm) of the explosive formulation Composition B was examined and compared to dissolution from macroscopic particles (>0.5 mm). The dissolution of explosives from detonation soot was also examined. The measured mass transfer coefficients for the microscale particles were one to two orders of magnitude greater than the macroscopic particles. When normalized to particle surface area, mass transfer coefficients of microscale and macroscale particles were similar, indicating that the bulk dissolution processes were similar throughout the examined size range. However, an inverse relationship was observed between the particle diameter and the RDX:TNT mass transfer rate coefficient ratio for dry-attritted particles, which suggests that RDX may be more readily dissolved (relative to TNT) in microscale particles compared to macroscale particles. Aqueous weathering of larger Composition B residues generated particles that possessed mass transfer coefficients that were on the order of 5- to 20-fold higher than dry-attritted particles of all sizes, even when normalized to particle surface area. These aqueous weathered particles also possessed a fourfold lower absolute zeta-potential than dry-attritted particles, which is indicative that they were less hydrophobic (and hence, more wettable) than dry-attritted particles. The increased wettability of these particles provides a plausible explanation for the observed enhanced dissolution. The wetting history and the processes by which particles are produced (e.g., dry physical attrition vs. aqueous weathering) of Composition B residues should be considered when calculating mass transfer rates for fate and transport modeling.     

Catalytic oxidation of TNT by activated carbon

Activated carbon can remove 2,4,6-trinitrotoluene (TNT) and 1,3,5-trinitrobenzene (TNB) from aqueous solution and promote oxidation of TNT. After equilibrating a 0.35 mM TNT solution with activated carbon (0.2-1% w/v), HPLC and GC/MS analysis confirmed the presence of 2,4,6-trinitrobenzaldehyde (TNBAld) and 2,4,6-trinitrobenzene (TNB), and provided strong evidence supporting 2,4,6-trinitrobenzyl alcohol (TNBAlc) as an intermediate of TNT oxidation. After 6 d, TNT and its oxidation products were strongly bound to the activated carbon, while TNB was extractable with acetonitrile. Observations indicate that activated carbon catalyzes TNT oxidation to TNBAlc, which is readily oxidized to TNBAld and TNB in the absence of activated carbon under dark conditions. While adsorbed TNB was extractable with acetonitrile, activated carbon promoted rapid TNT oxidation and formation of unextractable residues. Strong binding is attributed to catalyzed oxidation of the TNT methyl group, probably through a free radical mechanism, and subsequent chemisorption of oligomers and polymerized products that are not desorbed from micropores. Our observations indicate TNT oxidation and bound residue formation after sorption by activated carbon increases the effectiveness of activated carbon to decontaminate water.     

Halide salts accelerate degradation of high explosives by zerovalent iron

Zerovalent iron (Fe(0), ZVI) has drawn great interest as an inexpensive and effective material to promote the degradation of environmental contaminants. A focus of ZVI research is to increase degradation kinetics and overcome passivation for long-term remediation. Halide ions promote corrosion, which can increase and sustain ZVI reactivity. Adding chloride or bromide salts with Fe(0) (1% w/v) greatly enhanced TNT, RDX, and HMX degradation rates in aqueous solution. Adding Cl or Br salts after 24h also restored ZVI reactivity, resulting in complete degradation within 8h. These observations may be attributed to removal of the passivating oxide layer and pitting corrosion of the iron. While the relative increase in degradation rate by Cl(-) and Br(-) was similar, TNT degraded faster than RDX and HMX. HMX was most difficult to remove using ZVI alone but ZVI remained effective after five HMX reseeding cycles when Br(-) was present in solution.     

Age dependent acute oral toxicity of hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) and two anaerobic N-nitroso metabolites in deer mice (Peromyscus maniculatus)

Hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) transforms anaerobically into N-nitroso compounds: hexahydro-1-nitroso-3,5-dinitro-1,3,5-triazine (MNX), hexahydro-1,3-dinitroso-5-nitro-1,3,5-triazine (DNX), and hexahydro-1,3,5-trinitroso-1,3,5-triazine (TNX). Exposure to these N-nitroso metabolites may occur in areas contaminated with explosives, as anaerobic degradation occurs via some bacteria and is one remediation strategy used for RDX. Few papers report acute oral toxicity and none have evaluated age dependent toxicity of RDX or its N-nitroso metabolites. Median lethal dose (LD₅₀) was determined in deer mice (Peromyscus maniculatus) of three age classifications 21 d, 50 d, and 200 d for RDX, MNX, and TNX using the US EPA up-and-down procedure (UDP). Hexahydro-1,3,5-trinitro-1,3,5-triazine and N-nitroso metabolites caused similar overt signs of toxicity. Median lethal dose for 21 d deer mice were 136, 181, and 338 mg/kg for RDX, MNX, and TNX, respectively. Median lethal dose for 50 d deer mice were 319, 575, and 338 mg/kg for RDX, MNX, and TNX, respectively. Median lethal dose for 200 d deer mice were 158, 542, and 999 mg/kg for RDX, MNX, and TNX, respectively. These data suggest that RDX is the most potent compound tested, and age dependent toxicity may exist for all compounds and could play a role in RDX and RDX N-nitroso metabolite ecological risk evaluation of terrestrial wildlife at RDX contaminated sites.     

Electrolytic transformation of ordinance related compounds (ORCs) in groundwater: laboratory mass balance studies

Electrolytic reactive barriers (e(-) barriers) consist of closely spaced permeable electrodes installed across a groundwater contaminant plume in a permeable reactive barrier format. Application of sufficient potential to the electrodes results in sequential oxidation and reduction of the target contaminant. The objective of this study was to quantify the mass distribution of compounds produced during sequential electrolytic oxidation and reduction of ordinance related compounds (ORCs) in a laboratory analog to an e(-) barrier. In this study, a series of column tests were conducted using RDX (hexahydro-1,3,5-trinitro-1,3,5-triazine) and TNT (2,4,6-trinitrotoluene) as representative ORCs. The experimental setup consisted of a plexiglass column packed with quartz-feldspar sand to simulate aquifer conditions. A single set of porous electrodes consisting of expanded titanium-mixed metal oxide mesh was placed at the midpoint of the sand column as a one-dimensional analog to an e(-) barrier. Constant current of 20mA (variable voltage) was applied to the electrode set. Initial studies involved quantification of reaction products using unlabeled RDX and TNT. Approximately 70% of the influent concentration was transformed, in one pass, through sequential oxidation-reduction for both contaminants. Following the unlabeled studies, (14)C labeled RDX and TNT were introduced to determine the mass balance. An activity balance of up to 96% was achieved for both (14)C-RDX and (14)C-TNT. For both contaminants, approximately 21% of the influent activity was mineralized to (14)CO(2). The proportion of the initial activity in the dissolved fraction was different for the two test contaminants. Approximately 30% of the initial (14)C-RDX was recovered as unreacted in the dissolved phase. The balance of the (14)C-RDX was recovered as non-volatile, non-nitroso transformation products. None of the (14)C-RDX was sorbed to the column sand packing. For (14)C-TNT approximately 51% of the initial activity was recovered in the dissolved phase, the majority was unreacted TNT. The balance of the (14)C-TNT was either sorbed to the sand packing (approximately 24%) or dissolved/mineralized as unidentified ring cleavage products ( approximately 4%).     

Photocatalytic Treatment of RDX Wastewater with Nano-Sized Titanium Dioxide (5 pp)

Background, Aim and Scope The polynitramines, hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX), octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX), are important military explosives and regulated toxic hazardous compounds. Production, testing and use of the compounds has resulted in numerous acres of contaminated soils and groundwater near many munitions facilities. Economical and efficient methods for treatment of wastewater and cleanup of soils or groundwater containing RDX and HMX are needed. This study focuses on the photocatalytic treatment of RDX wastewater with nano-sized titanium dioxide (nano-TiO2) under simulated sunlight, whose intensity and wavelength are similar to that of the real sunlight in Xi'an at noon. The objective is to determine the potential for RDX destruction with nano-TiO2 in aqueous solution. Materials and Methods: An activated carbon fiber (ACF) cloth-loaded with nano-TiO2 was put into the RDX containing solution, and the concentration of RDX was measured (by HPLC–UV) at regular time intervals under simulated sunlight. Results: The RDX degradation percentage of the photocatalytic process is higher than that of Fenton oxidation before 80 min, equivalent after 80 min, and it reaches 95% or above after 120 min. The nano-TiO2 catalyst can be used repeatedly. Discussion: The photocatalytic degradation kinetics of RDX under simulated sunlight can be described by a first-order reaction kinetics equation. The possible degradation mechanism of RDX was presented and the degradation performance was compared with that of biological method. Conclusions: It was demonstrated that the degradation of RDX wastewater is very effective with nano-TiO2 as the photocatalytic catalyst under simulated sunlight. The efficiency of the nano-TiO2 catalyst for RDX degradation under simulated sunlight is nearly identical to that of Fenton oxidation. Recommendations and Perspectives: To date, a number of catalysts show poor absorption and utilization of sunlight, and still need ultraviolet light irradiation during wastewater degradation. The nano-TiO2 used in the described experiments features very good degradation of RDX under simulated sunlight, and the manufacturing costs are rather low (around 10 Euro/m2). Moreover, the degradation efficiency is higher compared to that of the biological method. This method exhibits great potential for practical applications owing to its easiness and low cost. If it can be applied extensively, the efficiency of wastewater treatment will be enhanced greatly.     

Phytotoxicity of nitroaromatic energetic compounds freshly amended or weathered and aged in sandy loam soil

The toxicities of 2,4,6-trinitrotoluene (TNT), 1,3,5-trinitrobenzene (TNB), 2,4-dinitrotoluene (2,4-DNT), and 2,6-dinitrotoluene (2,6-DNT) to terrestrial plants alfalfa (Medicago sativa L.), Japanese millet (Echinochloa crusgalli L.), and perennial ryegrass (Lolium perenne L.) were determined in Sassafras sandy loam soil using seedling emergence, fresh shoot, and dry mass measurement endpoints. A 13-week weathering and aging of energetic materials in soils, which included wetting and drying cycles, and exposure to sunlight of individual soil treatments, was incorporated into the study design to better reflect the soil exposure conditions in the field than toxicity determinations in freshly amended soils. Definitive toxicity tests showed that dinitrotoluenes were more phytotoxic for all plant species in freshly amended treatments based on EC20 values for dry shoot ranging from 3 to 24mgkg(-1) compared with values for TNB or TNT ranging from 43 to 62mgkg(-1). Weathering and aging of energetic materials (EMs) in soil significantly decreased the toxicity of TNT, TNB or 2,6-DNT to Japanese millet or ryegrass based on seedling emergence, but significantly increased the toxicity of all four EMs to all three plant species based on shoot growth. Exposure of the three plant species to relatively low concentrations of the four compounds initially stimulated plant growth before the onset of inhibition at greater concentrations (hormesis).