腐殖质氧化还原和电子转移特性研究进展

腐殖质在无氧和有氧条件下都具有一定的氧化还原能力,其氧化还原能力与氧化还原电势有关,而腐殖质的氧化还原电势受芳香度、取代基类型、取代位置等因素影响.除氧化还原能力外,腐殖质还能介导电子转移,其电子转移能力受腐殖质结构和所处环境两大因素影响.水体腐殖酸比土壤和沉积物腐殖酸具有相对较小的电子接受能力(EAC)和较大的提供电子能力(EDC);p H、温度、光照、氧气条件和微生物活动等因素均对腐殖质氧化能力和电子转移能力具有重要影响.腐殖质可以介导重金属和有机污染物的还原降解,不同重金属还原反应效率差异较大,其中Fe(Ⅲ)盐还原速率最高;有机污染物降解速率从大到小为六氯乙烷(HCE)>四氯化碳>三溴甲烷.目前在腐殖质氧化还原特性和电子转移能力研究中还存在诸多不足,需要广大学者做进一步探究.     

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.     

土壤腐殖质氧化还原电位及其相应电子转移能力分布

本实验以土壤提纯腐殖酸及国际标准腐殖酸(Pahokee Peat Humic Acid,PPHA)为研究对象,测定腐殖酸与3种不同氧化还原Eh的铁矿物(水铁矿(Ferrihydrite)Eh0'=0 m V,赤铁矿(Fe2O3)Eh0'=-287 m V,磁铁矿(Fe3O4)Eh0'=-314 m V及溶解性铁铁氰化钾Eh0'(Ferricyanide=+430 m V)的氧化还原反应,结合Eh-p H计的实验体系,分析腐殖质分子氧化还原官能团的分布规律.磁铁矿同时拥有二价和三价铁离子,具有与腐殖质发生氧化或者还原反应的条件.不同土壤腐殖酸与磁铁矿反应表现的还原/氧化能力不同,这是由于腐殖酸的不同Eh引起,在此基础上测量显示原态下腐殖酸Eh值大约为245 m V,H2还原后,Eh值降低至-620 m V,表明腐殖酸的氧化还原Eh是不同种类和数量的氧化还原官能团Eh叠加值.分析标准腐殖酸在不同氧化还原Eh下的氧化/还原能力显示原态下标准腐殖酸的氧化还原Eh分布比较均匀,还原态腐殖酸在Eh0范围存在易于被氢气还原的官能团,具有显著的还原能力.     

电子穿梭体介导土壤锑还原成矿的微生物机制

微生物锑还原成矿有助于降低土壤锑的生物有效性和移动性,是土壤锑污染修复的重要策略之一。电子穿梭体AQDS能够加速土壤富集菌群锑还原速率,可能与其促进微生物呼吸及细胞生长有关。理解电子穿梭体（ES）介导微生物锑还原过程与机制可为土壤锑污染控制提供关键理论支撑。醌类和黄素类电子穿梭体（AQDS和FMN）存在时可能改变微生物呼吸代谢中的电子传递过程,然而ES介导下的微生物锑还原过程及转录响应机制尚不清楚。利用锑污染稻田土壤分离的兼性厌氧锑还原细菌Mesobacillus jeotgali PS1作为研究对象,探究醌类和黄素类电子穿梭体（AQDS和FMN）对菌株PS1锑还原过程及关键功能基因转录活性的影响。结果表明,菌株PS1驱动Sb(Ⅴ)还原为Sb(Ⅲ)过程中水溶态Sb(Ⅲ)随培养时间先累积后下降,培养72 h后水溶态锑去除率为64%,生成十四面体方锑矿,表明菌株PS1驱动锑还原成矿有助于锑的钝化。两种ES能够加速细菌锑还原反应,而对胞外生成的方锑矿晶型没有影响。通过定量分析菌株PS1潜在功能基因转录表达活性,结果表明AQDS相比FMN更能促进菌株PS1细胞膜二甲基亚砜还原酶（DMSOR）基...     

硫自养高氯酸盐还原菌和反硝化菌的培养和驯化

为了提高硫自养高氯酸盐和硝酸盐的还原效率,进行了以单质硫(S0)和好氧污泥分别作为电子供体和接种污泥培养驯化硫自养高氯酸盐还原菌和反硝化菌的过程研究.结果显示,在厌氧条件下采用间歇周期运行的培养方式,高氯酸盐和硝酸盐的初始浓度分别从80 mg/L和40 mg/L逐渐增加到240 mg/L和120 mg/L时,去除率达到99%以上的周期随培养驯化时间的增加而逐渐缩短,从最初的7 d稳定在4 d,高氯酸盐和硝酸盐最终分别被还原为Cl-和N2.由于S0的歧化反应,SO42-的实际产生量高于理论产生量.培养驯化过程中pH在6.5-7.3范围内变化,适合硫自养高氯酸盐还原菌和反硝化菌生长、发育和繁殖的条件.PCR-DGGE图谱分析表明随着培养和驯化时间的增加微生物种群数量逐渐减少,污泥微生物群落能够迅速进行优胜劣汰,达到适应环境的目的.培养驯化末期的污泥中β变形杆菌纲处于优势地位,是硫自养高氯酸盐还原菌和反硝化菌的主要组成部分.因此,经培养驯化的微生物菌群具有较高的高氯酸盐和硝酸盐还原能力,本研究可为水中高氯酸盐和硝酸盐净化技术提供一定的理论依据和技术支持.     

微生物砷还原机制的研究进展

砷是一种剧毒物质,环境中的砷对人体健康存在潜在威胁,因此长期以来备受关注.微生物的各种代谢过程对砷在环境中的归趋起着重要作用,其中砷还原微生物能将吸附于固体矿物中的As(Ⅴ)还原为可溶性强的As(Ⅲ),使砷进入液相,从而加剧了地下水等饮用水源的砷污染.论文主要介绍了两种微生物砷还原机制(异化砷还原和细胞质砷还原)在作用...     

环境中汞的微生物还原过程及机制

汞是一种全球性的环境污染物.汞的还原过程可降低地表环境汞浓度,促进汞的大气传输,对汞的区域/全球循环、甲基化及生物积累具有重要的作用.地表环境微生物还原是汞还原的重要过程,在多种环境介质中均可发生.本文介绍了多种环境介质中微生物汞还原在汞生物地球化学循环中的重要作用,详细总结了有氧与缺氧条件下微生物汞还原的途径与机制,提出了微生物还原汞的其它可能机制,并对相关领域的研究进行了展望.     

腐殖质的光化学降解及其对环境污染物环境行为的影响

腐殖质是地表环境中最重要的有机组分,也是生态环境中最主要的吸光物质之一,对环境污染物的形态、迁移、毒性和生物可利用性有着重要的影响。文章综述了腐殖质的结构特征和光化学降解反应过程和机理,指出腐殖质的光敏化和光化学降解过程对环境污染物的环境行为和归宿有重要的影响。通常,腐殖质的光敏化作用在低质量浓度下,尤其在一定铁离子的协同作用下可促进有机污染物的降解,但高质量浓度的腐殖质由于其本身的吸光作用以及参与自由基的竞争则抑制有机污染物的降解。腐殖质的光化学降解过程降低了环境体系的pH和腐殖质的分子量、破坏了腐殖质的芳环结构、改变了紫外和可见光区域的吸收等,导致其与重金属离子和有机污染物结合能力的下降,造成水体或颗粒态中游离的污染物质量浓度增加,对生态系统将造成更大的危害。目前对腐殖质和环境污染物本身的光化学降解机理已较为清晰,今后应加强对自然水体或土壤系统中腐殖质光化学降解的影响因素,腐殖质光化学降解过程中结构特性的变化机理,以及腐殖质的结构特性与环境污染物结合性质之间的构效关系等方面的研究。特别是随着平流层臭氧空洞的增加,增强了到达地球表面的紫外线强度,研究紫外线增强对腐殖质和有机污染物的降解以及对生态系统的影响可进一步深刻理解太阳光辐射对污染物环境行为和归宿的影响。     

阻燃剂四溴双酚A的厌氧-好氧生物降解

采用清远电子垃圾拆解区附近河流底泥作为菌源,研究了四溴双酚A(TBBPA)在不同厌氧条件下的还原脱溴,并用驯化微生物好氧降解双酚A(BPA).实验发现,添加电子供体和产甲烷条件下,TBBPA分别在117 d和42 d实现100%去除.硫酸盐条件下,TBBPA在观察期内(160 d)的去除率为63%.驯化微生物可以将BPA矿化,并在pH 8、34℃、接种量10%条件下,40 mg·L~(-1)BPA在6 d内可被完全降解,具有最优的降解效果.BPA经对羟基苯乙酮、乳酸而最终转化为CO_2和水.厌氧-好氧微生物作用可实现TBBPA的彻底降解,为受TBBPA污染区域的原位修复提供了科学基础.     

垃圾渗滤液中有机物分子量的分布及在MBR系统中的变化

利用凝胶层析方法分析了垃圾渗滤液中有机物分子量的分布情况,并考察了利用膜生物反应器(MBR)处理垃圾渗滤液系统中有机污染物分子量的分布以及水溶性腐殖质(AHS)含量的变化．研究发现,垃圾渗滤液中的有机物主要由两部分组成,即分子量大于6000的大分子物质和分子量小于1500的小分子物质．大分子物质主要是水溶性腐殖质,而小分子物质主要由挥发性有机酸及水溶性腐殖质组成．大分子的AHS难以被微生物降解,但能被微滤膜截留．大部分小分子的AHS既难以被微生物降解,又不能被膜截留,是构成MBR处理出水COD的主要成分．     

腐殖质对BDE209、Pb和Cd在水/沉积物界面吸附行为的影响

水/沉积物界面是有机和无机污染物的物理、化学等过程的重要载体和场所。为了探究溴代阻燃剂与重金属在水/沉积物体系的分布规律,以电子垃圾拆解地水体中常见的溴代阻燃剂十溴联苯醚(BDE209)和重金属Pb、Cd为目标污染物,考察了腐殖质对BDE209、Pb和Cd在水/沉积物界面吸附行为的影响。红外光谱分析表明沉积物腐殖质活性基团包括醇、酚和羧基类等官能团;1H核磁共振分析显示沉积物腐殖质主要由碳水化合物与脂肪族类化合物组成。吸附试验结果表明,水体中腐殖质能够促进沉积物表面BDE209、Pb和Cd的释放,BDE209在水/沉积物体系的吸附行为主要受水溶性腐殖质的影响,而对Pb、Cd而言,负载于沉积物表面的碱溶性腐殖质比水溶性腐殖质对其分配行为的作用更显著。此外,沉积物组分对BDE209在水/沉积物体系的分配行为无显著影响;粘土组分对Pb、Cd的富集能力高于砂粒,并且对Pb的富集能力比Cd更为突出。     

沉积物不同天然有机组分对氨氮吸附特征的影响

为估算沉积物不同天然有机组分吸附态氨氮携载量．采用平衡吸附法研究西辽河沉积物不同天然有机组分对氨氮吸附特征的影响。结果表明,去除有机质后的沉积物对氨氮的吸附能力大大降低,其碳标化饱和吸附量（Гmoc）和吸附分配系数（Koc）分别为重组的55．30％和69．49％,说明有机质是影响氨氮在沉积物上吸附特征的主要因素。氨氮在轻组有机组分上的吸附以分配作用为主（Koc=85．57）;稳结态和紧结态腐殖质是形成沉积物疏松多孔团聚体结构的重要胶结物质,氨氮在重组有机组分上的吸附除分配作用外,还存在孔隙填充方式的吸附;重组有机组分中的紧结态腐殖质（胡敏素）对氨氮吸附起关键作用（Гmoc,=5857．78mg·kg-1）。轻组有机质、稳结态腐殖质和紧结态腐殖质携载的吸附态氨氮可分别按重组（Гmoc=3477．81mg·kg-1）的0．32、1．21和1．68倍估算。关键词：沉积物;天然有机组分;氨氮;吸附;碳标化吸附分配系数;碳标化饱和吸附量     

西湖沉积物有机质特征

分析了西湖沉积物腐殖质的组成及腐殖酸的红光谱特性,结果显示西湖沉积物腐殖质具有典型的湖泊沉积物腐质特征,腐殖化程度较高;结合形分析表明,腐殖质中：胡敏素〉胡敏酸〉富里酸〉脂类,钱塘江引水工程、水面种植荷花明显改变了沉积物有机质的构成,对西湖的碳和富营养化状况有显著影响。     

Determination of Microbial Activity in Marine Sediments by Resazurin Reduction

A simple method is presented to evaluate microbial activity in aquatic sediments. The method is based on resazurin reduction by microbial electron transport chains and reduced chemical compounds present in the sample. The addition of m-cresol, which inhibits enzyme activity, allows one to measure microbial metabolism by difference. Small aliquots of sediment (about 1 g FW) are incubated at 20°C with resazurin solution, with and without m-cresol. The sample is then filtered and the unreduced resazurin is measured at 600 nm.

Testing the method with a bacterial suspension gave a resazurin reduction of 89 μg/h/10⁹ cells. In a few marine coastal sediment samples, the resazurin reduction in aerobic conditions was in the range of 0.31 to 219.3 μg/h/g DW, which is equivalent to an oxygen consumption of 0.02 to 15.32 μg/h/g DW.     

The effect of microbial activity upon the sedimentary sulphur cycle

The sulphate content of an intertidal sediment at Anglesey (UK) was shown to vary during the year, the sulphate-reducing activity of the microbial population being limited by low temperature during winter, and by the low numbers of sulphate-reducing bacteria during May, 1969. A corresponding annual variation of the sedimentary sulphide could not be demonstrated, and the sulphide which was formed biologically during the course of the year was almost entirely lost from the sediment. This loss of sulphide was probably due to subsurface oxidation; and flushing, by water entering at the base of the sediment. It is suggested that sulphide was only precipitated within the sediment during summer when sulphate reduction was active, and even then only during part of the tidal cycle when flushing did not occur.     

Microbial activities in a permanently stratified estuary. I. Primary production and sulfate reduction

Physical, chemical and biological parameters have been measured in the water column of Saelenvann, a shallow estuary in western Norway, over a period of nearly 4 years. Due to the presence of a permanent pycnocline, a layer of anoxic water with high sulfide and ammonia concentrations persists under a layer of oxic water with normal photosynthetic and heterotrophic microbial activities. The magnitude of the sulfate reduction in the estuary was correlated with the magnitude of primary productivity. Increases in sulfate reduction following increased primary productivity occurred first in the free anoxic water, and only after an appreciable time lag in the upper sediment layers. The highest rates of sulfate reduction were found just below the interface with the oxic water and in the upper few centimeters of the sediment. It is estimated that twice as much sulfate is reduced in the free water mass as in the sediment. During the summer, the amount of organic material produced by primary productivity exceeds the amount of organic material mineralized by sulfate reduction, the inverse being the case during the winter.     

风沙土不同有机组分对氨氮的解吸特征影响

采用平衡解吸法研究了风沙土不同有机组分对氨氮的解吸特征影响。结果表明,去除腐殖质后的风沙土氨氮解吸比例增加（由0.58增加到0.68）,同时,解吸迟滞性指数显著降低（由0.067降低到0.021）,说明腐殖质是影响风沙土氨氮解吸特征的重要因素;氨氮在轻组有机组分上的表面分配作用吸附是导致解吸比例增大,解吸迟滞性指数减小的原因;重组有机组分中的紧结态腐殖质（胡敏素）对氨氮的解吸起关键作用,它不但解吸比例较低（Dr=0.23）,而且解吸迟滞性指数较大（TⅡ=0.458）;氨氮在紧结态和稳结态腐殖质所形成的团聚体颗粒微孔隙中的不可逆吸附是导致解吸比例降低、解吸迟滞性指数增大的根本原因;考查土壤对氨氮的解吸特征不但要考虑有机质的含量,更要考虑有机质的存在形态,它也是影响土壤氨氮解吸特征的重要因素,轻组有机组分、重组有机组分及重组有机组分中的稳结态加紧结态腐殖质（HⅡ＋HⅢ组）和紧结态腐殖质（HⅢ组）携载的吸附态氨氮进入水体后,对上覆水体的扩散通量可分别按其饱和吸附量的0.94、0.58、0.33和0.23倍估算。     

Impact of the polychaete Capitella sp. I on microbial activity in an organic-rich marine sediment contaminated with the polycyclic aromatic hydrocarbon fluoranthene

Polychaetes belonging to the genus Capitella are often present in high numbers in organic-rich sediments polluted with, e.g., oil components, and Capitella spp. may have a great impact on the biogeochemistry of these sediments. We examined the influence of Capitella sp. I on microbial activity in an organic-rich marine sediment contaminated with the polycyclic aromatic hydrocarbon, fluoranthene. Capitella sp. I were added to microcosms (10 000 ind m⁻²) and the impact of a pulse-sedimentation of fluoranthene-contaminated sediment (3 mm layer) was studied for a period of 12 d after sedimentation. The sediment oxygen uptake and total sediment metabolism (TCO₂ production) increased in cores with worms (71 to 131%), whereas the anaerobic activity, measured as sulfate reduction rate 12 d after sedimentation, was lower compared to cores without worms. The effect of fluoranthene on sulfate reduction was most pronounced in the presence of worms, with a 34% reduction versus 16% in cores without worms. The reduced sulfur pools in cores with worms were smaller than in cores without worms, suggesting that the reduced anaerobic activity was caused by increased oxidation of the sediment, which may favor O₂ and other electron-acceptors (e.g. NO₃ ⁻, Fe³⁺, Mn⁴⁺) in organic matter decomposition. The sediment oxygen uptake and TCO₂ production did not show significant changes due to fluoranthene treatment, indicating that these parameters were either less sensitive to fluoranthene stress or recovered more rapidly (i.e. within 48 h) than sulfate reduction rates. Bioturbation by Capitella sp. I altered the depth profile of fluoranthene such that fluoranthene was found in deeper sediment layers (down to 2 cm) where diffusional loss and microbial breakdown probably are reduced relative to surface layers. In cores without worms, fluoranthene was found down to 1 cm, with 75% remaining in the upper 5 mm. Received: 5 December 1996 / Accepted: 11 February 1997     

Microbial responses to the use of NaClO in sediment treatment

• Chlorine addition enhanced the release of TOC, TN from the sediment. • Chlorine has a long-term negative effect on microbial richness. • Usually enzymes lose activity, and expression of genes was downregulated. • Carbon degradation and nitrification might be strongly inhibited. Chlorine is often used in algal removal and deodorization of landscape waters, and occasionally used as an emergency treatment of heavily polluted sediments. However, the ecological impact of this practice has not been fully studied and recognized. In this study, NaClO at 0.1 mmol/g based on dry weight sediment was evenly mixed into the polluted sediment, and then the sediment was incubated for 150 days to evaluate its microbial effect. Results showed that NaClO addition enhanced the release of TOC, TN, Cr and Cu from the sediment. The microbial richness in the examined sediment decreased continuously, and the Chao1 index declined from 4241 to 2731, in 150 days. The microbial community composition was also changed. The abundance of Proteobacteria and Bacteroidetes increased to 54.8% and 4.2% within 7 days compared to the control, and linear discriminant analysis (LDA) showed gram-negative bacteria and aerobic bacteria enriched after chlorination. The functional prediction with PICRUSt2 showed the functions of the microbial community underwent major adjustments, and the metabolic-related functions such as carbon metabolism, including pyruvate and methane metabolisms were significantly inhibited; besides, 15 out of 22 analyzed key enzymes involved in C cycling and 6 out of 12 key enzymes or genes involved in N cycling were strongly impacted, and the enzymes and genes involved in carbon degradation and denitrification showed remarkable downregulation. It can be concluded that chlorination posed a seriously adverse effect on microbial community structure and function. This study deepens the understanding of the ecological effects of applying chlorine for environmental remediation.     

A simulation model for organic phosphorus transformation in a forest soil ecosystem

A numerical model which simulates the decomposition of litter and mineralization and immobilization of P in the humus layer of a temperate forest (beech site of Solling) is described. The model takes into account the effect of moisture, temperature and C/N ratio. The simulated concentration of P in the effluent of the humus layer agrees well with the measured values. The model predicts an increase in the C/P ratio of the unde-composed litter with time and that there is no direct mineralization of P from litter without passing through a microbial body. The net rate of mineralization is, however, always positive with its highest peak in July. Maximum immobilization of P from solution occurs in June and the minimum in January.The model is stable against changes in the litter input, its C/P ratio and other initial conditions, but it is very sensitive to changes in the efficiency factor which represents the fraction of decomposed C incorporated into microbial tissue. This is a site-specific model but can be used for grassland or agricultural systems with changes in certain parameters.