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 ([email protected]₂NH₂). This adsorbent was prepared by grafting amino groups onto [email protected]₂ 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 [email protected]₂ 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 [email protected]₂NH₂ 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 [email protected]₂NH₂ NPs makes these remediation materials promising for applications.     

Dendroremediation of trinitrotoluene (TNT) Part 2: Fate of radio-labelled TNT in trees

BACKGROUND, AIM AND SCOPE: Problems of long-term existence of the environmental contaminant 2,4,6-trinitrotoluene (TNT) and necessities for the use of trees ('dendroremediation') in sustainable phytoremediation strategies for TNT are described in the first part of this paper. Aims of the second part are estimation of [14C]-TNT uptake, localisation of TNT-derived radioactivity in mature tree tissues, and the determination of the degree of TNT-degradation during dendroremediation processes. METHODS: Four-year-old trees of hybrid willow (Salix spec., clone EW-20) and of Norway spruce (Picea abies) were cultivated in sand or ammunition plant soil (AP-soil) in wick supplied growth vessels. Trees were exposed to a single pulse application with water solved [U-14C]-TNT reaching a calculated initial concentration of 5.2 mg TNT per kg dry soil. Two months after application overall radioactivity and extractability of 14C were determined in sand/soil, roots, stem-wood, stem-bark, branches, leaves, needles, and Picea May sprouts. Root extracts were analysed by radio TLC. RESULTS: 60 days after [14C]-TNT application, recovered 14C is accumulated in roots (70% for sand variants, 34% for AP-soil variant). 15-28% of 14C remained in sand and 61% in AP-soil. 3.3 to 14.4% of 14C were located in aboveground tree portions. Above-ground distribution of 14C differed considerably between the angiosperm Salix and the gymnosperm Picea. In Salix, nearly half of above-ground-14C was detected in bark-free wood, whereas in Picea older needles contained most of the above-ground-14C (54-69%). TNT was readily transformed in tree tissue. Approximately 80% of 14C was non-extractably bound in roots, stems, wood, and leaves or needles. Only quantitatively less important stem-bark of Salix and Picea and May shoots of Picea showed higher extraction yields (up to 56%). DISCUSSION: Pulse application of [14C]-TNT provided evidence for the first time that after TNT-exposure, in tree root extracts, no TNT and none of the known metabolites, mono-amino-dinitrotoluenes (ADNT), diaminonitrotoluenes (DANT), trinitrobenzene (TNB) and no dinitrotoluenes (DNTs) were present. Extractable portions of 14C were small and contained at least three unknown metabolites (or groups) for Salix. In Picea, four extractable metabolites (or groups) were detected, where only one metabolite (or group) seemed to be identical for Salix and Picea. All unknown extractables were of a very polar nature. CONCLUSIONS: Results of complete TNT-transformation in trees explain some of our previous findings with 'cold analytics', where no TNT and no ADNT-metabolites could be found in tissues of TNT-exposed Salix and Populus clones. It is concluded that 'cold' tissue analysis of tree organs is not suited for quantitative success control of phytoremediation in situ. RECOMMENDATIONS AND OUTLOOK: Both short rotation Salicaceae trees and conifer forests possess a dendroremediation potential for TNT polluted soils. The degradation capacity and the large biomass of adult forest trees with their woody compartments of roots and stems may be utilized for detoxification of soil xenobiotics.     

评价爆炸超压作用的一个新指标及其在一次型FAE中的应用

利用单自由度体系在爆炸载荷作用下的动力响应的数值解,提出了一个近似关系式,进而得到一个新评价指标△P0.742m i0.258 .同时给出了一次型FAE的TNT比当量的计算方法,分别以超压峰值△Pm和△P0.742m i0.258 为评价指标计算了某一次型FAE的TNT比当量,并进行了比较.结果表明,单纯以超压峰值为评价指标的TNT比当量结果低估了一次型FAE的超压作用.鉴于爆炸超压场测试仪器与技术已能够容易地准确测量超压峰值与比冲量,建议以△P0.742m i0.258 为一次型FAE的TNT比当量的评价指标.     

共基质条件下TNT降解菌的选育及其处理效果

选取SBR弹药销毁废水处理系统中的活性污泥作为菌源,在共基质条件下,经过驯化和筛选,分离出11株可降解TNT的单菌,从中选出生长速度较快的3株菌JT1,JT2,JT3进行了单菌及混菌降解能力测试,结果表明:混合菌JTH降解能力最强,其适宜环境条件为25℃～30℃,pH7.5～9.0,基质中添加2g/L葡萄糖可显著增强混菌JTH生长并可使24h内的TNT降解率达到96 1%;模拟废水的处理实验表明:混菌JTH对COD的去除率>80%,TNT降解率80%～90%;生物强化实验表明:以0.1的菌量污泥比在SBR系统中投加混合菌可使系统的出水COD稳定在100mg/L左右,出水TNT浓度<5mg/L。     

Phytoremediation of Selected Explosives

The phytoremediation of trinitrotoluene (TNT), nitroglycerine (NG) and pentaerytritoltetranitrate (PETN) using in vitrocultures of Rheum palmatum, Saponaria officinalisand Populus simonii were studied. All above mentioned explosives were degradated to less toxic products and finally probably bound to the cell wall or further involved in the metabolism. The formation of trinitrobenzene (TNB) during degradation of TNT which is a product of alternative degradation pathway was found too.     

Characteristic overpressure–impulse–distance curves for the detonation of explosives, pyrotechnics or unstable substances

A number of models have been proposed to calculate overpressure and impulse from accidental industrial explosions. When the blast is produced by explosives, pyrotechnics or unstable substances, the TNT equivalent model is widely used. From the curves given by this model, data are fitted to obtain equations showing the relationship between overpressure, impulse and distance. These equations, referred to here as characteristic curves, can be fitted by means of power equations, which depend on the TNT equivalent mass. Characteristic curves allow determination of overpressure and impulse at each distance.     

膜生物法降解TNT弹药销毁废水的重要影响因素

采用水解酸化一好氧膜生物工艺对弹药销毁废水中TNT进行降解试验研究。结果表明,共代谢外加碳源对TNT的生物降解影响显著。无共代谢外加碳源的情况下,HRT=40h,TNT的去除率仅为53．4％。有共代谢外加碳源的情况下,外加碳源COD与TNT提供COD比值宜大于4．8,系统对TNT的去除率可高达99％。温度对水解酸化影响重大,当温度低于15℃时,水解酸化对TNT去除率低于33．3％,而当温度高于20℃时,水解酸化对TNT的去除率不小于83％。     

Binding of trinitrotoluene (TNT) to water extractable humus

Solid-state ¹⁵N NMR was applied to the aqueous extracts of a ¹³C-enriched plant slurry (Lolium perenne), anaerobically incubated with ¹⁵N₃-trinitrotoluene (TNT). Almost all ¹⁵N₃-TNT transformation products became covalently bound to the plant-derived organic material extractable with water. DCPMAS ¹⁵N ¹³C NMR revealed a three-step reaction scheme. After reduction of TNT, the aryl amines are acetylated. Subsequent alkylation of the resulting amides strengthens the incorporation of TNT-transformation products into humic material. Comparable results have been recently obtained under aerobic conditions, which indicates that this pathway is a common process during biological TNT transformation.     

新型纳米材料光催化反应器研究

为了充分发挥纳米材料的光催化性能,研制了一种带有旋转叶片且可负载光催化纳米材料的光催化反应器.并以制备的纳米TiO2/硅藻土复合材料作为光催化剂、TNT生产废水为处理对象,考察了催化材料附载量、废水浓度和多次重复使用对反应器催化降解效率的影响.结果表明:附载有光催化纳米材料的反应器经过6次6h重复使用,对TNT生产废水催化降解效率仍然保持在75%以上,远高于直接分散在废水中纳米材料的处理效率(47.25%),即多次重复使用并保持高降解效率;而且可较好地避免纳米光催化材料的团聚.避免因回收造成的纳米材料光催化效率降低以及回收不完全造成的水体二次污染等现象.     

电压对使用三维电极处理TNT废水的影响

本试验比较了三维电极电解法和二维电极电解法处理TNT废水的效果,考察了采用三维电极电解法时不同槽电压对电解效果的影响,并对电解机理作了初步探讨.实验表明,极板间距为4 cm、电动搅拌器转速250 r/min、电解时间为2h时,最佳的电解槽电压为15 V,此工艺条件下的COD、TOC的去除率分别为77.6%、62.7%.