海洋沉积物甲烷厌氧氧化作用(AOM)及其对无机硫循环的影响

甲烷厌氧氧化作用(AOM)在调控全球甲烷收支平衡以及缓解因甲烷引起的温室效应等方面扮演着十分重要的角色,成为近些年来海洋生物地球化学领域的研究热点之一.一般而言,海洋沉积物孔隙水硫酸盐还原主要是通过2种反应途径来完成,即氧化有机质途径和AOM途径.长期以来,与有机质氧化途径相关的硫酸盐还原作用研究已有充分展示,而由AOM驱动的硫酸盐还原及其对自生硫化铁形成与埋藏的重要贡献却被严重低估.侧重从生物地球化学、同位素地球化学等角度,综述近些年来不同环境条件下海洋沉积物AOM作用发生的地球化学证据和AOM对沉积物孔隙水硫酸盐消耗比例的贡献大小及其调控因素.AOM过程产生的H2S会与沉积物中活性铁结合形成自生铁硫化物.与沉积物浅表层条件相比,AOM过程固定的自生铁硫化物不容易发生再氧化,更利于在沉积物中埋藏保存起来.AOM与海洋沉积物硫酸盐还原作用相偶联,由AOM驱动的硫酸盐还原过程对海底自生铁硫化物形成与埋藏的重要贡献不容忽视.该综述有助加深对海洋沉积物AOM作用的认识及其对硫循环的全面理解.     

海洋中溶存甲烷研究进展

CH₄是大气中的重要微量气体，对全球变暖和大气化学有重要作用。海洋是大气甲烷的重要源和汇。开展海洋中溶存甲烷的研究，有助于了解海洋对大气甲烷和全球变化的贡献。综述了海洋中溶存甲烷的研究现状，着重介绍了海洋中溶存甲烷的分布特征、海气交换通量的估算及其生物地球化学循环，并探讨了该领域研究中存在的问题。     

海洋天然气水合物勘查和识别新技术:地质微生物技术

当前国内外海洋天然气水合物勘查和评价发展趋势要求有更多具有精细探测和评价功能的技术,这给地质微生物水合物探测技术的研发和应用提出了需求和挑战。简要介绍了当前水合物成藏或沉积环境研究中所涉及的主要微生物类别及其主要关系,它们绝大多数是适应海底深部低温高压环境的厌氧极端生物。其中重要类群是为天然气提供气源的产甲烷古生菌、参与甲烷厌氧氧化过程的甲烷氧化古生菌和硫酸盐还原细菌。介绍了国内外几个地质微生物探测技术的实例,包括历史悠久的"微生物油气勘探"技术、近十年来发展起来的微生物计数法、群落结构和标志类别法;另外,对新露头角的微生物生物标志物法等其他方法也给予简要介绍。     

产甲烷菌生物地球化学作用的研究

地壳中,工业甲烷的形成机制主要受微生物和热作用两种因素的制约。70年代以来,国外对生物甲烷的形成机理进行了大量的研究,尤其是在产甲烷菌生物化学方面,取得了很大进展。HS-CoM和CH_3-S-CoM的发现,为深入研究成岩作用早、中期天然气的形成及微生物所进行的生物地球化学作用提供了可能性。本文对这一问题进行了综述,并论述了这项研究工作的重大意义。     

微生物介导的土壤甲烷循环及全球变化研究

甲烷是主要的温室气体之一, 目前在大气中的含量达1.7×10-6m3·m-3, 比工业革命前增加了115%, 并以1%年增长速度稳定增长. 甲烷吸收太阳远红外光的能力比CO2高20～30倍, 对全球增温的贡献率达15%. 多年来对大气甲烷的产生、转运和循环以及调控的研究表明, 80%以上的甲烷是通过微生物的活动产生的, 一部分在进入大气前被微生物吸收利用, 这样, 大气中甲烷的净含量绝大部分是甲烷产生微生物和甲烷营养微生物相互作用的结果. 因此, 研究甲烷产生菌和甲烷氧化菌的活动规律和生态学特征, 有利于揭示微生物介导的甲烷循环过程, 并探索减排的措施. 已知有80多种甲烷产生菌和100余种甲烷氧化菌, 它们的种类和生态多样性比较广泛, 环境差异和波动影响它们的生理代谢活性, 从而导致甲烷排放的波动性和不确定性. 在未来全球变化条件下, 天然湿地作为重要的甲烷源之一, 如何响应和反馈环境的变化是研究的重点领域.     

天然气水合物分解及其生态环境效应研究进展

了解大陆／大洋边缘地区天然气水合物形成与分解及其在海底沉积物、水体及海底化学自氧生物群落中的一系列物理、化学及生物作用有助于我们在全球和区域尺度上探讨天然气水合物分解对气候变化的影响;天然气水合物在碳循环中的作用和大陆边缘流体活动与物质交换机制等问题。从水合物分解与全球变暖、贫／缺氧甲烷氧化作用、自生矿物沉淀、化学自养生物群落等方面综述了水合物的环境生态效应研究进展。天然气水合物的形成／分解及 其对海洋乃至全球环境生态变化的影响,深刻地反映了地球上岩石圈、水圈、大气圈和生物圈之间相互联系与相互作用,生物,特别是微生物对全球CH 4的平衡和自生矿物沉淀至关重要。     

华北地台串岭沟组砂脉中自生碳酸盐沉淀和自生黄铁矿——中元古代甲烷厌氧氧化的沉积证据

华北中元古界串岭沟组暗色页岩中普遍发育的砂脉构造被解释为气体逃逸形成的沉积构造。在砂脉和相邻围岩中发现有自生碳酸盐沉淀和自生黄铁矿。自生碳酸盐主要由白云石组成,表现为微晶质条带或隐晶质斑块状胶结物。微晶白云石条带多出现在有机质纹层密集发育的部位,沿微生物膜两侧发育;而隐晶质斑块多以胶结物形式充填粒间孔隙或沿砂脉外缘密集产出。围岩中共生草莓状黄铁矿,砂脉中有具环带黄铁矿。这种特殊的矿物组构以及富有机质沉积和丰富的微生物成因构造(MISS)均表明串岭沟组形成于缺氧环境。层面发育的气泡构造为砂脉的气体逃逸成因提供了支持,而自生碳酸盐和黄铁矿则是沉积浅层硫酸盐-甲烷转换带(SMTZ)甲烷厌氧氧化(AOM)和细菌硫酸盐还原(BSR)的产物;气体源于有机质的厌氧分解和甲烷菌活动。砂脉中发现有疑似微生物化石,围岩含古菌和硫细菌生物标志物,表明有发生AOM和BSR作用的条件。串岭沟组砂脉中识别的自生碳酸盐沉淀及其AOM成因对进一步认识中元古代古海洋与古气候条件具有重要意义。由于海洋的低硫酸盐浓度,SMTZ带很浅,海底沉积层的甲烷仅少量被AOM消耗;而大量甲烷进入大气必然导致中元古代强烈的温室气候效应。     

垃圾填埋场覆层甲烷生物减排技术综述

垃圾填埋场服役期间会因微生物降解有机物释放大量甲烷,即使有气体收集装置,仍有甲烷逃逸到大气中。甲烷气体是造成温室效应的重要气体之一。甲烷氧化菌是以甲烷为唯一碳源的微生物,具有其优良的甲烷氧化效能。在中小型填埋场、老旧填埋场及开启集气装置已不再经济的大型填埋场,可在填埋场覆层中掺入甲烷氧化菌,对甲烷进行生物氧化,减少垃圾填埋场的甲烷释放量,从而减少温室效应,达到环保的目的。文章回顾了近些年国内外对甲烷氧化菌及其甲烷氧化效能的相关研究,对甲烷氧化菌的分类及其甲烷氧化机理,影响甲烷氧化菌氧化效能的因素以及甲烷氧化菌在垃圾填埋场中的应用等研究成果进行了总结,并对其今后的研究和应用提出了展望。     

微生物对金属元素的浸出作用及其应用研究进展

文章简述了表生地质环境中的微生物对Au、Ag等贵金属元素和Cu、Pb、Cd、As、Hg等重金属元素的浸出作用及其在探矿、浸取选矿、土壤污染评价和修复、城市污泥和废水处理等方面的应用研究进展。指出：深入研究地质体中的微生物与金属元素的相互作用和机理，将是地球科学的重要研究动态之一。     

论河北丰宁牛圈银（金）矿床的成矿时限问题

南沙海槽的构造和沉积受控于南海的构造运动和加里曼丹西北大陆边缘的演化,具有适于天然气水合物形成的物源基础、温压条件、输导系统和储藏场所。似海底反射层(BSR)出现在水深650~2 800 m、海底下65~350 m深的晚中新世沉积物中,与褶皱、逆冲推覆构造及穹窿构造有关;沉积物中的甲烷含量和孔隙水的SO24-含量表现出异常变化特征,硫酸盐-甲烷界面(SMI)深度仅为8~11 m;表层沉积的自生石膏和黄铁矿的成岩环境与甲烷流体排溢引起的厌氧甲烷氧化(AOM)有关,这些地球物理和地球化学指标均指示南沙海槽发育天然气水合物。研究表明,南沙海槽沉积物的甲烷以二氧化碳还原型微生物成因为主,少量为混合气,海槽东南部可能是最有潜力的天然气水合物远景区。     

Simulation of advective methane flux and AOM in Shenhu area, the northern South China Sea

Anaerobic oxidation of methane (AOM) occurring in the marine sediment is an important process for methane cycle and methane sequestration. In this work, a one-dimensional numerical model was developed to study the distribution of advective methane flux with the AOM process. The model has been applied to investigate the gas hydrates bearing sediments of Shenhu areas located in the northern South China Sea, where advective methane transport was detected. The modeling results suggest that methane flux will be consumed in the sediment column via dissolution, sorption, and AOM reaction. Only when the methane flux was one order of magnitude higher than current level, then a portion of methane will enter water column and possibly escape to the atmosphere. The numerical simulation also revealed that, due to the lower permeability of the silt–clay sediments, a much thicker sulfate-methane transition zone exists in the Shenhu area, where AOM is able to consume more.     

Anaerobic oxidation of methane (AOM) in marine sediments from the Skagerrak (Denmark): II. Reaction-transport modeling

A steady-state reaction-transport model is applied to sediments retrieved by gravity core from two stations (S10 and S13) in the Skagerrak to determine the main kinetic and thermodynamic controls on anaerobic oxidation of methane (AOM). The model considers an extended biomass-implicit reaction network for organic carbon degradation, which includes extracellular hydrolysis of macromolecular organic matter, fermentation, sulfate reduction, methanogenesis, AOM, acetogenesis and acetotrophy. Catabolic reaction rates are determined using a modified Monod rate expression that explicitly accounts for limitation by the in situ catabolic energy yields. The fraction of total sulfate reduction due to AOM in the sulfate-methane transition zone (SMTZ) at each site is calculated. The model provides an explanation for the methane tailing phenomenon which is observed here and in other marine sediments, whereby methane diffuses up from the SMTZ to the top of the core without being consumed. The tailing is due to bioenergetic limitation of AOM in the sulfate reduction zone, because the methane concentration is too low to engender favorable thermodynamic drive. AOM is also bioenergetically inhibited below the SMTZ at both sites because of high hydrogen concentrations (∼3-6 nM). The model results imply there is no straightforward relationship between pore water concentrations and the minimum catabolic energy needed to support life because of the highly coupled nature of the reaction network. Best model fits are obtained with a minimum energy for AOM of ∼11 kJ mol⁻¹, which is within the range reported in the literature for anaerobic processes.     

综合大洋钻探计划311航次沉积物中自生碳酸盐岩碳、氧稳定同位素特征

为了探索水合物背景下沉积物中自生矿物响应,对采自综合大洋钻探计划（IODP）311航次沉积物中自生碳酸盐岩颗粒进行了矿物组成、形貌特征和碳、氧稳定同位素特征等研究。X光粉晶衍射（XRD）和扫描电镜（SEM）结果显示碳酸盐岩颗粒的主要矿物成分是铁白云石和方解石,呈多孔状结核和不规则状集合体产出。碳酸盐岩颗粒的碳稳定同位素δ¹³C_PDB低至-41.50‰,证实其碳源源自甲烷,其成因与甲烷厌氧氧化过程有关,印证了研究区存在海底甲烷渗漏现象,是甲烷水合物赋存区重要的识别标志之一。碳酸盐岩颗粒的氧稳定同位素δ¹⁸O_PDB总体上随着沉积物深度增加而减小,可能指示沉积物的背景温度由下而上（从早到晚）逐渐降低。研究结果提供了现代海洋天然气水合物背景下沉积物中自生碳酸盐岩的碳、氧稳定同位素记录,对于寻找我国海域天然气水合物资源,探索地史时期古海洋沉积物中类似的甲烷事件记录具有重要的理论和实践指导意义。     

综合大洋钻探计划311航次沉积物中自生黄铁矿及其硫稳定同位素研究

对综合大洋钻探计划(IODP)311航次652个岩心沉积物样品进行了自生黄铁矿颗粒筛选、显微形貌特征及其硫稳定同位素组成等初步研究。扫描电镜(SEM)照片显示黄铁矿以微球粒状和立方体状形貌产出,其成因与微生物作用和无机作用有关。黄铁矿的δ34SCDT值变化范围较大,从-35.4‰到+53.6‰,其成因与甲烷厌氧氧化作用(AOM)的关系密切。海水源为主的硫酸盐参与了沉积物上部的AOM过程,黄铁矿硫稳定同位素正偏的原因可能与较强的AOM作用和较多的残余硫酸盐参与有关。冷泉背景站位中黄铁矿的δ34SCDT值随着深度增加而增加,从浅表层的-35.83‰增加到深处的32.49‰,反映深处沉积物内黄铁矿形成过程中曾有过较多的残余硫酸盐参与还原,暗示其背景曾经是更高的甲烷通量和更强的AOM作用。研究结果提供了现代海洋天然气水合物背景下沉积物中自生黄铁矿及其硫稳定同位素特征记录,对于寻找我国海域天然气水合物资源,探索地史时期古海洋沉积物中甲烷事件记录具有重要的意义。     

南海北部白云凹陷08CF7岩心沉积物的磁化率特征及其意义

海洋沉积物的磁性异常与甲烷渗漏活动及其产物密切相关。为揭示南海北部天然气水合物区沉积物磁化率的变化特征及其意义,对白云凹陷08CF7岩心331个沉积物样品的磁化率进行测定和分析。08CF7岩心沉积物磁化率变化范围为554×10-6~2656×10-6SI,平均值为1141×10-6SI。磁化率随深度变化可分为0~188 cm、188~240 cm及240 cm以下等3段,分别与硫酸盐富集带、硫酸盐-甲烷转换界面(SMT)的上部过渡带及SMT相对应。研究表明,海底天然气渗漏是08CF7岩心沉积物磁化率异常变化的可能原因,其机理是：在强烈的还原环境中,甲烷厌氧氧化反应的产物HS-与沉积物中的Fe3+发生反应,形成顺磁性的黄铁矿。沉积物磁化率变化能快速了解SMT状况及其深度,提供了一种识别南海北部天然气水合物的间接方法。     

Global hydrocarbon seep-carbonate precipitation correlates with deep-water temperatures and eustatic sea-level fluctuations since the Late Jurassic

The anaerobic oxidation of methane (AOM) in marine sediments, most obviously at cold seeps, is a major sink for this important greenhouse gas and is associated with the precipitation of carbonates. The geological record of seep carbonates provides insights into the long-term dynamics of this process. Since the Late Jurassic, rates of seep-carbonate precipitation have been high during times of low sea levels and cold deep-water temperatures, and vice versa. One possibility is that sea-level fall decreases the thickness of the methane hydrate stability zone in the sediment so that gas hydrates decompose in deeper sediments, thereby increasing seepage and carbonate precipitation. Alternatively, low deep-water temperature facilitates gas hydrate formation on continental slopes and may thereby increase methane availability for AOM-performing consortia and associated carbonate precipitation. These correlations and their potential causes may be of interest for the modelling of global carbon budgets and of past and future climates.     

Formation of iron sulfide nodules during anaerobic oxidation of methane

The biomarker compositions of iron sulfide nodules (ISNs; upper Pliocene Valle Ricca section near Rome, Italy) that contain the ferrimagnetic mineral greigite (Fe₃S₄) were examined. In addition to the presence of specific terrestrial and marine biomarkers, consistent with formation in coastal marine sediments, these ISNs contain compounds thought to originate from sulfate reducing bacteria (SRB). These compounds include a variety of low-molecular-weight and branched alkanols and several non-isoprenoidal dialkyl glycerol diethers (DGDs). In addition, archaeal biomarkers, including archaeol, macrocyclic isoprenoidal DGDs and isoprenoidal glycerol dialkyl glycerol tetraethers are also present. Both SRB and archaeal lipid δ¹³C values are depleted in ¹³C (δ¹³C values are typically less than −50‰), which suggests that the SRB and archaea consumed ¹³C depleted methane. These biomarker and isotopic signatures are similar to those found in cold seeps and marine sediments where anaerobic oxidation of methane (AOM) occurs with sulfate serving as the terminal electron acceptor. Association of AOM with formation of greigite-containing ISNs could provide an explanation for documented remagnetization of the Valle Ricca sediments. Upward migration of methane, subsequent AOM and associated authigenic greigite formation are widespread processes in the geological record that have considerable potential to compromise paleomagnetic records.     

Anaerobic oxidation of methane and sulfate reduction along the Chilean continental margin

Anaerobic oxidation of methane (AOM) and sulfate reduction (SR) were investigated in sediments of the Chilean upwelling region at three stations between 800 and 3000 m water depth. Major goals of this study were to quantify and evaluate rates of AOM and SR in a coastal marine upwelling system with high organic input, to analyze the impact of AOM on the methane budget, and to determine the contribution of AOM to SR within the sulfate-methane transition zone (SMT). Furthermore, we investigated the formation of authigenic carbonates correlated with AOM. We determined the vertical distribution of AOM and SR activity, methane, sulfate, sulfide, pH, total chlorins, and a variety of other geochemical parameters. Depth-integrated rates of AOM within the SMT were between 7 and 1124 mmol m⁻² a⁻¹, effectively removing methane below the sediment-water interface. Single measurements revealed AOM peaks of 2 to 51 nmol cm⁻³ d⁻¹, with highest rates at the shallowest station (800 m). The methane turnover was higher than in other diffusive systems of similar ocean depth. This higher turnover was most likely due to elevated organic matter input in this upwelling region offering significant amounts of substrates for methanogenesis. SR within the SMT was mostly fuelled by methane. AOM led to the formation of isotopically light DIC (δ¹³C: −24.6‰ VPDB) and of distinct layers of authigenic carbonates (δ¹³C: −14.6‰ VPDB).