Sulphate reduction in the sediment of the Venice canals (Italy)

The sulphur cycle in the sediment of the Venice canal network was investigated by considering the sulphate reduction rate (SRR) and the distribution of sulphur compounds, in both pore water and sediment. Sulphate reduction (SR) is the main process in the metabolism of the organic matter supplied to the network by untreated urban effluents. Although it might account for the decomposition of only a limited percentage of the total organic-C inputs, the estimated rates are among the highest observed in coastal sediments. Measured rates range from 0.26 to 0.99 micromolcm(-3)d(-1), while mean annual values, estimated by a diagenetic model, vary from 0.16 to 0.43 micromolcm(-3)d(-1). The speciation of S in the sediment reveals that pyrite-S is the most abundant component of the total reduced S pool, whereas acid volatile sulphides and elemental sulphur together account for less than 45%. A preliminary budget indicates that the rate of burial of solid-phase S is small compared to the S produced by SR (from 10 to 25%). A large amount of reduced S is then lost from the canal deposits to be re-oxidised at the sediment-water interface or in the overlying water column.     

Excess of bottom-released methane in an Arctic shelf sea polynya in winter

Latent heat polynyas are regions generating strong ice formation, convection and extensive water mass formation. Here we report on the effects of these processes on resuspension of sediments and subsequent methane release from the seafloor and on the resulting excess methane concentration in surface water on a polar shelf during winter. The study is based on measurements of concentration and δ¹³C values of methane, water temperature, salinity, light transmission and sea ice data collected in March 2003 in Storfjorden, southern Svalbard. In winter, strong and persistent northeasterly winds create polynyas in eastern Storfjorden and cause ice formation. The resulting brine-enriched water cascades from the Storfjordbanken into the central depression thereby enhancing the turbulence near the seafloor. A distinct benthic nepheloid layer was observed reflecting the resuspension of sediments by the cascading dense bottom water. High concentrations of ¹³C-depleted methane suggest submarine discharge of methane with the resuspended sediments. As the source of the submarine methane, we propose recent bacterial methanogenesis near the sediment surface because of extremely high accumulation rates of organic carbon in Storfjorden. Convective mixing transports newly released methane from the bottom to the sea surface. This eventually results in an excess concentration in surface water with respect to the atmospheric equilibrium, and a sea-air flux of methane during periods of open water. When a new ice cover is formed, methane becomes trapped in the water column and subsequently oxidized. Thus, the residual methane is strongly enriched in ¹³C in relation to the δ¹³_CCH4${\delta }^{13}{\mathrm{C}}_{{\mathrm{CH}}_4}$ signature of atmospheric methane. Our results show that latent heat polynyas may induce a direct pathway for biogases like methane from sediments to the atmosphere through coupling of biogeochemical and oceanographic processes. Extrapolating these processes to all Arctic ocean polynyas, we estimate a transfer of CH₄ between 0.005 and 0.02 Tg yr⁻¹. This is not a large contribution but the fluxes from the polynyas are 20–200 times larger than the ocean average and the methane evasion process in polynyas is certainly one that can be altered under climate change.     

广西新元古代BIF的铁同位素特征及其地质意义

通过分析广西三江地区新元古代条带状含铁建造的Fe同位素和主量元素组成,对海水的氧化还原状态提供了制约,为富禄期的地球处于间冰期提供了证据。相对于标准物质IRMM-014,新元古代含铁建造不同条带全岩样品的δ57Fe值变化范围1.60‰～2.20‰,平均值为1.85‰,表明BIF样品富集铁的重同位素。条带状含铁建造主要由Fe2O3和SiO2组成,但却具有较高的Al2O3含量。这表明条带状含铁建造样品不是纯净的化学沉积物,而是具有一定的碎屑物质输入。碎屑输入量的不同引起深色和浅色条带之间铁同位素组成存在着0.4‰的差别。剔除碎屑的影响,新元古代BIF从海水中沉淀的赤铁矿δ57Fe的平均值在2‰左右,略高于太古代条带状铁建造的Fe同位素组成,这表明当时海水的氧逸度可能比太古代还低。这说明在富禄期绝大部分海洋仍旧被冰盖覆盖,只在局部出现融化。因此,富禄期的地球可能出于冰期的相对温暖阶段,而不是间冰期。     

河北宽城地区中元古代高于庄组碳酸盐岩碳氧同位素特征

对河北宽城地区中元古代高于庄组碳酸盐岩的碳氧同位素进行了测定和原始性验证,表明其原始组分保存良好。δ13C、δ18O值分布范围和平均值分别为-5.03‰～0.07‰、-9.92‰～-4.12‰和-0.90‰、-6.58‰,整体上稍低于前人测定的天津蓟县剖面和北京十三陵剖面数据。分析认为:研究区δ13C值主要受有机碳氧化与有机碳的埋藏速率因素影响,有机碳的埋藏速率与蓝绿藻等生物数量关系密切,藻类繁盛的时期一般都具有较高的δ13C值,藻类稀少的时期则具有较低的δ13C值。在浅水潮坪环境中,δ13C值与海平面的变化呈正相关关系;研究区δ18O值则主要受海平面变化影响,与之呈负相关关系;研究区古盐度Z值主要介于120～125之间,相关性分析表明Z值不仅反映氧同位素组成,也反映了碳同位素组成,δ18O和δ13C均与沉积介质的盐度有关,其变化趋势是盐度越大,其δ值越高。     

硝酸盐氮氧同位素反硝化细菌法测试研究

进入21世纪,硝酸盐氮氧同位素测试技术的显著进展是反硝化细菌法测试技术的建立。反硝化细菌法具有可同时分析浓度低至μg/L的硝酸盐氮氧同位素组成、免去复杂的样品预处理、分析时间大大缩短以及从复杂溶液中只转化NO3-为N2O等优点。实验过程由细菌挑选和培养、样品NO3-转化为N2O、N2O提取纯化、同位素测试以及同位素测试结果校正等几个关键步骤组成。国外研究结果显示该技术不仅可用于海水和淡水中硝酸盐同位素测试,而且还可用于土壤样品,并得到不断的完善和应用;国内建立了这一技术,在包气带和地下水硝酸盐污染研究中取得重要进展。由于该技术诸多优点,建议大力促进这一技术在我国的研究和应用,希望有关部门加大支持力度,进一步完善该技术并推广应用。     

Paleoclimatic implications of the spatial patterns of modern and LGM European land-snail shell δO

The oxygen isotopic composition of land-snail shells may provide insight into the source region and trajectory of precipitation. Last glacial maximum (LGM) gastropod shells were sampled from loess from Belgium to Serbia and modern land-snail shells both record δ¹⁸O values between 0‰ and − 5‰. There are significant differences in mean fossil shell δ¹⁸O between sites but not among genera at a single location. Therefore, we group δ¹⁸O values from different genera together to map the spatial distribution of δ¹⁸O in shell carbonate. Shell δ¹⁸O values reflect the spatial variation in the isotopic composition of precipitation and incorporate the snails' preferential sampling of precipitation during the warm season. Modern shell δ¹⁸O decreases in Europe along a N-S gradient from the North Sea inland toward the Alps. Modern observed data of isotopes in precipitation (GNIP) demonstrate a similar trend for low-altitude sites. LGM shell δ¹⁸O data show a different gradient with δ¹⁸O declining toward the ENE, implying a mid-Atlantic source due to increased sea ice and a possible southern displacement of the westerly jet stream. Balkan LGM samples show the influence of a Mediterranean source, with δ¹⁸O values decreasing northward.     

Deciphering the depositional environment of the laminated Crato fossil beds (Early Cretaceous,Araripe Basin,North‐eastern Brazil)

The laminated limestones of the Early Cretaceous Crato Formation of the Araripe Basin (North‐eastern Brazil) are world‐famous for their exceptionally well‐preserved and taxonomically diverse fossil fauna and flora. Whereas the fossil biota has received considerable attention, only a few studies have focused on the sedimentary characteristics and palaeoenvironmental conditions which prevailed during formation of the Crato Fossil Lagerstätte. The Nova Olinda Member represents the lowermost and thickest unit (up to 10 m) of the Crato Formation and is characterized by a pronounced rhythmically bedded, pale to dark lamination. To obtain information on palaeoenvironmental conditions, sample slabs derived from three local stratigraphic sections within the Araripe Basin were studied using high‐resolution multiproxy techniques including detailed logging, petrography, μ‐XRF scanning and stable isotope geochemistry. Integration of lithological and petrographic evidence indicates that the bulk of the Nova Olinda limestone formed via authigenic precipitation of calcite from within the upper water column, most probably induced and/or mediated by phytoplankton and picoplankton activity. A significant contribution from a benthonic, carbonate‐secreting microbial mat community is not supported by these results. Deposition took place under anoxic and, at least during certain episodes, hypersaline bottom water conditions, as evidenced by the virtually undisturbed lamination pattern, the absence of a benthonic fauna and by the occurrence of halite pseudomorphs. Input of allochthonous, catchment‐derived siliciclastics to the basin during times of laminite formation was strongly reduced. The δ¹⁸O values of authigenic carbonate precipitates (between ?7·1 and ?5·1‰) point to a ¹⁸O‐poor meteoric water source and support a continental freshwater setting for the Nova Olinda Member. The δ¹³C values, which are comparatively rich in ¹³C (between ?0·1 and +1·9‰), are interpreted to reflect reduced throughflow of water in a restricted basin, promoting equilibration with atmospheric CO₂, probably in concert with stagnant conditions and low input of soil‐derived carbon. Integration of lithological and isotopic evidence indicates a shift from closed to semi‐closed conditions towards a more open lake system during the onset of laminite deposition in the Crato Formation.     

河南栾川百炉沟铅锌矿床地质、流体包裹体和稳定同位素地球化学

百炉沟矿床是近年来在盛产斑岩_矽卡岩型钼矿床的河南栾川地区新发现的一处铅锌矿床,位于豫西南牛心剁穹状背斜之西侧,与栾川地区的南泥湖、三道庄、上房沟、马圈等斑岩型及斑岩_矽卡岩型钼矿床相毗邻。矿体呈脉状、板状产在中元古界变质碳酸盐岩-碎屑岩层中,受NWW向层间断裂构造控制。矿石由闪锌矿、方铅矿、黄铁矿、石英、方解石等矿物组成。矿石中石英和闪锌矿所捕获的原生流体包裹体有富液体气液两相包裹体、富气体气液两相包裹体、纯气体包裹体、含子矿物三相包裹体等4种类型,邻近分布,其均一温度相近,表明成矿过程中可能存在流体沸腾作用。气液两相包裹体的均一温度为180～327℃,以中温（250～260℃）为主;盐度 w (NaCl_eq)为4.0%～14.0%,以5.0%～9.0%为主;依据均一温度峰值所对应的压力（38.94～44.87 MPa）,求得成矿深度为1.44～1.66 km。表明该矿床明显具有浅成、中温、低盐度热液成矿的特征。单个流体包裹体的气相成分至少有纯H₂O蒸汽、N₂+CO₂+CH₄、N₂+CO₂和N₂+CH₄等4种组合。矿石中石英和方解石内包裹体水的δD_V-SMOW为-76‰～-90‰,方解石的δ¹³C_V-PDB为-0.44‰～1.80‰,选取所对应的流体包裹体均一温度,计算得到包裹体水的δ¹⁸O_水为2.51‰～10.96‰,反映出成矿流体的主体为岩浆热液。矿石中硫化物的δ³⁴S_V-CDT为-1.2‰～10.9‰,其峰值（1‰～2‰）与该地区斑岩型钼矿床中的硫化物相近,指示其具有岩浆来源硫的特征。矿石中硫化物²⁰⁶Pb/²⁰⁴Pb=17.552～18.426,²⁰⁷Pb/^{204Pb=15.451～15.5794,208Pb/204Pb=38.264～39.637,反映出成矿金属主要来自于岩浆,有少量地层岩石铅的加入。百炉沟铅锌矿床应属受层间构造控制的中温岩浆热液充填-交代矿床。}     

Neoproterozoic chemostratigraphy

Chemostratigraphy has diverse applications to investigating the rock record, such as reconstructing paleoenvironments, determining the tectonic setting of sedimentary basins, indirect dating, and establishing regional or global correlations. Chemostratigraphy is thus an integral component of many investigations of the ancient sedimentary record. In this contribution, we review the principle inorganic geochemical methods that have been applied to the Neoproterozoic sedimentary record. Analysis of the traditional stable and radiogenic isotope systems, such as δ¹³C, δ¹⁸O, δ³⁴S, and ⁸⁷Sr/⁸⁶Sr, is routine, particularly in successions rich in carbonate. These mainstay applications have yielded invaluable data and information bearing on the chronology and evolution of this eventful era in Earth history. Alongside the growing database of traditional data, a series of novel geochemical techniques have given rise to important new models and constraints on Neoproterozoic biogeochemical change. In particular, a range of proxies for water column redox, mainly obtained from black shales, have shed light on the pace and tempo of Neoproterozoic oxygenation and its link to the appearance of early animal evolution. Increased integration of diverse geochemical, sedimentological, and paleontological datasets, and the gradual radiometric calibration of the stratigraphic record promise to bring the details of the evolution of the Neoproterozoic Earth system into ever greater focus.