Microecological characteristics of water bodies/sediments and microbial remediation strategies after 50 years of pollution exposure in ammunition destruction sites in China.

The effects of long-term ammunition pollution on microecological characteristics were analyzed to formulate microbial remediation strategies. Specifically, the response of enzyme systems, N/O stable isotopes, ion networks, and microbial community structure/function levels were analyzed in long-term (50 years) ammunition-contaminated water/sediments from a contamination site, and a compound bacterial agent capable of efficiently degrading trinitrotoluene (TNT) while tolerating many heavy metals was selected to remediate the ammunition-contaminated soil. The basic physical and chemical properties of the water/sediment (pH (up: 0.57-0.64), nitrate (up: 1.31-4.28 times), nitrite (up: 1.51-5.03 times), and ammonium (up: 7.06-70.93 times)) were changed significantly, and the significant differences in stable isotope ratios of N and O (nitrate nitrogen) confirmed the degradability of TNT by indigenous microorganisms exposed to long-term pollution. Heavy metals, such as Pb, Zn, Cu, Cd, Cs, and Sb, have synergistic toxic effects in ammunition-contaminated sites, and significantly decreased the microbial diversity and richness in the core pollution area. However, long-term exposure in the edge pollution area induced microorganisms to use TNT as a carbon and nitrogen sources for life activities and growth and development. The Bacteroidales microbial group was significantly inhibited by ammunition contamination, whereas microorganisms such as Proteobacteria, Acidobacteriota, and Comamonadaceae gradually adapted to this environmental stress by regulating their development and stress responses. Ammunition pollution significantly affected DNA replication and gene regulation in the microecological genetic networks and increased the risk to human health. Mg and K were significantly involved in the internal mechanism of microbial transport, enrichment, and metabolism of TNT. Nine strains of TNT-utilizing microbes were screened for efficient TNT degradation and tolerance to typical heavy metals (copper, zinc and lead) found in contaminated sites, and a compound bacterial agent prepared for effective repair of ammunition-contaminated soil significantly improved the soil ecological environment.

Arsenic species in soil profiles from chemical weapons (CWs) burial sites of China: Contamination characteristics, degradation process and migration mechanism.

In this study, soil profiles and pore water from Japanese abandoned arsenic-containing chemical weapons (CWs) burial sites in Dunhua, China were analyzed to understand the distribution of arsenic (As) contamination, degradation, and migration processes. Results of As species analysis showed that the As-containing agents underwent degradation with an average rate of 87.55 ± 0.13%, producing inorganic pentavalent arsenic (As5+) and organic arsenic such as 2-chlorovinylarsonic acid (CVAOA), triphenylarsenic (TPA), and phenylarsine oxide (PAO). Organic arsenic pollutants accounted for 1.27-18.20% of soil As. In the vertical profiles, total As concentrations peaked at about 40-60 cm burial depth, and the surface agricultural soil exhibited moderate to heavy contamination level, whereas the contamination level was insignificant below 1 m, reflecting As migration was relatively limited throughout the soil profile. Sequential extraction showed Fe/Al-bound As was the predominant fraction, and poorly-crystalline Fe minerals adsorbed 33.23-73.13% of soil As. Oxygen-susceptible surface soil formed poorly-crystalline Fe3+ minerals, greatly reducing downward migration of arsenic. However, the reduction of oxidizing conditions below 2 m soil depth may promote As activity and require attention.

Oxygen-insensitive nitroreductase bacteria-mediated degradation of TNT and proteomic analysis.

2,4,6-trinitrotoluene (TNT) is a nitroaromatic compound that causes soil and groundwater pollution during manufacture, transportation, and use, posing significant environmental and safety hazards. In this study, a TNT-degrading strain, Bacillus cereus strain T4, was screened and isolated from TNT-contaminated soil to explore its degradation characteristics and proteomic response to TNT. The results showed that after inoculation with the bacteria for 4 h, the TNT degradation rate reached 100% and was transformed into 2-amino-4,6-dinitrotoluene (2-ADNT), 4-amino-2,6-dinitrotoluene (4-ADNT), 2,4-diamino-6-nitrotoluene (2,4-DANT), and 2,6-diamino-4-nitrotoluene (2,6-DANT), accompanied by the accumulation of nitrite and ammonium ions. Through proteomic sequencing, we identified 999 differentially expressed proteins (482 upregulated, 517 downregulated), mainly enriched in the pentose phosphate, glycolysis/gluconeogenesis, and amino acid metabolism pathways. In addition, the significant upregulation of nitroreductase and N-ethylmaleimide reductase was closely related to TNT denitration and confirmed that the strain T4 converted TNT into intermediate metabolites such as 2-ADNT and 4-ADNT. Therefore, Bacillus cereus strain T4 has the potential to degrade TNT and has a high tolerance to intermediate products, which may effectively degrade nitroaromatic pollutants such as TNT in situ remediation in combination with other bacterial communities.

Defense mechanisms of alfalfa against cyclic tetramethylene tetranitramine (HMX) stress.

Much attention has been paid to the environmental toxicity and ecological risk caused by cyclic tetramethylene tetranitramine (HMX) pollution in military activity sites. In this study, the response mechanism of alfalfa plants to HMX was analyzed from the aspects of the photosynthetic system, micromorphology, antioxidant enzyme system, mineral metabolism, and secondary metabolism, in order to improve the efficiency of plant restoration. Exposure to 5 mg·L-1 HMX resulted in a significant increase in leaf N content and a significant increase and drift of the Fourier transform infrared protein peak area. Transmission electron microscopy images revealed damage to the root system subcellular morphology, but the plant leaves effectively resisted HMX pressure, and the photosynthetic parameters essentially maintained steady-state levels. The root proline content decreased significantly by 23.1-47.2 %, and the root reactive oxygen species content increased significantly by 1.66-1.80 fold. The roots regulate the transport/absorption of many elements that impart stress resistance, and Cu, Mn, and Na uptake is significantly associated with secondary metabolism. The metabolism of roots was upregulated in general by HMX exposure, with the main differences appearing in the content of lipids and lipid-like molecules, further confirming damage to the root biofilm structure. HMX causes an imbalance in the energy supply from oxidative phosphorylation in roots and generates important biomarkers in the form of pyrophosphate and dihydrogen phosphate. Interestingly, HMX had no significant effect on basic metabolic networks (i.e., glycolysis/gluconeogenesis and the tricarboxylic acid cycle), confirming that alfalfa has good stress resistance. Alfalfa plants apparently regulate multiple network systems to resist/overcome HMX toxicity. These findings provide a scientific basis for improving plant stress tolerance and understanding the HMX toxicity mechanism.

Physiological response mechanism of alfalfa seedlings roots to typical explosive cyclotrimethylene trinitramine (RDX).

This study explored the physiological response mechanism of alfalfa seedlings roots to a typical explosive, cyclotrimethylenetrinitramine (RDX), so as to improve the efficiency of phytoremediation. The response of plants to different levels of RDX were analyzed from the perspectives of mineral nutrition and metabolic networks. Exposure to RDX at 10-40 mg L-1 had no significant effect on root morphology, but the plant roots significantly accumulated RDX in solution (17.6-40.9%). A 40 mg L-1 RDX exposure induced cell gap expansion and disrupted root mineral metabolism, The key response elements, P, Cu, and Mg, were significantly increased by 1.60-1.66, 1.74-1.90, and 1.85-2.50 times, respectively. The 40 mg L-1 RDX exposure also significantly disturbed root basal metabolism, resulting in a total of 197 differentially expressed metabolites (DEMs). The main response metabolites were lipids and lipid-like molecules, and the key physiological response pathways were arginine biosynthesis and aminoacyl-tRNA biosynthesis. A total of 19 DEMs in root metabolic pathways, including L-arginine, L-asparagine, and ornithine, were significantly responsive to RDX exposure. The physiological response mechanism of roots to RDX therefore involve mineral nutrition and metabolic networks and are of great significance for improving phytoremediation efficiency.

Spatial-vertical variations of energetic compounds and microbial community response in soils from an ammunition demolition site in China.

Ammunition-related activities have caused severe energetic compound (EC) contamination and pose serious risks to ecosystems. However, little is known regarding the spatial-vertical variations of ECs or their migration in soils at ammunition demolition sites. Although the toxic effect of some ECs to microorganisms have been reported through laboratory simulations, the responses of indigenous microbial communities to ammunition demolition activities are unclear. In this study, the spatial-vertical variations of ECs in 117 topsoil samples and three soil profiles from a typical ammunition demolition site in China were studied. Heavy contamination of ECs was concentrated in the top soils of the work platforms, and ECs were also detected in the surrounding area and nearby farmland. ECs showed different migration characteristics in the 0-100 cm soil layer of the different soil profiles. Demolition activities and surface runoff play critical roles in the spatial-vertical variations and migration of ECs. These findings suggest that ECs are able to migrate from the topsoil to the subsoil and from the core demolition area to further ecosystems. The work platforms exhibited lower microbial diversity and different microbiota compositions compared to the surrounding areas and farmlands. Using the random forest analysis, pH and 1,3,5-trinitrobenzene (TNB) were characterized as the most important factors affecting microbial diversity. Network analysis revealed that Desulfosporosinus was highly sensitive to ECs and may be a unique indicator of EC contamination. These findings provide key information in understanding EC migration characteristics in soils and the potential threats to indigenous soil microorganisms in ammunition demolition sites.

[Distribution Characteristics and Pollution Assessment of Heavy Metals in Soils of a Testing Range].

Heavy metal pollution in testing ranges is one of the most widely concerning environmental problems. The ammunition static detonation test area, the bomb falling area, and the living area of a testing range in Jilin were selected as the study objects. The contents of heavy metals (As, Cd, Cr, Cu, Ni, Pb, and Zn) in 112 topsoil samples and two soil profiles were analyzed, and their distribution characteristics and sources were analyzed in detail. After that, the pollution degree and potential ecological risk of heavy metals were investigated using multiple pollution index assessment methods. The results showed that the average contents of As, Cd, Cu, Ni, and Zn in the soil of the ammunition static detonation test area were higher than the soil background values in Jilin province, and the contents of Cu, Zn, As, and Cd showed strong spatial heterogeneity. The average concentrations of As, Cd, and Ni in the soil of the bomb falling area exceeded their background values. The average contents of As and Cd in the soil of the living area were higher than the background values, and the variation coefficients of Pb, Cd, Zn, and Cr were relatively high, indicating that they may have been affected by human activities. In different test areas, the contents of As, Cr, Cu, Ni, and Zn in the soil samples were significantly different (P<0.05). The ammunition static detonation test area was more strongly affected by the test activities than the bomb falling area, and the heavy metal contents in the surface layer of the soil profile were significantly higher. There was no obvious vertical migration of heavy metals in the soil profiles. The results of multivariate statistics and source identification analysis using absolute principal component score-multiple linear regression (APCS-MLR) showed that Zn, Pb, and Cd were mainly affected by pollution sources related to test activities; Cr and Ni were mainly affected by natural sources of soil forming materials; and the sources of As and Cu were more complicated. The geo-accumulation index showed that Cd in the three areas and Ni in the bomb falling area belonged to pollution level 1 (uncontaminated to moderately contaminated). The Nemerow comprehensive pollution index showed that the pollution levels among the different functional areas were:living area>ammunition static detonation test area>bomb falling area, and the three functional areas were slightly polluted. The potential ecological risk index showed that the study area was at moderate ecological risk level, and Cd was considered to be the main soil pollution factor.

Arsenic and heavy metals at Japanese abandoned chemical weapons site in China: distribution characterization, source identification and contamination risk assessment.

As-containing chemical weapons (CWs) and their degraded products pose a great threat to the environment and to human health. In this study, concentration and distribution characteristics, source identification, and health risk assessments were determined for As, Cr, Ni, Cu, Zn, Cd and Pb in environmental samples from Lianhuapao (LHP), a typical site of Japanese abandoned chemical weapons (JACWs) in China. The results show that the concentration levels of As, Cr and Ni in the LHP soils are abnormally high, with 69.57%, 83.33% and 91.67%, respectively, of the total sample exceeding the risk screening values for soil contamination of agricultural land. As levels in water samples were generally within safety limits, with the exception of perched water in the core contamination area. In the study area, none of the dominant plant species were enriched with As, except for the Pteris vittata L. Pentavalent arsenic was found to be the predominant arsenic species in the topsoil and water samples. Source identification using statistical approaches indicated that the concentrations of As, Pb, Cu, Cd and Zn are likely influenced by JACWs, while Cr and Ni levels may be related to the natural weathering process. The total concentrations of As, Cr and Ni showed a significant degree of contamination, but only As displayed high potential ecological risk. The calculated indexes of health risk evaluation strongly indicate an unacceptable carcinogenic risk (1E-04) to children, and higher non-carcinogenic risk, relative to that of adults. Our data indicate that the health risk from the resulting As contamination is still a cause for concern, although the JACWs were excavated decades ago from these soils.

Study on the composition and distribution characteristics of As in As-containing agent contaminated soil.

In recent years, China and Japan are cooperating in the destruction of the Japanese army abandoned chemical weapons in China (JACWs). During the long-term burial of JACWs, As-containing agents leaked into the environment due to the corrosion of the shell, resulting in soil As pollution. This paper studied the fraction, speciation, and composition of As in the soil polluted by the As-containing agent in Jilin, China. The results showed that As was mainly distributed in the forest soil in the study area, with the highest concentration of 110 mg/kg, and had the trend of migration to the downhill farmland soil. As mainly accumulated in the amorphous Fe/Al oxides bounded fraction and residual states, the proportion of potentially risky fractions in the soil of downhill farmland is higher than that of uphill farmland. The speciation of As in the soil is mainly As(V), with an average content of 25.02 mg/kg. The transformation behavior of As in the horizontal migration of topsoil is mainly the oxidation of As (III). The residual organic As in soil mainly includes 2-chlorovinylarsonic acid, triphenylarsine, phenylarsine oxide, and diphenylarsonic acid. Similar to the influence factors of As, both speciation and organic compounds of As are significantly affected by Fe/Al/Mn-oxides, and degradation and transformation reactions such as redox occur during migration.

Stimulus-Responsiveness of Thermo-Sensitive Polymer Hybridized with N-Doped Carbon Quantum Dots and Its Applications in Solvent Recognition and Fe3+ Ion Detection.

To fabricate N-CQDs hybrid thermo-sensitive polymer (poly-N-CQDs), N-doped carbon quantum dots (N-CQDs) with strong blue fluorescence and poly(N-isopropylacrylamide-co-acrylic acid) (poly(NIPAAm-co-AAc)) copolymer with thermo-sensitivity were synthesized, respectively. Subsequently, the coupling reaction between. the -COOH groups of poly(NIPAAm-co-AAc) and the -NH2 groups on the surface of the N-CQDs was carried out. The fluorescence spectra show that the coil-globule transition of the poly-N-CQDs coincided with intensity changes in the scattering peak at excitation wavelength with the temperature variations. The phase transition temperature and the fluorescent intensity of poly-N-CQDs can be regulated by modulating the composition and concentration of poly-N-CQDs as well as the temperature and pH of the local medium. The thermo-sensitivity and fluorescent properties of the poly-N-CQDs displayed good stability and reversibility. The fluorescence intensity and emission wavelengths of the poly-N-CQDs significantly changed in different solvents for solvent recognition. The poly-N-CQDs was employed as a fluorescent probe for Fe3+ detection ranging from 0.025 to 1 mM with a limit of detection (LOD) of 9.49 µM. The hybrid polymer materials have the potential to develop an N-CQDs-based thermo-sensitive device or sensor.

Biomineralized Nano-Assemblies of Poly(Ethylene Glycol) Derivative with Lanthanide Ions as Ratiometric Fluorescence Sensors for Detection of Water and Fe3+ Ions.

An effective strategy was developed to fabricate novel lanthanide ions-pyromellitic acid-methoxy poly(ethylene glycol) (Ln-PMA-MPEG) nano-assemblies. The amphiphilic partially esterified derivative (PMA-MPEG) of pyromellitic acid with methoxy poly(ethylene glycol) was designed and synthesized via the coupling reaction. Ln-PMA-MPEG nano-assemblies were rapidly fabricated using PMA-MPEG as a polymer ligand with Eu3+ ions or mixed Eu3+/Tb3+ ions through biomimetic mineralization in neutral aqueous systems. The size of the as-prepared materials could be designed in the range 80-200 nm with a uniform distribution. The materials were readily dispersed in various solvents and displayed visible color variations and different photoluminescent properties for solvent recognition. The mixed Eu/Tb-PMA-MPEG nanomaterials were investigated as ratiometric sensors for the detection of trace water in DMF and Fe3+ ions in aqueous solutions. The sensor materials can quantitatively detect trace water in DMF from 0% to 10% (v/v). The resultant materials also display a strong correlation between the double luminescence intensity ratios (ITb/IEu) and Fe3+ concentration, with a good linear detection concentration in the range of 0-0.24 mM and a limit of detection of 0.46 µM, and other metal ions did not interfere with the sensing mechanism for Fe3+ ions. The novel nano-assemblies have potential applications as ratiometric fluorescent nanosensors in the chemical industry as well as in biomedical fields.

Development of a two-in-one integrated bioassay for simultaneous and rapid on-site detection of Pb2+ and Hg2+ in water.

Exposure to heavy metal pollution represents a serious health risk and requires rapid, sensitive, and accurate detection to protect human health. However, the existing methods had various limitations for simultaneous detection of heavy metals. Herein, a novel two-in-one integrated bioassay was constructed for simultaneous on-site determination of Hg2+ and Pb2+ through combining all-fiber bicolor fluorescence biosensor (ABFB), functional nucleic acids (FNAs), and FRET. Hg2+ biosensor, consisting of BQ-T14 and CY-A14, performed its detection based on specifical binding of Hg2+ and T bases to form T-Hg2+-T mismatch structure. GR-5 DNAzyme, consisting of GR-5S and GR-5E, is applied for Pb2+ biosensor. The higher concentration of Hg2+ and Pb2+ results in the more T-Hg2+-T mismatch structure formed and the GR-5E to cleave the more GR-5S, respectively, thus allowing higher detectable fluorescence intensities in two signal channels. Thanks to high selectivity of two FNAs-biosensors and excellent time-resolved effect of the ABFB, the Hg2+ and Pb2+ could be directly and simultaneously quantitated in 12 min, and had the LODs of 4.22 nM and 1.55 nM, respectively. The satisfied recovery rate of real samples was verified by ICP-OES. Our strategy could serve as a simple and cost-effective on-site high-frequency detection of heavy metal ions.

Arsenic in soils contaminated by arsenic-containing chemical weapons in a site of Jilin, China: fraction and bioaccessibility.

At the end of World War II, the Japanese abandoned arsenic (As)-containing chemical weapons (CWs) in China. During the long-term burial process, the As-containing agents leaked into the environment due to the corrosion of weapon shells. This study explored the surface distribution, fraction composition, and bioaccessibility of As in the soil contaminated by chemical weapons in a site of Jilin Province, China. Results showed that As was enriched in the soil of CWs buried and the maximum concentration of As in this area was 110 mg/kg (dry weight). In terms of fraction, As primarily accumulated in amorphous Fe/Al-oxides bound and residual fractions. Moreover, from the perspective of fractions with potential environmental risks, As accounted for 45.6-82.0% and 61.0-80.7% of the fractions extracted by Wenzel and Shiowatana sequential extraction procedure (SEP), respectively. Bioaccessibility can also be used to assess environmental risks. The mean values of As bioaccessibility were as follows: gastric phase (15.0%) > colon phase (14.8%) > small intestinal phase (13.3%), and the As bioaccessibility was closely related to the Fe/Al oxide bound fraction. Compared with the surrounding farmland, the potential environmental risk of soil pollution was more significant in the CW burial areas. This study provided support for remediation of As-containing agent-contaminated soil in China.

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.

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.

Analysis of the biodegradation and phytotoxicity mechanism of TNT, RDX, HMX in alfalfa (Medicago sativa).

The aim of this study was to reveal the mechanism underlying the toxicity of TNT (trinitrotoluene), RDX (cyclotrimethylene trinitroamine), and HMX (cyclotetramethylene tetranitramine) explosives pollution in plants. Here, the effects of exposure to these three explosives were examined on chlorophyll fluorescence, antioxidant enzyme activity, and the metabolite spectrum in alfalfa (Medicago sativa) plants. The degradation rates for TNT, RDX, and HMX by alfalfa were 26.8%, 20.4%, and 18.4%, respectively, under hydroponic conditions. TNT caused damage to the microstructure of the plant roots and inhibited photosynthesis, whereas RDX and HMX induced only minor changes. Exposure to any of the three explosives caused disturbances in the oxidase system. Non-targeted metabolomics identified a total of 6185 metabolites. TNT exposure induced the appearance of 609 differentially expressed metabolites (189 upregulated, 420 downregulated), RDX exposure induced 197 differentially expressed metabolites (155 upregulated and 42 downregulated), and HMX induced 234 differentially expressed metabolites (132 upregulated and 102 downregulated). Of these differentially expressed metabolites, lipids and lipid-like molecules were the main metabolites induced by explosives poisoning. TNT mainly caused significant changes in the alanine, aspartate, and glutamate metabolism metabolic pathways, RDX mainly caused disorders in the arginine biosynthesis metabolic pathway, and HMX disrupted the oxidative phosphorylation metabolic pathway. Taken together, the results show that exposure to TNT, RDX, and HMX leads to imbalances in plant photosynthetic characteristics and antioxidant enzyme systems, changes the basic metabolism of plants, and has significant ecotoxicity effects.

Degradation of aniline in water with gaseous streamer corona plasma.

This paper demonstrated the effects and influencing factors in degrading aniline by gaseous streamer corona plasma along water surface under different discharging gas atmospheres. For aniline with an initial concentration of 100 mg l-1, the degradation was fastest when the reactor was not ventilated, and the degradation rate is 98.5% under 7.5 min treatment. While the degradation was slowest when Ar was ventilated, the degradation rate is 98.6% after treatment for 60 min. Some active particles were detected using a multi-channel fibre-optic spectrometer during the discharge, such as Ar, OH, N2, N 2 + and N. In particular, NO was detected during air discharge. The NO and N 2 + could produce NO 3 - ; then generated nitric acid would affect the pH value of the solution. The intermediate product by N2 discharge is nitrophenol, and nitrophenol would be converted to p-benzoquinone. The O2 discharge could produce an intermediate product of aminophenol. The intermediate products in Ar discharge were in small amounts and the final mineralization effect was the best.

Biodegradation and physiological response mechanism of Bacillus aryabhattai to cyclotetramethylenete-tranitramine (HMX) contamination.

This study aims to reveal the biodegradation and interaction mechanism of cyclotetramethylenete-tranitramine (HMX) by a newly isolated bacteria. In this study, a bacterial strain (Bacillus aryabhattai) with high efficiency for HMX degradation was used as the test organism to analyze the changes in growth status, cell function, and mineral metabolism following exposure to different stress concentrations (0 and 5 mg L-1) of HMX. Non-targeted metabonomics was used to reveal the metabolic response of this strain to HMX stress. The results showed that when the HMX concentration was 5 mg L-1, the removal rate of HMX within 24 h of inoculation with Bacillus aryabhatta was as high as 90.5%, the OD600 turbidity was 1.024, and the BOD5 was 225 mg L-1. Scanning electron microscope (SEM) images showed that the morphology of bacteria was not obvious Variety, Fourier transform infrared spectroscopy (FTIR) showed that the cell surface -OH functional groups drifted, and ICP-MS showed that the cell mineral element metabolism was disturbed. Non-targeted metabonomics showed that HMX induced the differential expression of 254 metabolites (133 upregulated and 221 downregulated). The main differentially expressed metabolites during HMX stress were lipids and lipid-like molecules, and the most significantly affected metabolic pathway was purine metabolism. At the same time, the primary metabolic network of bacteria was disordered. These results confirmed that Bacillus aryabhattai has a high tolerance to HMX and can efficiently degrade HMX. The degradation mechanism involves the extracellular decomposition of HMX and transformation of the degradation products into intracellular purines, amino sugars, and nucleoside sugars that then participate in cell metabolism.

A turn-on fluorescent probe based on N-(rhodamine-B)-thiolactam-2-n-butane with ionic liquids for selective and sensitive detection of mustard gas stimulant.

Sulfur mustard (SM) is recognized as one of the most lethal warfare agents. It has the potential to seriously affect public health and safety. To employ appropriate medical countermeasures and treat victims as quickly as possible, the development of a rapid and simple SM detection technique is crucial. The aim of the present study was to explore novel detection systems exhibiting excellent selectivity and high sensitivity. An SM probe, namely N-(rhodamine-B)-thiolactam-2-n-butane (SRB-NB), which was based on a thiolactam structure, was effectively designed and synthesized. The rhodamine and thiourea moieties played the roles of the chromogenic and reacting groups, respectively. Subsequently, using ionic liquids (ILs) as the solvents, a turn-on fluorescence detection system was constructed. Notably, it was found that imidazole-based ILs displayed good solubility for an SM simulant, specifically 2-chloroethyl ethyl sulfide (2-CEES). Moreover, 1-butyl-3-methylimidazolium dicyandiamide ([BMIm]DCA) IL held the maximum amount of 2-CEES (132.5 g/100 g). The SRB-NB probe exhibited better ultraviolet (UV) absorption and fluorescence properties in ILs than in other organic solvents. SRB-NB/IL was able to detect 2-CEES in liquid form with remarkable selectivity and sensitivity. The limit of detection (LOD) was established at 3.0 × 10-6 M. Importantly, SRB-NB/ILs also showed good optical response to gaseous 2-CEES and SM.

Rapid activation of basic hydrogen peroxide by borate and efficient destruction of toxic industrial chemicals (TICs) and chemical warfare agents (CWAs).

The activation process of the B(OH)3-activated H2O2 solution and its performance toward toxic industrial chemicals (TICs) and chemical warfare agents (CWAs) were investigated to find an efficient way to destroy TICs and CWAs. 11B NMR analysis proved that B(OH)3 reacted rapidly with basic H2O2 to produce peroxoborates ([B(OH)(4-x)(OOH)x]-), and the proportional contents were closely related to the pH and temperature. 1O2 and ·O2- were generated, and their production increased exponentially with pH. TICs thioanisole and paraoxon were used as simulants of CWAs to investigate the decontamination performance and nucleophilic/oxidizing reactivity of the B(OH)3-activated H2O2. Batch experiments proved that peroxoborates acted as the oxidants for the primary oxidation of the sulfide at a pH range of 8-12 and that ·O2- was responsible for the further oxidation of sulfoxide. Paraoxon degraded through OOH--mediated SN2 displacement with high stereo-selectivity, and the degradation rate increased exponentially with pH. Mustard gas, soman, and VX degraded effectively into nontoxic products in the B(OH)3-activated H2O2 solution. A pH of 9-11 was recommended as the suitable acidity for developing the B(OH)3-activated H2O2 solution to be a candidate for nucleophilic/oxidizing decontaminant, with advantages in rapid activation and low loss rate of reactive oxygen species.