填埋场中铁的生物化学循环对反硝化的影响

在模拟填埋体系中,以填埋场稳定的垃圾为接种物,通过控制有机物和硝氮负荷,研究了铁的生物化学循环对反硝化的影响.结果表明,垃圾填埋场内蕴藏着能实现铁的厌氧氧化还原并同步还原硝氮的复合功能菌群.通过改变有机物和硝氮的负荷,可使得填埋场内持续进行着铁的氧化还原循环和同步氮素转化.从氮素转化产物来看,铁的循环体系中氨氮浓度比传统的反硝化体系低4 mmol·L-1.填埋场内铁的生物化学循环过程对于原位脱氮具有极大贡献.     

Photocatalytic mechanisms of indoleamine destruction by the quinalphos metabolite 2-hydroxyquinoxaline: a study on melatonin and its precursors serotonin and N-acetylserotonin

The redox-active quinalphos main metabolite, 2-hydroxyquinoxaline, is particularly effective under excitation by light. We have studied the photocatalytic destruction of melatonin and its precursors, because the cytoprotective indoleamine has been detected in high quantities in mammalian skin. In photooxidation reactions, in which melatonin, N-acetylserotonin and serotonin are destroyed by 2-hydroxyquinoxaline, the photocatalyst is virtually not consumed. Rates of melatonin and serotonin destruction are not changed by the singlet oxygen quencher 1,4-diazabicyclo-(2,2,2)-octane, indicating that this oxygen species is not involved in the primary reactions, so that the persistence of 2-hydroxyquinoxaline has to be explained by redox cycling. This should imply formation of an organic radical, presumably the quinoxaline-2-oxyl radical, from which 2-hydroxyquinoxaline is regenerated by electron abstraction from indolic radical scavengers. Electron donation by 2-hydroxyquinoxaline is demonstrated by reduction of the 2,2′-azino-bis-(3-ethylbenzthiazolinyl-6-sulfonic acid) cation radical under ultrasound excitation. The compound 2-hydroxyquinoxaline interacts with the specific superoxide anion scavenger Tiron. Formation of oligomeric products from melatonin and serotonin is strongly inhibited by sodium dithionite. Products from photocatalytic indolamine conversion are predominantly dimers and oligomers. No kynuramines were detected in the case of serotonin oxidation, and melatonin's otherwise prevailing oxidation product N ¹-acetyl-N ²-formyl-5-methoxykynuramine, another cytoprotective metabolite, is only formed in relatively small quantities. The proportion between products from melatonin is changed by 1,4-diazabicyclo-(2,2,2)-octane: singlet oxygen, also formed under the influence of excited 2-hydroxyquinoxaline, only affects secondary reactions.     

无砾石微孔管地下渗滤系统试验研究

针对传统无砾石管式地下渗滤系统存在的处理性能差,渗滤通量低两个问题,通过去掉包裹织物,提高渗滤管开孔率、改变开孔方式,设计了无砾石微孔管地下渗滤系统。通过实验研究表明,无砾石微孔管地下渗滤系统对COD、氨氮的去除率比传统管式系统分别提高了10.8%、12.7%,总磷去除率并无显著差异,ORP值提高约85 mV,渗滤通量提高26.8%。在3.3 cm/d的水力负荷下,无砾石微孔管地下渗滤系统出水COD、氨氮、总磷平均浓度分别为19 mg/L,0.62 mg/L,0.048 mg/L。渗滤管下10 cm的土壤层去除了约70%的COD,80%的氨氮和91%的总磷,向下随着土壤深度的增加,单位厚度的土壤层去除的污染物量呈显著下降趋势。     

介体厌氧催化活性艳红K-2BP脱色及构效特性研究

研究了筛选出的4种结构相似的醌类氧化还原介体对活性艳红K-2BP厌氧脱色的促进作用,并分析了介体促进效果与其化学结构活性相关性. 在35℃中温厌氧条件下,采用间歇批量实验法,测定不同体系中介体催化活性艳红K-2BP脱色效果.结果表明,①结构相似的醌类氧化还原介体蒽醌(AQ)、1,5-二氯蒽醌(1,5-AQ)、1,8-二氯蒽醌(1,8-AQ)和1,4,5,8-四氯蒽醌(1,4,5,8-AQ),均促进活性艳红K-2BP脱色,反应速率提高了1.4～3倍;②当醌类介体投加浓度为4 mmol·L^-1,活性艳红K-2BP染料浓度为300 mg·L^-1时,促进作用由大到小的顺序为:1,8-AQ>1,5-AQ>AQ>1,4,5,8-AQ;③ 当活性艳红K-2BP染料浓度为300 mg·L^-1时,1,8-AQ促进效果最佳且脱色速率常数随1,8-AQ浓度的增加而增加呈线性关系;④介体促进效果与介体取代基团数量、位置和电子共轭效应相关.本研究初步建立了氧化还原介体定性/定量构-效关系数学模型,探究和完善非水溶性氧化还原介体催化强化理论体系.     

污染场地地下水中汞污染反应运移模拟

汞（Hg）是人们持续关注的全球环境污染物之一,其对地下水的污染严重威胁着与地下水相关的生态环境系统.汞在地下水系统中的物理与地球化学反应过程的准确刻画是研究汞迁移转化规律的重点和难点.基于某工业场地汞污染数据,首先采用PHREEQC研究地下水中无机二价汞的存在形态,然后利用PHT3D程序建立汞污染物反应性溶质运移二维剖面模型.该模型考虑了汞污染物在地下水系统中的对流、弥散过程及地球化学反应过程（包括水相络合作用、表面络合吸附作用及受动力学控制的氧化还原作用）.结果表明,无机二价汞的存在形态以HgCl₂和Hg（OH）Cl占主导地位,氧化还原作用是影响地下水中汞污染反应性运移的主要控制因素;另一方面,水合氧化铁HFO对汞迁移的阻滞影响较小,而溶解性有机质对汞较强的络合作用不能忽视.本文研究成果可为预测与评估特定污染场地地下水汞污染的变化趋势及制定相应的修复策略提供科学依据.     

水固液微界面氧化还原反应过程与污染物控制研究

本文介绍了3个反应体系,包括铁锰复合氧化物氧化吸附除砷体系、铁氧化物包覆零价铁光芬顿催化和负载型多价态锰氧化物臭氧催化体系,通过固液微界面不同的氧化还原反应,实现了对水中砷和难降解有机污染物的高效去除.重点介绍了不同氧化还原反应对污染物转移转化的作用机制,说明了水体中固液微界面氧化还原反应,对污染物的转移转化起着重要作用.     

零价铁（ZVI）去除Cu2+的特性及机制研究

研究了零价铁去除水溶液中铜离子的影响因素及动力学特性,并利用X射线衍射(XRD)分析对反应机制进行了探讨.结果表明,当溶液中Cu2+的浓度为300 mg/L,零价铁的用量为1 g/L时,Cu2+的去除率99%.Cu2+的去除速度很快,且反应前30min零价铁去除Cu2+的过程可以用一级反应动力学方程模拟.零价铁去除Cu2+的机制主要基于氧化还原反应,Cu2+的还原产物主要为Cu和Cu2O.     

Quinone-mediated decolorization of sulfonated azo dyes by cells and cell extracts from Sphingomonas xenophaga

The effects of various quinone compounds on the decolorization rates of sulfonated azo dyes by Sphingomonas xenophaga QYY were investigated. The results showed that anthraquinone-2-sulfonate (AQS) was the most effective redox mediator and AQS reduction was the rate-limited step of AQS-mediated decolorization of sulfonated azo dyes. Based on AQS biological toxicity tests, it was assumed that AQS might enter the cells to kill them. In the cytoplasmic extracts from strain QYY, AQS effectively increased decolorization rates of sulfonated azo dyes than other quinone compounds. In addition, we found a NADH/FMN-dependent AQS reductase using nondenaturing polyacrylamide gel electrophoresis (Native-PAGE).     

Effects of WOx modification on the activity, adsorption and redox properties of CeO2 catalyst for NOx reduction with ammonia

A series of WO₃/CeO₂ (WOx/CeO₂) catalysts were synthesized by wet impregnation of ammonium metatungstate on a CeO₂ support. The resulting solid acid catalysts were characterized by X-ray diffraction (XRD), UV-Vis spectroscopy (UV-Vis), Raman spectroscopy (Raman), in-situ Fourier transform infrared spectroscopy (in-situ FT-IR) of ammonia adsorption, NH₃-TPD, H₂ temperature-programmed reduction (H₂-TPR), NH₃/NO oxidation and activity measurements for NOx reduction by NH₃ (NH₃-SCR). The results show that polytungstate (WOx) species are the main species of tungsten oxide on the surface of ceria. The addition of tungsten oxide enhances the Brönsted acidity of ceria catalysts remarkably and decreases the amount of surface oxygen on ceria, with strong interaction between CeO₂ and WOx. As a result, the N₂ selectivity of NH₃ oxidation and NH₃-SCR at high temperatures (> 300℃) is enhanced. Therefore, a wide working temperature window in which NOx conversion exceeds 80% (NOx conversion > 80%) from 200 to 450℃, is achieved over 10 wt.% WOx/CeO₂ catalyst. A tentative model of the NH₃-SCR reaction route on WOx/CeO₂ catalysts is presented.     

不同氧化还原条件下土壤中Cd/Zn/Cu共运移特征及数值模拟

以重金属离子镉（Cd）、锌（Zn）、铜（Cu）为研究对象,通过室内土柱混合置换实验和数值模拟方法,分析了5种不同氧化还原电位（E_h）对Cd、Zn、Cu在土壤中运移的影响.结果表明,不同E_h下,Cu的竞争吸附能力均大于Cd和Zn,移动性较小;并产生了“滚雪球效应”,导致出流液中Cd和Zn的浓度大于输入浓度.与原土相比,E_h的增加或降低均促进了Zn、Cd的迁移速率,但对实验周期内回收率的影响不同;E_h的增加促进了Cu的迁移.两点非平衡模型（TSM）和单点非平衡吸附模型（OSM）较好地模拟了重金属的迁移,且进一步表明了土壤对重金属的吸附受吸附反应速率的限制（f<0.7）.在复合污染土壤评价和防治中,不仅要考虑E_h的影响,还要关注由竞争吸附所产生的浓度叠加效应,避免低估重金属的污染风险.