Mn(Ⅲ)在水钠锰矿氧化Cr(Ⅲ)反应中的作用

环境中的氧化锰矿物是可氧化Cr(Ⅲ)的唯一天然无机氧化剂,氧化锰矿物与Cr(Ⅲ)相互作用的反应速率与机制备受关注.本研究以水钠锰矿为对象,采用批量动力学方法研究了其结构中Mn(Ⅲ)在氧化Cr(Ⅲ)反应中的作用及动力学特点.结果表明,水钠锰矿氧化Cr(Ⅲ)符合准一级动力学方程,表观速率常数Kobs为0.0313 min-1,以Na4P2O7预处理水钠锰矿可络合出结构中的部分Mn(Ⅲ),使其Mn的平均氧化度升高.当处理Na4P2O7浓度为10、20、50 mmol/L时,其Mn氧化度由3.50升高至3.63、3.73和3.78,处理后的水钠锰矿对Cr(Ⅲ)的平衡氧化率增加,但初始氧化速率变化并不明显,其相应表观速率常数分别为0.0351、0.0325和0.0309 min-1.水钠锰矿氧化Cr(Ⅲ)的反应历程中,Mn(Ⅳ)→Mn(Ⅲ)的电子转移过程生成的Mn(Ⅲ)显著影响水钠锰矿氧化Cr(Ⅲ)的速率.当新生成Mn(Ⅲ)被Na4P2O7络合后,反应速率降低45%~88%,且水钠锰矿的氧化度较低时,结构中Mn(Ⅲ)含量高,反应中被络合的新生态Mn(Ⅲ)多,反应速率降低幅度相对较大.因此,反应新生成的Mn(Ⅲ)具有较高的反应活性和较快的电子转移速率,而Mn(Ⅳ)→Mn(Ⅲ)的电子转移速率较慢,可能为水钠锰矿氧化Cr(Ⅲ)的反应速率控制步骤.     

潜流型人工湿地污水处理系统的研究

研究中等负荷有较高去除率的潜流型人工湿地污水处理系统的环境状况,湿地中水体有出水溶解氧值均为０,氧化还原电位－２００－３００ｍＶ之间,ＰＨ值偏酸,出水ＰＨ值稍低于进水,系统中Ｎ化合物主要为ＮＨ３－Ｎ,是ＮＯ３－Ｎ的４－１０倍,ＮＯ３Ｎ的１００－２００倍,说明易于进行氨化作用,而硝化作用在较低水上进行     

醌化合物强化偶氮染料的生物脱色

考察了醌还原菌群利用氧化还原介质对偶氮染料脱色的强化作用.结果表明,该菌群以AQDS(2,6-二磺酸蒽醌)作为氧化还原介质可强化多种偶氮染料的生物脱色,其中,对活性艳红KE-3B脱色的适宜条件为pH6～9;外加葡萄糖浓度0.05%～0.10%;AQDS浓度10～100mg/L;染料起始浓度≤600mg/L.在此条件下,最大脱色率约为90%,达到最大脱色率的时间<18h.该菌群能以多种蒽醌染料中间体作为氧化还原介质强化偶氮染料活性艳红KE-3B的生物脱色.     

Fenton试剂法降解餐厨垃圾异味

自行设计Fenton试剂法降解还原性气体异味的反应器,研究了Fenton试剂法处理餐厨垃圾异味主要成分(苯、乙酸乙酯、苯乙烯)的降解效果。以苯为典型代表物,优化得出该实验的最佳反应条件为:pH=3,FeSO4.7H2O投加量为1 g/L液相,30%H2O2投加量为10 mL/L液相,紫外光源辅助。结果证明,Fenton试剂法处理单一异味气体的效果较理想,在前180 min内能达到90%以上,该法在处理气态异味污染物方面具有广阔的应用前景。     

Wild fire impact on copper, zinc, lead and cadmium distribution in soil and relation with abundance in selected plants of Lamiaceae family from Vidlic Mountain (Serbia)

Fire has been considered as an improving factor in soil quality, but only if it is controlled. Severe wild fire occurred in the summer 2007 on the Vidlic Mountain (Serbia) overspreading a huge area of meadows and forests.Main soil characteristics and content of heavy metals (Cu, Pb, Cd, Zn) in different fractions obtained after sequential extraction of soil from post-fire areas and from fire non disturbed areas were studied. In four plant species of Lamiaceae family (Ajuga genevensis L., Lamium galeobdolon (L.) L., Teucrium chamaedrys L., Acinos alpinus (L.) Moench.), that grow in typical habitats of the mountain, distribution of heavy metals in aerial parts and roots was investigated too.For all samples from post-fire area cation exchange capacity and soil organic matter content are increased while rH is decreased. Fire caused slightly increased bioavailability of the observed metals but more significant rise happened in metal amounts bound to oxides and organics. The plants showed variable behavior. T. chamaedrys collected on the post-fire area contained elevated concentrations of all analyzed metals. A. alpinus showed higher phytoaccumulation for Zn and Cd, while the other two plant species for Pb and Cd in the post-fire areas.     

Aqueous free radical chemistry of mercury in the presence of iron oxides and ambient aerosol

The effect of goethite (α-FeOOH), hematite (α-Fe₂0₃) and maghemite (γ-Fe₂0₃) on the aqueous photoreduction of divalent mercury with organic acids (oxalate, formate and acetate) is investigated. Laboratory photochemistry experiments with synthetic iron oxides and simulated sunlight were performed to assess the role of the oxides on the photoreduction. Ambient aerosol was also collected and introduced as the solid phase to compare its effect with that of synthetic oxides. It is observed that the presence of various iron oxides or aerosol particles enhances the photoreduction. It is also found that the hydroxyl radicals produced in the hematite-oxalate systems can re-oxidize the reduced mercury back to Hg(II). Based on the experimental observations, mechanisms responsible for the Hg(II) reduction are proposed. The kinetics of Hg⁰ oxidation by hydroxyl radicals was also studied by a steady-state kinetic technique using nitrate photolysis as the * OH radical source. The second-order rate constant is determined to be 2.0 × 10⁹ M⁻ s⁻¹. The implications of the studied reactions on the atmospheric chemistry of mercury are discussed.     

基于三维荧光光谱特征研究土壤腐殖质氧化还原特性

以国际腐殖质协会腐殖酸和实验室提纯腐殖酸为研究对象,发现被H2还原前后腐殖酸的三维荧光光谱明显不同,但有共同的变化趋势:还原态腐殖酸的三维荧光光谱图的波峰荧光强度均明显低于还原前,说明腐殖酸还原过程有类似π-π*化学键断开的结构变化.对苯醌是腐殖酸氧化还原醌基官能团的代表化合物,将其还原前后与腐殖酸还原前后的荧光光谱对比,发现两组变化趋势一致,这一发现是利用荧光特性量化腐殖质氧化还原官能团的基础.利用铁氰化钾测定腐殖酸的得失电子能力,发现不同土壤提纯的腐殖酸得失电子能力有一定差别:鹰潭土壤腐殖酸和桃源土壤腐殖酸在原态下对三价铁的还原能力都较弱,分别为0.998和0.465 meq.g-1C(原态转移电子数);但还原后得电子数(还原态转移电子数减原态转移电子数)分别为3.384 meq.g-1C(鹰潭土壤腐殖酸)和1.187 meq.g-1C(桃源土壤腐殖酸).鹰潭土壤腐殖酸具有较高的得电子数,与其具有较高荧光峰值这一结果互相支持.结合得失电子能力测定,利用光学分析方法,量化官能团,预测氧化还原反应进程,使三维荧光光谱法测定土壤有机质的氧化还原性在实际应用中具有广阔的前景.     

Shewanella oneidensis MR-1异化还原Fe(III)介导的As(III)氧化转化

在实验室模拟条件下,研究了Shewanella oneidensis MR-1作用下Fe(III)还原和As(III)氧化动力学及其影响因素.结果表明,Fe(III)被还原为Fe(II)的同时伴随着As(III)氧化为As(V);S. oneidensis MR-1 在含低浓度As(III)培养基上生长良好,在高浓度培养基上生长被抑制;As(III)通过制约菌体的生长与活性来抑制Fe(III)异化还原.同样,适量浓度的Fe(III)含量对As(III)氧化转化有很强的促进作用,但是过高浓度的Fe(III)浓度使得溶液中产生过多的Fe(II),从而对As(III)氧化转化有一定程度的抑制作用.此外,弱碱环境更有利于As(III)氧化转化.     

用于碳烟燃烧的Cu0.05Ce0.95O催化剂活性氧物种的研究 ——等离子体的强化效应

研究等离子体对柠檬酸络合法制备的Cu0.05Ce0.95-CA催化剂表面结构和物种的强化效应. TPO、H2-TPR、O2-TPD、XRD、BET和XPS等测试结果表明,催化剂处于等离子放电区时,其氧化碳烟燃烧的活性显著增强.在介质阻挡放电电压为9kV时,起燃温度为243.1℃,比无等离子的情况降低了65.1℃;燃烧峰值温度为302.8℃,降低92.7℃.在等离子体存在下,Cu0.05Ce0.95-CA催化剂有着更大的比表面积和更小的晶粒粒径;等离子体可以提高催化剂表面游离态的CuO的分散度,并使得更多的Cu2+进入CeO2晶格,形成更多的Cuy2+Ce1-y4+O2-y2-□y固熔体,催化剂储氧容量增大,在催化剂表面生成更多的活性氧物种,其流动、迁移和转化促进催化剂产生更多的氧空穴,如此循环,持续促进碳烟催化燃烧.     

The reduction of selenate by fulvic acids in soils of a high gastric cancer risk area in Sri Lanka∗

In order to elucidate the probable etiological factors for the incidence of gastric cancer, the interaction between selenate and fulvic acids was investigated under chemically controlled conditions. The reduction ability of selenate by fulvic acids was enhanced in acidic conditions. The fulvic acids may play an important role in the nitrosation process. Thus the investigations of the mechanism by which selenate interact with fulvic acids will provide a new insight into the chemical activation process by which selenium supplementation is supposed to act as an anticarcinogen.