Photocatalytic demethylation of 2,4,6-trinitrotoluene (TNT) by porphyrins

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.     

Enhanced bioavailability of sorbed 2,4,6-trinitrotoluene (TNT) by a bacterial consortium

Large quantities of trinitrotoluene (TNT) have been associated with past and present military activities worldwide. Because this contaminant is highly toxic and strongly sorbs to soil particles, bacteria that are able to transform it have had very little success, if any. This study was conducted to evaluate the bioavailability of 14C-labeled TNT in soil for microbial mineralization. Sorption-desorption experiments indicated that a Kendaia loam soil effectively adsorbs this explosive compound, with approximately 30-45% of the added TNT remaining sorbed to the soil after a total of 10 washings. A bacterial consortium isolated from explosive-contaminated sites was prepared in liquid medium and then tested in a TNT-spiked Kendaia loam soil. The concentration of TNT in the soil that was inoculated with the bacterial consortium was reduced by more than 30% of the initial concentration compared to the soil that did not contain the bacterial consortium within a period of 20 weeks. Nearly half of the TNT was mineralized as determined by the percentage of 14CO2 produced. Only one member of the consortium (i.e., Enterobacter sp.) significantly mineralized 25% of TNT although the extent of mineralization was significantly enhanced to 35% in the presence of the other two members of the consortium. The data suggest that some of the strongly adsorbed TNT may be accessible for metabolism if conditions for the right combination of microorganisms with specialized capabilities are optimized. The remaining sorbed fraction of substrate is presumably sequestered and thus unavailable to the microorganisms.     

Effect of different soil types on the enchytraeids Enchytraeus albidus and Enchytraeus luxuriosus using the herbicide Phenmedipham

Soil ecotoxicology studies are usually performed in standard soils, such as the OECD (Organization for Economic Cooperation and Development) artificial soil or the LUFA St. 2.2, a natural soil. When assessing the toxic effects in the environment, soil properties are often different from those in standard soils, which might lead to a different exposure situation for the test species and, therefore, to a different evaluation of the risk of the test substance. Selected to cover a broad range of properties and based on the Euro-Soils concept, 18 different soils were studied regarding their suitability to two test species: Enchytraeus albidus and Enchytraeus luxuriosus (Enchytraeidae). In reproduction tests, the test species reacted differently to the tested soils, but both enchytraeids did not survive in acid soils (i.e. pH相似文献   

Ecotoxicological evaluation of in situ bioremediation of soils contaminated by the explosive 2,4,6-trinitrotoluene (TNT)

To evaluate the environmental relevance of in situ bioremediation of contaminated soils, effective and reliable monitoring approaches are of special importance. The presented study was conducted as part of a research project investigating in situ bioremediation of topsoils contaminated by the explosive 2,4,6-trinitrotoluene (TNT). Changes in soil toxicity within different experimental fields at a former ordnance factory were evaluated using a battery of five bioassays (plant growth, Collembola reproduction, soil respiration, luminescent bacteria acute toxicity and mutagenicity test) in combination to chemical contaminant analysis. Resulting data reveal clear differences in sensitivities between methods with the luminescent bacteria assay performed with soil leachates as most sensitive toxicity indicator. Complete test battery results are presented in so-called soil toxicity profiles to visualise and facilitate the interpretation of data. Both biological and chemical monitoring results indicate a reduction of soil toxicity within 17 months of remediation.     

Coupling of 2,4,6-trinitrotoluene (TNT) metabolites onto humic monomers by a new laccase from Trametes modesta

During degradation of trinitrotoluene (TNT) by Trametes modesta, addition of humic monomers prevented the accumulation of all major stable TNT metabolites (aminodinitrotoluenes [AMDNT]) by at least 92% in the presence of 200 mM ferulic acid and guaiacol. Acute toxicity tests with individual TNT metabolites and in T. modesta cultures supplemented with 200 microM TNT demonstrated that the TNT biodegradation process lead to less toxic metabolites. Toxicity decreased in the order TNT>4-HADNT (4-hydroxylaminodinitrotoluene)>2-HADNT>2,6-DNT (2,6-dinitrotoluene)>2',2',6,6-azoxytetranitrotoluene>4-AMDNT>2-AMDNT>2,4-diamninonitrotoluene (2,4-DAMNT) while 2,4-DNT and 2,6-DAMNT were the least toxic. Ferulic acid is the best candidate for immobilization TNT biodegradation metabolites since it prevented the accumulation of AMDNTs in cultures during TNT biodegradation and its products were less toxic. All humic monomers were very effective in immobilizing 2-HADNT [100%], 4-HADNT [100%] and 2,2,6,6-azoxytetranitrotoluene [100%]. Two distinct laccase isoenzymes (LTM1 and LTM2) potentially involved in immobilization of TNT degradation products were purified to electrophoretic homogeneity. LTM1 and LTM2 have molecular weights of 77.6 and 52.5 kDa, are 18% and 24% glycosylated, have pI values of 3.6 and 4.2, respectively. Both enzymes oxidized all the typical laccase substrates tested. LTM1 showed highest kinetic constants (K(m)=0.03 microM; K(cat)=8.8 4x 10(7)s(-1)) with syringaldazine as substrate.     

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

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

Bioaccumulation and elimination of 14C-lindane by Enchytraeus albidus in artificial (OECD) and a natural soil

Bioaccumulation and elimination of 14C-lindane in Enchytraeus albidus was studied in artificial OECD soil and a silty loam from an agricultural field in Central West Portugal. Results showed that enchytraeids were able to bioaccumulate the chemical with a kinetic pattern similar to that of earthworms: fast uptake within a few days and a biphasic elimination pattern. A 10 day period to study uptake was sufficient, but a few more days were probably necessary for elimination. Bioaccumulation was influenced by soil type. The authors suggest that higher organic matter (OM) content and also the higher content on sand particles in the OECD soil may have led to a faster elimination: hydrophobic chemicals tend to adsorb to OM being in this way less bioavailable and therefore less bioaccumulated having bioaccumulation factor value around 6 while in natural soil is 10; the sand could act as abrasive particles (helpers) in the elimination process leading to an elimination of 90% of the chemical in two days while in natural soil 67% was eliminated in the same period of time.     

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

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

Reproduction and biochemical responses in Enchytraeus albidus (Oligochaeta) to zinc or cadmium exposures

To better understand chemical modes of action, emphasis has been given to stress responses at lower levels of biological organization. Cholinesterases and antioxidant defenses are among the most used biomarkers due to their crucial role in the neurocholinergic transmission and in cell homeostasis preventing DNA damage, enzymatic inactivation and lipid peroxidation. The main goal of this study was to investigate the effects of zinc and cadmium on survival and reproduction of E. albidus and to assess metals oxidative stress potential and neurotoxic effects at concentrations that affected reproduction. Both metals affected the enchytraeids’ survival and reproduction and induced significant changes in the antioxidant defenses as well as increased lipid peroxidation, indicating oxidative damage. This study demonstrates that determining effects at different levels of biological organization can give better information on the physiological responses of enchytraeids in metal contamination events and further unravel the mechanistic processes dealing with metal stress.     

Degradation of 2,4,6-trinitrotoluene by selected helophytes

Four emergent plants (helophytes, synonyms emersion macrophytes, marsh plants, etc.) Phragmites australis, Juncus glaucus, Carex gracillis and Typha latifolia were successfully used for degradation of TNT (2,4,6-trinitrotoluene) under in vitro conditions. The plants took up and transformed more than 90% of TNT from the medium within ten days of cultivation. The most efficient species was Ph. australis which took up 98% of TNT within ten days. The first stable degradation products 4-amino-2,6-dinitrotoluene (4-ADNT) and 2-amino-4,6-dinitrotoluene (2-ADNT) were identified and analysed during the cultivation period. [14C] TNT was used for the detection of TNT degradation products and their compartmentalization in plant tissues after two weeks of cultivation. Forty one percent of 14C was detected as insoluble or bound in cell structures: 34% in roots and 8% in the aerial parts. These results open the perspective of using the above-mentioned plants for the remediation of TNT contaminated waters.     

Avoidance response of Enchytraeus albidus in relation to carbendazim ageing

In this study, avoidance response of Enchytraeus albidus to LUFA 2.2 soil contaminated with pesticide carbendazim was investigated. The aim was to clarify minimal test duration and temporal changes in avoidance response due to contamination ageing. Firstly, the concentration causing 50% avoidance (EC₅₀) was determined as 7.6 mg/kg. Then, test duration needed to reach this value (ET₅₀ = approximately 18 h) was identified. Finally, the capability of E. albidus avoidance test to reflect the changes of pollutant bioavailability was tested. The soil was spiked with carbendazim at the EC₅₀ concentration 1, 14, or 28 days before the test started and avoidance effects of fresh versus aged contamination were compared. The results indicated that enchytraeids preferred soil contaminated for 28 days prior to assay where carbendazim was probably less bioavailable than in freshly spiked soil. Our results open an interesting research area of potential use of avoidance tests for contaminant bioavailability assessment.     

Avoidance test with Enchytraeus albidus (Enchytraeidae): effects of different exposure time and soil properties

Enchytraeids are ecologically relevant soil species and are commonly used in standardized toxicity tests. Their rapid reaction to a chemical exposure can be used as a toxicological measurement endpoint that assesses the avoidance behavior. The objectives of this investigation were to determine the effects of soil properties on the avoidance behavior of Enchytraeus albidus and to optimize the duration of avoidance test. The avoidance tests included (1) exposures in OECD artificial soil with standard or modified properties (pH, clay or peat content), and (2) exposures to copper chloride, cadmium chloride, and to the organic pesticides dimethoate and phenmedipham for different time periods. Results showed that alteration of OECD soil constituents significantly affected the avoidance behavior of enchytraeids, and that the 48-h exposure was the optimal duration of the test. Consideration of soil properties is important for selecting appropriate experimental design and interpreting the results of the enchytraeid avoidance test.     

Chemically catalyzed uptake of 2,4,6-trinitrotoluene by Vetiveria zizanioides

The efficiency of vetiver grass (Vetiveria zizanioides) in removing 2,4,6-trinitrotoluene (TNT) from aqueous media was explored in the presence of a common agrochemical, urea, used as a chaotropic agent. Chaotropic agents disrupt water structure, increasing solubilization of hydrophobic compounds (TNT), thus, enhancing plant TNT uptake. The primary objectives of this study were to: (i) characterize TNT absorption by vetiver in hydroponic media, and (ii) determine the effect of urea on chemically catalyzing TNT uptake by vetiver grass in hydroponic media. Results showed that vetiver exhibited a high TNT uptake capacity (1.026 mgg(-1)), but kinetics were slow. Uptake was considerably enhanced in the presence of urea, which significantly (p<0.001) increased the 2nd-order reaction rate constant over that of the untreated (no urea) control. Three major TNT metabolites were detected in the roots, but not in the shoot, namely 1,3,5-trinitrobenzene, 4-amino 2,6-dinitrotoluene, and 2-amino 4,6-dinitrotoluene, indicating TNT degradation by vetiver grass.     

Assessing joint toxicity of chemicals in Enchytraeus albidus (Enchytraeidae) and Porcellionides pruinosus (Isopoda) using avoidance behaviour as an endpoint

Contamination problems are often characterized by complex mixtures of chemicals. There are two conceptual models usually used to evaluate patterns of mixture toxicity: Concentration Addition (CA) and Independent Action (IA). Deviations from these models as synergism, antagonism and dose dependency also occur. In the present study, single and mixture toxicity of atrazine, dimethoate, lindane, zinc and cadmium were tested in Porcellionides pruinosus and Enchytraeus albidus, using avoidance as test parameter. For both species patterns of antagonism were found when exposed to dimethoate and atrazine, synergism for lindane and dimethoate exposures (with the exception of lower doses in the isopod case study) and concentration addition for cadmium and zinc occurred, while the exposure to cadmium and dimethoate showed dissimilar patterns.This study highlights the importance of dose dependencies when testing chemical mixtures and that avoidance tests can also be used to asses the effects of mixture toxicity.     

Ecotoxicity of nickel to Eisenia fetida, Enchytraeus albidus and Folsomia candida

Despite growing concern about the potential adverse effects of elevated nickel concentrations in the environment, only a few toxicity data are available for terrestrial invertebrates. Therefore, chronic toxicity of nickel was assessed for Eisenia fetida, Enchytraeus albidus and Folsomia candida, the three invertebrates for which standard test protocols are available. The 21 d EC50 for the cocoon production of E. fetida was 362 (241-508) mg Ni/kg dry wt. For the reproduction of E. albidus, a 42 d EC50 of 275 (217-346) mg Ni/kg dry wt was observed. The 28 d EC50 for the reproduction of F. candida was 476 (347-671) mg Ni/kg dry wt. The obtained toxicity data were very similar to those of related species reported in literature. Although the presented data can be considered as a step forward in the assessment of the potential risks of nickel in terrestrial environments, further research is needed to evaluate the influence of soil parameters on the toxicity of nickel and to quantify the effect of ageing on bioavailability.     

Uptake and metabolism of 2,4,6-trinitrotoluene in higher plants

The fate of the explosive 2,4,6-TNT in plants is of major interest. Therefore, a method was developed to analyse TNT and derivatives in plant tissue. The method was utilized to investigate the uptake and metabolism of TNT inMedicago sativa andAllium schoenoprasum grown in hydroponic cultures containing TNT levels of 0.1 to 10 mg/1. Detectable concentrations of nitrotoluenes were significantly higher inAllium schoenoprasum than inMedicago sativa. The uptake of TNT in plants was directly related to the initial TNT level. The principal nitroaromatic components in roots and shoots of both plant species were identified as 4-ADNT and 2-ADNT in equal amounts, with substantially less TNT.     

Multi-generation toxicity of zinc, cadmium, copper and lead to the potworm Enchytraeus albidus

In standard chronic terrestrial toxicity tests with invertebrates, adult organisms are exposed to the contaminants and the number of offspring is quantified. These procedures do not allow the assessment of possible effects on all life stages of the organism, which may lead to an underestimation of the toxicity of the test substance. To evaluate the importance of this issue, the potworm Enchytraeus albidus was exposed to zinc, cadmium, copper and lead for two subsequent generations. Juvenile production was assessed for both generations. Considering the variability of metal toxicity data reported in the literature, it is concluded that the two generation assay did not markedly increase the sensitivity of the standard E. albidus test for the tested metals. Therefore, toxicity data obtained with the proposed test guideline with E. albidus are protective for all life stages.     

The use of amino compounds for binding 2,4,6-trinitrotoluene in water

Sites polluted with 2,4,6-trinitrotoluene (TNT) constitute a worldwide problem. In this work, chemical reactions for binding TNT to amino-compounds are proposed as an initial step for developing new remediation techniques to clean-up groundwater and soils contaminated with TNT. Indeed, addition of aniline and an amino acid-like cysteine caused a decrease in free TNT of 86% and 68-100%, respectively. Using 13C-NMR spectroscopy, it was shown that TNT chemically forms a Meisenheimer complex with cysteine and aniline in 1/1 (by vol.) H2O/d6-acetone.     

Photolysis of nitroaromatics in aquatic systems. I. 2,4,6-trinitrotoluene

Photolysis of 2,4,6-trinitrotoluene (TNT) occurs rapidly in pure and natural waters irradiated with sunlight, with half-lives of less than a half-hour in some natural waters. Experiments to study the TNT photolysis products and to obtain evidence for complexation of TNT with natural substances are discussed.