An organic geochemical study of KP-2 core on the mud volcano at Nankai Trough

Organic geochemical data was collected from a KP-2 piston core sample obtained from a mud volcano in the Nankai Trough, off the southeast coast of Japan. The Nankai Trough was investigated geologically and was found to have a large amount of methane hydrates. Biomarkers indicating anaerobic oxidation of methane (AOM) were expected to be found in the sediment of the mud volcano collected by KP-2 core. But the gas chromatography-mass spectrometry (GC-MS) analysis of the samples showed only one biomarker related to the methane-oxidizing Archaea, namely 2,6,10,15,19-pentamethyleicosane (PME), could be detected throughout the KP-2 core. Phytane was predominant in the upper part of the KP-2 core; however, a series of 2,2-dimethylalkanes (2,2-DMAs) were characterized in the lower part of KP-2 core. The individual δ¹³C values of 2,2-DMAs, which were − 29.1 to − 27.3‰ indicate that the origin of 2,2-DMAs was not related to methane-oxidizing Archaea.     

Humic Substances as a Mediator for Microbially Catalyzed Metal Reduction

The potential for humic substances to serve as a terminal electron acceptor in microbial respiration and to function as an electron shuttle between Fe(III)-reducing microorganisms and insoluble Fe(III) oxides was investigated. The Fe(III)-reducing microorganism Geobacter metallireducens conserved energy to support growth from electron transport to humics as evidenced by continued oxidation of acetate to carbon dioxide after as many as nine transfers in a medium with acetate as the electron donor and soil humic acids as the electron acceptor. Growth of G. metallireducens with poorly crystalline Fe(III) oxide as the electron acceptor was greatly stimulated by the addition of as little as 100 μM of the humics analog, anthraquinone-2,6-disulfonate. Other quinones investigated, including lawsone, menadione, and anthraquinone-2-sulfonate, also stimulated Fe(III) oxide reduction. A wide phylogenetic diversity of microorganisms capable of Fe(III) reduction were also able to transfer electrons to humics. Microorganisms which can not reduce Fe(III) could not reduce humics. Humics stimulated the reduction of structural Fe(III) in clay and the crystalline Fe(III) forms, goethite and hematite. These results demonstrate that electron shuttling between Fe(III)-reducing microorganisms and Fe(III) via humics not only accelerates the microbial reduction of poorly crystalline Fe(III) oxide, but also can facilitate the reduction of Fe(III) forms that are not typically reduced by microorganisms in the absence of humics. Addition of humic substances to enhance electron shuttling between Fe(III)-reducing microorganisms and Fe(III) oxides may be a useful strategy to stimulate the remediation of soils and sediments contaminated with organic or metal pollutants.     

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.     

Labile barite contents and dissolved barium concentrations on Blake Ridge: New perspectives on barium cycling above gas hydrate systems

Blake Ridge hosts an extensive gas hydrate system where escaping CH₄ is consumed through anaerobic oxidation of methane (AOM) at a sulfate–methane transition (SMT) in shallow sediment. Previous geochemical work on ridge crest sediment has documented Ba fronts above the SMT, and has suggested that these horizons can be used to constrain the evolution of the SMT and AOM over time. We expand on this concept and further test it by determining the labile Ba contents of sediment and the dissolved Ba²⁺ concentrations of pore waters at four ODP sites on Blake Ridge (on the crest at Sites 994, 995 and 997, and on the southern flank at Site 1059). Labile Ba contents are fairly low at all four sites (0.44 and 1.32 mmol/kg), except within 3 m above the SMT at Sites 994, 995 and 997, where they typically exceed 1.24 mmol/kg and can reach 11.3 mmol/kg. These Ba fronts have a diagenetic origin, and SEM analyses show them to be composed of microcrystalline barite. Site 1059 lacks a prominent Ba front. The lowest labile Ba contents generally underlie the Ba fronts and correlate to the base of the SMT. Dissolved Ba²⁺ concentrations are low (< 1–4 μM) from the seafloor to within 2 m above the main Ba front. Below this depth, they rapidly increase at Sites 994, 995, and 1059, reaching peak concentrations (to 57 μM) at the base of the SMT. By contrast, a rapid rise in dissolved Ba²⁺ is not observed at Site 997. Dissolved Ba²⁺ concentrations are only moderately high (10–25 μM) below the SMT at all four sites. Collectively, this information supports a diagenetic model where barite passing into the SMT dissolves, and some of the dissolved Ba²⁺ then migrates up to form an authigenic barite peak. The contrasting signatures at the different sites indicate non-steady-state differences in the overall process. The size of the peaks on the crest of Blake Ridge necessitates that the recycling of Ba across the SMT has been operating at the current sub-bottom depths for > 100 kyr. Thus, CH₄ escaping through the AOM has likely been fairly constant over this time. It is possible that the SMT is currently rising toward the seafloor at Site 1059.     

Biodegradability of trimethylbenzene isomers under the strictly anaerobic conditions in groundwater contaminated by gasoline

Trimethylbenzene (TMB), as a constituent of gasoline, is often expected to be used as a conservative tracer in anaerobic BTEX-contaminated groundwater site to correct for attenuation due to dispersion, dilution and sorption along a flow path. To evaluate the suitability of using TMB as a tracer and to better understand biodegradability of TMB in contaminated groundwater by gasoline under anaerobic conditions, laboratory microcosms were conducted with mixed nitrate/iron/sulfate electron-acceptor amendments, using aquifer materials collected from Canadian Forces Base (CFB), Borden, Ontario, Canada. The results showed that under denitrifying conditions, biodegradation of 1,3,5-TMB, 1,2,4-TMB and 1,2,3-TMB were relatively slow and after 204 days of incubation approximately 27, 24, and 16% of the initial concentrations, respectively, were degraded in the microcosms. Under sulfate-reducing conditions, TMB isomers were recalcitrant. In contrast, significant biodegradation of TMB was observed under iron-reducing conditions. 1,3,5-TMB, 1,2,4-TMB and 1,2,3-TMB were degraded to 44, 47, and 24% of initial concentrations with first-order biodegradation rate constants of 0.003, 0.006 and 0.013 d⁻¹, respectively. This study indicates that TMB biodegradation is insignificant under nitrate and sulfate-reducing conditions but significant under iron-reducing conditions. Therefore, the use of TMB as a tracer for interpreting removal of other biodegradable gasoline constituents such as BTEX requires caution, especially in the presence of iron-reducing conditions.     

南海北部琼东南海域HQ-48PC站位地球化学特征及对天然气水合物的指示意义

南海北部陆坡琼东南海域是中国天然气水合物勘探最具潜力的区域之一。对该海域的HQ-48PC站位沉积物样品的顶空气甲烷含量、孔隙水阴、阳离子及微量元素含量等地球化学特征进行综合分析,结果显示:在硫酸盐-甲烷界面(SMI,Sulfate-Methane Interface)(推算深度约为6.05 mbsf)发生了强烈的甲烷厌氧氧化反应(AMO,Anaerobic Meth-ane Oxidation),主要表现为SO24-含量线性降低接近于0、CH4含量发生骤增、有机碳和黄铁矿含量达到最大值及形成一个"钡锋"等特征。在SMI之上,HCO3-浓度随深度的增加呈明显上升的趋势,Ca2+、Mg2+、Sr2+等离子浓度随深度的增加呈降低的趋势,Mg2+/Ca2+比值随深度的增加呈明显增加的趋势,自生碳酸盐矿物以方解石为主;在SMI之下,HCO3-浓度随深度的增加呈缓慢下降的趋势,Ca2+浓度变化不大,Mg2+、Sr2+浓度和Mg2+/Ca2+比值随深度的增加呈降低的趋势,自生碳酸盐矿物以白云石为主。沉积物孔隙水的PO34-和NH4+含量较高,它们随深度的增加呈明显升高的趋势,且这种变化趋势与SO42-含量的下降趋势大致呈镜像关系。这些地球化学异常特征与国际上已发现有天然气水合物地区的地球化学特征相类似,暗示该采样站位深部沉积物中可能赋存有天然气水合物藏。     

Vertical migration of Daphnia galeata – Evidence for the use of an alternative resource from a lethal environment

Metazoans normally avoid anaerobic environments, at least when they are combined with toxic stress due to hydrogen sulfide. In Lake Speldrop, a small but deep gravel pit lake at the Lower Rhine, Daphnia galeata was found not only to dominate the zooplankton community, but was also regularly found in anoxic and even sulfidic layers during summer. We conducted field experiments with a newly developed “Zooplankton In-situ Incubator”, simulating vertical migrations of D. galeata. When daphnids were exposed to sulfidic conditions, mortality increased with exposure time, revealing LT₅₀-values between 129 and 42 min in relation to increasing concentrations of sulfide. Additionally, those experimental individuals originating from 12.5 m depth showed significantly higher mortality rates than those from 7.5 m depth. Further migration experiments showed that an interruption period of sulfidic exposition in less stressful environments reduced mortality rates significantly. Daphnids found in the hypolimnion belonged partly to moribund parts of the population; however, the majority of daphnids showed regular mowing activity and was able to withstand sulfidic conditions in the hypolimnion for a limited time. It is so far unclear what maybe the major ultimate factor for this type of short term migratory behavior, to seek for shelter or to use high amounts of sulfur bacteria as an alternative food resource.     

Variations of methane induced pyrite formation in the accretionary wedge sediments offshore southwestern Taiwan

The accretionary wedge of offshore southwestern Taiwan contains abundant deposits of gas hydrate beneath the sea floor. High concentrations of methane in pore waters are observed at several locations with little data concerning historical methane venting available. To understand temporal variation of methane venting in sediments over geologic time, a 23-m-long Calypso piston core (MD05-2911) was collected on the flank of the Yung-An Ridge. Pore water sulfate, dissolved sulfide, dissolved iron, methane, sedimentary pyrite, acid volatile sulfide, reactive iron, organic carbon and nitrogen as well as carbonate δ¹³C were analyzed.Three zones with markedly different pyrite concentration were found at the study site. Unit I sediments (>20 mbsf) were characterized with a high amount of pyrite (251–380 μmol/g) and a δ¹³C-depleted carbonate, Unit II sediments (15–20 mbsf) with a low pyrite (15–43 μmol/g) and a high content of iron oxide mineral and Unit III sediments (<10 mbsf) by a present-day sulfate–methane interface (SMI) at 5 m with a high amount of pyrite (84–221 μmol/g) and a high concentration of dissolved sulfide.The oscillation records of pyrite concentrations are controlled by temporal variations of methane flux. With an abundant supply of methane to Unit I and III, anaerobic methane oxidation and associated sulfate reduction favor diagenetic conditions conducive for significant pyrite formation. No AOM signal was found in Unit II, characterized by typical organically-limited normal marine sediments with little pyrite formation. The AOM induced pyrite formation near the SMI generates a marked pyrite signature, rendering such formation of pyrite as a useful proxy in identifying methane flux oscillation in a methane flux fluctuate environment.     

Authigenic barite nodules and carbonate concretions in the Upper Devonian shale succession of western New York – A record of variable methane flux during burial

Authigenic barite nodules associated with modestly ¹³C-depleted calcium carbonate concretions and ³⁴S-enriched pyrite at the bottom of the Upper Devonian Hanover Shale of western New York provide evidence of sulfate reduction coupled with anaerobic oxidation of methane (AOM). The methane, much of it biogenic in origin, may have diffused upward from Middle Devonian Marcellus Shale and perhaps the Upper Ordovician Utica Shale. Strong ³⁴S enrichment and high δ³⁴S/δ¹⁸O values of the barite nodules reflect: (1) substantial kinetic fractionation induced by microbial sulfate reduction perhaps intensified by a low seawater sulfate recharge rate and (2) upward delivery of Ba²⁺- and CH₄- bearing pore fluid sourced within underlying sulfate-depleted deposits. However, the association of authigenic calcium carbonate and barite in the same stratigraphic interval, especially the presence of barite overgrowths on carbonate concretions, is not consistent with what is known of AOM-related mineralization of a sediment column passing downward through the sulfate–methane transition (SMT). The documented early formation of authigenic carbonate followed by barite observed relations may reflect a diminished rate of methanogenesis and/or CH₄ supply. The tempered methane flux would have induced the SMT to descend the sediment column enabling barite to form within the same stratigraphic horizon that ¹³C-depleted calcium carbonate had most recently precipitated. Diminished methane flux may have been caused by burial-related passage of the organic-rich Marcellus Shale below the depth of peak biogenic methane generation and its replacement at that depth interval by organic-lean deposits of the upper part of the Hamilton Group. Subsidence of the SMT would have increased the preservation potential of authigenic barite. However, continued survival of the labile barite as it eventually moved through the SMT suggests that the underlying sulfate-depleted zone was strongly enriched in Ba²⁺.     

Reassessment of HF/HNO3 Decomposition Capability in the High‐Pressure Digestion of Felsic Rocks for Multi‐Element Determination by ICP‐MS

Complete dissolution is essential to obtain accurate analytical results for geological samples. Felsic rocks are known to be very difficult to dissolve because of the presence of refractory minerals such as zircon. In this study, we undertook a systematic evaluation of the effect of the HF/HNO₃ ratio, digestion time, digestion temperature, digested test portion mass and the presence of insoluble fluorides on analytical results for the felsic rock GSP‐2 using high‐pressure HF and HF/HNO₃ digestion. Digestion in mixtures of HF and HNO₃ acids is a commonly used method of dissolution for geological samples. However, our results clearly indicate that adding HNO₃ inhibited the digestion capabilities of HF for refractory minerals such as zircon. It took 8–12 hr for Zr to be completely recovered in GSP‐2 at 190 °C, whereas it needed about 36 and 72 hr at 160 and 140 °C, respectively. White precipitates were observed in the final solution for test portion mass > 100 mg, irrespective of which of the five different digestion solutions was used (1 ml HF, 2 ml HF, 1 ml HF + 0.5 ml HNO₃, 1 ml HF + 1 ml HNO₃ and 1.5 ml HF + 1.5 ml HNO₃). Environmental scanning electron microscopy showed that these precipitates were mainly composed of AlF₃. Instead of further HCl, HNO₃ or HClO₄ attack, we propose that using ultra‐fine samples and a small sample size is a good way to avoid the formation of insoluble residues (e.g., fluorides). To further investigate the precision and accuracy of the proposed method (using HF alone as the digestion solution during the first acid attack step), a suite of silicate rock reference materials was analysed. Most of the results were found to be in reasonable agreement with the reference values, with a relative error of < 10%.