A study on the determination of the metabolites of 2,4,6-Trinitrotoluene using a dual-drift tube ion mobility spectrometer.

2,4,6-Trinitrotoluene (TNT) and its four metabolites, namely 2-ADNT, 4-ADNT, 2,4-DANT, and 2,6-DANT, are highly toxic substances. These metabolites also serve as biomarkers for assessing the health of individuals exposed to TNT. In this study, a homemade DDT-IMS apparatus was utilized to detect these metabolites. Under negative detection mode, the drift times of 2-ADNT and 4-ADNT showed subtle shifts within a drift tube temperature range of 100 °C-120 °C, aiding in their differentiation. In positive detection mode for 2,4-DANT and 2,6-DANT, significant variations were observed in both the number and drift time of their positive product ions across a drift tube temperature range of 80 °C-120 °C. Consequently, optimal analytical performance for these metabolites was achieved at approximately 100 °C. Evaluation of the instrumental response during the measurement of the four metabolites in both positive and negative modes revealed that negative detection mode offered greater advantages of detecting these compounds. The working ranges for measuring the four metabolites spanned two orders of magnitude, with detection limits for each metabolite nearly below 1 ng. Notably, clear identification of the signals for these metabolites was achieved even when samples were mixed in urine, highlighting the ability of the DDT-IMS in detecting TNT metabolites. The developed DDT-IMS detection method has significant potential for enhancing environmental risk assessment and biological hazard evaluation, particularly in relation to human exposure to TNT.

Movement of TNT and RDX from composition B detonation residues in solution and sediment during runoff.

Energetics used in military exercises can potentially contaminate ground and surface waters. This study was conducted to evaluate the movement of Composition B, a formulation that includes TNT (2,4,6-trinitrotoluene), RDX (hexahydro-1,3,5-trinitro-1,3,5-triazine), and HMX (octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine), in runoff. Mechanisms of transport we examined include movement of energetics dissolved in runoff, as particles and adsorbed to suspended sediment, and in infiltration. Rainfall simulations were conducted under controlled conditions with two rainfall rates (approximately 30 and 50 mm h-1), two soils with different infiltration capacities, and four energetic particle sizes (4.75-9.51 mm, 2.83-4.75 mm, 2-2.83 mm, and <2 mm). Particles remaining on the soil surface after rainfall were measured as well as energetics dissolved in runoff, in suspended sediment, and in infiltration. Greater concentrations of TNT than RDX and HMX were found dissolved in runoff due to its higher solubility and dissolution rates. We also found that particle transport in runoff increased with decrease in particle size. Smaller particle sizes also led to greater transport dissolved in solution. Relationships were found relating runoff and sediment yield to the transport of RDX and TNT. The results of this study allow improved prediction of Composition B transport in runoff and therefore its contamination potential.

Interaction, Insensitivity and Thermal Conductivity of CL-20/TNT-Based Polymer-Bonded Explosives through Molecular Dynamics Simulation.

Binders mixed with explosives to form polymer-bonded explosives (PBXs) can reduce the sensitivity of the base explosive by improving interfacial interactions. The interface formed between the binder and matrix explosive also affects the thermal conductivity. Low thermal conductivity may result in localized heat concentration inside the PBXs, causing the detonation of the explosive. To investigate the binder-explosive interfacial interactions and thermal conductivity, PBXs with polyurethane as the binder and 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane/2,4,6-trinitrotoluene (CL-20/TNT) co-crystal as the matrix explosive were investigated through molecular dynamics (MD) simulations and reverse non-equilibrium molecular dynamics (rNEMD) simulation. The analysis of the pair correlation function revealed that there are hydrogen bonding interactions between Estane5703 and CL-20/TNT. The length of the trigger bonds was adopted as a theoretical criterion of sensitivity, and the effect of polymer binders on the sensibility of PBXs was correlated by analyzing the interfacial trigger bonds and internal trigger bonds of PBXs for the first time. The results indicated that the decrease in sensitivity of CL-20/TNT mainly comes from the CL-20/TNT contact with Estane5703. Therefore, the sensitivity of CL-20/TNT-based PBXs can be further reduced by increasing the contact area between CL-20/TNT and Estane5703. The thermal conductivity of PBXs composed of Estane5703 and CL-20/TNT (0 0 1), (0 1 0) and (1 0 0) crystal planes, respectively, were calculated through rNEMD simulations, and the results showed that only the addition of Estane5703 to the (1 0 0) crystal plane can improve the thermal conductivity of PBX100.

A novel 3D-printed graphite/polylactic acid sensor for the electrochemical determination of 2,4,6-trinitrotoluene residues in environmental waters.

Here, lab-made graphite and polylactic acid (Gpt-PLA) biocomposite materials were used to additively manufacture electrodes via the fused deposition modeling (FDM) technique for subsequent determination of the explosive 2,4,6-trinitrotoluene (TNT, considered a persistent organic pollutant). The surface of the 3D-printed material was characterized by SEM and Raman, which revealed high roughness and the presence of defects in the graphite structure, which enhanced the electrochemical response of TNT. The 3D-printed Gpt-PLA electrode coupled to square wave voltammetry (SWV) showed suitable performance for fastly determining the explosive residues (around 7 s). Two reduction processes at around -0.22 V and -0.36 V were selected for TNT detection, with linear ranges between 1.0 and 10.0 µM. Moreover, detection limits of 0.52 and 0.66 µM were achieved for both reduction steps. The proposed method was applied to determine TNT in different environmental water samples (tap water, river water, and seawater) without a dilution step (direct analysis). Recovery values between 98 and 106% confirmed the accuracy of the analyses. Additionally, adequate selectivity was achieved even in the presence of other explosives commonly used by military agencies, metallic ions commonly found in water, and also some electroactive camouflage species. Such results indicate that the proposed device is promising to quantify TNT residues in environmental samples, a viable on-site analysis strategy.

Explosives removal and quantification using porous adsorbents based on poly(2-oxazoline)s with various degree of functionalization.

Polymeric porous adsorbents are reported for removal of explosives, namely picric acid, 1,3,5-trinitro-1,3,5-triazinane (RDX), and pentaerythritol tetranitrate (PETN) and their subsequent quantification using direct analysis with ambient plasma mass spectrometry. The adsorbents are obtained by functionalization of short-chain poly(2-oxazoline)s with methyl ester side chains using 4-(aminomethyl)pyridine with a degree of functionalization equal to 0, 5, 10, and 20%. The subsequent step consist of cross-linking using a high internal phase emulsion procedure by further side-chain amidation with diethylenetriamine as crosslinker. Picric acid, RDX, and PETN were chosen as the model compounds as they belong to three different groups of explosives, in particular nitroaromatics, nitroamines, and nitrate esters, respectively. The adsorption isotherms, kinetics, as well as the influence of pH and temperature on the adsorption process was investigated. The porous adsorbents showed the highest maximum adsorption capacity towards picric acid, reaching 334 mg g-1, while PETN (80 mg g-1) and RDX (17.4 mg g-1) were less efficiently adsorbed. Subsequent quantification of the adsorbed explosives is performed by a specially designed ambient mass spectrometry setup equipped with a thermal heater. The obtained limits of detection were found to be 20-times improved compared to direct analysis of analyte solutions. The effectiveness of the proposed analytical setup is confirmed by successful quantification of the explosives in river water samples. The research clearly shows that functional porous adsorbents coupled directly with ambient mass spectrometry can be used for rapid quantification of explosives, which can be, e.g., used for tracking illegal manufacturing sites of these compounds.

2H-MoS2/Co3O4 nanohybrid with type I nitroreductase-mimicking activity for the electrochemical assays of nitroaromatic compounds.

A type I nitroreductase-mimicking nanocatalyst based on 2H-MoS2/Co3O4 nanohybrids for trace nitroaromatic compounds detection is reported in this work. For the preparation of nanocatalyst, ultrathin Co3O4 nanoflakes array was in-situ grown onto 2H-MoS2 nanosheets forming three-dimensional (3D) nanohybrid with large specific surface area as well as abundant active sites. The as-prepared nanocatalyst shows a specific affinity as well as high catalytic activity towards nitroaromatic compounds. Given the favorable nitroreductase-mimicking catalytic activity of 2H-MoS2/Co3O4 nanohybrid, a sensitive and efficient electrochemical microsensor has been constructed for the detection of 2, 4, 6-trinitrotoluene (TNT). Under optimized conditions, the microsensor displayed sensitive response from µM to pM levels with a limit of detection (LOD) of 1 pM. We further employed photoelectron spectroscopy (XPS) analysis and high-performance liquid chromatography tandem mass spectrometry (HPLC-MS/MS) method to identify the nitroreductase-mimicking mechanism of 2H-MoS2/Co3O4 nanohybrids towards 2, 4, 6- TNT. It was found that the abundant oxygen vacancies in ultrathin Co3O4 nanoflakes played an essential role in determining its catalytic performance. Moreover, the developed MoS2/Co3O4 nanozyme has a lower Michaelis-Menten constant (km) than that of nature nitroreductase demonstrating a good enzymatic affinity towards its substrates, and further generating a high catalytic activity. This research not only proposed a new type of nanozyme, but also developed a portable electrochemical microsensor for the detection of 2, 4, 6-TNT.

Characteristics of ionization behaviors of aminonitrotoluene isomers produced by atmospheric pressure chemical ionization.

RATIONALE: Six of the isomers of aminonitrotoluene (ANT) are 2-amino-3-nitrotoluene (2A3NT), 2A4NT, 2A5NT, 2A6NT, 4A2NT, and 4A3NT. Some of them can be identified by chromatography and spectroscopy. Biochemical transformation of 2,4,6-trinitrotoluene (TNT) and dinitrotoluenes (DNTs) is very complex and ANTs are decomposition products of TNT and DNTs. METHODS: Each isomer in acetone was ionized using atmospheric pressure chemical ionization in positive and negative ion modes, and kinds and abundances of the product ions were analyzed. Energy-minimized structures of the product ions and their energies were calculated to explain the analysis results. RESULTS: The [M + H]+ , [M + H + Acetone - H2 O]+ , and [M + H + Acetone]+ ions as positive product ions were detected, while [M - H]- , M•- , and [M + O2 ]•- ions as negative ones were observed. The order of the ionization efficiencies for the positive product ions was 4A3NT > 4A2NT > 2A4NT > 2A6NT > 2A5NT > 2A3NT, while that of the negative ones was 2A5NT > 2A3NT > 4A3NT > 2A4NT > 2A6NT > 4A2NT. Ion abundance ratios for 2A3NT and 2A5NT showed very similar trends, while those of 2A6NT and 4A2NT also showed similar trends. Differences in the ionization behaviors were explained using the heats of reaction. CONCLUSIONS: The product ions were produced by ion-molecule reactions with the reactant ions of [2Acetone + H]+ and [Acetone + O2 ]•- . The [M + H + Acetone]+ ion was fragmented to produce [M + H]+ and [M + H + Acetone - H2 O]+ , while the [M + O2 ]•- ion was fragmented to generate the [M - H]- and M•- ions. Differences in the ionization behaviors of the ANTs can be used for their differentiation.

Development of an environmental hazard-based rating assessment for defence-related chemical compounds in ecological soil systems.

Environmental hazard-based methods are commonly used to categorise the severity of chemical contamination to ecological soil systems, although a traffic-light approach (green, amber, red) has never been used to assess these consequences. A traffic light approach is an easy to interpretate data as it has a clear visual display which can provide an early warning approach for stakeholders to identify areas that require further investigation. This approach should be underpinned by extensive research data and systematic methods of development. However, the extent of reliable data available for specific chemicals can be limited and therefore decision making may rely on expert judgement. Therefore, in this study, an environmental hazard-based rating methodology was developed by combining the guidelines from the European Chemical Agency (ECHA) and the USEPA for Predicted Non-effect Concentration (PNEC) and Ecological Soil Screening Levels (Eco-SSL) for defence-related chemicals (2,4,6-trinitrotoluene (TNT), 1,3,5-trinitro-1,3,5-triazinane (RDX), cypermethrin, perfluorooctanoic acid (PFOA) and perfluorooctanesulfonic acid (PFOS)). The developed hazard-based rating assessment was design to categorise the chemicals into low, medium and high environmental hazards priority to inform and ease the decision-making process for contaminated areas to ensure that sustainable operations are carried out.

Protamine gold nanoclusters - based fluorescence turn-on sensor for rapid determination of Trinitrotoluene (TNT).

Determination of trace residues of 2,4,6-trinitrotoluene (TNT) is an analytical challenge as it is widely used in military, mining industry, civilian and counter-terrorism purposes. In this study, a gold nanocluster - based turn-on fluorescence sensor was developed for TNT determination. A one-pot approach was used to synthesize the fluorescent protamine - stabilized gold nanoclusters (PRT-AuNC). The proposed turn-on fluorometric sensor relies on the aggregation-induced emission enhancement mechanism. As a result of the donor-acceptor interaction between the non-fluorescent Meisenheimer anion formed from TNT and the amino groups of weakly fluorescent protamine, the PRT-AuNCs aggregate and an accompanying enhancement in fluorescence intensity is observed with a large Stokes shift (λex = 300 nm, λem = 600 nm). The fluorescence enhancement increased linearly with TNT with an LOD of 12.44 µg/L. Similar energetic materials, common soil ions and explosive camouflage materials did not affect the proposed fluorometric sensing method. TNT in artificially contaminated soil was determined, and the results were comparable to those obtained by the HPLC-DAD system. The proposed turn-on sensor is an important tool for simple, fast, rapid and sensitive TNT determination, and has a potential to be converted to a kit format.

Detection of explosives in vapor phase by field asymmetric ion mobility spectrometry with dopant-assisted laser ionization.

Detection of low-volatile explosives in concentrations below 10-14 g/cm3 is a great challenge for portable ion mobility spectrometers (IMS) and field asymmetric IMS (FAIMS). We study the capabilities of FAIMS detector with ultraviolet laser ionization combined with organic additives (dopants) toluene and 1-methylnaphtalene to sense nitro-explosives: trinitrotoluene (TNT) and low-volatile cyclonite (RDX) and nitropentaerythritol (PETN). Differential mobility coefficients were measured for target ion peaks of TNT, RDX and PETN. Presence of dopants in the sample results in multiple growth of ion yield at laser intensities lower than 2 × 107 W/cm2. Limits of detection with dopant-assisted laser ionization were determined: 4.7 × 10-16 g/cm3 for RDX and 9.8 × 10-15 g/cm3 for PETN. Obtained results propose a way to further improve sensitivity of detectors along with improvement of portability of current laser-based FAIMS prototypes by using less powerful and smaller lasers.

Reshaping the microenvironment and bacterial community of TNT- and RDX-contaminated soil by combined remediation with vetiver grass (Vetiveria ziznioides) and effective microorganism (EM) flora.

Explosive pollutants remaining in global soils are serious threats to human health and ecological safety. Soils contaminated by trinitrotoluene (TNT) and cyclotrimethylene trinitramine (RDX) are simulated in this study and remediated using vetiver grass and effective microorganism (EM) flora to determine the efficacy of combined remediation in reshaping the microenvironment and bacterial community of soils contaminated by explosives. The degradation rates of TNT and RDX after 60 days of combined remediation were 95.66% and 84.37%, respectively. Soil microbial activity and enzyme activities related to the nitrogen cycle were upregulated. The content of soil elements in the remediation group changed significantly. Vetiver remediation increased the diversity and significantly changed the structure of the microbial community. Notably, bacteria, such as Sphingomonadaceae and Actinobacteriota, which can degrade explosives, occupied the soil niche, and the Proteobacteria and Bacteroidota, which are involved in sugar metabolism, showed particularly increased abundance. The metabolism of soil carbohydrates, fatty acids, and amino acids was upregulated in the vetiver, EM flora, and combined vetiver+EM flora remediation groups, and the most significantly upregulated pathway was galactose metabolism. The combined vetiver and EM flora treatment of soil contaminated by explosives greatly improved the ecology of the soil microenvironment.

A sketch of microbiological remediation of explosives-contaminated soil focused on state of art and the impact of technological advancement on hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) degradation.

When high-energy explosives such as hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX), Octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX), 2,4,6-trinitrotoluene (TNT) are discharged into the surrounding soil and water during production, testing, open dumping, military, or civil activities, they leave a toxic footprint. The US Environmental Protection Agency has labeled RDX as a potential human carcinogen that must be degraded from contaminated sites quickly. Bioremediation of RDX is an exciting prospect that has received much attention in recent years. However, a lack of understanding of RDX biodegradation and the limitations of current approaches have hampered the widespread use of biodegradation-based strategies for RDX remediation at contamination sites. Consequently, new bioremediation technologies are required to enhance performance. In this review, we explore the requirements for in-silico analysis for producing biological models of microbial remediation of RDX in soil. On the other hand, potential gene editing methods for getting the host with target gene sequences responsible for the breakdown of RDX are also reported. Microbial formulations and biosensors for detection and bioremediation are also briefly described. The biodegradation of RDX offers an alternative remediation method that is both cost-effective and ecologically acceptable. It has the potential to be used in conjunction with other cutting-edge technologies to further increase the efficiency of RDX degradation.

Contamination characteristics of energetic compounds in soils of two different types of military demolition range in China.

The pollution of energetic compounds (ECs) in military ranges has become the focus of worldwide attention. However, few studies on the contamination of ECs at Chinese military ranges have been reported to date. In this study, two different types of military demolition range in China, Dunhua (DH) and Taiyuan (TY), were investigated and the ECs in their soils were determined. 10 ECs were detected at both ranges. While all the contamination characteristics were distinct, 2,4,6-trinitrotoluene (TNT) was the most abundant contamination source in soils at DH range, with an average concentration of 1106 mg kg-1 and a maximum concentration of 34,083 mg kg-1. Hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) and two mono-amino degradation products of TNT were also found to have high concentrations, with potential ecological and human health risks. In contrast, the concentrations of ECs in soils of TY range were much lower. The content of RDX was most significant, with average and maximum concentrations of 7.8 and 158 mg kg-1, respectively. However, the potential threat to human health of 2,4-dinitrotoluene and 2,6-dinitrotoluene in soils at both ranges should not be ignored. The differences in pollution characteristics of the ECs at DH and TY are closely related to the types and amounts of the munitions destroyed. Moreover, the spatial distribution of ECs at the demolition ranges was extremely heterogeneous, which may be attributed to the use of open burning / open detonation and the non-homogeneous composition of the munitions.

A 'sandwich' structure for highly sensitive detection of TNT based on surface-enhanced Raman scattering.

Ultra-sensitive detection of 2,4,6-trinitrotoluene (TNT) plays an important role in society security and human health. The Raman probe molecule p-aminothiophenol (PATP) can interact with TNT in three ways to form a TNT-PATP complex. In this paper, a 'sandwich' structure was developed to detect TNT with high sensitivity. Au nano-pillar arrays (AuNPAs) substrates modified by low-concentration PATP through Au-S bonds were acted as capture probe for TNT. Meanwhile, Ag nano-particles (AgNPs) modified by PATP at higher concentration were employed as tags for surface-enhanced Raman scattering (SERS). The formation of the TNT-PATP complex is not only the means by which AuNPAs substrates recognize and capture TNT, but also links the SERS tags to TNT, forming an AuNPAs-TNT-AgNPs 'sandwich' structure. The Raman signal of PATP was greatly enhanced mainly because novel 'hot spots' formed between the AuNPAs and AgNPs of the 'sandwich' structure. The Raman signal of PATP was further amplified by the chemical enhancement effect induced by the TNT-PATP complex formation. Based on this mechanism, the limit of detection (LOD) of TNT was determined from the Raman signal of PATP. The LOD reached 10-9 mg/mL (4.4 × 10-12 M), much lower than that suggested by the US Environmental Protection Agency (88 nM). Moreover, TNT was selectively detected over several TNT analogues 2,4-dinitrotoluene (DNT), p-nitrotoluene (NT) and hexogen (RDX). Finally, the 'sandwich' structure was successfully applied to TNT detection in environmental water and sand.

Environmental Characterization of Underwater Munitions Constituents at a Former Military Training Range.

As a result of military activities, unexploded ordnance and discarded military munitions are present in underwater environments, which has resulted in the release of munitions constituents including the high explosives 2,4,6-trinitrotoluene (TNT) and hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX), along with their primary degradation products, to the water column and adjacent sediments. The present study focused on the characterization of underwater exposure and concentrations of energetics such as TNT and RDX at the former Vieques Naval Training Range at Bahia Salina del Sur (Vieques, Puerto Rico, USA), a bay with documented high incidence of munitions. In situ passive sampling using polar organic chemical integrative samplers (POCIS) was used for the detection and quantification of constituents in water at target locations approximately 15 to 30 cm from 15 individual potentially leaking munitions, and also at 15 unbiased locations approximately evenly spaced across the Bay. For comparison with POCIS-derived concentrations, grab samples were taken at the POCIS target locations. The POCIS-derived and averaged grab samples agreed within a factor of 3. When detected, munitions constituent concentrations (primarily TNT and RDX) were observed at ultratrace concentrations (as low as 4 ng/L for RDX), except 30 cm from one General Purpose bomb where the TNT concentration was 5.3 µg/L, indicating that low-level contamination exists at Bahia Salina del Sur on a very localized scale despite the relatively high density of munitions, similar to previously reported results for other munitions sites around the world. Sediment and porewater sampled at 4 stations where munitions constituents were detected in the water column had concentrations below detection (approximately 5 µg/kg and 5 ng/L, respectively), suggesting that the sediment was not a sink for these constituents at those locations. Environ Toxicol Chem 2022;41:275-286. © 2021 SETAC. This article has been contributed to by US Government employees and their work is in the public domain in the USA.

MoS2 QDs/8-Armed Poly(Ethylene Glycol) Fluorescence Sensor for Three Nitrotoluenes (TNT) Detection.

In this work, ammonia cross-linked 8-armed polyethylene glycol hydrogel material was successfully synthesized and used as a template for synthesizing nanoparticles with fluorescent properties. The 8-armed polyethylene glycol hydrogel template was used to prepare molybdenum disulfide quantum dots (MoS2 QDs). The ammonium tetrathiomolybdate functioned as a molybdenum source and hydrazine hydrate functioned as a reducing agent. The fluorescence properties of the as-prepared MoS2 QDs were investigated. The bursting of fluorescence caused by adding different concentrations of explosive TNT was studied. The study indicated that the synthesized MoS2 QDs can be used for trace TNT detection with a detection limit of 6 nmol/L and a detection range of 16-700 nmol/L. Furthermore, it indicated that the fluorescence-bursting mechanism is static bursting.

Application of LC-QTOF/MS for the validation and determination of organic explosive residues on Ionscan® swabs.

The identification and confirmation of trace explosive residues along with potential precursors and degradation products require a comprehensive laboratory analysis procedure. This study presents the determination of organic explosives consisting of hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX), 2,4,6-trinitrotoluene (TNT), 2,4,6,N-tetranitro-N-methylaniline (Tetryl), 1,3,5-trinitrobenzene (1,3,5-TNB) and pentaerythritol tetranitrate (PETN) by a high-resolution liquid chromatography quadrupole time-of-flight mass spectrometry (LC-QTOF/MS). The qualitative information including retention time, collision energy, precursor ions, and characteristic fragmentation pattern of each explosive were collected using an atmospheric pressure chemical ionization (APCI) in negative ion mode. The separation efficiency among five compounds was greatly achieved in this study. Four real explosive samples consisting of TNT, RDX, PETN and Tetryl and 12 Ionscan® quality control swabs from the Royal Thai Army were also tested to validate and verify the viability of the GC-MS method used to validate results from an Ionscan® system. The results showed that LC-QTOF/MS is a powerful technique for the identification and confirmation of thermally unstable organic explosives on Ionscan® swabs compared to a conventional GC-MS technique.

Microbial community structure and metabolome profiling characteristics of soil contaminated by TNT, RDX, and HMX.

This experiment was conducted to evaluate the ecotoxicity of typical explosives and their mechanisms in the soil microenvironment. Here, TNT (trinitrotoluene), RDX (cyclotrimethylene trinitramine), and HMX (cyclotetramethylene tetranitramine) were used to simulate the soil pollution of single explosives and their combination. The changes in soil enzyme activity and microbial community structure and function were analyzed in soil, and the effects of explosives exposure on the soil metabolic spectrum were revealed by non-targeted metabonomics. TNT, RDX, and HMX exposure significantly inhibited soil microbial respiration and urease and dehydrogenase activities. Explosives treatment reduced the diversity and richness of the soil microbial community structure, and the microorganisms able to degrade explosives began to occupy the soil niche, with the Sphingomonadaceae, Actinobacteria, and Gammaproteobacteria showing significantly increased relative abundances. Non-targeted metabonomics analysis showed that the main soil differential metabolites under explosives stress were lipids and lipid-like molecules, organic acids and derivatives, with the phosphotransferase system (PTS) pathway the most enriched pathway. The metabolic pathways for carbohydrates, lipids, and amino acids in soil were specifically inhibited. Therefore, residues of TNT, RDX, and HMX in the soil could inhibit soil metabolic processes and change the structure of the soil microbial community.

Monodisperse amino-modified nanosized zero-valent iron for selective and recyclable removal of TNT: Synthesis, characterization, and removal mechanism.

Nitroaromatic explosives are major pollutants produced during wars that cause serious environmental and health problems. The removal of a typical nitroaromatic explosive, 2,4,6-trinitrotoluene (TNT), from aqueous solution, was conducted using a new recyclable magnetic nano-adsorbent (Fe@SiO2NH2). This adsorbent was prepared by grafting amino groups onto Fe@SiO2 particles with a well-defined core-shell structure and demonstrated monodispersity in solution. The removal performance of the nano-adsorbent towards TNT was found to be 2.57 and 4.92 times higher than that towards two analogous explosives, 2,4-dinitrotoluene (2,4-DNT) and 2-nitrotoluene (2-NT), respectively, under neutral conditions. The difference in the removal performance among the three compounds was further compared in terms of the effects of different conditions (pH value, ionic strength, humic acid concentration, adsorbent modification degree and dosage, etc.) and the electrostatic potential distributions of the three compounds. The most significant elevation is owing to modification of amino on Fe@SiO2 which made a 20.7% increase in adsorption efficiency of TNT. The experimental data were well fit by the pseudo-second-order kinetic model and the Freundlich adsorption isotherm model, indicating multilayer adsorption on a heterogeneous surface. The experimental results and theoretical considerations show that the interactions between Fe@SiO2NH2 NPs and TNT correspond to dipole-dipole and hydrophobic interactions. These interactions should be considered in the design of an adsorbent. Furthermore, the adaptability to aqueous environment and excellent regeneration capacity of Fe@SiO2NH2 NPs makes these remediation materials promising for applications.

One-Step Instantaneous Detection of Multiple Military and Improvised Explosives Facilitated by Colorimetric Reagent Design.

Although colorimetric detection based on reagents has been widely used in the fields of practical trace analysis, its versatility for detecting multitargets remains the most challenging problem. As a proof of concept, a general colorimetric reagent based on potassium isopropanol (C3H7KO) and dimethyl sulfoxide for one-step instantaneous detection and discrimination of typical military and improvised explosives was designed. Vivid colors from none to purple red, blue green, yellow green, and green were shown, respectively, when detecting 2,4,6-trinitrotoluene (TNT), 2,4-dinitrotoluene (DNT), elemental sulfur (S), and potassium permanganate (KMnO4). The unique design including the specific nucleophilic addition reaction and the base-catalyzed oxidation-induced electron transfer ensures perfect selectivity even upon facing more than 20 interferents. It is further experimentally demonstrated that the confinement effect introduced by Tween-20 plays an essential role in enhancing the color signal on the surface and thus boosts the detection performance even with a mass as low as 1.45 ng. The applicability of this versatile colorimetric reagent was further verified by integrating the reagent onto paper strips for the in-field identification of TNT, DNT, S, and KMnO4 with the help of a portable smartphone-based microscope apparatus, and a practical detection mass of 10.3 ng could be realized. We expect the present colorimetric reagent design strategy would pave a way for one-step instantaneous visual detection toward trace multianalytes.