铁/锰氧化菌诱导土壤重金属生物成矿研究进展

综述了铁锰氧化菌诱导成矿对重金属环境行为的影响,分别从铁/锰氧化菌与生物成矿、铁/锰氧化菌诱导铁锰氧化物沉淀耦合重金属稳定化以及铁锰氧化物对土壤中重金属的作用方面进行阐述;并从铁/锰氧化菌生物成矿方式、铁/锰氧化菌诱导生物成矿过程对土壤重金属的稳定化机制等方面进一步总结了铁/锰氧化菌在不同重金属生物成矿修复中的应用,以及微生物诱导成矿过程的调控因素,分析胞外聚合物、温度与酸碱度、共存离子和其他因素对成矿过程的影响,以期为微生物诱导成矿修复重金属污染提供理论参考。未来工作可进一步关注生成矿物稳定重金属的长效性,不同微生物菌群组合对成矿效果的调控,以及铁/锰氧化菌在重金属复合污染场地土壤修复中的应用等方面。     

土壤微生物铁循环及其环境意义

铁是土壤中重要的高活性高丰度元素。铁的生物地球化学循环包括铁还原与亚铁氧化两个过程,需要微生物提供基本驱动力,已经成为陆地表层系统研究的国际热点。铁循环控制着土壤有机物矿化、反硝化、甲烷产生、重金属固定等环境过程,是连结土壤养分循环与污染物转化的纽带。从生物地球化学循环的角度,综述了微生物作用下的铁还原、亚铁氧化过程及其主要微生物类群,重点论述了厌氧条件铁还原与亚铁氧化的环境效应及其地球化学机理,以及铁还原与亚铁氧化两个过程的协调及其调控因子。本文将有助于深入理解地球表层的关键环境过程与驱动机制。     

低分子量有机还原性物质与土壤的相互作用 Ⅱ. 低分子量有机还原性物质与土壤作用的化学反应

论述了有机还原性物质与土壤作用的吸附、氧化还原和络合反应。土壤对该类物质的吸附量达加入量的60%～75%,其中强、弱还原性有机物质各约占1/2。负电荷物质的吸附量随土壤铁、锰氧化物及其所带负电荷量而变,并表现为电性吸附。对含—COOH、—C—NOH2功能团物质的吸附佐证了固相表面存在络合作用;在氧化-还原平衡中该类物质作为电子供体还原了铁、锰而自身被氧化;络合态亚铁、亚锰的形成服从络合-离解平衡,有机配位体的数量和H+离子争夺配位体的络合基可对其产生强烈的影响。     

土壤铁矿物的生物-非生物转化过程及其界面重金属反应机制的研究进展

铁矿物作为土壤的重要组成成分,一般可通过吸附、络合和共沉淀等方式影响重金属的生物有效性和毒性.此外,土壤中有机物的存在会影响铁矿物的转化,导致转化产物的结构和表面特性发生改变,进一步影响重金属的环境行为.本文从铁矿物、有机质和重金属等要素入手,综述了反应pH、温度、亚铁和微生物等因素影响下土壤铁矿物非生物和生物转化过程...     

豫西旱作褐土剖面土壤的氧化铁还原与亚铁氧化特征

土壤铁氧化物的氧化还原过程不仅与重金属的生物有效性和有机污染物降解转化关系密切,也与旱地土壤肥力关系密切,因而备受关注。然剖面土壤耕层以下是否存在铁氧化物的还原、氧化过程,其特征如何尚未可知。本文采用恒温厌氧泥浆培养的方法研究旱地褐土剖面中铁的氧化还原特征。结果表明,旱地土壤剖面0~100cm中均存在铁的厌氧还原过程,还原潜势、最大速率均随剖面深度增加而显著降低;剖面0~80cm土层中均存在光合型Fe(II)氧化现象,0~40cm土层Fe(II)氧化量和氧化速率显著高于40~80cm。剖面的铁氧化还原过程不仅受有机碳含量影响,也受N、K等养分元素的影响。结果可为拓展对铁氧化还原微生物生境的认识、深入理解土壤剖面中铁氧化还原过程提供依据。     

高级氧化技术修复萘污染土壤和地下水研究进展

多环芳烃是土壤和地下水中普遍存在的持久性有机污染物。其中，萘是结构最简单的多环芳烃，具有迁移性强的特点，可通过多种途径在土壤和地下水中富集，是焦化、化工等历史遗留地块重点关注的污染物之一。高级氧化技术高效、安全且经济，因此，基于高级氧化的萘污染土壤和地下水修复技术受到越来越多的关注。本文综述了芬顿和类芬顿氧化、臭氧氧化和过硫酸盐氧化的反应机理，重点阐述了二价铁、微纳级零价铁、铁矿物、铁螯合物等均相及非均相活化剂活化的氧化技术在修复萘污染土壤和地下水方面取得的研究进展，介绍了多种高级氧化技术联合修复以及高级氧化技术与生物降解技术协同修复的研究现状，指出了目前萘的高级氧化技术研究存在的问题，并对研究做出了展望。     

金属离子在铁(氢)氧化物与腐殖质微界面上的吸附机理和模型研究进展

铁(氢)氧化物和腐殖质是广泛分布在土壤中的重要天然活性物质,因其具有较大的比表面积并且铁(氢)氧化物表面的-OH与腐殖质表面的-COOH、-OH等活性官能团可通过静电作用、配体交换等多种机制对重金属离子产生较强吸附,从而影响重金属离子在环境中的迁移、转化和生物效应。深入了解重金属离子在铁(氢)氧化物-腐殖质复合体微界面相互作用的分子机理,对于阐明重金属离子在环境中的迁移、转化过程具有重要意义。本文综述了金属离子在铁(氢)氧化物与腐殖质上吸附机理和模型的研究进展,为重金属污染土壤的风险评估和控制提供理论依据。     

白浆型床土人参红皮病发生原因的研究

本文采用生态样块的方法，对白浆土区人参红皮病发生条件做了较深入的研究。结果表明，在床土处于田间持水量且通气状况良好情况下，活性还原有机物质仍可形成，并促进土壤铁，锰氧化物活化，使亚铁，二价锰积累。人参红皮病是亚铁在参根周皮氧化沉积的结构，也可能是参根对亚铁毒害作用的保护性反应，而二价锰对红皮病有抑制作用。     

植物根表铁,锰氧化物胶膜及其在植物营养中的作用

在渍水土壤中，由于嫌气条件下存在有许多Ｆｅ＾２＋、Ｍｎ＾２＋，长期适应这种环境的植物具有氧化根际的能力，从而在其根表淀积形成铁、锰氧化物胶膜。研究表明，这些包被在根表的铁、锰氧化物胶膜在适应淹水条件、养分吸收及重金属离子进入植物体过程中起着重要作用，具有重要生态意义。本文综述了近年来国际上这方面的研究进展。     

亚热带土壤亚铁与厌氧反硝化

本文就亚热带土壤亚铁参与反硝化的可能性进行了探讨。研究结果表明:厌氧还原条件下加入KNO3的处理中,Fe2+浓度随培养时间延长而下降,且Fe2+浓度的降低和NO3–-N浓度的降低呈显著正相关。预培养结束后的亚铁浓度(In-Fe2+)和厌氧培养期间Fe2+浓度降低速率与反硝化势表征指标k、b、v7,以及与无定形铁氧化物(活性铁)含量的显著正相关性初步证明,活性铁通过不同价态铁离子(Fe2+和Fe3+)之间的转化,参与了反硝化的电子传递过程。当有机碳等电子供体受限时,Fe2+可作为电子供体参与反硝化还原NO3–-N。这一结果表明,NO3–-N作为电子受体参与厌氧条件下Fe2+氧化成Fe3+的反应可能在铁氧化物含量丰富的亚热带土壤中普遍存在。     

Iron compounds and oil biodegradation in overmoistened contaminated soils: A review of publications

In Russia, the areas of oil pollution gradually shift toward the north into the zone of increased moistening with widespread hydromorphic soils. In this zone, the role of the rapid aerobic degradation of hydrocarbons decreases, while that of slow anaerobic degradation increases. The biological reduction of Fe(III) only proceeds at the expense of the energy of oxidation of organic substances, including oil hydrocarbons, in the oil-polluted soils. This favors the development of technogenic gleying. In contrast to the uncontaminated background soils, in which gleying is correctly considered a degradation process, the same process in the oil-contaminated mineral soils plays a positive role, because it is accompanied by the oxidation of organic pollutants, which otherwise penetrate into rivers and lakes with water flows. The role of Fe(III) reduction may be significant: at one of the oil-spill sites, one-third of the organic pollutants degraded within twelve years after an accident in the anaerobic zone due to Fe(III) reduction. Both iron hydroxides and clay minerals enriched in Fe(III) participate in the reduction processes. In the anaerobic zone, the destruction of organic pollutants begins several years after the relevant natural microorganisms become active. The reduction of Fe(III) reaches its maximum faster than the process of methanogenesis. Upon the soil’s cooling in the winter, the reduction of Fe(III) is replaced by the spontaneous formation of iron oxides (oxidogenesis). Thus, alternating reduction ↔ oxidation reactions proceed in the soils with a contrasting temperature regime. Iron oxides formed in the winter are reduced to Fe(II) in the summer and, thus, resume the associated oxidation of organic pollutants upon the stagnant moisture regime. Therefore, upon monitoring of hydromorphic oilcontaminated soils, special attention should be paid to the forms of iron compounds.     

Catalysis of Dissolved and Adsorbed Iron in Soil Suspension for Chromium（Ⅵ） Reduction by Sulfide

The kinetics of Cr（Ⅵ） reduction by sulfide in soil suspensions with various pHs, soil compositions, and Fe（Ⅱ） concentrations was examined using batch anaeroblc experimental systems at constant temperature. The results showed that the reaction rate of Cr（Ⅵ） reduction was in the order of red soil 〈 yellow-brown soil 〈 chernozem and was proportional to the concentration of HCl-extractable iron in the soils. Dissolved and adsorbed iron in soil suspensions played an important role in accelerating Cr（Ⅵ） reduction. The reaction involved in the Cr（Ⅵ） reduction by Fe（Ⅱ） to produce Fe（ⅡI）, which was reduced to Fe（Ⅱ） again by sulfide, could represent the catalytic pathway until about 70% of the initially present Cr（Ⅵ） was reduced. The catalysis occurred because the one-step reduction of Cr（Ⅵ） by sulfide was slower than the two-step process consisting of rapid Cr（Ⅵ） reduction by Fe（Ⅱ） followed by Fe（Ⅲ） reduction by sulfide. In essence, Fe（Ⅱ）/Fe（Ⅲ） species shuttle electrons from sulfide to Cr（Ⅵ）, facilitating the reaction. The effect of iron, however, could be completely blocked by adding a strong Fe（Ⅱ）-complexing ligand, 1,10-phenanthroline, to the soil suspensions. In all the experiments, initial sulfide concentration was much higher than initial Cr（Ⅵ） concentration. The plots of In e[Cr（Ⅵ）] versus reaction time were linear up to approximately 70% of Cr（Ⅵ） reduction, suggesting a first-order reaction kinetics with respect to Cr（Ⅵ）. Elemental sulfur, the product of sulfide oxidation, was found to accelerate Cr（Ⅵ） reduction at a later stage of the reaction, resulting in deviation from linearity for the In c[Cr（Ⅵ）] versus time plots.     

旱作褐土中氧化铁的厌氧还原与光合型亚铁氧化特征

土壤中铁的氧还过程与碳氮转化及自净能力关系密切,已还原亚铁的氧化受土壤性质的影响。采用室内恒温培养试验研究了旱作褐土中铁还原氧化过程、及其与水溶性碳、NO3-、SO42-的关系。结果表明旱作褐土中铁氧化物在厌氧光照条件下可先被还原后被再次氧化,其再氧化量介于1.46~3.00 mg g-1之间,平均2.09 mg g-1;再氧化速率常数介于0.23~0.80 d-1之间,平均0.48 d-1。再氧化量与土壤无定形铁、水溶性硫酸盐含量、阳离子交换量显著负相关,与土壤总氮、总磷显著正相关;再氧化速率常数与土壤有机碳显著负相关,与黏粒含量极显著正相关。厌氧光照培养可使旱作褐土水溶性无机碳平均降低52.74%,水溶性NO3-降低92.15%,水溶性SO42-增加55.38%。研究结果为深入理解旱作土壤潜在的微生物铁循环转化方式提供理论支持。     

Specific features of iron behavior in soddy-podzolic and alluvial gleyed soils of the Middle Cis-Urals region

The regime of observations revealed that the Eh dynamics in soddy-podzolic and alluvial soils in the Middle Cis-Urals region depends not only on the rate of iron (hydr)oxides reduction but also on the rate of opposite reactions in the gleyed horizons. Both processes depend on the temperature. The Eh value decreases on heating in automorphic soils, when the reduction of Fe(III)-(hydr)oxide particles accelerates. On the contrary, in gley soils, the Eh decreases on cooling, probably, because of the reactions opposing the reduction of Fe(III)-(hydr)oxide particles, including Fe(II) fixation on the surface of mineral particles. Fe(III)-(hydr)oxides are, for the most part, preserved in gleyed soils of the Cis-Urals; the content of (Fe₂O₃)_dit reaches 3.3% with iron minerals being usually represented by goethite. The increase in moistening influences the soil parameters (i.e., the redoxpotential rH and the content of conventional red pigment Hem_conv) in an intricate manner. Both direct and reverse branches on the curve of the Hem_conv-rH dependence point to the equilibrium and nonequilibrium conditions in the soil. The reverse branch probably stands for the initial phase of gleying in strongly humified soils, where, despite extra electrons in the solution, the brown pigment in the form of Fe(III)-(hydr)oxides is preserved.     

The role of iron in the fixation of heavy metals and metalloids in soils: a review of publications

Iron’s contribution to fixing heavy metals and metalloids in soils is very important. Iron compounds participating in redox processes control the behavior of siderophilic elements with variable oxidation degrees (Cr, As, and Sb). The behavior of heavy elements with permanent oxidation (Zn, Co, and Ni) indirectly depends on iron compounds. In organic soils, iron competes with heavy metals for active places in the functional groups of organic substances. Organic pollutants intensify the reduction of iron (hydr)oxides in an anaerobic environment, which influences the release of arsenic. Iron compounds are used as ameliorating agents and geochemical barriers for fixing heavy elements.     

Arsenic from Groundwater to Paddy Fields in Bangladesh: Solid–Liquid Partition, Sorption and Mobility

The arsenic contamination of Bangladesh groundwater involves heavy arsenic inputs to irrigated rice fields. Beside adsorption on soil colloids, iron–arsenic co-precipitation phenomena can affect arsenic retention in soils. In paddy fields of Satkhira District, Bangladesh, the study of the arsenic and iron forms in the irrigation waters and in soils at different times and distances from the irrigation well evidenced that a higher Fe/As ratio in the well water was related to a faster oxidation of Fe(II) and As(III) in water and to a close Fe–As association in soils, together with a greater accumulation of arsenic and poorly ordered iron oxides. The concentration of arsenic and of labile iron forms decreased with the distance from the well and with the depth, as well as the reversibility of arsenic binding. The fate of the arsenic added to the soils by irrigation hence resulted strongly influenced by iron–arsenic co-precipitation, depending on the Fe/As ratio in water. Irrigation systems favouring the sedimentation of the Fe–As flocks could help in protecting the rice from the adverse effects of dissolved arsenic.     

Implications of iron solubilization on soil phosphorus release in seasonally flooded forests of the lower Orinoco River, Venezuela

The microbial reduction of Fe oxides is thought to contribute with the release of P in sedimentary environments. However, secondary reactions of the bioproduced Fe(II) with P in solution, can lead to a decrease in the soluble P concentration. In this study, we examined how the reduction of Fe(III) affects the soluble P concentration, when the soils of a seasonally flooded forest gradient are subjected to anaerobic conditions. Soil samples were collected during the dry season from two zones subjected to different flooding intensity: MAX and MIN zones that were inundated 8 and 2 months per year, respectively. When anaerobic conditions were applied to soils from both zones, a clear stimulatory effect on the Fe(III) reduction was observed. However, bioproduced Fe(II) underwent secondary chemical reactions, masking the extend of Fe(III) reduction of these soils. Iron was reduced mainly during the first 15 days of the anaerobic incubation and it was stimulated by a pulse of labile carbon. Iron dissolution did not lead to an increase of the soluble P content. However, in both zones P was high and positively correlated with Fe(II), implying that soil P mobilization was linked to Fe dissolution. In the MIN zone, soluble P concentration decreased, probably as a consequence of the secondary reactions of solubilized P with other non-redox sensitive soils elements. Fe solubilization also had an effect on the activity of acid phosphatase and consequently in the solubilization of P from the organic pool. In conclusion, the P cycle in these soils is strongly coupled to C and Fe cycles.     

Chromium and arsenic in contaminated soils (Review of publications)

In the last decades, the chromium clarke in the world’s soils has been revised and reduced; at present, it is equal to 70 mg/kg. No maximal permissible concentration is accepted for the total chromium content in the soils of Russia; it appears reasonable to use the Western European and North American standards in Russia and to take the average value of the maximal permissible concentration equal to 200 mg Cr/kg. Chromium toxicity depends on its oxidizing status. The hazardous effect decreases with the reduction of Cr(VI) to Cr(III). There are various chemical reducers of Cr(VI), including sulfides, dissolved organic substance, aqueous Fe(II) and minerals enriched in Fe(II), and Fe(0). As-containing ore tailings represent a powerful source of technogenic arsenic. Significant environment contamination with natural As is registered in a number of Asian countries. The maximal permissible concentration of total arsenic is equal to 2 mg/kg in Russian soils; it is probably underestimated, because it is lower than the As clarke in soil (5 mg/kg). The approximately permissible concentration (APC) values for As look more reasonable. Arsenic toxicity depends on its oxidation degree: As(III) is 2–3 times more toxic than As(V).     

抗坏血酸与针铁矿之间的电化学反应的研究

土壤在淹水条件下 ,氧化铁是土壤中主要的电子接受者之一。本文利用抗坏血酸和针铁矿模拟研究了土壤中的有机还原性物质与氧化铁之间的反应。结果表明 :在抗坏血酸与针铁矿作用的过程中 ,由于溶液中质子被消耗 ,溶液的pH上升 ,质子的消耗量随着抗坏血酸加入量的增加而增加。质子消耗的动力学曲线表明 ,抗坏血酸与针铁矿之间的作用属于异相反应 ,达到平衡所需要的时间较长。在反应的初期 ,二价铁的还原溶出速率很慢 ,在较长的时间内溶液中二价铁浓度不发生变化。pH对抗坏血酸与针铁矿之间的反应有影响 ,pH上升 ,反应速率受抑制 ,pH下降 ,反应速率加快。从不同pH条件下的抗坏血酸的峰电位的测定结果推断 ,pH对抗坏血酸与针铁矿反应的影响可能通过影响针铁矿表面化学性质来实现的。