南海东沙海域冷泉渗漏区沉积物稀土元素地球化学特征

东沙海域是我国典型的冷泉活动区,该区域表层沉积物的稀土元素地球化学特征不仅受其源区控制,同时也可能会受到冷泉渗漏活动的影响。本文选取位于南海北部陆坡973-4站位的柱状样为研究对象,该站位位于21°54.3247’N、118°49.0818’E,水深为1666m,柱状样总长1375cm,采用电感耦合等离子质谱(ICP-MS)、X射线荧光光谱(XRF)等分析测试方法,测得样品的稀土元素以及部分微量和主量元素数据,并结合总碳(TC)、总有机碳(TOC)以及有孔虫质量分数等数据,探讨了冷泉泄漏对周围成岩环境及沉积物稀土元素地球化学特征的影响。结果发现,973-4站位柱状样在海底以下459~619cm深度范围内稀土元素含量整体异常减少,但所有样品稀土元素分布模式及相关稀土元素参数均十分一致。结合冷泉活动研究,表明该区域沉积物元素地球化学特征的异常与物源无关,是受自生碳酸盐岩的增加所影响。此外,通过分析δCe值随深度的变化以及自生碳酸盐岩和硫酸盐-甲烷转换带(SMTZ)的分布情况发现三者相关度很高,表明自生碳酸盐岩的增加很可能是该区域发生的冷泉渗漏导致的甲烷厌氧氧化作用(AOM)所产生的。     

南海北部东沙海域沉积物地球化学特征及其反映的冷泉活动

南海北部东沙海域是典型的水合物成藏区,冷泉活动对其沉积物地球化学特征有显著影响。分析了东沙海域冷泉区973-4站位1 375 cm(水深1 666 m)和973-5站位935 cm(水深2 998 m)长的柱状样的总有机碳(TOC)、总硫(TS)含量,并挑选其中的底栖有孔虫进行了碳氧同位素测试。通过沉积物总硫含量分析和临近站位孔隙水数据分析表明,2个站位沉积物均有较浅的硫酸盐甲烷还原界面(SMI)深度和较大的甲烷通量,其中973-4站位硫酸盐甲烷界面深度为海水-沉积物界面以下约900 cm,973-5站位硫酸盐甲烷界面深度为海水-沉积物界面以下约750 cm。总碳/总硫比值表明冷泉流体活动对沉积物硫埋藏起主导作用。Uvigerina spp.的δ13C表明末次盛冰期(LGM)之前东沙海域有持续的冷泉活动,而自末次盛冰期以来Uvigerina spp.的δ13C其偏负程度逐渐变小、冷泉活动逐渐减弱,这可能是海平面上升扩大了天然气水合物稳定区范围,从而抑制了冷泉流体上涌的结果。     

南海神狐海域沉积物自生黄铁矿和石膏S同位素特征及对甲烷渗漏强度的示踪

The northern slope of the South China Sea is a gas-hydrate-bearing region related to a high deposition rate of organic-rich sediments co-occurring with intense methanogenesis in subseafloor environments.Anaerobic oxidation of methane(AOM) coupled with bacterial sulfate reduction results in the precipitation of solid phase minerals in seepage sediment,including pyrite and gypsum.Abundant aggregates of pyrites and gypsums are observed between the depth of 667 and 850 cm below the seafloor(cmbsf) in the entire core sediment of HS328 from the northern South China Sea.Most pyrites are tubes consisting of framboidal cores and outer crusts.Gypsum aggregates occur as rosettes and spheroids consisting of plates.Some of them grow over pyrite,indicating that gypsum precipitation postdates pyrite formation.The sulfur isotopic values(δ~(34) S) of pyrite vary greatly(from –46.6‰ to –12.3‰ V-CDT) and increase with depth.Thus,the pyrite in the shallow sediments resulted from organoclastic sulfate reduction(OSR) and is influenced by AOM with depth.The relative high abundance and δ~(34) S values of pyrite in sediments at depths from 580 to 810 cmbsf indicate that this interval is the location of a paleo-sulfate methane transition zone(SMTZ).The sulfur isotopic composition of gypsum(from–25‰ to –20.7‰) is much lower than that of the seawater sulfate,indicating the existence of a 34 S-depletion source of sulfur species that most likely are products of the oxidation of pyrites formed in OSR.Pyrite oxidation is controlled by ambient electron acceptors such as MnO_2,iron(Ⅲ) and oxygen driven by the SMTZ location shift to great depths.The δ~(34) S values of gypsum at greater depth are lower than those of the associated pyrite,revealing downward diffusion of 34 S-depleted sulfate from the mixture of oxidation of pyrite derived by OSR and the seawater sulfate.These sulfates also lead to an increase of calcium ions from the dissolution of calcium carbonate mineral,which will be favor to the formation of gypsum.Overall,the mineralogy and sulfur isotopic composition of the pyrite and gypsum suggest variable redox conditions caused by reduced seepage intensities,and the pyrite and gypsum can be a recorder of the intensity evolution of methane seepage.     

Rare earth elements in cold seep carbonates from the southwestern Dongsha area,northern South China Sea

The circulation of methane-rich fluids at cold seeps often leads to the precipitation of seep carbonates close to the seafloor along continental margins, which can be used as records of past fluid seepage. Rare earth element (REE) concentrations in seep carbonates have been used to trace fluid sources and provide information on associated biogeochemical processes at cold seeps. The REE concentrations of a series of carbonates collected from cold seeps in the southwestern Dongsha area of the northern South China Sea are analyzed in this study. The total REE contents (ΣREE) of the seep carbonates analyzed show a wide variation from 17 ppm to 523 ppm with an average ΣREE value of 54 ppm, which are higher than the typical marine carbonate values of ∼28 ppm commonly reported and also higher than those of the carbonates from other cold seep areas. A positive correlation between Fe–Mn content and ΣREE was observed. These results suggest that the seep carbonates of this study were primarily controlled by the methane-derived fluid from which they precipitated. The Fe-rich dolomite and siderite, which are the main components of the carbonates, are responsible for the enrichment of the REE. A slight positive Ce anomaly observed in the shale-normalized REE patterns of the studied seep carbonates suggests that they formed in anoxic conditions, and the correlations between Ce/Ce* and La_N/Sm_N, Ce/Ce* and Dy_N/Sm_N, Ce/Ce* and ΣREE further reveal that the REE characteristics of most seep carbonate samples preserve the original redox conditions in which they precipitated and late diagenesis has had little effect on the REE. However, the REE characteristics of sub-samples DS2-2B, DS1-6A and DS1-7A are very different from those of the other sub-samples, indicating a greater impact of late diagenesis and post-oxidation favored REE enrichment.     

Composition and spatial organization of a cold seep community on the South Barbados accretionary prism: Tectonic, geochemical and sedimentary context

Deep faunal assemblages were observed on cold seeps, between 1000 and 2000m depth, along the southern termination of the Barbados accretionary prism, during the Caracolante II and Diapicar cruises. Faunal composition and microdistribution of a cold seep community were analyzed at one site using deep-sea photographs and seismic (3.5 Kz) profiles. The community is dominated by large mussels up to 20cm long (possibly related to the genus Bathymodiolus), tiny vesicomyid clams, and vestimentiferan clusters in which animals are up to 2m long. There is a high density of sponges (three species), bryozoans and gorgonians. Other taxa occasionally associated with this assemblage include galatheid crabs, anemones, holothurians and possibly pennatulaceans which are numerous at boundaries of the site. A typical deep-sea fauna of fish, asteroids and ophiuroids is also scattered about the vicinity. This seep community is distributed as a band of discontinuous colonies, 40–50m in width and more than 10km in length. Living colonies alternate with accumulations shells and bare areas. The substratum is hard mud covered by a ferrugineous crust and cemented by carbonates. The early diagenetic character of the bottom and the occurrence of biological assemblages indicate that seepages of sulphur and/or methane, which have been revealed along the decollement zone of the Barbados prism, must diffuse through the sea floor. These biological and geological features are located on the crests of NE-SW anticlinal ridges and mud volcanoes which have been built by diaprism.     

胶州湾沉积物中有机硫来源及成因机制的研究

有机硫是海洋沉积物中重要的硫形态,其中成岩有机硫对有机质保存和微量元素形态具有重要影响。利用化学提取及硫稳定同位素研究了胶州湾沉积物中碱可提取的腐殖酸硫(HA-S)、富里酸硫(FA-S)以及铬不可还原有机硫(non-CROS)的垂直分布、来源及形成机制。结果表明,non-CROS、HA-S以及FA-S的含量范围分别为19.1~52.6、3.35~7.82和27.3~38.6μmol/g,均处于其他许多近海沉积物中含量的低值区,且3者均为海洋生物有机硫和成岩有机硫的混合物。HA-S和nonCROS以海洋生物有机硫为主,其份数分别为65%~68%和67%~77%,而FA-S则以成岩有机硫为主(54%~73%)。相对于生物有机硫,成岩有机硫更易被碱和酸性Cr(Ⅱ)溶液提取,因此腐殖质硫和non-CROS都不能全面反映沉积物中有机硫的组成和来源。黄铁矿和腐殖质中成岩有机硫含量随深度的同步增加表明黄铁矿形成并未明显地竞争性抑制有机质硫化。     

Using iron speciation in authigenic carbonates from hydrocarbon seeps to trace variable redox conditions

Seepage of hydrocarbon-rich fluids out of the marine sedimentary column is characterized by temporal changes of flow intensity and resultant spatially variable redox conditions. Authigenic carbonates at marine hydrocarbon seeps provide excellent geological and geochemical archives that serve to explore seepage dynamics over time. In this study, we investigated the potential of Mössbuaer spectroscopy and Fe contents of seep-related authigenic carbonates from the Congo Fan, the Gulf of Mexico, and the Black Sea for reconstructing past redox conditions and fluid seepage activity at cold seeps. The Fe speciation observed by Mössbauer spectroscopy and Fe contents suggest that (1) the Congo Fan carbonates precipitated in a sulfidic environment, (2) the formation conditions of seep carbonates were variable at the Gulf of Mexico seep site, ranging from oxic to suboxic and anoxic and even spanning into the methanogenic zone, and (3) the stratified water column of the Black Sea or suboxic condition resulted in low Fe contents of Black Sea carbonates. The study reveals that Fe speciation can provide constraints on the wide range of redox conditions that imprinted seep carbonates during the life span of seepage. Similarly, Mössbauer spectroscopy – particularly when used in combination with the analysis of redox-sensitive elements – is a promising tool to trace variable redox conditions in marine paleoenvironments other than seeps.     

大西洋中脊胶状黄铁矿的特征及其成因

大西洋中脊热液硫化物（矿床）中广泛出现松散粒状和胶状黄铁矿，利用1988年所采样品通过其形态、成份和热电性质的研究，对这种黄铁矿的成因、环带成因和热液演化特征进行初步探讨。结果表明，松散粒状和胶状黄铁矿是热液进入海底与海水混合后沉积形成，与固结粒状黄铁矿分属不同矿化阶段（期），反映热液活动的多阶段成矿特征；胶状黄铁矿环带和微环带是黄铁矿胶体沉淀后重结晶作用形成的；松散粒状黄铁矿和胶状黄铁矿同时出现是已经停止活动的烟囱物特征。     

Manganese carbonates in the upper quaternary sediments of the Deryugin basin (Sea of Okhotsk)

The mineral and chemical compositions of authigenic carbonates are studied by several methods in a sediment core obtained from the axial zone of the Deryugin riftogenic basin. Manganese carbonates (kutnahorite, rhodochrosite) associated with manganiferous calcite, manganiferous pyrite, and nontronite are first identified in the Sea of Okhotsk. Manganese carbonates in the Holocene diatomaceous ooze were presumably formed due to diagenetic transformation of sedimentary manganese hydroxides, organic matter, and biogenic silica, while those found in the underlying turbidites precipitated owing to the intermittent influx of endogenic fluids migrating along sand interbeds.     

南海冷泉分布特征及油气地质意义

在系统收集和分析南海海底冷泉资料基础上, 应用浅剖和多波束水体影像技术识别海底冷泉,结合地质条件综合研究南海冷泉分布特征,进而分析探讨其油气地质意义。研究结果表明,南海冷泉分布广泛,神狐、东沙西南部、东沙东北部、琼东南、西沙海槽、南沙南部和越南沿岸等海域均发现冷泉, 冷泉分布水深为200～3 000 m。海底冷泉与深部油气乃至浅层天然气水合物资源有着密切的成因联系。冷泉及其伴生物(冷泉碳酸盐岩)的探测与识别对海洋油气勘探,尤其是天然气水合物勘查的指示作用明显。浅剖和多波束水体影像技术不仅可以探测和识别冷泉, 而且两者结合可实现低成本、高效率的海底地质异常体(冷泉碳酸盐岩、泥底辟及气烟囱等)的声学异常探测, 极大地提高了海洋油气勘探及天然气水合物勘查的成功率。     

冷泉系统甲烷气体渗漏的声学特征及潜在环境效应

The amount of methane leaked from deep sea cold seeps is enormous and potentially affects the global warming,ocean acidification and global carbon cycle. It is of great significance to study the methane bubble movement and dissolution process in the water column and its output to the atmosphere. Methane bubbles produce strong acoustic impedance in water bodies, and bubble strings released from deep sea cold seeps are called "gas flares"which expressed as flame-like strong backscatter in the water column. We characterized the morphology and movement of methane bubbles released into the water using multibeam water column data at two cold seeps. The result shows that methane at site I reached 920 m water depth without passing through the top of the gas hydrate stability zone(GHSZ, 850 m), while methane bubbles at site II passed through the top of the GHSZ(597 m) and entered the non-GHSZ(above 550 m). By applying two methods on the multibeam data, the bubble rising velocity in the water column at sites I and II were estimated to be 9.6 cm/s and 24 cm/s, respectively. Bubble velocity is positively associated with water depth which is inferred to be resulted from decrease of bubble size during methane ascending in the water. Combined with numerical simulation, we concluded that formation of gas hydrate shells plays an important role in helping methane bubbles entering the upper water bodies, while other factors, including water depth, bubble velocity, initial kinetic energy and bubble size, also influence the bubble residence time in the water and the possibility of methane entering the atmosphere. We estimate that methane gas flux at these two sites is 0.4×10~6–87.6×10~6 mol/a which is extremely small compared to the total amount of methane in the ocean body, however, methane leakage might exert significant impact on the ocean acidification considering the widespread distributed cold seeps. In addition, although methane entering the atmosphere is not observed, further research is still needed to understand its potential impact on increasing methane concentration in the surface seawater and gas-water interface methane exchange rate, which consequently increase the greenhouse effect.     

Molecular signals for anaerobic methane oxidation in Black Sea seep carbonates and a microbial mat

Linked to gas seeps on the Ukrainian shelf (northwestern Black Sea), massive authigenic carbonates form as a result of anaerobic methane oxidation. Lipid distributions in these ‘cold seep’ carbonates and an associated microbial mat were investigated for process markers reflecting the presence and metabolic activity of distinctive methane-related biota. The samples contain free, irregular isoprenoid hydrocarbons, namely the tail-to-tail linked acyclic C₂₀-isoprenoid 2,6,11,15-tetramethylhexadecane (crocetane), its C₂₅-homologue 2,6,10,15,19-pentamethylicosane (PMI), and several unsaturated derivatives thereof. Furthermore, specific acyclic and cyclic C₄₀-isoprenoids were released upon ether cleavage of the polar fraction from the carbonate. The abundance of these compounds indicates a pronounced role of particular Archaea in the biogeochemical cycling of carbon at methane seeps. Stable carbon isotopic analyses of these lipids reveal extraordinary depletions in ¹³C corresponding to δ-values in the range of −100±30‰ PDB, whereas other compounds show isotopic compositions normally observed for marine lipids (around −30‰ PDB). The isotope data imply that the biosynthesis of the archaeal isoprenoids occurred in situ and involved the utilization of isotopically depleted, i.e. methane-derived, carbon. Apart from archaeal markers, the carbonate and the mat contain authigenic, framboidal pyrite and isotopically depleted fatty acids, namely iso-, and anteiso-branched compounds most likely derived from sulphate-reducing bacteria (SRB). The indications for a tight association of these normally competitive organisms support a model invoking a syntrophic relationship of SRB with Archaea responsible for the anaerobic oxidation of methane. The biomarker patterns obtained from the Black Sea samples were further compared to those from a Oligocene seep carbonate (Lincoln Creek Formation, WA, USA) in order to evaluate their biomarker potential for ancient settings. The prominent occurrence of isotopically light crocetane (−112‰) and PMI (−120‰) meets the findings for the contemporary materials. Thus, isotopically depleted isoprenoids provide diagenetically stable fingerprints for the reconstruction of carbon cycling in both, modern and ancient methane seep systems.     

Authigenic carbonates from methane seeps of the northern Congo fan: Microbial formation mechanism

Authigenic carbonates were collected from methane seeps at Hydrate Hole at 3113 m water depth and Diapir Field at 2417 m water depth on the northern Congo deep-sea fan during RV Meteor cruise M56. The carbonate samples analyzed here are nodules, mainly composed of aragonite and high-Mg calcite. Abundant putative microbial carbonate rods and associated pyrite framboids were recognized within the carbonate matrix. The δ¹³C values of the Hydrate Hole carbonates range from ?62.5‰ to ?46.3‰ PDB, while the δ¹³C values of the Diapir Field carbonate are somewhat higher, ranging from ?40.7‰ to ?30.7‰ PDB, indicating that methane is the predominant carbon source at both locations. Relative enrichment of ¹⁸O (δ¹⁸O values as high as 5.2‰ PDB) are probably related to localized destabilization of gas hydrate. The total content of rare earth elements (REE) of 5% HNO₃-treated solutions derived from carbonate samples varies from 1.6 ppm to 42.5 ppm. The shale-normalized REE patterns all display positive Ce anomalies (Ce/Ce* > 1.3), revealing that the carbonates precipitated under anoxic conditions. A sample from Hydrate Hole shows a concentric lamination, corresponding to fluctuations in δ¹³C values as well as trace elements contents. These fluctuations are presumed to reflect changes of seepage flux.     

Authigenic carbonates from active methane seeps offshore southwest Africa

The southwest African continental margin is well known for occurrences of active methane-rich fluid seeps associated with seafloor pockmarks at water depths ranging broadly from the shelf to the deep basins, as well as with high gas flares in the water column, gas hydrate accumulations, diagenetic carbonate crusts and highly diverse benthic faunal communities. During the M76/3a expedition of R/V METEOR in 2008, gravity cores recovered abundant authigenic carbonate concretions from three known pockmark sites—Hydrate Hole, Worm Hole, the Regab pockmark—and two sites newly discovered during that cruise, the so-called Deep Hole and Baboon Cluster. The carbonate concretions were commonly associated with seep-benthic macrofauna and occurred within sediments bearing shallow gas hydrates. This study presents selected results from a comprehensive analysis of the mineralogy and isotope geochemistry of diagenetic carbonates sampled at these five pockmark sites. The oxygen isotope stratigraphy obtained from three cores of 2–5?m length indicates a maximum age of about 60,000–80,000?years for these sediments. The authigenic carbonates comprise mostly magnesian calcite and aragonite, associated occasionally with dolomite. Their very low carbon isotopic compositions (–61.0?<?δ¹³C ‰ V-PDB?<?–40.1) suggest anaerobic oxidation of methane (AOM) as the main process controlling carbonate precipitation. The oxygen isotopic signatures (+2.4?<?δ¹⁸O ‰ V-PDB?<?+6.2) lie within the range in equilibrium under present-day/interglacial to glacial conditions of bottom seawater; alternatively, the most positive δ¹⁸O values might reflect the contribution of ¹⁸O-rich water from gas hydrate decomposition. The frequent occurrence of diagenetic gypsum crystals suggests that reduced sulphur (hydrogen sulphide, pyrite) from sub-seafloor sediments has been oxidized by oxygenated bottom water. The acidity released during this process can potentially induce the dissolution of carbonate, thereby providing enough Ca²⁺ ions for pore solutions to reach gypsum saturation; this is thought to be promoted by the bio-irrigation and burrowing activity of benthic fauna. The δ¹⁸O–δ¹³C patterns identified in the authigenic carbonates are interpreted to reflect variations in the rate of AOM during the last glacial–interglacial cycle, in turn controlled by variably strong methane fluxes through the pockmarks. These results complement the conclusions of Kasten et al. in this special issue, based on authigenic barite trends at the Hydrate Hole and Worm Hole pockmarks which were interpreted to reflect spatiotemporal variations in AOM related to subsurface gas hydrate formation–decomposition.     

Trace element diagenesis in pyrite-rich sediments of the Achterwasser lagoon, SW Baltic Sea

The early diagenesis of trace elements (V, Cr, Co, Cu, Zn, As, Cd, Ba, U) in anoxic sediments of the Achterwasser, a shallow lagoon in the non-tidal Oder estuary in the Baltic Sea, was investigated in the context of pyrite formation. The dissolved major redox parameters show a two-tier distribution with transient signals in the occasionally re-suspended fluid mud layer (FM) and a permanently established diagenetic sequence in the sediment below. Intense microbial respiration leads to rapid depletion of O₂ within the uppermost mm of the FM. The reduction zones of Mn, Fe and sulfate overlap in the FM and in the permanently anoxic sediment section which appears to be a typical feature of estuarine sediments, under low-sulfate conditions. Degrees of pyritization (DOP) range from 50% in the FM to remarkably high values > 90% at 50 cm depth. Pyrite formation at the sediment surface is attributed to the reaction of Fe-monosulfides with intermediate sulfur species via the polysulfide pathway. By contrast, intense pyritization in the permanently anoxic sediment below is attributed to mineral growth via adsorption of aqueous Fe-sulfide complexes onto pyrite crystals which had originally formed in the surface layer.The studied trace elements show differential behavior patterns which are closely coupled to the diagenetic processes described above: (i) Zn, Cu and Cd are liberated from organic matter in the thin oxic layer of the sediment and diffuse both upwards across the sediment/water boundary and downwards to be trapped as monosulfides, (ii) V, Cr, Co and As are released during reductive dissolution of Mn- and Fe-oxyhydroxides, (iii) U removal from pore water occurs concomitantly to Fe reduction in the FM and is attributed to reduction of U(VI) to U(IV), (iv) the Ba distribution is controlled by reductive dissolution of authigenic barite in the sulfate reduction zone coupled with upward diffusion and re-precipitation. The incorporation of trace elements into pyrite is most intense for Co, Mn and As, intermediate for Cu and Cr and little to negligible for U, Zn, Cd, V and Ba. The observed trend is largely in agreement with previous studies and may be explained with differing rates for ligand exchange. Slow and fast ligand exchange and thus precipitation kinetics are also displayed by downcore increasing (Mn, Cr, Co and As) or constantly low (Zn, Cu, Cd) pore water concentrations. The downward increasing degrees of trace metal pyritization (DTMP) for Co, Cu, Zn and As are, in analogy to pyrite growth, assigned to adsorption of sulfide complexes or As oxyanions onto preexisting pyrite minerals.     

Spatial and seasonal variations in depth profile of trace metals in saltmarsh sediments from Sapelo Island, Georgia, USA

This study was undertaken to elucidate the impact of early diagenetic processes on the accumulation of trace metals in Sapelo Island saltmarsh sediments as a function of time, space and sediment properties. Samples were collected from three sites in summer (May 1997) and winter (January 1998) along a transect from an unvegetated Creek Bank through a vegetated Tidal Levee to the vegetated midmarsh with evident lateral heterogeneity caused by hydrologic regime, macrophytes and microbial and macrofaunal activities. A suite of trace metals (As, Ba, Cr, Co, Cu, Cd, Mo, Ni, Pb, Th, Ti, U, V, Zn and Zr) was analyzed to obtain their depth-distribution at the three sites. Spatially marked differences were observed, that were primarily related to hydraulic flushing of trace metals away from the sites in high-energy regimes, rapid downward mixing and reworking of sediment via bioturbation, and below-ground degradation and production of Spartina biomass. Although sulfate reduction and the formation of acid volatile sulfide and pyrite were dominant processes throughout the marsh, the trace metal scavenging role of sulfides was not apparent. However, possible sulfurization of organic matter, leading to enhanced trapping of trace metals with organic carbon, may have played an important role in sequestration of trace metals.No similarity was observed visually between the depth trends of trace metals and sediment properties (grain size, iron-oxyhydroxide content, acid volatile sulfides and pyrite content) that are known to play a major role in trace metal partitioning. Only organic carbon content closely followed the trace metal profiles at all the three sites. Minor variation in depth-integrated sediment trace metal content was observed seasonally at each of the three sites. Furthermore, the depth trend of profiles of individual trace metals also did not vary significantly over the seasons either.     

A highly concentrated region of cold hydrocarbon seeps in the southeastern Mediterranean Sea

In July 1999, we conducted a side-scan sonar survey in the southeastern Mediterranean Sea, between 300- and 800-m water depths approximately 30 nautical miles from the Sinai Peninsula and Gaza Strip. Examination of the sonar imagery revealed numerous acoustic targets, each on the order of a few meters and surrounded by small depressions. Subsequent visual inspection of two of these targets by a remotely operated vehicle (ROV) revealed they were cold hydrocarbon seeps through which small bubbles of gas and shimmering fluids were emitted. Surrounding each cold seep were benthic communities of organisms. The ROV was used to gather video and still-camera imagery, map the surrounding microbathymetry, and collect samples of the seep structure and associated organisms. A sub-bottom profiler, which was attached to the ROV, was used to image the submerged structure of the second seep site. Further examination and analysis revealed that the seeps comprise hard deposits of calcium carbonate, and that the organisms are clams and polychaetes which are probably chemosymbiotic. The origin of the seep gas is hypothesized to be the natural decay of organic matter in the sapropel sediment, leading to the production of methane. Circulating fluids, which carry the dissolved gas through preferential pathways along small faults or bedding planes, percolate through the seafloor, precipitate calcium carbonate, release gas, and support the benthic organisms.     

Distribution pattern and morphochemical relationships of manganese nodules from the Central Indian Basin

In the Central Indian Basin manganese nodule abundance was variable in all sediment types. Mean abundance varied from 1.5 in calcareous ooze to 10.2 kg/m² in terrigenous-siliceous ooze sediments. Nodule grade and growth rates are positively correlated only up to 10 mm/My (million years), and grade shows no distinct relationship with abundance. Relationships between the morphochemical characteristics of the nodules and host sediment types are subtle. Both hydrogenetic and diagenetic nodules (with smooth and rough surfaces respectively) occur on almost all sediments, but in variable proportions. Thus, the overall distribution pattern shows that small nodules (<4-cm diameters) of lower grade (average value Ni+Cu+Co=1.21%) with smooth surfaces are more common on red clay, terrigenous, and terrigenous-siliceous ooze transition-zone sediments. By contrast, large nodules (>4-cm diameters) of higher grade (average value Ni+Cu+Co=1.80%) with rough surfaces are more prevalent on siliceous ooze, siliceous ooze-red clay, and calcareous ooze-red clay transition-zone sediments. This implies an enhanced supply of trace metals from pore waters to rough-surface nodules during early diagenesis.     

Mineralogy,geochemistry, and sulfur isotope characteristics of sediment-hosted hydrothermal sulfide minerals from the southern Okinawa Trough

Studies of the mineralogy and sulfur isotope composition of sediment-hosted hydrothermal sulfide minerals in cores are important for understanding the seafloor mineralization environment and material source and reconstructing the hydrothermal history. However, the source of ore-forming materials and the history of hydrothermal activity in the southern Okinawa Trough (SOT) remain unclear. Here, the mineralogy and sulfur isotope characteristics of sulfides from gravity core HOBAB4-S2, collected between the Yonaguni Knoll IV hydrothermal field (HF) and the Tangyin HF, was investigated. Enrichments in Zn (up to 321×10?6), Cu (up to 73.7×10?6), and Pb (up to 160×10?6) and the presence of pyrite, galena, pyrrhotite and minor sphalerite and chalcopyrite provide evidence for the input of hydrothermal materials into the sediments. The pyrite morphologies include disseminated cubic, pentagonal dodecahedron, and framboidal forms. Except for minor framboidal pyrite, euhedral pyrite from core HOBAB4-S2 is mainly of hydrothermal origin with Co/Ni ratios >1 and S/Fe atomic ratios <2 in the Cu-Zn-Pb-rich layers. The occurrences of hexagonal pyrrhotite, high-Co (up to 0.17%) pyrite and high-Fe sphalerite indicate that the hydrothermal precipitates formed at medium-high temperatures and low-sulfur fugacity (fS₂) environments. The δ34S values of sulfides (0.21‰–3.45‰) with low- fS₂ mineral assemblages (e.g., pyrrhotite ± high-Fe sphalerite) in the core are significantly lower than those of magmatic rocks and seawater, indicating possible incorporation of previously formed biogenic sulfur in the sediment. Combined with the age model of the core, it is suggested that hydrothermal activity likely began in the Tangyin HF before AD 1445–1483 and that at least three active episodes may have occurred since then.     

The use of diagenetic signatures to distinguish marine from continental deposits in Triassic-Jurassic sandstone reservoirs from the UK Central Graben

Poor biostratigraphic control for some Triassic-Jurassic successions in the North Sea Basin and sub-basins necessitates the use of alternative correlation methods. This study examines the use of diagenetic signatures to distinguish continenetal from marine sandstone successions (Triassic-Jurassic) in the UK Central Graben. The key diagenetic alterations encountered in these successions include kaolinitization of the framework grains and the development of sphaerosiderite and pyrite. The δ ¹³C_V-PDB values of siderite (−8.1 to −8.5‰) and of ankerite (−10.8 to −9.2‰), indicate a strong contribution of dissolved carbon from the decay of plant material in soil. However, marine water likely influenced diagenesis during periods of relative sea level rise by providing the dissolved sulfate (SO₄²⁻) required for the precipitation of pyrite. The presence of diagenetic alterations such as kaolinitization of framework grains and cementation by sphaerosiderite could indicate that the sediments were deposited in an overall continental setting. However, the occurrence of pyrite and scattered grains of deep-green colored glauconite suggests occasional marine influence. Such information on the changes of the diagenetic realm provides important clues for establishing a framework for stratigraphic correlations. Caution should be exercised when interpreting petrographic data as subsequent episodes of telodiagenesis can complicate petrographic interpretations.