Isotopic evidence for the incorporation of methane-derived carbon into foraminifera from modern methane seeps, Hydrate Ridge, Northeast Pacific

The presence of modern methane seeps at Hydrate Ridge, offshore Oregon, provide an opportunity to study the influence of methane seeps on the ecology and geochemistry of living foraminifera. A series of cores were collected from the southern summit of Hydrate Ridge in 2002. Samples were preserved and stained to determine the δ¹³C composition of three species of live (stained) and dead benthic foraminifera: Uvigerina peregrina, Cibicidoides mckannai, and Globobulimina auriculata. Specimens were examined under light and Scanning Electron Microscopy (SEM) and exhibit no evidence of diagenesis or authigenic carbonate precipitation. Individual living foraminifera from seep sites recorded δ¹³C values from −0.4‰ to −21.2‰, indicating the isotopic influence of high methane concentrations. Average δ¹³C values (calculated from single specimens) range from −1.28 to −5.64‰ at seep sites, and −0.81 to −0.85‰ at a control (off seep) site.Two distinct seep environments, distinguished by the presence of microbial mats or clam fields, were studied to determine environmental influences on δ¹³C values. Individual foraminifera from microbial mat sites exhibited more depleted δ¹³C values than those from clam field sites. We interpret these differences as an effect of food source and/or symbiotic microbes on foraminiferal carbon isotopic values, acting to magnify the negative δ¹³C values recorded via the DIC pool. No statistical difference was found between δ¹³C values of live vs. dead specimens. This suggests that authigenic carbonate precipitation did not play a dominant role in the observed isotopic compositions. However, a few dead specimens with extremely negative δ¹³C composition (<-12‰) do indicate potential evidence for an authigenic influence on the recorded δ¹³C composition.     

Factors influencing methane-derived authigenic carbonate formation at cold seep from southwestern Dongsha area in the northern South China Sea

This paper carried out mineral and geochemical studies on a profile through a diagenetic methane-derived authigenic carbonate sample that was collected from southwestern Dongsha area of the northern South China Sea. Five samples locating in the cross-sectional middle mainly consist of dolomite and quartz, and two samples close to the surface have a small amount of Mg-calcite. The δ¹³C values of the samples vary between ?30.59 and ?0.30 % VPDB, with δ¹⁸O values ranging from 3.07 to 3.59 % VPDB, δ^44/40Ca values ranging from 1.35 to 1.47 % SRM915a, indicating a contribution of methane to the carbon pool where the precipitation of authigenic carbonates occurred. Based on the isotope values alone, it can not be distinguished if the carbon source is thermogenic gas or a mixture of biogenic methane and marine dissolved inorganic carbon. The δ¹⁸O values are in general consistent with dolomite precipitation from a fluid similar to present seawater. The observed small variation might be related to the oxygen isotope composition of seep fluid. The relative small range in calcium isotope values suggests that relatively constant growth conditions and precipitation from seawater. The central part of the carbonate nodule formed under the strong influence of methane seepage, and the external part is less influenced by methane, either due to reduced methane flux to the surface or caused by erosional exhumation of the carbonate nodule from greater depth to the sediment surface.     

Palaeoceanographic changes in the North Atlantic during the Mid‐Pleistocene Transition (MIS 31–19) as inferred from planktonic foraminiferal and calcium carbonate records

Marine sediments from the Integrated Ocean Drilling Project (IODP) Site U1314 (56.36°N, 27.88°W), in the subpolar North Atlantic, were studied for their planktonic foraminifera, calcium carbonate content, and Neogloboqudrina pachyderma sinistral (sin.) δ¹³C records in order to reconstruct surface and intermediate conditions in this region during the Mid‐Pleistocene Transition (MPT). Variations in the palaeoceanography and regional dynamics of the Arctic Front were estimated by comparing CaCO₃ content, planktonic foraminiferal species abundances, carbon isotopes and ice‐rafted debris (IRD) data from Site U1314 with published data from other North Atlantic sites. Site U1314 exhibited high abundances of the polar planktonic foraminifera N. pachyderma sin. and low CaCO₃ content until Marine Isotope Stage (MIS) 26, indicating a relatively southeastward position of the Arctic Front (AF) and penetration of colder and low‐salinity surface arctic water‐masses. Changing conditions after MIS 25, with oscillations in the position of the AF, caused an increase in the northward export of the warmer North Atlantic Current (NAC), indicated by greater abundances of non‐polar planktonic foraminifera and higher CaCO₃. The N. pachyderma sin. δ¹³C data indicate good ventilation of the upper part of the intermediate water layer in the eastern North Atlantic during both glacial and interglacial stages, except during Terminations 24/23, 22/21 and 20/1. In addition, for N. pachyderma (sin.) we distinguished two morphotypes: non‐encrusted and heavily encrusted test. Results indicate that increases in the encrusted morphotype and lower planktonic foraminiferal diversity are related to the intensification of glacial conditions (lower sea‐surface temperatures, sea‐ice formation) during MIS 22 and 20.     

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。     

A comprehensive approach to the study of methane-seep deposits from the Lincoln Creek Formation, western Washington State, USA

ABSTRACT A comprehensive approach using palaeontology, petrography, stable isotope geochemistry and biomarker analyses was applied to the study of seven small methane‐seep carbonate deposits. These deposits are in the Oligocene part of the Lincoln Creek Formation, exposed along the Canyon and Satsop Rivers in western Washington. Each deposit preserves invertebrate fossils, many representing typical seep biota. Authigenic carbonates with δ¹³C values as low as ?51‰ PDB reveal that the carbon is predominately methane derived. Carbonates contain the irregular isoprenoid hydrocarbons 2,6,11,15‐tetramethylhexadecane (crocetane) and 2,6,10,15,19‐pentamethylicosane (PMI), lipid biomarkers diagnostic for archaea. These lipids are strongly depleted in ¹³C (δ¹³C values as low as ?120‰ PDB), indicating that archaea were involved in the anaerobic oxidation of methane. Small filaments preserved in the carbonate may represent methanotrophic archaea. Archaeal methanogenesis induced the formation of a late diagenetic phase, brownish calcite, consisting of dumbbell‐shaped crystal aggregates that exhibit δ¹³C values as high as +7‰ PDB. Clotted microfabrics of primary origin point to microbial mediation of carbonate precipitation. Downward‐directed carbonate aggregation in the seeps produced inverted stromatactoid cavities. Large filaments, interpreted as green algae based on their size, shape, arrangement and biomarkers, imply that deposition occurred, in places, in water no deeper than 210 m.     

Authigenic seep-carbonates cementing coarse-grained deposits in a fan-delta depositional system (middle Miocene, Marnoso-arenacea Formation, central Italy)

Seep‐carbonates (¹³C‐depleted) are present at different levels within the Miocene terrigenous succession of Deruta (Marnoso‐arenacea Formation, central Italy); they are associated with pebbly sandstones and conglomerates in a tectonically active fan‐delta slope depositional system. Most of these seep‐carbonates are included in slide/slump horizons as scattered blocks. The occurrence of seep‐carbonates is clear evidence of the flow of methane‐rich fluids pervading the sediments. Fluids, probably of biogenic origin, may have reached the sea‐bottom through thrust faults and selectively infiltrated the more permeable coarse‐grained horizons deposited along the slope. Different stages of fluid emissions are documented: slow flux stage, corresponding to the development of large carbonate bodies and dense chemosynthetic communities; and fast fluid flow associated with intense carbonate brecciation, pipes and veins. Large amounts of authigenic carbonates are reworked by slope failures triggered by tectonics and fluids reducing sediment strength; in situ cementation of slide blocks may also have occurred due to remobilization of methane‐rich fluids by mass‐wasting processes.     

冷泉区底栖有孔虫研究进展

海底冷泉区是海洋能源和生物资源同时富集的一类特殊区域。底栖有孔虫群落及其地球化学组成是海底冷泉区发育的重要指示标志之一。海底冷泉区的底栖有孔虫及其碳同位素研究,对于探讨冷泉演化、评估古冷泉甲烷排放对全球气候变化的影响有重要的研究意义。综述了全球一些主要冷泉区的底栖有孔虫研究方法及其进展,对比了各冷泉区底栖有孔虫群落结构的主要特征及地域差异,评述了冷泉区底栖有孔虫的碳同位素记录特征、影响因素及其对冷泉活动的潜在指示意义,最后提出了南海北部冷泉活动区底栖有孔虫方面的研究展望。     

南海东北部岩芯沉积物磁性特征及对甲烷事件的指示

在甲烷渗漏海域,沉积物磁化率通常表现出异常的低值特征,这与硫酸盐-甲烷转换带（SMTZ）内甲烷厌氧氧化反应（AOM）的发育而导致的自生矿物的形成作用有关。通过测定南海东北部Site DH-CL11、Site 973-2、Site 973-4三个站位400个岩芯沉积物样品的磁化率,并结合三个站位自生黄铁矿丰度和硫同位素等数据探讨了南海北部天然气水合物潜在区沉积物磁化率的变化特征及其对甲烷渗漏事件的指示意义。结果表明:在甲烷异常渗漏海域,上涌甲烷与下渗硫酸盐在SMTZ内发生AOM反应生成了大量的HS-,造成亚铁磁性矿物大量溶解,同时生成大量顺磁性自生黄铁矿,导致沉积物磁化率的异常降低;但是,在HS-不足时,铁硫化物黄铁矿化不充分,会优先生成胶黄铁矿,进而出现二次磁信号。在天然气水合物潜在海域,沉积物磁化率的异常特征可以反映下部甲烷通量的变化,从而指示下伏天然气水合物藏演化,因此能够成为探测天然气水合物藏的一种间接有效的手段,将有助于我国南海北部海域天然气水合物的勘探。     

海底天然气渗漏系统微生物作用及冷泉碳酸盐岩的特征

海底天然气渗漏系统是全球海洋环境中广泛分布的自然现象。部分渗漏天然气通过细菌作用转变为二氧化碳,同时海水硫酸盐被还原为硫化氢, 与孔隙水中的钙和铁结合而沉淀冷泉碳酸盐岩。冷泉碳酸盐岩的常见矿物有微晶方解石、文石、白云石和黄铁矿。冷泉碳酸盐岩常发育一些特殊的组构, 如黄铁矿环带结核、溶蚀面、平底晶洞、凝块和向下生长的叠层石组构等。碳酸盐岩特别负的δ13C值指示碳来源于生物成因的甲烷, 而18O富集可能与天然气水合物的分解有关。冷泉碳酸盐岩中黄铁矿的δ34S值低于海水的, 这指示硫来源于微生物还原的海水硫。冷泉碳酸盐岩中的生物标志化合物及其极负的δ13C值指示微生物的生命代谢活动。     

Late Quaternary sedimentation on the Southern Sohm Abyssal Plain

Six closely spaced sediment cores taken below the carbonate compensation depth penetrated fine silty muds and entered sandy sediment at 10–12 m below the seafloor. Foraminiferal assemblages and δ⁸O analyses on planktonic foraminifera indicated that the surface muds down to 2 m are Holocene and derived from local promontories above the CCD. Below these sediments are about 6 m of clays deposited during the late Wisconsin. These are unfossiliferous and have a possible northern source suggested by the higher chlorite content. Sandy sediments below 9 m in the cores contain well preserved benthic foraminifera from the Scotian Shelf. Glacial δ¹⁸O values on planktonic tests indicate the sandy sediments are most likely of latest Wisconsin age. Thus during the recent interglacial, the sand fraction of the southern Sohm Abyssal Plain sediments is mostly locally derived, but during glacial periods the sediments have a distant northern source containing quartz sand that was initially deposited on the Scotian Shelf 1,500 km to the north.     

南海北部甲烷渗漏系统环境变化的碳、氧同位素记录

冷泉碳酸盐岩记录了甲烷渗漏活动和流体组分随时间的变化过程,对示踪冷泉系统沉积环境变化具有非常重要的意义.对南海北部获取的冷泉碳酸盐岩进行了碳、氧同位素剖面研究,并对南海北部冷泉碳酸盐岩的碳、氧同位素变化范围进行了统计分析.研究结果及已发表的δ13C和δ18O剖面数据表明,南海北部冷泉碳酸盐岩剖面的δ13C和δ18O之间普遍存在相关性,相关系数R2最高可达0.933 1.经统计,南海北部冷泉碳酸盐岩样品δ13C和δ18O均具有较大的变化范围,其最大变化分别为34.50×10-3和5.89%(Vienna Pee Dee Belemnite,V-PDB).冷泉碳酸盐岩δ13C和δ18O的相关性特征可能指示了初始流体的变化、后期矿物形成/重结晶作用、渗漏系统较为复杂或者成岩作用等环境变化信息.对不同碳酸盐岩样品来说,δ13C的变化主要由海水的参与程度决定,而δ18O的变化可能与温度和Mg元素参与方解石沉淀的程度有关.      

Calcite cementation during bacterial manganese, iron and sulphate reduction in Jurassic shallow marine carbonates

Faunally restricted argillaceous wackestones from the Middle Jurassic of eastern England contain evidence of early diagenetic skeletal aragonite dissolution and stabilization of the carbonate matrix, closely followed by precipitation of zoned calcite cements, and precipitation of pyrite. Distinctive cathodoluminescence and trace element trends through the authigenic calcites, their negative δ¹³C compositions and the location of pyrite in the paragenetic sequence indicate that calcite precipitation took place during sequential bacterial Mn, Fe and sulphate reduction. Calcite δ¹⁸O values are compatible with cementation from essentially marine pore fluids, although compositions vary owing to minor contamination with ¹⁸O-depleted ‘late’cements. Mg and Sr concentrations in the calcites are lower than those in recent marine calcite cements. This may be a result of kinetic factors associated with the shallow burial cementation microenvironments. Bicarbonate for sustained precipitation of the authigenic calcites was derived largely from aragonite remobilization, augmented by that produced through anaerobic organic matter oxidation in the metal and sulphate reduction environments. Aragonite dissolution is thought to have been induced by acidity generated during aerobic bacterial oxidation of organic matter. Distinction of post-oxic metal reduction and anoxic sulphate reduction diagenetic environments in modern carbonate sediments is uncommon outside pelagic settings, and early bacterially mediated diagenesis in modern platform carbonates is associated with extensive carbonate dissolution. High detrital Fe contents of the Jurassic sediments, and their restricted depositional environment, were probably the critical factors promoting early cementation. These precipitates constitute a unique example of calcite authigenesis in shallow water limestones during bacterial Mn and Fe reduction.     

Punctuated environmental change along the Holocene (<6 ka) bank margin of south-west Exuma Sound, Bahamas

Characteristics of environmental change along the Holocene (<6 ka BP) bank margin of south‐west Exuma Sound, Bahamas, are defined by comparing mineral, isotope and lithologic stratigraphic patterns in deep‐water (1081 m) slope strata in ODP Hole 631A (Exuma Sound) with proximal (≈6 km) shoal‐water and insular geology of the Lee Stocking Island (LSI) region. After platform submergence, a bank‐top transition from non‐skeletal‐ to skeletal‐dominated deposition occurred in the LSI region by ≈3·8 ka, and is recorded in the adjacent slope sediments by a contemporaneous change in the abundance of transported allochems. The transition at Site 631 is punctuated by an anomalous shift in foraminiferal δ¹³C (–1‰) and δ¹⁸O (–3‰), which may represent a period of climate change that established a brackish coastal zone at least 6 km wide, coincident (≈3·8–4 ka) with bank‐top erosion and pedogenesis. Non‐skeletal allochems reappeared in Hole 631A sediments as the dominant transported allochem type by ≈2·4 ka, then again over the last several hundred years, and are contemporaneous with periods of increased platform‐margin circulation in the LSI region. Such rejuvenation of platform circulation may have resulted from rapid relative rises in sea level, superimposed on the net gradual post‐glacial rise. At Site 631, a prominent (25%) decline in aragonite abundance occurred during the period from 2·4 ka to the last few hundred years, and coincided with an increase in magnesian calcite and skeletal debris, and a positive shift in foraminiferal δ¹⁸O values. These patterns lend support to the hypothesis that, during this period, the LSI margin was barred by skeletal shoals, allowing bank‐top trapping of aragonite and hypersaline water, with increased coastal salinity (resulting from reflux of hypersaline waters through the shoals) and/or cooled coastal waters (caused by reduced exchange of warmed bank‐derived water relative to wind‐generated upwelling). Along the Exuma slope, a diagenetic overprint may further enhance the recent decline in aragonite accumulation. Integration of Holocene deep‐water slope and bank‐top stratigraphies along the bank margin of south‐west Exuma Sound reveals a pattern of punctuated environmental change superimposed on longer term development of interglacial conditions.     

Timing of diagenesis and very low‐grade metamorphism in the eastern sector of the Sierra de Cameros (Iberian Range,Spain): a U–Pb SHRIMP study on monazite

The Sierra de Cameros is an intracontinental orogen and represents the north‐western part of the Iberian Range in Northern Spain. It comprises a thick sequence of syn‐rift continental sediments (mainly sandstones and carbonates) deposited during lower Cretaceous times. A unique characteristic of the Sierra de Cameros in relation to the rest of the Iberian Range is the presence of low‐grade metamorphism in certain parts of the basin, an event that predates basin inversion. This paper describes the presence, textural relationships and geochemical aspects of authigenic and/or metamorphic monazite within different lithologies from the deepest parts of the basin. Sensitive high resolution ion microprobe (SHRIMP) U–Pb dating of monazite records the presence of two age populations: the first with ²⁰⁶Pb/²³⁸U ages ranging from 122 to 116 Ma which is considered as diagenetic in origin, whilst the second is dated at 99 ± 2 Ma and postdates the metamorphic climax.     

Cold seeps in Monterey Bay, California: Geochemistry of pore waters and relationship to benthic foraminiferal calcite

An extensive geochemical and biogeochemical examination of CH₄ seeps in the Clam Flats area of Monterey Bay provides insight into the character of relationships between seep geochemistry and benthic foraminiferal geochemistry. The area is characterized by sulfide-rich fluids. Sulfide increases are associated with large increases in alkalinity, as well as small decreases in dissolved Ca and Mg. In addition, only small increases in NH₄ are observed, but values of δ¹³C of dissolved inorganic C are as low as −60‰ at shallow depths (<3 cm). These observations indicate that all these processes are related to the bacterial oxidation of CH₄, which is transported upward by slow seepage of pore fluids. The geochemistry of the pore fluids should be relevant to the geochemistry of the carbonate tests of living and dead foraminifera. However, a profound disequilibrium of approximately an order of magnitude occurs between the δ¹³C values of stained (cytoplasm-containing) foraminiferal carbonate and the C isotope values of ambient pore water dissolved inorganic C. Reasons are unclear for this isotopic disequilibrium, but have important implications for interpretations of foraminiferal carbonate as a paleoenvironmental proxy. Much fine scale work is needed to fully understand the relationships between the biogeochemistry of benthic foraminifera and the geochemistry of the pore waters where they live.     

Oceanographic and climatic implications of the Palaeocene carbon isotope maximum

We have compared detailed planktonic and benthonic foraminiferal carbon and oxygen isotope records from the Palaeocene and early Eocene successions at DSDP Site 577 (Shatsky Rise, North Pacific), a composite section derived from DSDP Leg 74 sites (Walvis Ridge, South Atlantic) and a composite section from ODP Leg 113 sites (Maud Rise, Weddell Sea). The δ¹³C records of Palaeocene and early Eocene Foraminifera at Site 577 and the Leg 74 sites show that an increase in δ¹³C values in surface waters at 64 Ma (end of Zone P1) resulted in increased vertical carbon isotope gradients (δ¹³C) between surface and deeper dwelling planktonic foraminifera, and between surface-dwelling planktonics and benthonic foraminifera which became progressively steeper until the iniddle Late Palaeocene (Zone P4). This steepening also occurs in the latest Palaeocene of the composite Leg 113 section and can be explained by an increase in surface ocean productivity. This increase in productivity probably resulted in an expansion of the oxygen minimum zone (OMZ). Benthonic δ¹³C values increased during the late Palaeocene in Site 577 and the composite Leg 74 section, suggesting that the Palaeocene carbon isotope maximum was composed of both within-ocean reservoir (increased surface water productivity) and between-reservoir (organic carbon burial) ftactionation effects. The benthonic δ¹³C increase lags the surface ocean δ¹³C increase in the early Palaeocene (63–64 Ma) suggesting that surface water productivity increase probably led an increase in the burial rate of organic carbon relative to carbonate sedimentation. Moreover, inter-site δ¹³C comparisons suggest that the locus of deep to intermediate water formation for the majority of the Palaeocene and the earliest Eocene was more likely to have been in the high southern latitudes than in the lower latitudes. Oxygen isotope data show a decline in deeper water temperatures in the early and early late Palaeocene, followed by a temperature increase in the late Palaeocene and across the PalaeoceneEocene boundary. We speculate that these changes in deeper water temperatures were related to the flux of CO₂ between the oceans and the atmosphere through a mechanism operating at the high southern latitudes.     

台西南深海底栖有孔虫及其5万年来冷泉微生境变迁记录

为探讨冷泉区底栖有孔虫组合特征、受控因素及其冷泉微生境随时间的变迁,本文对台西南海盆取自九龙甲烷礁和海洋四号区冷泉区的973-4和973-5两根岩心展开了底栖有孔虫及其壳体氧碳同位素研究。测年结果揭示两根岩心为晚更新世约5万年来海洋氧同位素期(MIS)MIS 3至MIS 1早期的沉积序列。两个站位共识别了底栖有孔虫79属233种,优势类别在973-4组合中为Uvigerina(23.3%)、Bulimina(10.71%)和Cibicidoides(9.87%),在973-5组合中是Bulimina(20.6%),两站位的组合优势和常见属种均以内生类别为主。有孔虫分异度显然同时受到正常深海环境因子TOC和沉积物粒度的影响。总体上,优势和常见类群与TOC相关性较弱,但与δ¹⁸O_{Uvigerina spp.}有不同程度的相关性,说明有孔虫还受冷泉特殊营养物质和流体因子影响。5万年来,973-4和973-5站位底栖有孔虫组合生活的冷泉微生境,经历了由双壳-自生碳酸盐岩(MIS 3至MIS 2早期)向双壳-菌席(MIS 2晚期至MIS 1早期)的变迁。底栖有孔虫的优势类群也随微生境的变迁而演替,如973-4站位MIS 3-MIS 1的优势类群依次为U.peregrina、Cibicidoides-Bulimina、U.vadescens和Cibicides,973-5站位为Chilostomella+ Globobulimina、Cibicidoides、Bulimina。有孔虫壳体氧碳同位素特征也随时间改变,从MIS 3到MIS 2早期,在自生碳酸盐岩水岩交换背景下,具有富δ¹⁸O和亏损δ¹³C特点(3.5‰~4.49‰,-2‰~-0.2‰); MIS 2晚期—MIS 1早期因双壳和菌席的生物地球化学作用影响,具有略富集δ¹⁸O和略微亏损δ¹³C的特征(2.5‰~3.5‰,-1‰~-0.1‰)。自5万年来两个区甲烷渗漏逐渐减弱,其间发生了几次增强事件。973-4站位记录了1次持续时间约10 ka的增强事件(35~25 ka);973-5站位记录3次(45 ka,35 ka,14~12 ka)。其中,45 ka时海底上涌的甲烷通量可能最大,在海底表面形成水合物。35 ka时的甲烷喷溢增强事件可能为区域性事件。     

Isotopic signature of burial diagenesis and primary lithological contrasts in periplatform carbonates (Miocene, Great Bahama Bank)

The stable isotope geochemistry of Miocene sediments from the leeward margin of the Great Bahama Bank was examined to investigate burial diagenetic processes in periplatform carbonates. Data indicate that, in addition to differences in bulk proportions of neritic and pelagic carbonate along the slope, rhythmic variation in primary carbonate content has controlled patterns of burial diagenesis and associated geochemical signatures throughout much of the succession examined. The present study focuses on Ocean Drilling Program Sites 1006 and 1007, the most distal of five sites drilled from marginal to deep basin environments during Leg 166. These Miocene sections are characterized by their cyclic appearance, manifest as decimetre‐ to metre‐scale alternations between light‐coloured ooze/chalk/limestone and dark‐coloured marl/marlstone. The section at Site 1006 contains a high proportion of pelagic carbonate and is unlithified to a subbottom depth of ～675 m. Fluctuations in δ¹⁸O and δ¹³C values at this site are independent of lithological variation and reflect primary conditions. At Site 1007, located at the toe‐of‐slope and composed of a mixture of bank‐derived and pelagic carbonate, limestones are densely cemented, show little evidence of compaction and have δ¹⁸O values up to 2‰ higher than coeval sediments at Site 1006. Marlstones at Site 1007 are poorly cemented, exhibit an increase in compaction‐related features with depth and have lower and more variable δ¹⁸O values that are similar to those of coeval sediments at Site 1006. Isotopic and petrographic characteristics of limestone interbeds result from cement precipitation from cold sea water during the first ～100 m of burial. Higher proportions of insoluble materials and pelagic carbonate seem to have inhibited diagenetic alteration in adjacent marlstones; in spite of significant compaction and pressure solution during burial, original isotopic compositions appear to be best preserved in these intervals at Site 1007. The documented contrasts in petrographic and isotopic patterns illustrate the role of primary sediment composition in controlling lithification processes in periplatform carbonates and stress the importance of considering such factors when interpreting geochemical data from ancient shelf and slope limestones.     

Carbon, oxygen, strontium, and sulfur isotopic compositions in late Precambrian rocks of the Patom Complex, central Siberia: Communication 2. Nature of carbonates with ultralow and ultrahigh δ13C values

The Patom Complex is characterized by a unique association of carbonate rocks with ultralow (≤8‰) and ultrahigh (>6‰) δ¹³C values. The thickness, stable isotopic composition along the strike, and lithological and geochemical parameters suggest that these rocks could not form as a result of short-term local events or epigenetic processes. Ultralow δ¹³C values (less than ?8‰) in carbonate rocks of the Zhuya Group, which substantially exceed all the known negative C isotope anomalies in thickness (up to 1000 m) and amplitude (δ¹³C = ?10 ± 2‰), point to sedimentation under conditions of extreme “contamination” of water column by oxidized isotopically light organic (hereafter, light) carbon. The decisive role in this contamination belonged to melting and oxidation of huge volumes of methane hydrates accumulated in sediments during the powerful and prolonged Early Vendian glacial epoch. The accumulation of δ¹³C-depleted carbonates was preceded by the deposition of carbonates with anomalously high δ¹³C values. These carbonates formed at high rates of the burial of organic matter and methane in sediments during periods when the sedimentation basin consumed carbon dioxide from the atmosphere and organic carbon was conserved in sediments.     

Formation of carbonate concretions in surface sediments of two mud mounds,offshore Costa Rica: a stable isotope study

The surface sediments of two mud mounds (“Mound 11” and “Mound 12”) offshore southwest Costa Rica contain abundant authigenic carbonate concretions dominated by high-Mg calcite (14–20 mol-% MgCO₃). Pore fluid geochemical profiles (sulfate, sulfide, methane, alkalinity, Ca and Mg) indicate recent carbonate precipitation within the zone of anaerobic oxidation of methane (AOM) at variable depths. The current location of the authigenic carbonate concretions is, however, not related to the present location of the AOM zone, suggesting mineral precipitation under past geochemical conditions as well as changes in the flow rates of upward migrating fluids. Stable oxygen and carbon isotope analysis of authigenic carbonate concretions yielded δ¹⁸O_carbonate values ranging between 34.0 and 37.7 ‰ Vienna standard mean ocean water (VSMOW) and δ¹³C_carbonate values from ?52.2 to ?14.2 ‰ Vienna Pee Dee belemnite (VPDB). Assuming that no temperature changes occurred during mineral formation, the authigenic carbonate concretions have been formed at in situ temperature of 4–5 °C. The δ¹⁸O_carbonate values suggest mineral formation from seawater-derived pore fluid (δ¹⁸O_porefluid = 0 ‰ VSMOW) for Mound 12 carbonate concretions but also the presence of an emanating diagenetic fluid (δ¹⁸O_porefluid ≈5 ‰) in Mound 11. A positive correlation between δ¹³C_carbonate and δ¹⁸O_carbonate is observed, indicating the admixing of two different sources of dissolved carbon and oxygen in the sediments of the two mounds. The carbon of these sources are (1) marine bicarbonate (δ¹³C_porefluid ≈0 ‰) and (2) bicarbonate which formed during the AOM (δ¹³C_porefluid ≈?70 ‰). Furthermore, the δ¹⁸O_porefluid composition, with values up to +4.7 ‰ Vienna standard mean ocean water (VSMOW), is interpreted to be affected by the presence of emanating, freshened and boron-enriched fluids. Earlier, it has been shown that the origin of ¹⁸O-enriched fluids are deep diagenetic processes as it was indicated by the presence of methane with thermogenic signature (δ¹³C_CH4 = ?38 ‰). A combination of present geochemical data with geophysical observations indicates that Mounds 11 and 12 represent a single fluid system interconnected by deep-seated fault(s).