硫素对氧化还原条件下水稻土氧化铁和砷形态影响

通过充N2和充O2的氧化还原反应装置,在添加外源砷污染的水稻土中,施用不同形态的无机硫(不施硫S0,单质硫S1和硫酸盐S2),模拟水稻田的氧化还原状况.结果表明,通N2时,土壤溶液氧化还原电位(Eh)在-100~-200 mV之间,溶液pH在7.0~8.0之间,pe+pH为4~7之间;通O2时,溶液Eh在200mV左右,溶液pH在6.5~7.5之间,pe+pH为9~12之间.无论通N2还是通O2,土壤溶出铁的浓度在1.2~1.6 mg·L-1,均有处理S0>S1>S2和AsS0>AsS1>AsS2.在通N2时,各处理HCl提取土壤氧化铁的含量比原土[(21.4±0.3)g·kg-1]低5 g·kg-1,有利于结晶态氧化铁向无定形氧化铁转化和形成Fe2+,无定形氧化铁活化度比原土活化度46.8%有所增加,且处理AsS2(49.4%)AsS2(36.1%).通N2时,土壤溶液中砷浓度变化为AsS0[(1.13±0.04)mg·L-1]>AsS1[(0.89±0.01)mg·L-1]>AsS2[(0.77±0.04)mg·L-1];通O2时,土壤溶液中砷浓度变化AsS1[(0.77±0.01)mg·L-1]>AsS0[(0.20±0.09)mg·L-1]>AsS2[(0.09±0.01)mg·L-1].通N2时,不同处理各形态砷占总砷比例变化为残渣态(34.9%~41.4%)≈专性吸附态(37.4%~39.5%)>晶态铁锰结合态(23.3%~25.6%)>非专性吸附态(2.4%~3.3%)>无定形铁锰结合态(0.5%~0.8%).通O2时,各处理形态砷占总砷比例变化为残渣态(30.8%~39.3%)≈专性吸附态(30.3%~34.7%)>晶态铁锰结合态(26.0%~28.7%)>无定形铁锰结合态(9.3%~10.7%)>非专性吸附态(0.5%~1.6%),其中,无定形铁锰氧化物结合态砷比通N2时提高了约9%,也就是无定形铁锰的老化作用对砷形态转化的影响.这表明还原条件能够使氧化铁的活化度升高,砷的移动性增强,但硫酸盐体系降低氧化铁的活化度,单质硫体系的砷移动性要大于硫酸盐体系的砷移动性.     

复合垂直流人工湿地氧化还原特征及不同功能区净化作用研究

研究了复合垂直流人工湿地系统氧化还原电位（Eh）的时空变化规律及不同功能区中污染物的净化效果。结果表明：湿地系统下行流池表层、两池底层、上行流池表层Eh的变化范围分别为402～585、-87～-130、308～432 mV，沿水流方向依次形成了好氧A区/缺氧、厌氧区/好氧B区3个功能区。好氧A区是污染物去除的主要区域，BOD₅、COD_Cr、NH⁺_4- N的去除率分别为430%、484%、541%，特别是NH+4 N去除率占总去除率的79%；缺氧、厌氧区主要是进行反硝化反应和有机物的厌氧分解；好氧B区则主要是去除厌氧分解后的有机物以及进一步脱氮。另外，NH+4 N的去除率与系统各功能区Eh呈显著相关关系（〖WTBX〗p〖WTBZ〗＜001），而BOD₅、COD_Cr、NO^-_3-N的去除率与系统各功能区Eh相关性不显著。     

Variations among rice cultivars on root oxidation and Cd uptake

In order to understand the mechanisms on the variation between rice cultivars in Cd uptake and accumulation, two pot soil experiments were conducted with typical rice cultivars that varied greatly in soil Cd uptake. The experiments with six rice cultivars showed that the root oxidation abilities of rice differed with rice cultivars and also with types of the cultivars, the cultivars with indica consanguinity were significantly higher than the cultivars with japonica consanguinity. Root oxidation abilities of the rice cultivars correlated positively and significantly （P〈0.01） with their Cd concentrations and Cd quantity accumulations in rice plants. The experiments with two rice cultivars showed that significant differences also existed between the two cultivars in pot soil redox potentials, which of Shan you 63 （higher soil Cd accumulator） were significantly higher than that of Wu yun jing 7 （lower soil Cd accumulator） under different soil Cd levels, but the degrees of the differences varied with soil Cd levels. The differences were larger under soil Cd treatments than the control. The results indicate that root oxidation ability, especially in Cd contaminated soil, is one of the main mechanisms which dominate Cd uptake and accumulation by rice plant.     

Shewanellasp．XB缺氧反硝化降解苯酚

苯酚的生物降解一直受到关注。以苯酚为惟一电子供体,研究了Shewanellasp．XB对苯酚的缺氧降解特性。研究结果表明,在反硝化条件下,当C／N为13．3时,苯酚可以完全降解,NO2--N积累量很少。另外,当加入氧化还原介体,如核黄素3μmol／L、AQDS0．01mmol／L、AQS0．05mmol／L和LQ0．01mmol／L时,苯酚降解速率分别为不加介体时的1．45、1．77、1．67和1．63倍。当以氯化铵代替硝酸盐时,苯酚也能进行厌氧发酵降解。另外,菌株XB反硝化降解苯酚可能是厌氧和好氧降解的混合过程。     

Shewanella sp.XB缺氧反硝化降解苯酚

苯酚的生物降解一直受到关注。以苯酚为惟一电子供体,研究了Shewanella sp.XB对苯酚的缺氧降解特性。研究结果表明,在反硝化条件下,当C/N为13.3时,苯酚可以完全降解,NO-2-N积累量很少。另外,当加入氧化还原介体,如核黄素3μmol/L、AQDS 0.01 mmol/L、AQS 0.05 mmol/L和LQ 0.01 mmol/L时,苯酚降解速率分别为不加介体时的1.45、1.77、1.67和1.63倍。当以氯化铵代替硝酸盐时,苯酚也能进行厌氧发酵降解。另外,菌株XB反硝化降解苯酚可能是厌氧和好氧降解的混合过程。     

土壤原位覆盖对底泥的修复作用研究

在高度厌氧底泥和富营养化水体构成的模拟生态系统中,采用土壤和硅藻土进行原位覆盖,研究了覆盖技术对水．沉积物界面微环境的改善作用和不同覆盖材料对苦草生长的影响。这2种底质覆盖后,表层底泥氧化还原电位（Eh）分别提高了48．37％和46．77％,底层水体的溶解氧消耗降低,水体中的总氮（TN）和总磷（TP）含量降低;与对照箱体的苦草死亡相比,经过土壤和硅藻土覆盖的箱体中苦草正常萌发、定植和生长;硅藻土箱体苦草的生物量、叶绿素和根茎比均高于土壤覆盖箱体。因此,原位覆盖能有效改善底层水体和表层底泥的氧化还原环境,隔绝污染底泥和延缓营养盐释放,为沉水植物种子萌发和幼苗生长提供有利的生境条件。     

Selective redox degradation of chlorinated aliphatic compounds by Fenton reaction in pyrite suspension

Selective redox degradation of chlorinated aliphatics by Fenton reaction in pyrite suspension was investigated in a closed system. Carbon tetrachloride (CT) was used as a representative target of perchlorinated alkanes and trichloroethylene (TCE) was used as one of highly chlorinated alkenes. Degradation of CT in Fenton reaction was significantly enhanced by pyrite used as an iron source instead of soluble Fe. Pyrite Fenton showed 93% of CT removal in 140 min, while Fenton reaction with soluble Fe(II) showed 52% and that with Fe(III) 15%. Addition of 2-propanol to the pyrite Fenton system significantly inhibited degradation of TCE (99% to 44% of TCE removal), while degradation of CT was slightly improved by the 2-propanol addition (80-91% of CT removal). The result suggests that, unlike oxidative degradation of TCE by hydroxyl radical in pyrite Fenton system, an oxidation by the hydroxyl radical is not a main degradation mechanism for the degradation of CT in pyrite Fenton system but a reductive dechlorination by superoxide can rather be the one for the CT degradation. The degradation kinetics of CT in the pyrite Fenton system was decelerated (0.13-0.03 min⁻¹), as initial suspension pH decreased from 3 to 2. The formation of superoxide during the CT degradation in the pyrite Fenton system was observed by electron spin resonance spectroscopy. The formation at initial pH 3 was greater than that at initial pH 2, which supported that superoxide was a main reductant for degradation of CT in the pyrite Fenton system.     

Redox potential and uranium sorption onto sediments: kinetic and thermodynamic characteristics

ABSTRACT

The effects of the flooding and initial Eh of sediments on the sorption of uranium onto the sediments were analysed by flooding and static experiments. The changes in uranium species with Eh and kinetic and thermodynamic characteristics of the uranium sorption onto the sediments were investigated. The flooding experiment indicates that the initial Eh of the sediment gradually decreased with the increase in flooding time. Based on the redox potential in the flooding experiment, simulation results obtained using the geochemical simulation software PHREEQC show that the concentration of U (VI) decreased. In contrast, the concentrations of U (III), U (IV), and U (V) gradually increased. The pseudo-second-order kinetic model well fitted the experimental data, which shows that the sorption was mainly chemical sorption. The thermodynamic parameters suggest that the entropy and enthalpy under the used conditions were positive and that ΔG^θ was negative. A thermodynamic analysis shows that the sorption was endothermic and spontaneous. These results are useful for the understanding of the sorption mechanism and migration of uranium onto the sediment under different initial sediment redox potentials and provide a good theoretical foundation for radioactive pollution remediation.     

Microbially Mediated Redox Cycling at the Oxic–Anoxic Boundary in Sediments: Comparison of Animal and Plants Habitats

Microorganisms are responsible for the bulk of transformations that occur in surficial sediments. They are most active at redox boundaries where they can benefit from access to various oxidants and reductants generated during redox cycling events. To illustrate the dynamics of microbially mediated processes, especially those involving sulfur and metal cycles, processes were compared in habitats either bioturbated by a capitellid worm or inhabited by a salt marsh grass. The presence of macrofauna and macroflora greatly altered the three-dimensional array of redox gradients in sediments, but the type and form of reductants and oxidants provided varied greatly; clastic sedimentary infauna subducted solid phase organic material and iron oxides, whereas plant roots released dissolved organic matter and oxygen. These differences resulted in a bioturbated system that exhibited a rapid sulfur cycle (residence time of minutes), but a slower iron cycle (days), whereas vegetation caused a slow sulfur cycle and rapid iron cycle. Alteration of sediments by higher life forms also greatly affected the composition and relative abundances of sedimentary bacteria, even on short time scales. Although redox cycling at interfaces can be somewhat predictable, variations in response to biological and physical perturbations demonstrated wide differences in the dynamics of redox-mediated processes.     

Dissolved Oxygen and Nutrient Fluxes Across the Sediment–Water Interface of the Neckar River,Germany: In Situ Measurements and Simulations

A benthic in situ flume and a 1D biogeochemical sediment model to evaluate solute fluxes across the sediment–water interface have been developed. The flume was successfully used to determine oxygen and nutrient fluxes at various locations of the Neckar River in Germany. The experimental results were linked with vertical pore water concentration profiles and independently verified with the model. By combining experimental and model results we assessed the influence of dissolved oxygen concentrations in the water column and the availability of degradable organic matter on sediment oxygen demand. The results and the derived relations can be used to parameterize the sediment module of large scale water quality models, allowing one to assess the influence of sediment–water interactions on various aspects of river water quality. Moreover, the biogeochemical sediment model can help to improve the general understanding of the processes governing solute concentrations and fluxes in sediments and across their interfaces.