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Various thermal (radiative, conductive, and convective) initiation experiments are performed to demonstrate the importance of the gas phase role in combustion modeling of energetic materials (EM). A previously published condensed phase model that includes a predicted critical irradiance above which ignition is not possible is compared to experimental laser ignition results for octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) and 2,4,6-trinitrotoluene (TNT). Experimental results conflict with the predicted critical irradiance concept. The failure of the model is believed to result from a misconception about the role of the gas phase in the ignition process of energetic materials. The model assumes that ignition occurs at the surface and that evolution of gases inhibits ignition. High speed video of laser ignition, oven cook-off and hot wire ignition experiments captures the ignition of HMX and TNT in the gas phase. A laser ignition gap test is performed to further evaluate the effect of gas phase laser absorption and gas phase disruption on the ignition process. Results indicate that gas phase absorption of the laser energy is probably not the primary factor governing the gas phase ignition observations. It is discovered that a critical gap between an HMX pellet and a salt window of 6 mm±0.4 mm exists below which ignition by CO2 laser is not possible at the tested irradiances of 29 W/cm2 and 38 W/cm2 for HMX ignition. These observations demonstrate that a significant disruption of the gas phase, in certain scenarios, will inhibit ignition, independent of any condensed phase processes. These results underscore the importance of gas phase processes and illustrate that conditions can exist where simple condensed phase models are inadequate to accurately predict the behavior of energetic materials. [ABSTRACT FROM AUTHOR]

Microbiome studies focused on ecologically relevant vertebrate models like reptiles have been limited. Because of their relatively small home range, fast maturation, and high fecundity, lizards are an excellent reptilian terrestrial indicator species. For this study we used the green anole, Anolis carolinensis, to assess the impact of military relevant contaminants on fecal microbiome composition. Fourteen day sub-acute exposures were conducted via oral gavage with 2,4,6-Trinitrotoluene (TNT) and inorganic lead at doses of 60 mg/kg and 20 mg/kg of body weight, respectively. Body weights and food consumption were monitored and fecal samples were collected for high-throughput 16S rRNA gene amplicon sequencing and analytical chemistry at days 0 and 15. At the end of the study, liver and gut were harvested for body burden data. Chemical analysis confirmed accumulation of TNT, TNT transformation products, and lead in liver tissue and fecal samples. Bacterial community analysis of fecal material revealed significant differences between day 0 and day 15 of TNT exposed anoles with an operational taxonomic unit (OTU) within the genus Erwinia representing 32% of the microbial community in TNT exposed anoles. Predictable changes in gut microbiome composition could offer an easily assayed, noninvasive biomarker for specific chemical exposure providing enhanced scientific support to risk assessments on military installations. [ABSTRACT FROM AUTHOR]

We report the observation of a new physical phenomenon of the addition of 2 hydrogen atoms to molecular ions thus forming [M + 2H]+ ions. We demonstrate such second hydrogen atom abstraction onto the molecularions of pentaerythritol and trinitrotoluene (TNT). We used both gas chromatography mass spectrometry (GC-MS) with supersonic molecular beam (SMB) with methanol added into its make-up gas and electron ionization (EI) liquid chromatography mass spectrometry (LC-MS) with SMB with methanol as the LC solvent. We found that the formation of methanol clusters resulted upon EI in the formation of dominant protonated pentaerythritol ion at m/z = 137 plus about 70% relative abundance of pentaerythritol molecular ion with 2 additional hydrogen atoms at m/z = 138 which is well above the 5.7% natural C13 isotope abundance of protonated pentaerythritol. Similarly, we found an abundant protonated TNT ion at m/z = 228 and a similar abundance of TNT molecular ion with 2 additional hydrogen atoms at m/z = 229. Upon the use of deuterated methanol (CD3OD) as the solvent, we observed an abundant m/ z = 231 (M + 2D)+ of TNT with 2 deuterium atoms. We found such abundant second hydrogen atom abstraction with butylglycolate and at low abundances in dioctylphthalate, Vitamin K3, phenazine, and RDX. At this time, we are unable to report the magnitude and frequency of occurrence of this phenomenon in standard electrospray LC-MS. This observation could have important implications on the provision of elemental formula from mass spectra that are involved with protonated molecules. Accordingly, while accurate mass measurements can serve for the generation of elemental formula, their further support and improvement via isotope abundance analysis are questionable. Consequently, if a given compound can be analyzed by both GC-MS and LC-MS, its GC-MS analysis can be superior for the provision of accurate elemental formulae if its EI mass spectrum exhibits abundant molecular ions such as with GC-MS with SMB (also known as cold EI) [ABSTRACT FROM AUTHOR]

The explosive 2,4,6-trinitrotoluene ( TNT) is a significant, global environmental pollutant that is both toxic and recalcitrant to degradation. Given the sheer scale and inaccessible nature of contaminated areas, phytoremediation may be a viable clean-up approach. Here, we have characterized a Drosophila melanogaster glutathione transferase ( Dm GSTE6) which has activity towards TNT., Recombinantly expressed, purified Dm GSTE6 produces predominantly 2-glutathionyl-4,6-dinitrotoluene, and has a 2.5-fold higher Maximal Velocity ( Vmax), and five-fold lower Michaelis Constant ( Km) than previously characterized TNT-active Arabidopsis thaliana (Arabidopsis) GSTs. Expression of Dm GSTE6 in Arabidopsis conferred enhanced resistance to TNT, and increased the ability to remove TNT from contaminated soil relative to wild-type plants., Arabidopsis lines overexpressing TNT-active GSTs At GST-U24 and At GST-U25 were compromised in biomass production when grown in the absence of TNT. This yield drag was not observed in the Dm GSTE6-expressing Arabidopsis lines. We hypothesize that increased levels of endogenous TNT-active GSTs catalyse excessive glutathionylation of endogenous substrates, depleting glutathione pools, an activity that Dm GST may lack., In conclusion, Dm GSTE6 has activity towards TNT, producing a compound with potential for further biodegradation. Selecting or manipulating plants to confer Dm GSTE6-like activity could contribute towards development of phytoremediation strategies to clean up TNT from polluted military sites. [ABSTRACT FROM AUTHOR]

The effect of the amount of gaseous by-products from small chemical explosions on seismic source signatures is examined. The explosions analyzed in this article were conducted using different types of explosives (ammonium nitrate-fuel oil and Composition B) as a part of the New England Damage Experiment (NEDE) in Barre, Vermont. These explosives have different densities, burn rates, and energy contents per unit mass, and upon detonation they produce different amounts and compositions of gaseous by-products. The amount of gas products released during the detonation depends on the chemical composition of the explosives as well as on the presence of other compounds in and around the cavity that can vaporize or chemically decompose during the explosion (e.g., water). Analysis of the NEDE data suggests that the characteristics of the P spectra from these explosions depend on the amount of noncondensable gases released in the cavity during explosive detonation. The low-frequency amplitudes of the explosion spectra show strong correlation with the amount of gas produced by the explosions, which can be explained by higher steady-state pressure in the cavity resulting in a larger cavity and subsequently higher static value of the reduced displacement potential. Alternatively, the increase in low-frequency amplitudes can be due to a longer duration of the source function caused by the late time damage from gas-driven fracturing. The amplitudes in the high-frequency band around the corner frequencies (overshoot amplitudes) show a relationship with the trinitrotoluene (TNT)-equivalent yield and with the heat of the detonation. Thus, based on our dataset, the increase in the low-frequency amplitudes with the corresponding decrease in overshoot parameter can be explained by the increase of the amount of cavity gas released during the detonation. [ABSTRACT FROM AUTHOR]

A microwave-assisted method for the synthesis of polynitrostilbenes involving the condensation of 2,4,6-trinitro-m-xylene and 2,4,6-trinitrotoluene with aryl aldehydes in the presence of piperidine and silica-gel is reported. Compared with conventional methods, a shorter reaction time is required and this method has a lower environmental impact. A mechanism for the reaction is also proposed and supported by UV-Vis absorption spectroscopy. [ABSTRACT FROM AUTHOR]

In this paper, the unconfined and semi-confined condensed phase explosions of TNT will be studied using large eddy simulations based on the unsteady, compressible, reacting, multi-species Navier-Stokes equations to gain further understanding of the physical processes involved in a condensed phase explosion and the effect of confinement on the physical processes involved. The analysis of the mixing and afterburning of TNT explosions in free air (unconfined) and near the ground (semi-confined) indicates that the combustion region of detonation products and air is determined by the vorticity patterns, which are induced by the Richtmeyer-Meshkov instabilities that arise during the explosion. When the explosive is detonated in the vicinity of a surface, the surface affects the shock propagation by creating complex shock systems, thereby changing the orientation of the vorticity, giving the afterburning a mushroom shape, and increasing performance of an explosive charge by prolonging the existence of the mixing layer and thereby the afterburning. [ABSTRACT FROM AUTHOR]

New methods for determination of explosive substances as, for example, 2,4,6-trinitrotoluene (TNT), in a rapid way and at low cost are highly required. An electrochemical platform has been here developed with good characteristics of low dimension, fast response, low cost, and high selectivity. It is based on a commercially available screen printed cell with graphite ink working and auxiliary electrodes and a silver ink quasi-reference electrode. The whole cell is covered with a thick layer of cation exchanging acrylic polymer molecularly imprinted with 2,4,6-trinitrotoluene. The polymeric layer acts at the same time as electrolytic medium and selective receptor. It has been demonstrated that, in this medium, 2,4,6-trinitrotoluene is electroactive at graphite electrode, being reduced by a non-reversible reaction. The peak current (differential pulse voltammogram) is proportional to TNT concentration with limit of detection for TNT around 5 × 10 M and linearity range up to 2 × 10 M. The selectivity for TNT relative to other reducible compounds as, for example, nitroaromatic derivatives, and to other possible interfering substances, as negatively charged ions, is good. Measurements can be performed in not de-aerated solution and in small volumes (20 μl), so that the proposed platform is very promising for in situ determinations. [Figure not available: see fulltext.] [ABSTRACT FROM AUTHOR]

Performance of two handheld trace explosives detectors types: SABRE 4000 and MO-2M was compared in terms of the limits of detection determined for: trinitrotoluene, hexahydro-1,3,5-trinitro-1,3,5- triazine, pentaerythritol tetranitrate and nitroglycerin in the particle detection mode. SABRE 4000 detector is a conventional detector based on the ion mobility spectrometry (IMS) and radioactive nickel as the ionization source, whereas in the MO-2M type detector a variant of this technique, viz. the field asymmetric ion mobility spectrometry (FAIMS), and a different β emitter, tritium, as an ionization source are employed. In determining limits of detection the sampling technique was suggested which resorts to binomial distribution for the determination of the indispensable number of positive measurements required to regard a given amount of explosives detected as reliable. Lower limits of detection were achieved in the study for trinitrotoluene and hexahydro-1,3,5-trinitro-1,3,5-triazine with the MO-2M detector (10- and 100-fold, respectively) than with the SABRE detector, whereas for the remaining two substances limits of detection were identical for either detector. The results obtained were discussed in the aspect of the effect of the detector design, ionization mechanism and volatility of substance as the factors that determine the limits of detection values. [ABSTRACT FROM AUTHOR]

The highest Raman enhancement factors are obtained in a double resonance: molecular electronic resonance and plasmon resonance with a "hot spot" in surface-enhanced Raman scattering (SERS). However, for most molecules of interest the double resonance is not realized with the excitation frequencies normally used in Raman. The latter may limit the practical applications of SERS for trace analysis. Here, we report that Raman-inactive trinitrotoluene (TNT) lights up the ultrahigh Raman scattering of off-resonated p-aminobenzenethiol (PABT) through the formation of charge-transfer TNT-PABT complex on the top-closed flexible silver nanotube array. Raman hot spots can spontaneously form in a reversible way by the self-approaching of flexible nanotubes driven through the capillary force of solvent evaporation. Meanwhile, the PABT-TNT-PABT bridges between self-approaching silver nanotubes possibly form by the specific complexing and zwitterion interactions, and the resultant chromophores can absorb the visible light that matches with the incident laser and the localized surface plasmon of a silver nanotube array. The multiple spectral resonances lead to the huge enhancement of Raman signals of PABT molecules due to the presence of ultratrace TNT. The enhancement effect is repeatedly renewable by the reconstruction of molecular bridges and can selectively detect TNT with a limit of 1.5 × 1017 M. The results in this report provide the simple and supersensitive approach to the detection of TNT explosives and the possibility of building a robust Raman-based assay platform. [ABSTRACT FROM AUTHOR]

The vast majority of investigations into the bioavailability and toxicity of explosives to receptors in aquatic environments has focused on deriving toxicity metrics for discrete chemical exposures to single species using pure compounds at relatively high concentrations. This study assessed the environmental fate and potential for biological effects of a common military formulation, Composition B, under more realistic exposure scenarios (e.g., those that more closely simulate a breached artillery round or residual exposure following a low-order detonation). We used a novel approach incorporating multiple species and toxicity endpoints in sediment exposures over a 34-d exposure period. Composition B fragments exposed at the sediment surface rapidly released 2,4,6-trinitrotolune (TNT) and hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) to the overlying water column. In comparison, burial of fragments resulted in dramatically reduced exposure, bioconcentration, and toxicity. The addition of a conservative flow rate to the aquaria also reduced water and tissue concentrations by factors of two to three. Although the exposure system likely represented a worst-case scenario relative to most conditions found in coastal and estuarine environments, overlying water concentrations generally did not approach known toxicity thresholds, while porewater concentrations were sufficiently elevated above toxicity thresholds immediately adjacent to the fragments, limiting hazardous exposure only to very localized scales. Bioconcentration correlated closely with observed toxicity and was either not detectable (buried), or low (exposed), as is expected based on the low hydrophobicities of TNT and RDX. Environ. Toxicol. Chem. 2010;29:1330–1337. © 2010 SETAC [ABSTRACT FROM AUTHOR]

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. [Copyright &y& Elsevier]

The implementation of hand-held ion mobility spectrometers (IMS) requires the development and evaluation of miniature drift cells providing high sensitivity while maintaining reasonable resolution. This manuscript describes the construction of a miniature IMS designed for such an application and its characterization by evaluation of the detection limits and resolution of the system with seven explosive compounds including trinitrotoluene (TNT), cyclotrimethylenetrinitramine (RDX), pentaerythritol tetranitrate (PETN), 2,4,6-trinitrophenyl- N-methylnitramine (Tetryl), nitroglycerin (NG), 2,4-dinitrotoluene (2,4 DNT), and 2,6-dinitrotoluene (2,6 DNT). [Figure not available: see fulltext.] [ABSTRACT FROM AUTHOR]

In this study, the enhanced degradation of TNT using cultures of genome-shuffled Stenotrophomonas maltophilia OK-5 mt-3 has been examined and the proteome of shuffled strain was compared to the wild-type OK-5 strain. Genome shuffling of S. maltophilia OK-5 was used to achieve a rapid enhancement of TNT degradation. The initial mutant population was generated by NTG treatment and UV irradiation. The wild-type OK-5 strain was able to degrade 0.2 mM TNT within 6 days, yet barely tolerated 0.5 mM TNT while the shuffled OK-5 mt-3 was capable of completely degrading 0.5 mM TNT within 8 days, and 1.2 mM within 24 days. The proteomic analysis of the shuffled OK-5 mt-3 demonstrated the changes in the expression levels of certain proteins compared to wild-type OK-5. These results provide clues for understanding TNT tolerance and improved TNT degradation by shuffled S. maltophilia OK-5 mt-3 and have possible applications in the processing of industrial waste containing relatively high TNT concentrations. [ABSTRACT FROM AUTHOR]

The present study was aimed at providing data to be used at predicting exposure-based effects of 2,4,6-trinitrotoluene (TNT) aged in soil on endpoint organisms representing two trophic levels. These data can be used to define criteria or reference values for environmental management and conducting specific risk assessment. Long-term exposure tests were conducted to evaluate sublethal toxicity and uptake of aged soil-based explosives, with TNT as the main contaminant. In these tests, plants were exposed for 55 d, and biomass and explosives residues were determined. Worms were exposed for 28 and 42 d, and biomass, number, and tissue residues were determined. Biomass of Lolium perenne significantly decreased with soil-TNT concentration, and an effective concentration causing a 20% decrease in biomass (EC20) for TNT metabolites of 3.75 mg/kg was calculated. The concentrations of TNT metabolites in shoots and roots were significantly related to concentrations in soil, as were concentrations of hexahydro-1,3,5-trinitro-1,3,5 triazine (RDX) and octahydro-1,3,5,7-tetranitro-1,3,5,7- tetrazocine (HMX). The mean bioconcentration factors, indicating the potential of a chemical to accumulate in an organism, were 0.9 for TNT metabolites, 71.8 for RDX, and 12.2 for HMX in L. perenne shoots. Biomass of Eisenia fetida adults significantly decreased with soil-TNT concentration, and an EC20 for TNT of 3.70 mg/kg was calculated. The TNT, RDX, and HMX levels in E. fetida were below detection. [ABSTRACT FROM AUTHOR]

Abstract: The interaction of meso-tri(4-sulfonatophenyl)mono(4-carboxyphenyl) porphyrin (C1TPP) with 2,4,6-trinitrotoluene (TNT) has been explored by UV–vis and fluorescence spectroscopy. The influence of temperature on the interaction has also been studied. C1TPP binds to TNT at pH 7.0 at room temperature via 1.94kcal/mole hydrogen bonds with absorbance loss at 412–413nm and the appearance of a new peak at 422–424nm. The hydrogen binding of TNT to C1TPP was confirmed by the dissolution of the complex upon the addition of urea. Increasing the temperature results in the appearance of a new absorbance peak at 540nm and absorbance loss at 515nm with activation energy of 29.7kcal/mole in the range of the hydrophobic bond energy. This suggests the hydrophobic bonding of TNT with the pyrrole nitrogens in the porphyrin. Increasing the concentration of the TNT in the solution quenches the fluorescence of the porphyrin following the Stern–Volmer equation. The association constants calculated from absorbance and fluorescence are expectedly similar. [Copyright &y& Elsevier]

Oxidative degradation of dinitrotoluene (DNT) isomers and 2,4,6-trinitrotoluene (TNT) in spent acid was conducted by Electro-Fenton’s reagents. The electrolytic experiments were carried out to elucidate the influence of various operating parameters on the performance of mineralization of total organic compounds (TOC) in spent acid, including reaction temperature, dosage of oxygen, sulfuric acid concentration and dosage of ferrous ions. It deserves to note that organic compounds could be completely destructed by Electro-Fenton’s reagent with in situ electrogenerated hydrogen peroxide obtained from cathodic reduction of oxygen, which was mainly supplied by anodic oxidation of water. Based on the spectra analyzed by gas chromatograph/mass spectrometer, it is proposed that initial denitration of 2,4,6-TNT gives rise to formation of 2,4-DNT and/or 2,6-DNT, which undergo the cleavage of nitro group into o-mononitrotoluene, followed by denitration to toluene and subsequent oxidation of the methyl group. Owing to the removal of both TOC and partial amounts of water simultaneously, the electrolytic method established is potentially applied to regenerate spent acid from toluene nitration processes in practice. [Copyright &y& Elsevier]

The contamination of the environment by explosives is a worldwide problem resulting in part from 2,4,6-trinitrotoluene (TNT) production. In situ phytoremediation is an appropriate, alternative, cost-effective technology to detoxify extended contamination of surface soil. The ability of rice ( Oriza sativa) to both tolerate and assimilate 14C-labeled TNT was investigated over a 40-day exposure period. The germination rate decreased at 500 mg/kg TNT whereas root and shoot length increased significantly at high TNT concentrations, from 150 to 500 mg/kg. Rice took up TNT residues from soil and accumulated most in roots. Less than 25% of radioactivity taken up was translocated to aerial parts. Above 200 mg/kg TNT, the concentration of TNT residues in roots reached a maximum of approximately 0.7 mg/g. No TNT was found in plant extracts, good evidence for rapid metabolism of TNT. More than 60% of 14C activity was found as unextractable residues in roots. It was concluded that TNT metabolized and subsequently sequestered by roots could not be translocated to aerial parts. [ABSTRACT FROM AUTHOR]

Conventional explosives 2,4,6-trinitrotoluene (TNT), nitroglycerin (NG), and ethylene glycol dinitrate (EGDN) sorbed to hair can be directly detected by an ion mobility spectrometer (IMS) in E-mode (for explosives). Terrorist explosive, triacetone triperoxide (TATP), difficult to detect by IMS in E-mode, was detected in N-mode (for narcotics). Three modes of sample introduction to IMS vapor desorption unit were used: (i) placement of hair directly into the unit, (ii) swabbing of hair and placement of swabs (i.e., paper GE-IMS sample traps) into the unit, and (iii) acetonitrile extracts of hair positioned on sample traps and placed into the unit. TNT, NG, and EGDN were detected in E-mode by all three sample introduction methods. TATP could only be detected by the acetonitrile extraction method after exposure of the hair to vapor for 16 days because of lower sensitivity. With standard solutions, TATP detection in E-mode required about 10 times as much sample as EGDN (3.9 μg compared with 0.3 μg). IMS in N-mode detected TATP from hair by all three modes of sample introduction. [ABSTRACT FROM AUTHOR]

Abstract: Toxicological data on the effects of the explosive, 2,4,6-trinitrotoluene (TNT), and its degradation products suggests an unpredictable toxicological response in aquatic organisms. Several studies suggest TNT becomes more toxic as it degrades while others suggest TNT becomes less toxic. This study focused on the toxicity of TNT and several degradation products as well as the role of oxidative metabolism in the toxicity of TNT. The aquatic invertebrate Hyalella azteca was used to evaluate the toxicity of TNT and four of its degradation products. The most reduced degradation product, 2,4-diamino, 6-nitrotoluene (2,4-DANT) was the most toxic to H. azteca. However, 2,4-DANT was only a minor metabolite in H. azteca. The influence of metabolism on the toxicokinetics of TNT was assessed indirectly through the use of a CYP450 inducer and inhibitor. Treatment of organisms with β-napthoflavone (BNF), a CYP450 inducer, increased the toxicity of TNT and increased the rate of elimination and metabolism of TNT. Similar to BNF, organisms treated with clotrimazole (CTZ), a CYP450 inhibitor, resulted in increased toxicity and TNT metabolism. It is likely the ability to metabolize or bioactivate TNT to a more reactive intermediate plays a significant role in the sensitivity of organisms to TNT. [Copyright &y& Elsevier]

Abstract: An optimized microwave assisted extraction method for determination of trinitrotoluene (TNT) and related compounds in soil is presented. The new enhanced method exhibits improved extraction recovery and precision as well as sample handling time. For the separation and detection gas chromatography coupled to a thermoionic probe was used achieving TNT and dinitrotoluene detection limits per injection at the femtogram level. The generated extraction recovery and precision data are given for spiked and certified soil. Determined TNT and related compounds residues in soil collected from different parts of the world are presented. [Copyright &y& Elsevier]

Abstract: On-site colorimetric methods are a valuable, cost-effective tool to assess the nature and extent of contamination in remediated sites and to enable on-site screening for police criminology laboratories. The existing colorimetric method for cyclotrimethylenetrinitramine (RDX) based on a Griess reaction suffers from the non-quantitative reduction to nitrite and from the unstable character of HNO2 in acidic medium. Thus we propose a novel spectrophotometric RDX assay in explosive mixtures and residues, based on (Zn+HCl) reduction of RDX in a microwave oven, followed by neutralization of the reduction products to ammonia and low molecular-weight amines, and Berthelot reaction of these amine-compounds with phenol and hypochlorite in alkaline medium to give an intensely blue indophenol dye absorbing at 631nm. The molar absorptivity and limit of detection (LOD) for RDX were (1.08±0.04)×104 Lmol−1 cm−1 and 0.18mgL−1, respectively. Application of the method to synthetic mixture solutions of RDX and trinitrotoluene (TNT) at varying proportions showed that there was minimal interference from TNT (which could be compensated for by dicyclohexylamine colorimetry), since the Berthelot reaction was essentially non-responsive to m-substituted anilines derived from TNT upon (Zn+HCl) reduction. The proposed method was successfully applied to military-purpose explosive mixtures of (RDX+inert matter) such as Comp A5, Comp C4, and Hexal P30, and to (RDX+TNT) mixtures such as Comp B. The molar absorptivity of RDX was much higher than that of either ammonium or nitrate; RDX could be effectively separated from ammonium and nitrate in soil mixtures, based on solubility differences. The Berthelot method for RDX was statistically validated using Comp B mixtures against standard HPLC equipped with a Hypersil C-18 column with (40% MeOH–60% H2O) mobile phase, and against gas chromatography–thermal energy analysis (GC–TEA) system. [Copyright &y& Elsevier]

Trinitrotoluene (TNT), a nitroaromatics, is a major pollutant in explosive contaminated soils. Present study reports the effect of initial concentration of TNT on its degradation kinetics in soils. Soils from two contaminated sites viz. Clausthal and Elsnig, Germany, were mixed with an uncontaminated reference soil to get different initial concentrations (mg/kg) viz Clausthal-1 (54.29), Clausthal-2 (30.86), Clausthal-3 (7.05) Elsnig-1 (879.67), Elsnig-2 (86.43); Elsnig-3 (8.16) and Elsnig-4 (0.99) and were spiked with ring UL-14C-TNT (100KBq/50g soil). Except Elsnig-1 and Elsnig-2 soils, TNT degraded at same rate in all the soils. Higher persistence of TNT in Elsnig-1 and Elsnig-2 soils appears to be due to higher initial concentrations of nitroaromatics which may be toxic to soil microorganisms. 2-Amino-4,6-dinitrotoluene (2-ADNT) and 4-amino-2,6-dinitrotoluene (4-ADNT) were recovered as major metabolites of TNT. Distribution of bound 14C-activity in different soil organic matter (SOM) fractions (humic acid, fulvic acid and humin) was assayed by alkali extraction of solvent extracted Clausthal-1 and Elsnig-1 soils. Results indicate that humic acid accounted for maximum bound activity followed by fulvic acid and humin fractions. Expressing 14C-activity bound/unit weight of organic carbon content of SOM fractions showed that 3 times more 14C-activity was bound to Elsnig humic acid than Clausthal humic acid. Similarly, activity associated with Elsnig fulvic acid was 7 times higher than that of Clausthal fulvic acid suggesting that chemical nature of SOM fractions plays a significant role in binding of contaminants. [ABSTRACT FROM AUTHOR]

Detection of trace quantities of explosive residues plays a key role in military, civilian, and counter-terrorism applications. To advance explosives sensor technology, current methods will need to become cheaper and portable while maintaining sensitivity and selectivity. The detection of common explosives including trinitrotoluene (TNT), cyclotrimethylenetrinitramine, cyclotetramethylene-tetranitramine, pentaerythritol tetranitrate, 2,4,6-trinitrophenyl-N-methylnitramine, and trinitroglycerin may be carried out using a three-step process combining “turn-off” and “turn-on” fluorimetric sensing. This process first detects nitroaromatic explosives by their quenching of green luminescence of polymetalloles (λem ≈ 400–510 nm). The second step places down a thin film of 2,3-diaminonaphthalene (DAN) while “erasing” the polymetallole luminescence. The final step completes the reaction of the nitramines and/or nitrate esters with DAN resulting in the formation of a blue luminescent traizole complex (λem = 450 nm) providing a “turn-on” response for nitramine and nitrate ester-based explosives. Detection limits as low as 2 ng are observed. Solid-state detection of production line explosives demonstrates the applicability of this method to real world situations. This method offers a sensitive and selective detection process for a diverse group of the most common high explosives used in military and terrorist applications today. [ABSTRACT FROM AUTHOR]

This study examines the sorption of eight explosives (2,4,6-trinitrotoluene [TNT]; pentaerythritol tetranitrate [PETN]; hexahydro-1,3,5-trinitro-s-triazine [RDX]; diacetone diperoxide [DADP]; triacetone triperoxide [TATP]; ethylene glycol [EGDN], nitroglycerin [NG]; and 2,4-dinitrotoluene [DNT]) to human hair. The study uses only cut hair, which is exposed to explosive vapor. The vapor transfer studies reported herein indicated that hair did not reach saturation even after 2.5 years of exposure to TNT. While previous studies showed black hair sorbed more explosive than blond or brown, this study reports that red hair sorption is similar to black, while grey hairs, exposed along with black hair from the same individual, sorbed significantly less explosive than the same individual’s black hairs. In a study using only black hair, a slight racial bias was observed with sorption greater for Mongoloid hair as compared to Caucasian or Negroid. Only for Mongoloid hairs were enough samples studied to examine for a gender bias, but one was not observed. There was much variability in results in all categories (hair color, race, and gender) that trends were established only in general terms. Hair at different ages was tested for a few individuals. Detailed studies focused on the sorption of TATP and TNT as these appear to be sorbed most differently—TATP mainly on the hair surface and TNT both on the surface and in the cortex. The uptake of high vapor pressure explosives (e.g., TATP) and moderate vapor pressure explosives (e.g., TNT) by hair was rapid and could be detected within about 1 h of exposure. Both explosives were readily sorbed by pure melanin. [ABSTRACT FROM AUTHOR]

Nitroaromatics are common pollutants of soil and groundwater at military installations because of their manufacture, storage, and use at these sites. Long-term monitoring of these pollutants comprise a significant percentage of restoration costs. Further, remediation activities often have to be delayed, while the samples are processed via traditional chemical assessment protocols. Here we describe a rapid (<5 mm), cost-effective, accurate method using a KinExA Inline Biosensor for monitoring of 2,4,6-trinitrotoluene (TNT) in field water samples. The biosensor, which is based on KInExA technology, accurately estimated the concentration of TNT in double-blind comparisons with similar accuracy to traditional high- performance liquid chromatography (HPLC). In the assessment of field samples, the biosensor accurately predicted the concentration of TNT over the range of 1–30 000ug/L when compared to either HPLC or quantitative gas chromatography—mass spectrometry (GC-MS). Various pre-assessment techniques were explored to examine whether field samples could be assessed untreated, without the removal of particulates or the use of solvents. In most cases, the KinExA Inline Biosensor gave a uniform assessment of TNT concentration independent of pretreatment method. This indicates that this sensor possesses significant promise for rapid, on-site assessment of TNT pollution in environmental water samples. [ABSTRACT FROM AUTHOR]

A key factor in selecting surfactants to enhance chemical or biological transformation or physical removal of an organic pollutant from contaminated soil is knowledge of the pollutant’s solubility behavior in the surfactant solution. This study investigated the influence of nonionic surfactant structure on the solubility of 4-nitrotoluene (NT), 2,3-dinitrotoluene, 2,4-dinitrotoluene, 2,6-dinitrotoluene, and 2,4,6-trinitrotoluene (TNT) at room temperature. For a series of alkyl phenol ethoxylates (Tergitol NP-8 to NP-40), decreasing the ethoxylate chain length increased the solubility of these nitrotoluenes by a factor of two or less in 10gl−1 surfactant solutions, but did not significantly change their molar solubilization ratios (MSR, e.g. 0.02 for TNT) or their micelle–water partition coefficients (K m, e.g. 3.4 for TNT). For Tergitol NP-8 solutions ranging from 1.0 to 12.4gl−1, no enhancement in NT solubility was found, suggesting that the cloud point was reached. The MSRs for Tween 80 were higher than those of Tween 20 and the MSRs of Brij-58 were higher than those for Brij-35. When comparing solutes, NT had the highest solubility and MSR (0.28–0.41), while TNT had the lowest solubility and MSR (0.02–0.03). A linear relationship between K m values and octanol–water partition coefficients based on Triton X-100 predicted the log K m values within 0.5 of their measured values. A linear solvation free energy correlation for K m suggested the importance of solute volume and effective hydrogen bond basicity in the partitioning process while implying that the nitrotoluenes are solubilized in a polar portion of the micelle. [Copyright &y& Elsevier]

The fate and effects of 2,4,6-trinitrotoluene (TNT) at marine ammunition dumping sites are essentially unknown. The objective of this study was to examine the release from solid TNT to seawater when covered by sediment of two different types (sandy and fine-grained) and thickness (0, 1, 2, and 4cm), under different temperatures (5, 10, and 20°C), and light conditions (ambient daylight and darkness) in the laboratory. The water column was analysed for TNT and some of its common transformation products, and toxicity to the copepod Nitocra spinipes after 1, 2, 4, 8, 19, and 32 weeks. Leakage of TNT to seawater and the toxicity to N. spinipes was significantly reduced by sediment burial, especially in fine-grained sediment. Hence, this study suggests that adverse effects of TNT in dumped ammunition on aquatic organisms should be delayed/reduced at low temperature and when TNT is covered sediment, especially with fine-grained sediment. [Copyright &y& Elsevier]

Abstract: A chemical sensor was developed to detect the explosive 2,4,6-trinitrotoluene (TNT) utilizing planar integrated optical waveguide (IOW) attenuated total reflection spectrometry. Submicron thick films of organically modified sol–gel polymers were deposited on the waveguide surface as the sensing layer. Sol–gels were molecularly imprinted for TNT using covalently bound template molecules linked to the matrix through 1 or 2 carbamate linkages. Upon chemical cleavage of the template and displacement of the TNT-like pendant groups from the matrix, shape-selective binding sites were created that possess a primary amine group. The amine was used to deprotonate bound TNT yielding an anionic form that absorbs visible light. Binding of TNT and subsequent conversion to the anion results in the attenuation of light propagating through the waveguide, thus creating a spectrophotometric device. Sensitivity can be achieved by taking advantage of the substantial pathlength provided by the use of single mode IOWs. The limit-of-detection to gas-phase TNT was found to be five parts-per-billion (ppbV) in ambient air at a flow rate of 40mLmin−1 given a 60s sampling time. The sensor is highly selective for TNT due to the selectivity of binding site recognition of TNT and the subsequent generation of the TNT anion. Response to TNT is not reversible which results in an integrating sensor device which, in theory, can improve the ability to detect small amounts of the explosive if the exposure time is sufficient in length. [Copyright &y& Elsevier]

Previous research in our laboratory investigated the effectiveness of a common agrochemical, urea used as a chaotropic agent to facilitate 2,4,6-trinitrotoluene (TNT) removal by vetiver grass ( Vetiveria zizanioides L.). Chaotropic agents disrupt water structure, increasing solubilization of hydrophobic compounds (TNT), and enhancing plant TNT uptake. Our findings showed that urea significantly enhanced TNT uptake kinetics by vetiver. We hypothesized that the beneficial effect of urea on the overall TNT uptake by vetiver grass was not plant-specific. We explored this hypothesis by testing the ability of wheat ( Triticum aestivum L.) in removing TNT from aqueous media in the presence of urea. Results showed that untreated (no urea) wheat exhibited a slow, kinetically limited TNT uptake that was nearly half of the urea-treated wheat TNT capacity (250 mg kg−1). Chaotropic effects of urea were illustrated by the significant ( P < 0.001) increase in the TNT second-order reaction rate constants over those of the untreated (no urea) controls. Plant TNT speciation showed that TNT and several of its metabolites were detected in both root and shoot compartments of the plant, allowing for 110 and 36% recovery for the untreated and 0.1% urea treated plants. The lower % recovery of the urea-treated plants was attributed to a number of unknown polar TNT metabolites. [ABSTRACT FROM AUTHOR]

This paper gives a description of a high-speed X-ray tomographic technique and the results of its application to finding the density distribution of detonation products of condensed explosives from measurements using synchrotron radiation. The data obtained for a cylindrical charge of pressed TNT of diameter 12.5-mm and density 1.6 g/cm3 are compared with the results of solution of the corresponding gas-dynamic problem of steady-state detonation. The experimental and computational results are in satisfactory qualitative and quantitative agreement. The features of the employed technique and the distribution obtained are analyzed. The technique as a whole and the results obtained can be used to test and refine the known equations of state for detonation products and to construct new ones. [ABSTRACT FROM AUTHOR]

Previously, a displacement immunoassay for 2,4,6-trinitrotoluene (TNT) was demonstrated using the Luminex 100. The work presented utilized this same specialized flow cytometer to demonstrate a highly sensitive and rapid competitive immunoassay for TNT. This required a TNT analog to be attached to the microsphere surface. Various linkers were evaluated; bovine serum albumin provided over 3 times more binding sites in comparison to various shorter diamine linkers. For this assay TNB-coated microspheres were added to samples; then biotinylated anti-TNT antibody and the reporter molecule, Streptavidin-R-Phycoerythrin, were added. In the absence of TNT, a highly fluorescent complex was formed on the surface of the microsphere. The presence of TNT resulted in dose-dependent decreased fluorescence. Various anti-TNT antibodies were evaluated; Mab 30-1 gave the strongest response, yielding the lowest limit of detection (<1.0 ng/mL) and a dynamic range up to 1 μg/mL. Other factors such as reaction time, cross reactivity to other nitro-compounds, evaluation of acetone extracts of TNT contaminated soils, testing in environmental matrices such as fresh water and seawater were all completed. Finally, a multiplex assay for TNT and three protein toxins was successfully conducted using the competitive format. [ABSTRACT FROM AUTHOR]

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. [Copyright &y& Elsevier]

Environmental regulations for removal of trinitrotoluene (TNT) from wastewater have steadily become more stringent. This study focuses on the adsorption equilibrium, kinetics, and column dynamics of TNT on heterogeneous activated carbon. Adsorption equilibrium data obtained in terms of temperature (298. 15, 313. 15 and 323. 15K) and pH (3, 8 and 10) were correlated by the Langmuir equation. In addition, the adsorption energy distribution functions which describe heterogeneous characteristics of porous solid sorbents were calculated by using the generalized nonlinear regularization method. Adsorption breakthrough curves were studied in activated column under various operating conditions such as temperature, pH, concentration, flow rate, and column length. We found that the effect of pH on adsorption breakthrough curves was considerably higher than other operating conditions. An adsorption model was formulated by employing the surface diffusion model inside the activated carbon particles. The model equation that was solved numerically by an orthogonal collocation method successfully simulated the adsorption breakthrough curves. [Copyright &y& Elsevier]

Manufacture of nitroorganic explosives generates toxic wastes leading to contamination of soils and waters, especially groundwater. For that reason bacteria living in environments highly contaminated with 2,4,6-trinitrotoluene (TNT) and other nitroorganic compounds were investigated for their capacity for TNT degradation. One isolate, Raoultella terrigena strain HB, removed TNT at concentrations between 10 and 100 mg l-1 completely from culture supernatants under optimum aerobic conditions within several hours. Only low concentrations of nutrient supplements were needed for the cometabolic transformation process. Radioactivity measurements with ring-labelled 14C-TNT detected about 10-20% of the initial radioactivity in the culture supernatant and the residual 80-90% as water-insoluble organic compounds in the cellular pellet. HPLC analysis identified aminodinitrotoluenes (2-ADNT, 4-ADNT) and diaminonitrotoluenes (2,4-DANT) as the metabolites which remained soluble in the culture medium and azoxy-dimers as the main products in the cell extracts. Hence, the new isolate could be useful for the removal of TNT from contaminated waters. [ABSTRACT FROM AUTHOR]

2,4,6-Trinitrotoluene present in a culture of Escherichia coli K12, at a concentration of 200 mg/l, caused a decrease in the total cell population and the population of colony-forming units, increased permeability of the external lipoprotein envelope, and increased the refractive index of cells. The shape of some cells changed from rod-like to coccoid, and cell size decreased. The specific rate of glucose consumption and the content of NADH (NADPH) in cells decreased. The changes of these morphological and physiological features were reversible, tending to normalize after reduction of 2,4,6-trinitrotoluene concentration in the course of cultivation. [ABSTRACT FROM AUTHOR]

Escherichia coli grew aerobically with 2,4,6-trinitrotoluene (TNT) as sole nitrogen source and caused TNT's partial denitration. This reaction was enhanced in nongrowing cell suspensions with 0.516 mol nitrite released per mol TNT. Cell extracts denitrated TNT in the presence of NAD(P)H. Isomers of amino-dimethyl-tetra-nitrobiphenyl were detected and confirmed with U-15N-labeled TNT. [ABSTRACT FROM AUTHOR]

Abstract: A rapid spectrophotometric determination for 2,4,6-trinitrotoluene (TNT) is significant because this method is suitable for simultaneous analyses of the numerous samples. We found one problem that TNT reduction products interfere with the TNT detection in this assay, and we overcame this problem by heating the samples at 95 °C, resulting in the production of compounds that did not interfere. [Copyright &y& Elsevier]

Pseudomonas putida JLR11 can grow on 2,4,6-trinitrotoluene (TNT) as the sole nitrogen source. We created nasB (nitrite reductase), pnrA (nitroaromatic reductase) and pnrA nasB mutants and tested their growth with TNT as the sole N source. The nasB and pnrA mutants grew at a reduced rate on TNT, whereas the double nasB pnrA mutant did not. This suggests that P. putida JLR11 carries out multiple enzymatic attacks on TNT-releasing nitrite and/or ammonium. The PnrA nitroreductase plays a key role in the reduction of TNT to 2,6-dinitro-4-hydroxylaminotoluene and the subsequent release of ammonium for growth. [ABSTRACT FROM AUTHOR]

Abstract: Signal properties of the acoustic waves produced from meteoroids impacting the Earth''s atmosphere in the approximate size range of 0.1–10m diameter have been analyzed at infrasonic frequencies. From these data, we have produced a series of empirical relations between the far-field acoustic signature of the bolide shocks and meteor source energies by correlating infrasonic observations of those fireballs which are also detected by earth-observing satellites. Adopting a similar approach as has been previously employed for man-made explosives, signal properties such as acoustic amplitude, signal energy/power and signal-to-noise ratio, are shown, after high-altitude wind corrections, to be useful tools in estimating the kinetic energy of a bolide. Comparison of bolide infrasound data to ground-based explosive tests show that the acoustic amplitudes from airwaves generated by small bolide events (<7kt TNT equivalent) attenuate more rapidly than nuclear or chemical explosions. As well, acoustic amplitude values for bolides are systematically lower than acoustic amplitudes measured for equivalent ground-based explosions. This is interpreted to be largely due to bolide acoustic sources being at high altitudes in the atmosphere. We find from our analysis that these heights are on average located between 20 and 30km. Larger events (>7kt) mimic man-made explosions in terms of range dependence, but offset in amplitude equivalent to ∼20km source altitudes. This is consistent with instrumental observations of fireballs and the expectation that larger meteoroids (greater than a few meters in diameter), should penetrate deeper into the atmosphere on average. Applying these new relationships to historical events, we find that the August 3, 1963 bolide detected infrasonically near the Prince Edward Islands off the coast of South Africa, previously estimated to have an energy of 1100kt, may have had a much smaller energy of 266±90kt. This energy revision brings the infrasonically determined Near Earth Object (NEO) influx rate into much better agreement with that determined more recently using satellite and telescopic survey data. [Copyright &y& Elsevier]

Abstract: Illumination of tetraphenyl porphyrin sulfonate (TPPS), CuTPPs and FeTTPPS in solution with trinitrotoluene (TNT) at pH7 at room temperature using tungsten lamp illumination results in the degradation of TNT to yield trinitrobenzoic acid and trinitrobenzene. No other degradation products are observed. The rate of TNT degradation follows the series TPPS>FeTPPS>CuTPPS. [Copyright &y& Elsevier]

The presence of trace contamination of soil and ground-water with explosives is an ongoing concern, for which improved methods are required to facilitate their detection and quantification. This is true both for the monitoring of remediation and for site characterization. Immunosensors have been found effective for solution-phase detection of environmental contaminants. Our work utilized the Lu-minex100 (flow cytometer) to detect TNT in a multiplexed displacement immunoassay format. The Luminex100 can perform a multiplexed assay by discriminating between up to 100 different bead sets. We used this capability to evaluate four different TNT monoclonal antibodies, two recombinant TNT antibodies, and a control antibody simultaneously for the rapid detection of TNT and other nitroaromatics. TNT could be detected at 0.1 ppb and quantified over the range of 1.0 ppb to 10 ppm. In addition, the assay was shown to be effective in various matrixes such as lake water, seawater, and acetone extracts of soil. Seawater required dilution with two parts buffer to avoid loss of microspheres, while the acetone extracts were diluted 100-fold or more to minimize solvent affects. [ABSTRACT FROM AUTHOR]

No abstract available. [ABSTRACT FROM AUTHOR]

Fullerenes containing a trimetallic nitride template (TNT) within the cage are a particularly interesting class of endohedral metallofullerenes. Recently two exohedral derivatives of the Sc3N@C80 fullerene have been synthesized: a Diels-Alder and a fulleropyrrolidine cycloadduct. The successful isolation, purification, and structural elucidation of these metallofullerenes derivatives have encouraged us to understand how the chemical reactivity is affected by TNT encapsulation. First of all, we predicted the most reactive exohedral sites, taking into account the double bond character and the pyramidalization angle of the C-C bonds. For this purpose, a full characterization of all different types of C-C bonds of the following fullerenes was carried out: Ih-C60:1, D3-C68:6140, D3-Sc3N@C68, D5h-C70:1, D3h′-C78:5, D3h-Sc3N@C78, Ih-C80:7 and several isomers of Sc3N@C80. Finally the exohedral reactivity of these TNT endohedral metallofullerenes, via [4 + 2] cycloaddition reactions of 1,3-butadiene, was corroborated by means of DFT calculations. [ABSTRACT FROM AUTHOR]

The purpose of this study was to evaluate the potential of gamma irradiation to decompose 2,4,6-trinitrotoluene (TNT) in an aqueous solution; the concentration range of the TNT solution was 0.11-0.44 mmol/L The decomposition rate of TNT by gamma irradiation was pseudo-first-order kinetic over the applied initial concentrations. The dose constant was strongly dependent on the initial concentration of TNT. Increasing the concentration of dissolved oxygen in the solution was more effective on the decomposition of TNT as well as its mineralization. The required irradiation dose to remove 90% of initial TNT (0.44 mmol/L) was 58, 41, 32, 28, and 25 kGy at the dissolved oxygen concentration of 0.025, 0.149, 0.3, 0.538, and 0.822 mmol/L respectively. However, TOC still remained as 30% of the initial TOC (3.19 mmol/L) when 200 kGy irradiation dose was applied to the TNT solution (0.44 mmol/L) containing dissolved oxygen of 0.822 mmol/L. The removal of the TNT was more efficient at a pH below 3 and at a pH above 11 than at neutral pH (pH 5-9). The required irradiation dose to remove over 99% of the initial TNT (0.44 mmol/L) was 39, 76, and 10 kGy at pH 2, 7, and 13, respectively. The dose constant was increased 1.6-fold and over 15.6-fold at pH 2 and 13, respectively, compared to that at pH 7. When an irradiation dose of 200 kGy was applied, the removal efficiencies of the TOC (initial concentration 3.19 mmol/L) were 91, 46, and 53% at pH 2, 7, and 13, respectively. Ammonia and nitrate were detected as the main nitrogen byproducts of TNT, and glyoxalic acid and oxalic acid were detected as organic byproducts. [ABSTRACT FROM AUTHOR]

Abstract: Snow was used as a collection medium to examine 1,3,5-hexahydro-1,3,5-trinitrotriazine (RDX) and 2,4,6-trinitrotoluene (TNT) residues post-detonation of 60-, 81-, and 120-mm mortar rounds, 105- and 155-mm howitzer rounds, M67 hand grenades, 40-mm rifle grenades, and blocks of C4. Residue-covered snow samples were collected, processed, and analyzed for explosives without cross-contamination from previous detonations and other potential matrix interferences. Detonation trials were performed following standard military live-fire and blow-in-place techniques. When possible, replicate munitions were detonated under similar conditions to provide a more reliable estimation of the mass of unconsumed high explosive residues. Overall the amount of energetic residues deposited from live-fire detonations were considerably less than the energetic residues deposited by blow-in-place detonations. [Copyright &y& Elsevier]

Three NAD(P)H-dependent nitroreductases that can transform 2,4,6-trinitrotoluene (TNT) by two reduction pathways were detected in Klebsiella sp. C1. Among these enzymes, the protein with the highest reduction activity of TNT (nitroreductase I) was purified to homogeneity using ion-exchange, hydrophobic interaction, and size exclusion chromatographies. Nitroreductase I has a molecular mass of 27 kDa as determined by SDS-PAGE, and exhibits a broad pH optimum between 5.5 and 6.5, with a temperature optimum of 30–40°C. Flavin mononucleotide is most likely the natural flavin cofactor of this enzyme. The N-terminal amino acid sequence of this enzyme does not show a high degree of sequence similarity with nitroreductases from other enteric bacteria. This enzyme catalyzed the two-electron reduction of several nitroaromatic compounds with very high specific activities of NADPH oxidation. In the enzymatic transformation of TNT, 2-amino-4,6-dinitrotoluene and 2,2′,6,6′-tetranitro-4,4′-azoxytoluene were detected as transformation products. Although this bacterium utilizes the direct ring reduction and subsequent denitration pathway together with a nitro group reduction pathway, metabolites in direct ring reduction of TNT could not easily be detected. Unlike other nitroreductases, nitroreductase I was able to transform hydroxylaminodinitrotoluenes (HADNT) into aminodinitrotoluenes (ADNT), and could reduce ortho isomers (2-HADNT and 2-ADNT) more easily than their para isomers (4-HADNT and 4-ADNT). Only the nitro group in the ortho position of 2,4-DNT was reduced to produce 2-hydroxylamino-4-nitrotoluene by nitroreductase I; the nitro group in the para position was not reduced. [ABSTRACT FROM AUTHOR]

The explosive trinitrotoluene (TNT) is a prevalent contaminant in many military installations worldwide. Limited knowledge of the comparative toxicity of sediment-associated TNT and related compounds contributes to uncertainty when assessing ecological risks in contaminated sites. Trinitrotoluene undergoes transformation when associated with soils and sediments and typically occurs as a mixture dominated by its reduction products. The objective of this study was to comparatively evaluate the single-compound toxicity of TNT and its major transformation products to the freshwater midge Chironomus tentans in 10-day exposures to sediment spiked with TNT, 2-aminodinitrotoluene (2-ADNT), 2,4-diaminonitrotoluene (2,4-DANT), or trinitrobenzene (TNB). In addition, the nature of the toxicological interactions of the latter compounds in a mixture was evaluated. Upon spiking to sediment, TNT and TNB rapidly degraded to reduced products, and disappearance of extractable compounds suggested irreversible binding to sediment particles. The high degree of transformation and reactivity occurring during 10 days at spiking concentrations as high as 4000 μmol/kg dry weight suggests that TNT and related compounds are unlikely to be encountered in fine-grained sediments at contaminated sites. Similar to previous investigations, the high reactivity of the spiked compound hampered determination of accurate toxic concentrations of TNT and related compounds, and of the nature of toxicological interaction of compounds in a mixture in this study. Sediment concentrations associated with decreased survival were similar for all four compounds, with the 10-d median lethal concentrations (LC50s) determined using initial concentrations ranging from 175 (2-ADNT) to 605 (2,4-DANT) μmol/kg dry weight. Sublethal decrease in growth was not observed for any compound. Results from the mixture experiment suggest additive interaction among TNT and related compounds in sediment exposures. [ABSTRACT FROM AUTHOR]

This article focuses on the simulation of phytoremediation of a trinitrotoluene (TNT)-contaminated soil using the coupled transport of water, heat, and solutes in the soil-plant-atmosphere continuum model. Organic contaminants are ubiquitous in soil and ground water systems throughout the world. One such organic contaminant is TNT, which was introduced into soil and ground water mainly through improper explosive manufacturing, storage, testing, and packaging. Incineration, compost application, and oxygen releasing compounds are currently available technologies for remediation of highly toxic soils contaminated with TNT. Phytoremediation is the use of plants to remediate selected contaminants in contaminated soil, sludge, sediment, ground water, surface water, and waste water. Uptake of TNT by plants has been studied during the past decade. These studies were initially prompted by a concern over effects on the food chain of plants ex- posed to TNT contamination and are recently driven by interests in phytoremediation.

A novel pathway for biodegradation of 2,4,6-trinitrotoluene (TNT) was investigated where TNT was the sole carbon, nitrogen, and energy source. Results showed the ability of microorganisms to metabolize TNT through removal of a nitro-group, oxygenation of the aromatic ring, and production of a metabolite that is typically a precursor to oxygenolytic ring cleavage. Nitrite production was observed in active systems, and TNT degradation activity was repeatable and transferable. The metabolic intermediate, 3-methyl-4,6-dinitrocatechol, was positively identified through stable isotope mass spectrometry and tandem mass spectrometry. Experimentation with 14C-TNT showed >3% 14C-labeled CO2 in active systems after 30 d exposure to microorganisms. An increasing fraction of 14C-labeled material was associated with biomass with time, where 11.41 ± 2.91% and 17.09 ± 1.49% of 14C was associated with biomass in active systems after 20 and 30 d, respectively, as compared with 5.68 ± 1.33% and 6.08 ± 1.27% in inactive systems. Parallel degradation of TNT and production of organic metabolites and nitrite were observed in shake flasks constructed with soil from historically contaminated sites, indicating that the novel pathway identified herein is disturbed in the environment. Therefore, results presented provide evidence of a previously unreported pathway for oxidative degradation of TNT. [ABSTRACT FROM AUTHOR]