Fenton氧化处理爆炸物污染土壤的实验研究

采用摇瓶和玻璃柱试验考察了Fenton氧化处理爆炸物污染土壤中2,4-DNT、2,6-DNT以及COD等的去除效果及其最佳参数.当3%H2O2投加量达到26.46mmol、FeSO4和H2O2的物质的量之比约为1∶73.56时,2,4-DNT和2,6-DNT均可被完全氧化,COD去除率可达到87%.对于2,4-DNT和2,6-DNT,反应时间只需要2h,但要同时去除其它芳香族硝基化合物,则反应时间需要超过8h.土壤直接Fenton氧化的效果并不理想,而对洗出液进行Fenton氧化可以取得很好的效果.通过反应动力学分析和丙酮抑制试验得出,2,4-DNT比2,6-DNT容易氧化.GC-MS分析结果表明,不仅土壤中的2,4-DNT、2,6-DNT可被氧化,其它的硝基芳香族有机化合物也可被氧化去除.     

Investigation of ammonium nitrate based emulsion ignition characteristic

This paper presents an analysis of the observed ignition behaviors of ammonium nitrate (AN) and emulsion explosives (EE). Pure AN and EE locally ignited by a heat source do not undergo sustained combustion when the pressure is lower than some threshold value usually called the Minimum Burning Pressure (MBP). A reason for pure AN's and EE's incapable of burning was suggested, and the roles of sample water, inorganic salts, oil phase, and sensitizer were discussed. Accelerating rate calorimeter (ARC) was used to study the thermal stability of EE and AN. The results also showed that MBP is of vital importance and useful for the manufacture and application of AN and EE in terms of accident prevention.     

Transport and Immobilization of 2,4,6 15N-Trinitrotoluene in Soil Microcosms Subjected to Long Term Incubation Under Aerobic Conditions

¹⁵N-labeling and solid-state ¹³C and ¹⁵N nuclear magnetic resonance (NMR) spectroscopy was applied to study the immobilization of 2,4,6 trinitrotoluene (TNT) into soil organic matter (SOM). Uncontaminated soil from the Ap horizon of a Luvisol was mixed with ¹⁵N-TNT (enrichment: 99 atm%) and laid over an unspiked layer of the same material. The latter covered soil from the Bt horizon. The microcosms were aerobically incubated under laboratory conditions for up to 11 months. After 1 week, within the total microcosm approximately 90% of the added ¹⁵N (¹⁵N_add) were recovered, mostly in the top layer (87%). After 11 months, this amount decreased to 71%, indicating losses due to denitration or transamination. Within two months, half of ¹⁵N_add had been immobilized in the residues not extractable with organic solvents and water. The amount of the sequestered ¹⁵N_add remained fairly constant until the end of the experiment pointing towards a high stability of TNT-SOM associates. Solid-state ¹⁵N NMR revealed their formation by covalent binding, most tentatively as amides. Complete reduction of TNT to triaminotoluene (TAT) was not prerequisite. The most pronounced downwards movement of ¹⁵N-TNT occurred during the first two months. The major part of it, however, experienced quick immobilization, leaving approximately 10% of ¹⁵N_add recovered in the leachate at the end of the experiment. Calculations indicated contributions of inorganic ¹⁵N_add. Approximately 25% of its organic ¹⁵N_add originated from condensed N, suggesting that in soils the transport of partly reduced TNT is in close association with the organic matter of the soil solution to which they are covalently bound.     

Uptake and Metabolism of TNT and GTN by Plants Expressing Bacterial Pentaerythritol Tetranitrate Reductase

The manufacture and improper disposal of explosives has resulted in a significant amount of land requiring remediation. The compound 2,4,6-trinitrotoluene (TNT) is the most persistent and toxic of the explosive pollutants with current treatment methods being energy intensive and costly. Bacterial enzymes such as pentaerythritol tetranitrate reductase (PETNR) from Enterobacter cloacae PB2 have been found to have activity against TNT; however, microbes often lack the biomassnecessary for remediation applications. The PETNRgene (onr1) was transformed into tobacco plants in an attempt to combine the metabolic diversity of microbes with the sequestering properties of plants. The resulting transgenic plants were shown to have enhanced tolerance to TNT during germination and as seedlings. Phytoremediation applications with these plants may provide an alternative treatment of TNT contamination.     

起爆药污染场地土壤中锑的环境风险评估

为研究起爆药污染场地土壤中Sb（锑）的环境风险,利用微波消解原子荧光光度法、Tessier逐级提取法、TCLP（toxicity characteristic leaching procedure）毒性浸出法及SBET（simplied bioaccessibility extraction test）方法,分析了某起爆药场地表层土壤中Sb的价态、形态、浸出水平和生物可给性及其对人体健康风险水平和地下水环境风险水平的影响.结果表明:①土壤中w（TSb）为26.7~4 255.0 mg/kg,是GB 36600-2018《土壤环境质量建设用地土壤污染风险管控标准》中第一类用地筛选值的1.33~212.75倍,最大值超过相应管制值的10.82倍.土壤样品中Sb主要以Sb5+存在,w（Sb5+）在w（TSb）中的占比达65.57%~95.46%.②土壤中不同形态Sb的比例由高到低依次为残渣态（38.05%~94.22%）、铁锰氧化物结合态（0.01%~31.80%）、有机结合态（0.32%~21.55%）、碳酸盐结合态（0.01%~11.16%）和可交换态（0.42%~3.70%）.土壤中w（可交换态Sb）与CEC（阳离子交换量）呈负相关,w（铁锰氧化物结合态Sb）与w（Fe）、w（Mn）均呈正相关.③土壤中Sb的浸出浓度为0.22~35.49 μg/L,并随土壤中w（砂粒）、w（TSb）、w（碳酸盐结合态Sb）和w（可交换态Sb）的增大而升高,随CEC的增大而降低.④土壤中Sb的生物可给性范围在8.03%~67.69%之间,w（Fe）和w（OM）的增加能够降低Sb的生物可给性.⑤基于Sb生物可给性健康风险水平和基于Sb价态健康风险水平的结果分别是以w（TSb）为暴露浓度计算的传统风险评估模型预测结果的8.00%~67.69%和62.00%~77.01%,土壤中Sb的实际浸出浓度较常规模型（三相平衡耦合地下水稀释模型）预测值低3~5个数量级.研究显示,充分考虑Sb在起爆药污染场地土壤中的赋存特征能够降低常规风险评估方法的保守性.