腐殖质在环境污染物生物降解中的作用研究进展*

腐殖质物质在地球的生态环境中大量存在,它不仅可以在有毒化合物的生物降解和生物转化过程中起到氧化还原中间体的作用,加速有毒物质的降解和转化。也可以作为唯一末端电子受体,接受来自一些有机酸或者甲苯等环境中有毒物质提供的电子,偶联能量的产生,支持菌体的生长,形成一种新的细菌厌氧呼吸形式——腐殖质呼吸。因此,对腐殖质在环境有毒物质的生物降解和生物转化过程中的作用进行研究,不仅对于深入理解细菌呼吸的本质具有重要的理论意义,而且对于环境有毒物质的降解和转化以及元素的生物地球化学循环具有重要的生态学意义,同时对地球表面     

中国希瓦氏菌D14^T的厌氧腐殖质呼吸

实验证明,希瓦氏菌新种(ShewanellacinicaD14T)在厌氧条件下可以利用多种有机酸盐和甲苯等环境有毒污染物作为电子供体,以腐殖质作为唯一末端电子受体进行厌氧呼吸(即醌呼吸)。电子在细胞膜呼吸链的传递过程中,偶联能量的产生来支持菌体的生长,1mmol/LAQDS可支持细胞增殖约60倍。电子供体的氧化和唯一电子受体腐殖质还原之间存在着动态的偶联过程,随着电子供体量的增加腐殖质还原的量也随之增加。典型呼吸链抑制剂诸如:抑制Fe-S中心的Cu2 ,甲基萘醌类似物标桩菌素,抑制甲基萘醌氧化型向还原型转化的双香豆素和细胞色素P450的专一抑制物甲吡酮等对腐殖质的还原有着极为显著的抑制作用,为进一步证明希瓦氏菌(Shewanellacinica)D14T可利用腐殖质进行厌氧呼吸提供了有力的佐证。而D14T在进行腐殖质呼吸的同时,对于甲苯,苯胺等环境有毒物质的有效降解则具有着重要的环境学意义。     

中国希瓦氏菌D14T的厌氧腐殖质呼吸

实验证明,希瓦氏菌新种（Shewanella cinicaD14T）在厌氧条件下可以利用多种有机酸盐和甲苯等环境有毒污染物作为电子供体,以腐殖质作为唯一末端电子受体进行厌氧呼吸（即醌呼吸）。电子在细胞膜呼吸链的传递过程中,偶联能量的产生来支持菌体的生长,1mmol/L AQDS可支持细胞增殖约60倍。电子供体的氧化和唯一电子受体腐殖质还原之间存在着动态的偶联过程,随着电子供体量的增加腐殖质还原的量也随之增加。典型呼吸链抑制剂诸如：抑制FeS中心的Cu2+ ,甲基萘醌类似物标桩菌素,抑制甲基萘醌氧化型向还原型转化的双香豆素和细胞色素P450的专一抑制物甲吡酮等对腐殖质的还原有着极为显著的抑制作用,为进一步证明希瓦氏菌（Shewanella cinica）D14T可利用腐殖质进行厌氧呼吸提供了有力的佐证。而D14T在进行腐殖质呼吸的同时,对于甲苯,苯胺等环境有毒物质的有效降解则具有着重要的环境学意义。     

腐殖质呼吸作用及其生态学意义

腐殖质呼吸是厌氧环境中普遍存在的一种微生物呼吸代谢模式.自1996年发现以来,日益成为生态学与环境科学领域的研究热点.在厌氧条件下,一些微生物能以腐殖质作为唯一电子受体,氧化环境中的有机质或者甲苯等环境有毒物质,产生CO2,参与碳循环;同时,腐殖质呼吸作用产生的还原态腐殖质可以还原环境中的一些氧化态物质,如Fe(III)、Mn(IV)、Cr(VI)、U(VI) 、硝基芳香化合物和多卤代污染物.因此,腐殖质呼吸能够影响环境中C、N、Fe、Mn以及一些痕量金属元素的生物地球化学循环,并且能够促进重金属以及有机污染物的脱毒,在水体自净、污染土壤原位修复、污水处理等方面具有积极作用.     

西太平洋多金属结核区12个站位沉积物中可培养潜在腐殖质转化菌的多样性

【背景】海洋环境作为地球上最大的有机碳库贮藏着大量腐殖质,其中可能蕴藏着丰富的腐殖质转化菌。【目的】从深海沉积物环境中分离具有潜在腐殖质转化能力的细菌,为难降解天然有机多聚物的生物转化提供菌种资源。【方法】利用以腐殖质为唯一碳源的培养基,对西太平洋多金属结核区12个站位沉积物样品中的腐殖质转化菌进行富集培养和纯化,通过16S rRNA基因测序分析比对初步确定分离菌株的分类地位,并利用含苯胺蓝的培养基筛选潜在的腐殖质转化菌。【结果】从12个沉积物样品中共分离获得菌株276株,隶属于放线菌纲(Actinobacteria)、纤维粘网菌纲(Cytophagia)、黄杆菌纲(Flavobacteria)、 α变形菌纲(Alphaproteobacteria)和γ变形菌纲(Gammaproteobacteria)中的14个目37个属56个种(含1个潜在新属和2个新种),其中49个种呈现木质素修饰酶阳性。【结论】利用以腐殖质为唯一碳源和能源的培养基可以分离获得具有较高多样性的潜在腐殖质转化菌。     

水环境中腐殖质-金属离子键合作用研究进展

腐殖质 (主要指腐殖酸和富里酸 )普遍存在于各种水体中 ,它对金属离子的形态、迁移转化、生物可利用性等地球化学行为起着重要作用。本文概述了水环境中腐殖质的一些基本性质 ,以及腐殖质 金属离子之间的键合作用机理、研究方法和影响因素。并且对各种金属离子键合到腐殖质上的现代物理化学模型 ,尤其对ModelⅥ及NICA Donnan模型进行了简要回顾和评述。它们在许多条件下模拟腐殖质 -金属离子键合作用可以得到令人欣喜的结果。还简述了腐殖质对水环境中金属离子各种水环境地球化学行为的影响。但是 ,若要更深入了解和阐述金属离子在水环境中的各种行为 ,还需考虑腐殖质与颗粒物质、胶体物质以及微生物等的相互作用。     

堆肥化中木质素的生物降解

木质素是堆肥化原料中一种重要的限速高聚物,其有效降解对堆肥化速度、堆肥质量有重要作用.综述了堆肥化中木质素生物降解的研究进展,包括堆肥化中降解木质素的微生物种类及其降解过程和机理,以及木质素的降解与堆肥化中腐殖质形成的关系.     

铜绿假单胞菌生物降解特性的研究进展

近年来在环境污染物的生物降解研究方面有了很大进展。铜绿假单胞菌(Pseudomon asaeruginosa,PA)作为重要的降解菌株之一,具有较强的降解能力,可降解物质种类广泛,在环境污染物的生物降解中具有重要作用并占据重要地位。本文综述了PA的降解特性、代谢途径、遗传基础与酶系及促降解物质在生物降解方面的研究进展。     

厌氧条件下希瓦氏菌腐殖质还原对偶氮还原的影响

以希瓦氏菌属的3个代表种为研究对象,研究了在厌氧条件下腐殖质的存在对偶氮还原的影响。实验结果表明:3个代表菌株在厌氧条件下都有高效的偶氮还原和腐殖质还原功能,1mmol/L偶氮染料在24h内完全脱色,并且偶氮还原与电子供体氧化存在着紧密的偶联关系。腐殖质物质模式物2-磺酸蒽醌AQS在小于1~2mmol/L条件下能显著加速偶氮还原,12h就完全脱色,3mmol/L时18h完全脱色。但当浓度大于3mmol/L时则对偶氮还原产生明显抑制作用。另一腐殖质模式物2,6-双磺酸蒽醌AQDS其浓度在1~3mmol/L以内亦使脱色在12h内完成,4~6mmol/L时15h左右完成脱色。7~12mmol/L仍有一定的脱色促进作用,但随着浓度的提高,其促进作用也逐渐减弱。这说明腐殖质的确可以作为氧化还原中间体穿梭于电子供体与染料的偶氮双键之间促进偶氮还原。但当其浓度达到某一阈值时它就显出与偶氮键竞争电子的本质,从而使偶氮还原速率下降。原因在于他们的氧化还原电势的差异,导致细菌呼吸链的电子递体对腐殖质物质和偶氮键的亲和力不同,从而使不同腐殖质浓度对偶氮键还原产生了不同的影响。     

堆肥中木质素降解微生物对腐殖质形成的作用

堆肥化是处理有机固体废物的主要方法之一。但传统堆肥法存在历时长、肥效低等问题 ,因此加速腐殖化进程可提高堆肥效率和堆肥质量。综述了堆肥中降解木质素的微生物种类的腐殖质的组成 ,介绍了木质素降解与腐殖质形成的关系 ,最后阐述了堆肥中各木质素降解微生物对腐殖质形成的作用。     

Bacterial anaerobic respiration and electron transfer relevant to the biotransformation of pollutants

Bacterial anaerobic respiration is one of the most ancient and essential metabolism processes, possessing the characteristics of both flexibility and high diversity, and a very close relationship with the physiological function in the ecological environment. Under anaerobic conditions, bacteria and anthropogenic substances can form coupling process facilitating terminal electron transfer. Several forms of bacterial anaerobic respiration and electron transfer related to the biotransformation of pollutants, including respiration with humics, sulfonates, halogenated chemicals, azo compounds, TNTs, metallic and non-metallic elements, are reviewed in this paper. These respirations and electron transfers on diverse electron acceptors in the environment have important biotechnological implications because these biochemical reactions have their roles on the transformation/degradation of toxic substances and the cycling of organic carbon as well as many inorganic elements. Furthermore, remediation of sites contaminated with toxic pollutants based on bacterial anaerobic respirations is being recognized widely.     

Contribution of quinone-reducing microorganisms to the anaerobic biodegradation of organic compounds under different redox conditions

The capacity of two anaerobic consortia to oxidize different organic compounds, including acetate, propionate, lactate, phenol and p-cresol, in the presence of nitrate, sulfate and the humic model compound, anthraquinone-2,6-disulfonate (AQDS) as terminal electron acceptors, was evaluated. Denitrification showed the highest respiratory rates in both consortia studied and occurred exclusively during the first hours of incubation for most organic substrates degraded. Reduction of AQDS and sulfate generally started after complete denitrification, or even occurred at the same time during the biodegradation of p-cresol, in anaerobic sludge incubations; whereas methanogenesis did not significantly occur during the reduction of nitrate, sulfate, and AQDS. AQDS reduction was the preferred respiratory pathway over sulfate reduction and methanogenesis during the anaerobic oxidation of most organic substrates by the anaerobic sludge studied. In contrast, sulfate reduction out-competed AQDS reduction during incubations performed with anaerobic wetland sediment, which did not achieve any methanogenic activity. Propionate was a poor electron donor to achieve AQDS reduction; however, denitrifying and sulfate-reducing activities carried out by both consortia promoted the reduction of AQDS via acetate accumulated from propionate oxidation. Our results suggest that microbial reduction of humic substances (HS) may play an important role during the anaerobic oxidation of organic pollutants in anaerobic environments despite the presence of alternative electron acceptors, such as sulfate and nitrate. Methane inhibition, imposed by the inclusion of AQDS as terminal electron acceptor, suggests that microbial reduction of HS may also have important implications on the global climate preservation, considering the green-house effects of methane.     

Exocellular electron transfer in anaerobic microbial communities

Exocellular electron transfer plays an important role in anaerobic microbial communities that degrade organic matter. Interspecies hydrogen transfer between microorganisms is the driving force for complete biodegradation in methanogenic environments. Many organic compounds are degraded by obligatory syntrophic consortia of proton-reducing acetogenic bacteria and hydrogen-consuming methanogenic archaea. Anaerobic microorganisms that use insoluble electron acceptors for growth, such as iron- and manganese-oxide as well as inert graphite electrodes in microbial fuel cells, also transfer electrons exocellularly. Soluble compounds, like humic substances, quinones, phenazines and riboflavin, can function as exocellular electron mediators enhancing this type of anaerobic respiration. However, direct electron transfer by cell-cell contact is important as well. This review addresses the mechanisms of exocellular electron transfer in anaerobic microbial communities. There are fundamental differences but also similarities between electron transfer to another microorganism or to an insoluble electron acceptor. The physical separation of the electron donor and electron acceptor metabolism allows energy conservation in compounds as methane and hydrogen or as electricity. Furthermore, this separation is essential in the donation or acceptance of electrons in some environmental technological processes, e.g. soil remediation, wastewater purification and corrosion.     

Humate-induced activation of human granulocytes

Naturally occurring humic substances are particular chemical compounds which are found in humus. They bind to carbohydrates, amino acids and steroids by means of hydrogen bonds, covalent bonds and epsilon donor-acceptor complexes. Three specimens of low-molecular humic substances were tested (two naturally occurring humates and one synthetically prepared humate). They were all capable of stimulating certain functions of human neutrophils (PMN), such as the respiratory burst which results in the production of toxic oxygen compounds. This PMN stimulation can be demonstrated with the help of chemiluminescence, as well as by cytochemistry and with the electron microscope. The main product of the humate-induced PMN response is H2O2. There was no activation of neutrophilic chemokinesis or chemotaxis. It is suggested that the low-molecular humic substances originating from decaying organic material contain chemical structures which can act as signals to change dormant PMN into activated cells.     

Degradation and transformation of humic substances by saprotrophic fungi: processes and mechanisms

Humic substances represent the main carbon reservoir in the biosphere, estimated at 1600 × 10¹⁵ g C. Due to their crucial role in reductive and oxidative reactions, sorption, complexation and transport of pollutants, minerals and trace elements, sustaining plant growth, soil structure and formation, and control of the biogeochemistry of organic carbon in the global ecosystem, humic substances are extremely important to environmental processes. Saprotrophic fungi active in the decomposition process of humic substances include mainly ascomycetes and basidiomycetes, which are both common in the upper layers of soils. White rot and litter decomposing fungi are the most important organisms in the degradation and mineralization of refractory organic matter (OM), whereas ascomycetes are mainly involved in the modification and polymerization of humic substances. The mechanisms of degradation probably involve mainly a variety of non specific oxidizing enzymes. This review provides an overview of the subject, while bridging two main disciplines: soil OM chemistry and fungal microbiology. It is aimed to highlight problems, unsolved questions and hypotheses.     

Reduction of humic substances by halorespiring, sulphate-reducing and methanogenic microorganisms

Physiologically distinct anaerobic microorganisms were explored for their ability to oxidize different substrates with humic acids or the humic analogue, anthraquinone-2,6-disulphonate (AQDS), as a terminal electron acceptor. Most of the microorganisms evaluated including, for example, the halorespiring bacterium, Desulfitobacterium PCE1, the sulphate-reducing bacterium, Desulfovibrio G11 and the methanogenic archaeon, Methanospirillum hungatei JF1, could oxidize hydrogen linked to the reduction of humic acids or AQDS. Desulfitobacterium dehalogenans and Desulfitobacterium PCE1 could also convert lactate to acetate linked to the reduction of humic substances. Humus served as a terminal electron acceptor supporting growth of Desulfitobacterium species, which may explain the recovery of these microorganisms from organic rich environments in which the presence of chlorinated pollutants or sulphite is not expected. The results suggest that the ubiquity of humus reduction found in many different environments may be as a result of the increasing number of anaerobic microorganisms, which are known to be able to reduce humic substances.     

Formation of non-bioavailable organic residues in soil: Perspectives for site remediation

Whenever possible, total clean-up of soils and sediments should have priority over methods to contain the pollutants in the soil environment in a way which reduces their potential eco-toxicological effects. Nevertheless, often a very important fraction of the pollutant remains non-available to the cleaning process, either physico-chemical or biological. This constitutes a major obstacle for both environmental technologists and legislators. Yet, the concept of non-extractable organic residues is well accepted in the EU-legislation for pesticides. In this context, an assessment is made to bind organic pollutants to soil. Physical sorption (comprising surface adsorption, absorption and migration in micro- and nanopores) and chemical binding are examined in terms of quantities and kinetics. Chemical binding offers at present no direct possibilities for practice. Making toxic pollutants less bioavailable by increasing physical sorption represents a pragmatic approach to contractors and regulators. For organic pollutants with acceptable concentration in the soil solution of the order of 1 mg/l, a sorptive loading of the order of 10 000 mg pollutant per kg activated carbon respectively organic matter appears a workable assumption. In case of toxic substances such as pesticides which have a 1000 times lower acceptable level, a sorptive loading of up to 10 mg organic pollutant per kg sorbent can be used. Non-bioavailable pollutants can be considered as representing no direct harm to the environment. In practice, the application of up to 100–200 kg dry weight quality compost per ton dry weight soil or alternatively the supplementation of other sorbents such as powdered activated carbon (up to 100 kg per ton soil) offer possibilities to cost-effective remediation of organic pollutants. Yet, aspects of worst-case ecotoxicology as e.g. excessive leaching with dissolved humic substances or ingestion of soil containing substantial amounts of poorly extractable contaminants by human and soil organisms, need to be examined.     

A shift in the current: new applications and concepts for microbe-electrode electron exchange

Perceived applications of microbe-electrode interactions are shifting from production of electric power to other technologies, some of which even consume current. Electrodes can serve as stable, long-term electron acceptors for contaminant-degrading microbes to promote rapid degradation of organic pollutants in anaerobic subsurface environments. Solar and other forms of renewable electrical energy can be used to provide electrons extracted from water to microorganisms on electrodes at suitably low potentials for a number of groundwater bioremediation applications as well as for the production of fuels and other organic compounds from carbon dioxide. The understanding of how microorganisms exchange electrons with electrodes has improved substantially and is expected to be helpful in optimizing practical applications of microbe-electrode interactions, as well as yielding insights into related natural environmental phenomena.