铁还原菌介导的氧化铁还原与硝酸盐还原的竞争效应研究

中性厌氧条件下,脱色希瓦氏菌Shewanella decolorationis(S12)能够使用多种电子受体进行厌氧呼吸,包括溶解态的硝酸盐以及难溶态的氧化铁基质。因此,本文通过构建"脱色希瓦氏菌/铁氧化物/硝态氮"的交互反应体系,研究这一体系中铁还原与硝态氮还原的相互作用过程,并对相互作用机制进行初步探讨。结果表明,交互反应体系中氧化铁还原与硝酸盐还原存在明显的竞争关系;随着氧化铁比表面积、可利用态铁含量的增大,硝酸受抑制作用逐渐增强;通过不同温度煅烧而得到的不同结晶度的赤铁矿对硝态氮的抑制作用也被研究。结果还表明,氧化铁结晶度越高,S12对硝态氮的还原抑制作用越小。循环伏安电化学测试结果发现,加入硝酸条件下,铁氧化峰几乎完全消失,表明硝态氮存在条件下,铁还原受到明显抑制。针对以上结果,初步探讨了铁还原与硝态氮还原竞争的原因,即:(1)Fe(Ⅲ)与NO3–同时作为电子受体,因竞争电子而受到抑制;(2)吸附态Fe(Ⅱ)物种还原NO3–,导致Fe(Ⅱ)累积减少,NO3–还原因产生的Fe(Ⅱ)的低速率而被抑制。     

不同施肥处理对水稻根表铁和砷形态的影响

采用XAFS研究盆栽试验砷污染土壤中添加不同肥料后,苗期水稻根表铁膜和砷的矿物学特征.Fe的K边EXAFS谱表明,铁膜主要由2-line水铁矿组成,还有少部分针铁矿和赤铁矿等晶体矿;As的EXAFS谱显示,除了KNO3和K2SO4处理外,其余处理的铁膜中砷以三价砷为主.KNO3处理显著减少了水稻根表铁膜的形成,而且抑制了水稻对砷的吸收.不同的肥料可以影响铁膜中砷的存在形态.     

土壤还原过程对氯代有机污染物还原脱氯的影响与机制

自然环境中,大多数氯代有机污染物厌氧还原脱氯反应是与土壤环境中一些生源要素的生物化学还原过程相伴生。有机污染物的种类、生物有效性以及毒性能够显著影响这些生源要素的转化,反过来,土壤中活跃的氧化还原反应也可以显著影响有机污染物的动力学转化过程。本文从氧化还原顺序上综述了反硝化过程、铁还原过程、硫酸盐还原过程和产甲烷过程对氯代有机污染物厌氧还原脱氯过程的影响与作用机制,旨在为氯代有机污染物在厌氧环境中还原脱氯的过程与机理的进一步研究、以及还原脱氯与微生物介导的生源要素氧化还原过程的耦合作用机制的揭示提供参考。     

微生物砷代谢机制的研究进展（Progress in Study of Mechanisms of Microbial Arsenic Transformation in Environment）

环境砷污染是一个全球性问题.研究砷的生物地球化学循环可以明确环境中砷的来源及其转化特征,为探索砷污染治理的方法提供参考.越来越多的研究表明,自然界中的微生物在砷的迁移转化过程中发挥了重要作用.根据微生物对砷的代谢机制不同将其分为:砷氧化微生物、砷还原微生物和砷甲基化微生物.砷氧化微生物可以将环境中的As(Ⅲ)氧化为毒性较弱并且容易被铁铝矿物吸附固定的As(Ⅴ),因此对降低环境中的砷毒性具有重要作用;微生物对砷的甲基化作用的产物通常为毒性较低的有机砷,因此也被认为是理想的修复环境砷污染的生物手段之一;然而在还原环境中,砷还原微生物却可以将游离态和结合态的As(Ⅴ)还原为毒性更强的As(Ⅲ),从而加重环境中的砷污染状况.由此可见,明确微生物的砷代谢机制及其对砷污染环境中砷迁移转化的影响,是实现生物修复砷污染环境的必要前提.论文总结了近年来国内外微生物砷代谢机制的研究进展,以期为深入研究微生物代谢砷的机理及其在砷污染治理中的应用提供参考.     

稻田体系中铁的生物地球化学过程及铁同位素分馏机制研究进展

铁是地球上丰度排第四的元素,其地球化学行为作为稻田体系循环的重要组成部分而具有重大意义。铁也是植物维持正常生命活动的必需微量元素之一,参与众多生物代谢过程。十几年来,铁同位素方法在表生地球化学的应用得到了广泛关注,铁同位素方法已被广泛地用来追踪异化铁还原、亚铁的生物和非生物氧化以及吸附、沉淀等铁的生物地球化学过程。文章综述了水稻土铁同位素分馏特征及影响因素,以及水稻中铁吸收转运的分子生理机制和铁同位素分馏特征和机制。水稻土在发育过程中缺损轻铁,且不同的发育过程导致土壤中铁形态、价态的改变而会形成特有的分馏特征。植物铁同位素分馏效应的研究表明,植物吸收铁的机制不同,产生的铁同位素分馏程度呈现出显著的差异。当植物以机理I的方式,即通过将三价铁还原为二价铁再吸收铁时,植物优先吸收轻的铁同位素,且铁同位素在植物内部的分馏程度较大[-0.13‰-(-1.64‰)]。当植物通过机理II的方式,即通过螯合三价铁,再吸收至植物体内的过程,植物优先吸收重的铁同位素,且铁同位素的分馏程度较小(-0.11‰-0.17‰)。水稻铁同位素组成不同于典型的机理II植物,水稻富集轻铁,且铁同位素在水稻植株中存在较大分馏。这可能是因为水稻在根吸收铁的过程中同时采用机理I和机理II途径,且铁在水稻内的转运过程、配体改变及价态改变等都会导致铁的同位素分馏。铁同位素方法在揭示水稻对铁元素的吸收机制方面表现出巨大应用潜力。文章还分别对如何将铁同位素方法结合土壤-水稻体系的土壤发育背景,以及通过制样方法的改进、结合质量平衡计算、动力学分馏、综合多个表征手段等方式来解释水稻铁同位素机制进行了讨论和展望。     

水稻根表铁膜对水稻根吸收铅的影响

采用土-砂联合培养方法诱导水稻根表形成不同数量的铁膜:高铁膜(HP)和低铁膜(LP),探讨铁膜形成的多少对水稻离体根系吸收铅的影响.结果表明,在水稻生长期间,水分显著影响根表形成铁膜的数量.水稻吸收的铅大部分结合在根组织中(平均75%),少部分富集在根表铁膜中(平均25%).与低铁膜相比,高铁膜可以增强铅在水稻根表铁膜和根中的积累,由此可见,铁膜可能在一定程度上促进铅向水稻根内的转运.     

水稻土嗜中性微好氧亚铁氧化菌多样性及微生物成矿研究

微生物驱动亚铁氧化过程在水稻土中十分普遍,该过程被认为是水稻土中联接各生物地球化学过程的中心枢纽。嗜中性微好氧亚铁氧化菌能够利用氧气作为电子受体将亚铁氧化成三价铁,获得生长所需能量。然而,对水稻土中微好氧亚铁氧化菌的多样性与分布及其微生物成矿类型仍然未知。采用铁氧反向浓度梯度管法富集培养并分离水稻土中微好氧亚铁氧化菌,利用16S r RNA基因测序手段分析培养过程中微好氧亚铁氧化菌群落多样性与分布,并初步研究分离得到的亚铁氧化菌的亚铁氧化能力与生物成矿类型。结果表明,在富集培养和传代培养过程中,Azospira、Magnetospirillum、Clostridium和Rhodoplanes等属在群落中占优势。在分离最后阶段,得到几种细菌的混合菌团,可能是由于这几种亚铁氧化菌存在互养关系而难以纯化分离,其中占优势的为Azospira(63.9%)。Azospira是一类已知硝酸盐依赖型Fe OB,可以利用硝酸盐、氯酸盐和高氯酸盐为电子受体进行厌氧亚铁氧化。混合菌团具有活跃的亚铁氧化能力,反应第15天生成6.9 mmol·L-1 HCl-Fe。XRD结果表明菌团氧化亚铁形成的三价铁矿物类型为无定形铁氧化物。TEM结果显示微好氧Fe OB菌体呈杆状,细菌表面和周围散布着颗粒状的物质,可能是由无定形铁氧化物组成。综上所述,认为反硝化细菌可能在水稻土有氧-无氧界面进行微好氧亚铁氧化,其氧化亚铁的产物为无定形铁氧化物。     

铁氨氧化污水脱氮的应用研究进展

铁氨氧化(Feammox)是一种以廉价、易得的铁作为微生物电子供体的新型自养生物脱氮技术，即Fe(Ⅲ)还原与厌氧氨氧化的结合工艺，拥有成本低廉、无需有机碳源、污泥产量小、无温室气体产生等优势，是污水处理的一种潜在脱氮途径.本文对铁氨氧化反应的机理、功能菌种的种类和特性及电子穿梭体对其的影响进行了介绍，总结了铁氨氧化在污水环境中的脱氮效果及其与厌氧氨氧化、硝酸盐依赖型亚铁氧化和生物电化学系统的耦合技术，并指出目前铁氨氧化的应用问题及该技术未来的研究方向和重点可能是菌分离纯化、工艺参数控制.     

硝酸盐还原和亚铁氧化对贪铜菌还原砷的影响

华南红壤区水稻土具有含铁量较高、氮元素输入量较大的特性,且部分矿区周边的水稻田受砷污染严重,不仅影响水稻产量,还对食品安全和人类健康造成威胁。利用多轮传代富集的方法,从华南红壤水稻土中纯化获得一株具有硝酸盐还原、亚铁氧化和砷还原功能的贪铜菌Cupriavidus metallidurans Paddy-2。以该细菌为研究对象,探讨纯细菌体系中,硝酸盐还原和亚铁氧化过程对微生物还原As(Ⅴ)的影响,测试了反应体系中As(Ⅴ)和硝酸盐的还原动力学,以及Fe(Ⅱ)的氧化动力学,并对体系中Fe(Ⅱ)氧化所生成的矿物沉淀进行表征分析。As(Ⅴ)还原动力学结果表明,中性厌氧条件下贪铜菌对As(Ⅴ)的还原率为100%,而分别加入硝酸盐和Fe(Ⅱ)均能有效抑制贪铜菌对As(Ⅴ)的还原作用(还原率为27%~49%),两者同时存在对As(Ⅴ)还原的抑制作用最大(还原率只有21%)。硝酸盐作为末端电子受体,由于其氧化还原电位比As(Ⅴ)更高,因此比As(Ⅴ)更容易接收电子,从而减缓贪铜菌对As(Ⅴ)的还原效率。Fe(Ⅱ)氧化动力学和矿物表征结果表明,只有在硝酸盐和Fe(Ⅱ)共存的体系里,Fe(Ⅱ)的氧化才能得到有效的促进,并生成含Fe(Ⅲ)的无定形矿物。这些Fe(Ⅲ)矿物覆盖在菌株表面,有可能降低菌株的代谢活性,并有效吸附As(Ⅴ),从而减低体系中As的浓度,达到降低As毒性的效果。研究结果可为受砷污染农田的生物修复技术的开发提供科学依据。     

零价铁还原和过硫酸盐氧化联合降解水中硝基苯

将零价铁(Fe0)的还原和过硫酸盐(persulfate,PS)的高级氧化技术结合用于水中难降解有机污染物硝基苯的去除.研究结果表明,Fe0在常温常压下可将硝基苯还原生成苯胺,随着Fe0投加量的增加,硝基苯还原为苯胺的速率逐渐增大.PS本身对硝基苯氧化作用不明显,但在Fe0与PS二者联合体系中,硝基苯和苯胺同时被去除,而且随着PS投加量的增加二者被去除的速度也随之增加.在Fe0还原和PS氧化联合处理硝基苯的体系中可能存在两个过程,一是Fe0还原硝基苯产生苯胺和二价铁离子Fe2+,二是Fe2+催化PS产生强氧化性的硫酸根自由基将苯胺氧化降解.     

铁循环微生物对环境中重金属的影响研究进展

铁循环微生物包括铁氧化菌(Fe(Ⅱ)-oxidizing bacteria,FeOB)和铁还原菌(Fe(Ⅲ)-reducing bacteria,FeRB),在由它们介导Fe2+(Fe3+)氧化(还原)的过程中,往往也伴随着一系列重金属元素的迁移转化,对重金属在环境中的生物有效性和迁移性方面有重要作用.本文综述了环境中...     

Tropical forest soil microbial communities couple iron and carbon biogeochemistry

We report that iron-reducing bacteria are primary mediators of anaerobic carbon oxidation in upland tropical soils spanning a rainfall gradient (3500-5000 mm/yr) in northeast Puerto Rico. The abundant rainfall and high net primary productivity of these tropical forests provide optimal soil habitat for iron-reducing and iron-oxidizing bacteria. Spatially and temporally dynamic redox conditions make iron-transforming microbial communities central to the belowground carbon cycle in these wet tropical forests. The exceedingly high abundance of iron-reducing bacteria (up to 1.2 x 10(9) cells per gram soil) indicated that they possess extensive metabolic capacity to catalyze the reduction of iron minerals. In soils from the higher rainfall sites, measured rates of ferric iron reduction could account for up to 44% of organic carbon oxidation. Iron reducers appeared to compete with methanogens when labile carbon availability was limited. We found large numbers of bacteria that oxidize reduced iron at sites with high rates of iron reduction and large numbers of iron reducers. The coexistence of large populations of iron-reducing and iron-oxidizing bacteria is evidence for rapid iron cycling between its reduced and oxidized states and suggests that mutualistic interactions among these bacteria ultimately fuel organic carbon oxidation and inhibit CH4 production in these upland tropical forests.     

Iron oxidation-reduction and its impacts on cadmium bioavailability in paddy soils: a review

Redox conditions in paddy soils may vary as they are submerged and drained during rice growth. This change may bring about reductive dissolution of iron (Fe) oxides and subsequent formation of secondary Fe-bearing minerals in rice paddies. The mobility and bioavailability of metal contaminants such as cadmium (Cd) in paddy soils are closely related to the chemical behaviors of Fe. Therefore, in this paper, advances in the study of paddy Fe redox transformations and their effects on Cd availability to rice are briefly reviewed. Current concepts presented in this review include the forms of Fe in paddy soils, the reactions involved in Fe oxidation-reduction, chemical factors affecting Fe redox processes, Cd availability to rice and the impacts of Fe transformation on Cd uptake and translocation in rice. Prospects for future research in this area are also discussed.     

Comparison of different valent iron on anaerobic sludge digestion: Focusing on oxidation reduction potential,dissolved organic nitrogen and microbial community

• ORP value from −278.71 to −379.80 mV showed indiscernible effects on methane yield. • Fe(II) and Fe(III) promoted more degradation of proteins and amino acids than Fe⁰. • The highest enrichment of Geobacter was noted in samples added with Fe⁰. • Cysteine was accumulated during iron enhanced anaerobic sludge digestion. • Both iron content and valence were important for methane production. This study compared effects of three different valent iron (Fe⁰, Fe(II) and Fe(III)) on enhanced anaerobic sludge digestion, focusing on the changes of oxidation reduction potential (ORP), dissolved organic nitrogen (DON), and microbial community. Under the same iron dose in range of 0−160 mg/L after an incubation period of 30 days (d), the maximum methane production rate of sludge samples dosed with respective Fe⁰, Fe(II) and Fe(III) at the same concentration showed indiscernible differences at each iron dose, regardless of the different iron valence. Moreover, their behavior in changes of ORP, DON and microbial community was different: (1) the addition of Fe⁰ made the ORP of sludge more negative, and the addition of Fe(II) and Fe(III) made the ORP of sludge less negative. However, whether being more or less negative, the changes of ORP may show unobservable effects on methane yield when it ranged from −278.71 to −379.80 mV; (2) the degradation of dissolved organic nitrogen, particularly proteins, was less efficient in sludge samples dosed with Fe⁰ compared with those dosed with Fe(II) and Fe(III) after an incubation period of 30 d. At the same dose of 160 mg/L iron, more cysteine was noted in sludge samples dosed with Fe(II) (30.74 mg/L) and Fe(III) (27.92 mg/L) compared with that dosed with Fe⁰ (21.75 mg/L); (3) Fe⁰ particularly promoted the enrichment of Geobacter, and it was 6 times higher than those in sludge samples dosed with Fe(II) and Fe(III) at the same dose of 160 mg/L iron.     

铁基生物炭钝化Cd大田试验研究

近年来,稻田Cd污染引起的环境及健康问题日益突出。应用钝化技术对土壤中有效性Cd进行钝化对稻田生态系统中Cd的生物地球化学循环具有重要的理论和实际意义。在广东省韶关市仁化县董塘镇红星村一受Cd污染的稻田上,设置大田试验,研究铁基生物炭对Cd在大田土壤-水稻系统迁移的影响以及对作物产量的影响。试验共设6个处理:(1)空白对照;(2)每一季水稻插秧前,一次性施加1500 kg·hm^-2的普通生物炭;(3)每一季水稻插秧前,一次性施加75 kg·hm^-2的零价铁(Fe0);(4)每一季水稻插秧前,一次性施加1500 kg·hm^-2、ω(Fe)=1%的铁基生物炭(ω(Fe)=1%in Fe-Biochar);(5)每一季水稻插秧前,一次性施加1500 kg·hm^-2、ω(Fe)=3%的铁基生物炭(ω(Fe)=3%in Fe-Biochar);(6)每一季水稻插秧前,一次性施加1500 kg·hm^-2、ω(Fe)=5%的铁基生物炭(ω(Fe)=5%in Fe-Biochar)。结果表明:(1)施用生物炭、铁粉和铁基生物炭土壤钝化调理剂可以增加水稻产量,显著降低籽粒重金属Cd含量;(2)施用铁基生物炭可以显著增加水稻根表铁膜Fe含量,同时显著增加水稻根表铁膜固定的Cd量,抑制重金属Cd向籽粒的运输累积。综合考虑施用成本和钝化效果,对于Cd污染稻田,建议施用1500 kg·hm^-2、ω(Fe)=3%的铁基生物炭材料。     

Simultaneous Feammox and anammox process facilitated by activated carbon as an electron shuttle for autotrophic biological nitrogen removal

• The autotrophic nitrogen removal combining Feammox and Anammox was achieved. • Activated carbon can be used as an electron shuttle to enhance Feammox activity. • Fe(III) was reduced to Fe(II) and the secondary Fe(II) mineral (FeOOH) was obtained. • The iron-reducing bacteria and Anammox consortium was enriched simultaneously. Ferric iron reduction coupled with anaerobic ammonium oxidation (Feammox) is a novel ferric-dependent autotrophic process for biological nitrogen removal (BNR) that has attracted increasing attention due to its low organic carbon requirement. However, extracellular electron transfer limits the nitrogen transformation rate. In this study, activated carbon (AC) was used as an electron shuttle and added into an integrated autotrophic BNR system consisting of Feammox and anammox processes. The nitrogen removal performance, nitrogen transformation pathways and microbial communities were investigated during 194 days of operation. During the stable operational period (days 126–194), the total nitrogen (TN) removal efficiency reached 82.9%±6.8% with a nitrogen removal rate of 0.46±0.04 kg-TN/m³/d. The contributions of the Feammox, anammox and heterotrophic denitrification pathways to TN loss accounted for 7.5%, 89.5% and 3.0%, respectively. Batch experiments showed that AC was more effective in accelerating the Feammox rate than the anammox rate. X-ray photoelectron spectroscopy (XPS) analyses showed the presence of ferric iron (Fe(III)) and ferrous iron (Fe(II)) in secondary minerals. X-ray diffraction (XRD) patterns indicated that secondary iron species were formed on the surface of iron-AC carrier (Fe/AC), and Fe(III) was primarily reduced by ammonium in the Feammox process. The phyla Anaerolineaceae (0.542%) and Candidatus Magasanikbacteria (0.147%) might contribute to the Feammox process, and Candidatus Jettenia (2.10%) and Candidatus Brocadia (1.18%) were the dominative anammox phyla in the bioreactor. Overall, the addition of AC provided an effective way to enhance the autotrophic BNR process by integrating Feammox and anammox.     

Biogeochemical cycling of ferric oxyhydroxide affecting As partition in groundwater aquitard

High arsenic (As) concentration in groundwater potentially poses a serious threat to the health of local residents in southwestern Taiwan. Although the As release to groundwater is responsible for the reducing bacteria-mediated reductive dissolution of As-rich Fe hydroxides, the influences of FeRB and different organic substrates on As and Fe mobility and transformation were rarely discussed. An experiment that involved As-adsorbed synthetic amorphous Fe(III) hydroxide (HFO) and the inoculation of in situ Fe-reducing bacteria (FeRB) was performed to evaluate the contribution of FeRB to the As mobility and transformation. The batched experiment of As-free HFO showed that the reducing bacteria rapidly induced the reduction of amorphous Fe oxyhydroxide to Fe(II) by reductive dissolution of HFO and formation of Fe-citrate complexation. For aqueous As(V) reduction experiment, arsenate was effectively reduced to As(III) by the facultative anaerobic bacterium in the cultured FeRB. In the experiment of As-containing HFO reduction, the aqueous As(V) acts as an electron acceptor and reduced to As(III) after the reductive dissolution of Fe(III) on HFO. However, the increase in the As(III) concentrations with time for various organic substrates in the As-adsorbed HFO-reducing experiment differ from the rates of As(V) reduction with various organic substrates in the As(V)-reducing experiment. The decrease in sorption sites by coupled reductive dissolution of HFO and the competitive desorption of small molecular organic carbon is apparently the important factor of As mobility. For large molecular organic carbon (i.e., citrate), the significant contribution of citrate on As mobility is the complexation of iron citrate. A working hypothesis model of As biogeochemical cycling is proposed to illustrate the relevant processes in the groundwater aquitard of southwestern Taiwan.     

电子穿梭体及其介导的环境与地球化学过程研究进展

电子穿梭体是一类可通过自身氧化还原介导电子转移的化学物质的统称.在地球表层系统中,电子穿梭体可加速微生物向细胞外部进行的电子传递,参与矿物的微生物还原,驱动碳、氮、硫元素循环,并偶联有机污染物降解和重金属迁移转化.电子穿梭在自然界中存在广泛,对于元素循环、污染物环境行为以及微生物的生存行为影响深远,具有重要的环境地球化...     

Geochemical and microbial effects on the mobilization of arsenic in mine tailing soils

Arsenic (As) contamination has become a serious environmental problem in many countries. We have performed batch-type leaching experiments on mine tailing soils collected from three abandoned mine areas in South Korea with the objective of evaluating the effect of indigenous bacterial activity on As mobilization. The analysis of physicochemical properties and mineralogical compositions of the samples indicated that the secondary minerals or phases formed as a result of the oxidation or alteration of primary minerals were associated with the labile and bioleachable fractions of As. Compared to simulated abiotic processes using sterilization, the indigenous bacteria activated using a carbon source were able to enhance the dissolution of As under both aerobic and anaerobic conditions. The bacterial dissolution of iron (Fe) and manganese (Mn) was found to occur simultaneously with the dissolution of As, suggesting that the main bacterial mechanism was via the dissimilatory reduction of Fe(III), Mn(IV), and As(V). An anaerobic environment was more favorable for the prominent dissolution of As in the tailing soils. These results indicate that the mobilization of As can be enhanced in the oxygen-depleted part of the tailing dump, particularly with the infiltration of organic substrates. The difference in the degree of As lixiviation between the three tailing soils was found to be related to the bioavailability of As as well as the original biomass in the tailing soils.