零价铁-氧化剂联合降解土壤中硝基氯苯及土壤性质变化

硝基氯苯是重要的化工原料和中间体,其在土壤中的不断积累对生态环境和人体健康构成了严重威胁.高级氧化修复技术可以将有机污染物直接或间接矿化为CO_2和H_2O,从而成为近年来研究的重点.本文针对南京某化工厂搬迁遗留的硝基氯苯污染的场地土壤,研究了零价铁还原与氧化剂氧化的联合体系对硝基氯苯的降解率,并对反应过程的中间产物和动力学进行了分析,研究了降解后土壤性质的变化.结果表明,当采用KMnO_4、Fenton试剂、30%H_2O_2和Na_2S_2O_44种氧化剂直接氧化时,土壤中硝基氯苯的降解率分别为75.0%、62.9%、58.1%和41.5%;经零价铁还原1 h后,再施加氧化剂氧化处理,硝基氯苯降解率大幅提高,分别达到91.5%、88.5%、87.4%和70.4%.零价铁还原体系中间产物氯代苯胺浓度4 h时达到最大,施加氧化剂后迅速下降,4 h后下降至最低并维持较稳定水平;硝基氯苯氧化反应在单一氧化剂反应体系符合一级动力学方程,但在零价铁与氧化剂联合反应体系符合二级动力学方程;降解后的土壤性质有较大变化,CEC、TOC和土壤养分显著下降,Eh和EC显著增加,土壤pH除施加Na2S2O4下降显著外,施加KMnO_4、Fenton试剂、30%H_2O_2时下降较小,但同时添加零价铁土壤pH下降显著;土壤全N、全P、全K变化不显著,这些可为修复后土壤的再利用提供数据参考.     

不同铁营养状况下根系特征及蒸腾对黄瓜幼苗吸收镉的影响

采用营养液培养方法,研究了不同铁营养状况下的根系形态变化及蒸腾作用对不同品种黄瓜幼苗吸收镉的影响.结果表明,不加铁处理对地上部生物量的影响大于对根系的影响,并且不同品种间生物量差异显著.不加铁处理和低水平铁处理时,黄瓜根长变长、根表面积变大.与不加铁处理相比,加铁处理显著抑制了黄瓜根系对镉的吸收,中农5号(缺铁敏感黄瓜品种)和津春4号(缺铁不敏感黄瓜品种)每克根对镉的吸收量分别降低了25.5%~45.5%和28.8%~55.0%;但却增加了镉向地上部的转运,镉在叶中的分配系数分别增加了2.2~3.6倍(中农5号)和2.6~3.7倍(津春4号).缺铁敏感的中农5号吸镉总量与根长、根表面积都呈显著正相关性,而缺铁不敏感的津春4号吸镉总量与根长、根表面积之间的关系不显著.不管是中农5号还是津春4号,其蒸腾速率与每克根吸收镉的量均呈显著的正相关关系.不同铁营养状况影响了黄瓜幼苗的根系形态和蒸腾速率,从而影响了根系对镉的吸收,高铁水平显著抑制了黄瓜根系对镉的吸收.     

改性生物炭负载纳米零价铁去除水体中头孢噻肟

抗生素对环境的危害已经引起了人们的广泛重视.本实验以改性生物炭(MB)为载体制备了负载纳米零价铁的功能生物炭(Fe/MB).以头孢噻肟(CFX)为目标抗生素,研究了该材料对头孢噻肟的降解特性及影响因素,并探讨了去除机理.实验结果表明,50 min内头孢噻肟的去除率为92%(Fe/MB用量为0.4 g·L~(-1),溶液p H=5.0,头孢噻肟浓度为20 mg·L~(-1),振荡速率为200 r·min~(-1),柠檬酸浓度为1.47 mmol·L~(-1)).头孢噻肟的去除过程存在改性生物炭的吸附和纳米零价铁还原降解的协同作用,数据符合伪二级反应动力学方程(R20.99).采用紫外可见光谱结合质谱分析了降解产物的结构并提出头孢噻肟的降解途径.     

Dechlorination of PCBs in the simulative transformer oil by microwave-hydrothermal reaction with zero-valent iron involved

The conventional hydrothermal reaction with iron powder, NaOH and H₂O as reactants was reported to occur at temperature above 423 K, and iron oxides (Fe₃O₄ and NaFeO₂) and hydrogen were produced. In this study, microwave heating was adopted to take the place of conventional heating to induce the hydrothermal reaction. Under microwave irradiation, NaOH and H₂O absorbed microwave energy by space charge polarization and dipolar polarization and instantly converted it into thermal energy, which initiated the hydrothermal reaction that involved with zero-valent iron. X-ray diffraction (XRD) analysis found Fe₃O₄/NaFeO₂ and confirmed the occurrence of microwave-induced hydrothermal reaction. The developed microwave-hydrothermal reaction was employed for the dechlorination of PCBs. Hexadecane containing 100 mg L⁻¹ of Aroclor1254 was used as simulative transformer oil, and the dechlorination of PCBs was evaluated by GC/ECD, GC/MS and ion chromatography. For PCBs in 10 mL simulative transformer oil, almost complete dechlorination was achieved by 750 W microwave irradiation for 10 min, with 0.3 g iron powder, 0.3 g NaOH and 0.6 mL H₂O added. The effects of important factors including microwave power and the amounts of reactants added, on the dechlorination degree were investigated, moreover, the dechlorination mechanism was suggested. Microwave irradiation combined with the common and cheap materials, iron powder, NaOH and H₂O, might provide a fast and cost-effective method for the treatment of PCBs-containing wastes.     

零价铁类Fenton试剂氧化降解废水中有机污染物的研究进展

综述了近年来国内外Fe0类Fenton试剂氧化反应降解废水中有机污染物的研究现状，介绍了Fe0-H2O2体系、紫外光-Fe0-H2O2体系和可见光-Fe0-H2O2体系处理有机污染物的机理、特点和效果，并对未来Fe0类Fenton试剂氧化反应体系处理有机污染物的发展前景进行了展望。     

Ecogenetic features and functions of solods in transural forest-steppes (within Sverdlovsk Oblast)

Specific ecogenetic features of solods in the forest-steppe zone has been studied, and the role of biotic and abiotic factors of soil formation has been estimated. Differentiation of soil horizons with respect to the physical clay fraction accounts for specific features of their moistening, which is reflected in the ratio of strongly and weakly crystallized forms of iron. Periodic changes in redox conditions results in iron segregation, and a high content of fulvic acids accounts for its eluvial migration. These processes are controlled by soil geochemical barriers.     

铁屑粉煤灰组合处理含磷废水

实验研究了铁屑粉煤灰组合处理含磷废水的除磷效果.通过单因素实验,考查了铁屑粉煤灰质量比、反应时间、pH值和投加量对除磷效果的影响.实验结果表明,该法除磷的最优条件为铁屑和粉煤灰的质量比为2∶1,反应时间为20 min,pH值为6,投加量为20 g/L.在最优实验条件下磷的去除率达到了97.5％.对比了该法和粉煤灰吸附法与传统铁屑法的除磷效果.与单一粉煤灰吸附法和传统铁屑法除磷的结果相比较,铁屑粉煤灰组合除磷的方法具有明显优势.     

Degradation of pentachlorobiphenyl by a sequential treatment using Pd coated iron and an aerobic bacterium (H1)

The reductive dechlorination and biodegradation of 2,2^′4,5,5^′-pentachlorobiphenyl (PCB#101) was investigated in a laboratory-scale. Palladium coated iron (Pd/Fe) was used as a catalytic reductant for the chemical degradation of 2,2^′4,5,5^′-pentachlorobiphenyl, and an aerobic bacteria was used for biodegradation following the chemical reaction in this study. Dechlorination was affected by several factors such as Pd loading, initial soil pH and the amount of Pd/Fe used. The results showed that higher Pd loading, higher dosage of Pd/Fe and slightly acid condition were beneficial to the catalytic dechlorination of 2,2^′,4,5,5^′-pentachlorobiphenyl. In laboratory batch experiments, 2,2^′4,5,5^′-pentachlorobiphenyl was reduced in the presence of Pd/Fe bimetal, which was not further degraded by aerobic bacteria. 2,2^′,4-trichlorobiphenyl (PCB#17), a reduction product from 2,2^′4,5,5^′-pentachlorobiphenyl, was readily biodegraded in the presence of a aerobic bacterial strain. It is suggested that an integrated Pd/Fe catalytic reduction-aerobic biodegradation process may be a feasible option for treating PCB-contaminated soil.     

铁改性海泡石除锑的影响因素研究

选择廉价海泡石, 用氯化铁对其改性。研究铁改性海泡石对锑的吸附特性。结果表明，氯化铁浓度、吸附时间、初始锑浓度以及温度等因素对锑的吸附影响较大，溶液初始pH影响不明显。在初始锑浓度50 mg/L，pH 6.8，5%氯化铁改性海泡石投加量为2 g/L，吸附90 min, 温度35℃下，吸附量可达21.6 mg/g。海泡石对吸附锑具有缓冲特性，溶液的初始pH值在3.1～10.1范围时，吸附后溶液的最终pH值为8～8.5。IMS吸附锑是放热过程。改性后海泡石比表面积增大，表面羟基数量增加，导致其吸附能力增强。通过XRD谱图并未发现铁晶体的存在。     

Kinetics and pathways for the debromination of polybrominated diphenyl ethers by bimetallic and nanoscale zerovalent iron: effects of particle properties and catalyst

Polybrominated diphenyl ethers (PBDEs) are recognized as a new class of widely-distributed and persistent contaminants for which effective treatment and remediation technologies are needed. In this study, two kinds of commercially available nanoscale Fe⁰ slurries (Nanofer N25 and N25S), a freeze-dried laboratory-synthesized Fe⁰ nanoparticle (nZVI), and their palladized forms were used to investigate the effect of particle properties and catalyst on PBDE debromination kinetics and pathways. Nanofers and their palladized forms were found to debrominate PBDEs effectively. The laboratory-synthesized Fe⁰ nanoparticles also debrominated PBDEs, but were slower due to deactivation by the freeze-drying and stabilization processes in the laboratory synthesis. An organic modifier, polyacrylic acid (PAA), bound on N25S slowed PBDE debromination by a factor of three to four compared to N25. The activity of palladized nZVI (nZVI/Pd) was optimized at 0.3 Pd/Fe wt% in our system. N25 could debrominate selected environmentally-abundant PBDEs, including BDE 209, 183, 153, 99, and 47, to end products di-BDEs, mono-BDEs and diphenyl ether (DE) in one week, while nZVI/Pd (0.3 Pd/Fe wt%) mainly resulted in DE as a final product. Step-wise major PBDE debromination pathways by unamended and palladized Fe⁰ are described and compared. Surface precursor complex formation is an important limiting factor for palladized Fe⁰ reduction as demonstrated by PBDE pathways where steric hindrance and rapid sequential debromination of adjacent bromines play an important role.