Using sediment geochemistry to infer temporal variation of methane flux at a cold seep in the South China Sea

Release of methane from the seafloor throughout the world's oceans and the biogeochemical processes involved may have significant effects on the marine sedimentary environment. Identification of such methane release events in marine sediment records can hence provide a window into the magnitude of ancient seeps. Here, we report on analysis of the geochemical composition of samples in a 12.3 m long sediment core (DH-5) collected from a seep site in the South China Sea (SCS). Our aim has been to investigate whether the evidence for the presence of methane release event within sediments is discernible from solid-phase sediment geochemistry. We show that sedimentary total sulfur (TS), δ³⁴S values of chromium reducible sulfur (δ³⁴S_CRS) along with total organic carbon (TOC) and total inorganic carbon (TIC) content can be used to infer the presence of methane release events in cold seep settings. At least three methane release events were identified in the studied core (Unit I at 400–550 cm, Unit II at 740–820 cm, and Unit III at 1000–1150 cm). According to the characteristic of redox-sensitive elements (eg., Mo, U and Mn), we suggest that methane flux has been changed from relatively high (Unit I) to low (Unit II and III) rates. This inference is supported by the coupled occurrence of ³⁴S-enriched sulfides in Unit II and III. AMS ¹⁴C dates from planktonic foraminifera in Unit I suggest that high methane flux event occurred at ∼15.4–24.8 kyr BP, which probably resulted in locally-focused aerobic methane oxidation. Overall, our results suggest that TS, TOC, TIC and δ³⁴S_CRS have potential for identifying present and fossil methane release events in marine sediments.     

Variability of gas composition and flux intensity in natural marine hydrocarbon seeps

The relationship between surface bubble composition and gas flux to the atmosphere was examined at five large seeps from the Coal Oil Point seep field (Santa Barbara Channel, CA, USA). The field research was conducted using a flux buoy designed to simultaneously measure the surface bubbling gas flux and the buoy’s position with differential GPS, and to collect gas samples. Results show that the flux from the five seeps surveyed a total of 11 times ranged from 800–5,500 m³ day^?1. The spatial distribution of flux from the five seeps was well described by two lognormal distributions fitted to two flux ranges. The seafloor and sea surface composition of bubbles differed, with the seafloor bubbles containing significantly more CO₂ (3–25%) and less air (N₂ and O₂). At the sea surface, the mole fraction of N₂ correlated directly with O₂ (R ² = 0.95) and inversely with CH₄ (R ² = 0.97); the CO₂ content was reduced to the detection limit (<0.1%). These data demonstrate that the bubble composition is modified by gas exchange during ascent: dissolved air enters, and CO₂ and hydrocarbon gases leave the bubbles. The mean surface composition at the five seeps varied with water depth and gas flux, with more CH₄ and higher CH₄/N₂ ratios found in shallower seeps with higher flux. It is suggested that the CH₄/N₂ ratio is a good proxy for total or integrated gas loss from the rising bubbles, although additional study is needed before this ratio can be used quantitatively.     

Geologic control of natural marine hydrocarbon seep emissions, Coal Oil Point seep field, California

High-resolution sonar surveys, and a detailed subsurface model constructed from 3D seismic and well data allowed investigation of the relationship between the subsurface geology and gas-phase (methane) seepage for the Coal Oil Point (COP) seep field, one of the world’s largest and best-studied marine oil and gas seep fields, located over a producing hydrocarbon reservoir near Santa Barbara, California. In general, the relationship between terrestrial gas seepage, migration pathways, and hydrocarbon reservoirs has been difficult to assess, in part because the detection and mapping of gas seepage is problematic. For marine seepage, sonar surveys are an effective tool for mapping seep gas bubbles, and thus spatial distributions. Seepage in the COP seep field occurs in an east–west-trending zone about 3–4 km offshore, and in another zone about 1–2 km from shore. The farthest offshore seeps are mostly located near the crest of a major fold, and also along the trend of major faults. Significantly, because faults observed to cut the fold do not account for all the observed seepage, seepage must occur through fracture and joint systems that are difficult to detect, including intersecting faults and fault damage zones. Inshore seeps are concentrated within the hanging wall of a major reverse fault. The subsurface model lacks the resolution to identify specific structural sources in that area. Although to first order the spatial distribution of seeps generally is related to the major structures, other factors must also control their distribution. The region is known to be critically stressed, which would enhance hydraulic conductivity of favorably oriented faults, joints, and bedding planes. We propose that this process explains much of the remaining spatial distribution.     

南海北部大陆坡冷泉碳酸盐结核的发现:天然气水合物新证据

南海北部大陆坡是我国天然气水合物调查和研究的重点海域,目前已发现了多处水合物存在的地球物理、地球化学、海底地貌特征等证据。冷泉碳酸盐的析出是天然气水合物冷泉存在的重要明显标志之一,已成为南海北部继地球物理BSR标志后发现的与水合物存在相关的另一重要证据。中国科     

Benthic macrofauna in a shallow water carbonate sediment: major bioturbators at the Dry Tortugas

 Functional group analysis was used to determine the major bioturbators in the Dry Tortugas, Florida Keys. The surface community is dominated by surface deposit feeding polychaetes and burrowing bivalves capable of mixing the top 0–4 cm of the sediment on time scales of days to weeks. Bioturbation by the Notomastus sp. and Callianassa sp. deep community effectively removes primary sedimentary structures. Their fossilized burrow structures may be geologically important in this system. Surface microtopography is controlled by stabilizing and destabilizing forces that determine the potential for surface resuspension and sediment transport in the Dry Tortugas.     

海?气界面气体交换速率与二氧化碳气体通量的估算

海?气界面CO₂通量的估算采用块体公式,其等于气体交换速率、CO₂溶解度以及海水与大气的CO₂分压差的乘积,其中的气体交换速率通常与风速相联系,不同作者提出了气体交换速率为风速不同幂次多项式的参数化方案。本文对比了气体交换速率为风速函数的主要研究结果,发现与风速多项式的依赖关系相比,观测数据所基于的观测方法对于气体交换速率的影响更大。在此基础上,本文用多种不同的气体交换速率参数化公式计算了1982?2018年全球的CO₂通量,海洋整体上是大气CO₂的汇,赤道海区是源,南北半球40°附近的海域构成沿纬向的强吸收带。37 a间,海洋CO₂通量的年平均值(以碳计)为(?1.53±0.15) Pg/a, 1999年前,海洋吸收量逐年减小,1999年达到最小值,之后海洋吸收量开始增大,海洋吸收量的增大主要发生在南大洋。     

Dissolution of carbonate minerals in a subtropical shallow marine environment

Carbonate saturation state with respect to calcite and three different biogenic magnesian calcites has been determined by a modified saturometry technique. Measurements were made in the water column of Devil's Hole, a 25 m-deep basin in the Harrington Sound (Bermuda), which exhibits oxygen depletion in subthermocline waters during summer. Supersaturation in the entire water column was attained with respect to marble calcite. The biogenic carbonates analyzed became undersaturated below the thermocline within a narrow depth range, soon after P_CO2 exceeded 600 ppm. It is concluded that high magnesian calcites can be attacked during a significant portion of the year in these waters. Possible implications for the global CO₂ cycle are discussed.     

Reduced magnetization produced by increased methane flux at a gas hydrate vent

Magnetic susceptibility measurements on near-surface sediment cores from the North Cascadia accretionary sedimentary prism show that seismic blanking or wipe-out zones in the upper few hundred metres of sediments are associated with a prominent low magnetic susceptibility signature. Seismic blanking and low magnetization are both attributed to high upward methane flux within a vent zone, as evidenced by the presence of massive gas hydrate within the cores. Sedimentological analysis of these cores also reveals the presence of authigenic pyrite within the areas of magnetic susceptibility lows. This phenomenon is suspected to be produced by the reducing environment associated with the high upward methane flux and increased bacterial activity within the topmost sediments, resulting in diagenesis of highly magnetic detrital minerals such as magnetite into nearly non-magnetic pyrite. These low magnetic susceptibility zones may produce magnetic anomalies with a magnitude of 10–35 nT near the seafloor. Such anomalies might be detected using high-resolution near-bottom magnetometers to provide a means of mapping zones of methane venting.     

Petrographic and geochemical characterization of seep carbonate from Bush Hill (GC 185) gas vent and hydrate site of the Gulf of Mexico

Authigenic carbonates are common at cold seep sites as a result of microbial oxidation of hydrocarbons. Seep carbonate samples were collected from the surface of the Bush Hill (Green Canyon Block 185, Gulf of Mexico), a mound containing gas hydrate. The carbonates consisted of oily, porous limestone slabs and blocks containing bioclasts and matrix. Analysis by X-ray diffraction shows that aragonite is the dominant mineral (89–99 wt% with an average of 94 wt%) in the matrix of seep carbonate. This cement occurs in microcrystalline, microspar, and sparite forms. The moderate ¹³C depletion of the seep carbonate (the most depleted one has δ¹³C value of −29.4‰, and 26 of 38 subsamples have δ¹³C values >−20.0‰) indicates that the non-methane hydrocarbons was incorporated during seep carbonate precipitation. Relative enrichment of ¹⁸O may be related to localized destabilization of gas hydrate or derived from ¹⁸O-enriched pore water originated from smectite–illite transition in the deep sediments. The total content of rare earth elements (REE) of the 5% HNO₃-treated solution of the carbonates is from 0.40 ppm to 30.9 ppm. The shale-normalized REE patterns show varied Ce anomalies from significantly negative, slightly negative, and no to positive Ce anomalies. Variable content of trace elements, total REE, and Ce anomalies in different samples and even in the different carbonate mineral forms (microcrystalline, microspar and sparite) of the same sample suggest that the formation condition of the Bush Hill seep carbonate is variable and complex, which is possibly controlled by the rate of fluid flux.     

Compositional changes in natural gas bubble plumes: observations from the Coal Oil Point marine hydrocarbon seep field

Detailed measurements of bubble composition, dissolved gas concentrations, and plume dynamics were conducted during a 9-month period at a very intense, shallow (22-m water depth) marine hydrocarbon seep in the Santa Barbara Channel, California. Methane, carbon dioxide, and heavier hydrocarbons were lost from rising seep bubbles, while nitrogen and oxygen were gained. Within the rising seawater bubble plume, dissolved methane concentrations were more than 4 orders of magnitude greater than atmospheric equilibrium concentrations. Strong upwelling flows were observed and bubble-rise times were ~40 s, demonstrating the rapid exchange of gases within the bubble plume.     

Meiofauna and chlorophyll associated with Beggiatoa mats of a natural submarine petroleum seep

Previous studies at the Isla Vista oil seep have suggested that meiofauna, particularly nematodes, might be an important factor in explaining macrofaunal enrichment by making bacterial biomass available to the benthic food web. To explore this possibility, we analyzed meiofaunal abundance and microalgal pigments inside and just outside of bacterial mats at this natural oil seep.The bacterial mats occur where crude oil and natural gas are actively seeping out of the sediment; cores from within the mats contained a great deal of crude oil (up to 50 %). Meiofaunal abundances were the same in and out of the bacterial mats (averaging 1·-9 × 10⁶ individuals m^-2). However, dramatic changes in community structure were noticed. Harpacticoids made up 19 % of the fauna outside the mats but only 1 % inside. Pigment concentrations were also the same in both sites with phaeophytin dominating chlorophyll (120 compared to 29.8 mg m^-2). The variance of both microalgal pigments and meiofauna was much greater inside than outside, suggesting that the bacterial mats are a more heterogeneous environment.Although the effect of crude oil toxicity is not clear, the high abundances of microbial and meiofaunal biomass support the hypothesis of benthic enrichment via microbes and meiofauna.     

Authigenic Mg-calcite at a cold methane seep site in the Laptev Sea

Authigenic minerals were studied in Holocene shelf sediments of the Laptev Sea (cold methane seep site, water depth 71 m). The study presents the first finds of large hard carbonate concretions with Mg-calcite cement in recent sediments of the Arctic shelf seas. These concretions differ from previously reported glendonites and concretions from bottom sediments of the White Sea, Kara Sea, Sea of Okhotsk, etc. A study of the morphology, microstructure, and composition of these newly reported concretions revealed the multistage formation of carbonates (structural varieties of Mg-calcite and aragonite). It was shown that organic matter played an important role in the formation of authigenic carbonates, i.e., in the formation of sedimentary–diagenetic Mg-calcite. The role of methane as a possible source for authigenic carbonate formation was estimated. It was found that methane-derived Mg-calcite accounts for 17–35% of concretion materials. Mg-calcite had δ¹³С-С_carb values between–24 and–23‰ and δ¹³С-С_org values between–44.5 and–88.5‰.     

A numerical study of a shallow sea front generated by the buoyancy flux

We numerically investigated the physical process of water exchange caused by fluctuations of the front. This front is formed in a vertically two-dimensional NH-model (non-hydrostatic model) under steady forcing and simulates well the front observed during winter in the Kii Channel, Japan. The velocity field in the model has two kinds of oscillations. The first has a period of 6∼12 hr and is caused by intermittent gravitational convection in the frontal zone. The period and the intensity of intermittent convection are determined by buoyancy flux through the side boundaries as well as surface cooling. The other is associated with large scale circulation driven at the side boundaries and is controlled by the Coriolis force and the bottom stress. Its period of 3∼4 days is determined by the sum of the inertial period and the spin down time for the baroclinic mode of the along-front velocity component. These oscillations make the position of the front fluctuate with the same periods. We next examined water exchange across the fluctuating front by numerically tracking a number of labelled particles. Intermittent convection induces exchange of particles in the frontal zone and large scale circulations transport the exchanged particles toward offshore or onshore through the lower layer. The exchange rate and the dispersion coefficient are calculated in the NH-model as 0.85 and 2.3×10³ cm² sec⁻¹, respectively. On the other hand, in the H-model (hydrostatic model) parameterizing gravitational convections with a convective adjustment method, these values are reduced to 0.68 and 3.2×10² cm² sec⁻¹, respectively. This result implies that intermittent convections in the frontal zone have a large effect on water exchange across the front, and that no little water is exchanged across the fluctuating front in an actual shallow sea, such as observed in the Kii Channel.     

A natural laboratory for shallow gas: the Rías Baixas (NW Spain)

Interpretation of acoustic seismic records have allowed mapping of shallow gas accumulations and gas escape features in the Rías Baixas. X-ray photographs and voids of cores are semi-direct evidence of gassy sediments. Mapping of fluid-escape areas shows that these are related to the gas accumulations or at the intersections of faults. Analyses (GC-MS) of bubble samples collected in Simón Bay (Ría de Vigo) and across the whole ría confirm the presence of methane. The spatial distribution of gas escapes/accumulations and their vertical variations are interpreted as evidence of sedimentary facies control. The appearance of authigenic minerals (gypsum, pyrite and aragonite) and microbiological activity related to the seal facies are taken as evidence of the biogeochemical coupling processes. It is evident that these shallow-water coastal environments make significant contributions to the methane budget of the hydrosphere and atmosphere. It is also suggested that microbiological activity is favoured by gas escapes.     

The steady-state calcium carbonate ion activity product of recent shallow water carbonate sediments in seawater: a comparison of field observations and laboratory experiments

Closed system equilibration experiments between natural seawater and shallow water calcium carbonate-rich sediments from the Bahamas yielded steady-state calcium carbonate ion activity products (CCIAP). Results obtained from initially supersaturated and undersaturated solutions were in good agreement. Experiments conducted with the addition of a biocide and/or the destruction of sediment organic matter gave results similar to those obtained in systems where these treatments were not used. Excellent agreement was also found between CCIAP values for 8 day and more than 50 day equilibration times. Our results, therefore, meet the major criteria for at least metastable equilibrium between the solution and carbonate sediment.Fine-grained samples produced a CCIAP close to the value predicted for aragonite, which is the major carbonate phase in all samples. Coarse-grained sediments produced larger CCIAP values of up to 2.8 times that predicted for aragonite equilibrium. The CCIAP for the coarse-grained sediments is probably produced by high-Mg calcite which is a significant component of these sediments. Oolite samples were among the coarse-grained sediment samples studied. They also produced results much greater than expected for aragonite equilibrium. This brings into question their use as material for measuring aragonite solubility as has been done in the past.The CCIAP measured in the laboratory experiments are in good agreement with field observations of pore-water CCIAP values from the fine-grained sediments. Coarse-grained sediments showed greater variability, with higher CCIAP values generally occurring in the pore waters than in the laboratory experiments. Since the overlying waters were always at a higher CCIAP than the pore waters, the major factor causing this difference is believed to be the short residence time of pore waters in the coarse-grained sediments, which is the result of the high-energy hydrodynamic environments in which they reside.     

Compositional variability and air-sea flux of ethane and propane in the plume of a large, marine seep field near Coal Oil Point, CA

Large quantities of methane (C1), ethane (C2), and propane (C3) emanate from shallow marine seeps near Coal Oil Point (COP), California. Concentrations of these gases were analyzed in the surface water down-current of the seep field over a 15-month period. The variable proportions of C1, C2, and C3 analyzed in gas bubbles emitted from 16 distinct seeps in the COP field encompass much of the variability found in the surface waters down-current. However, waters with disproportionate levels of C1 suggest the presence of additional C1 sources. Based on three spatial surveys, covering areas up to 280 km², C2 and C3 air-sea fluxes were estimated to be in the order of 3.7 and 1.4 μmol day^?1 m^?2, respectively. Only 0.6% of C2 and 0.5% of C3 in the dissolved plume originating from the COP seep field are transferred to the atmosphere in the study area, with the fate of the remainder uncertain.     

Bacterial iron oxide reduction in a terrigenous sediment-impacted tropical shallow marine carbonate system, north Jamaica

Discovery Bay, a carbonate-dominated embayment in north Jamaica, has been subject to inputs for 40 years of iron-rich bauxite sediment associated with the local mining and transport of processed bauxite. As such, this site is an ideal natural laboratory to study the records and impacts of iron oxide inputs upon geochemical, diagenetic, and microbial processes in tropical carbonate sediments.Total Fe contents in sites in the bay not receiving bauxite inputs are negligible and porewater Ca²⁺, SO₄²⁻ and Cl⁻ indicate that bacterial sulphate reduction is an important process. In contrast, surface sediments receiving bauxite inputs contain significant total Fe, from 44 μmol/g in shallow (5 m water depth) sites to 110 μmol/g in deeper (20 m water depth) sites. Up-core increases in total Fe record increased temporal inputs into the bay. Within these Fe-rich sediments porewater data shows the presence of Fe^II released by bacterial Fe^III reduction. There is no direct evidence for significant bacterial sulphate reduction in these sediments. Iron oxides within all bauxite-impacted sediments display a high potential reducibility, from 40% to 80% of the total Fe present as dithionite-extractable Fe^III. Experimental analysis of the potential susceptibility to, and rates of, bacterial Fe^III reduction, utilising Discovery Bay sediment and Shewanella putrefaciens CN32 (a known Fe^III-reducer) has confirmed the high bacterial reducibility of iron oxides within the sediment. Up to 75% of initial dithionite-extractable Fe^III in the sediments was reduced over 15 days.The presence of iron oxides within the Discovery Bay shallow marine carbonate systems has markedly altered the chemical diagenetic processes taking place, with a shift from apparent dominance of bacterial sulphate reduction at non-impacted (Fe-poor) sites, to highly significant bacterial Fe^III reduction in Fe-rich bauxite-impacted sediments. Given the perceived global increases in terrigenoclastic sediment inputs into tropical carbonate systems as a result of land-use and climate changes, coupled with the documented role that iron oxide reduction plays in nutrient and contaminant cycling in sediment systems, more research into the perturbation of early diagenesis by iron oxide inputs is required.     

多波束水体数据对台西南盆地天然气水合物的揭示

在台西南盆地陆坡上进行了多波束测量,获取了海底地形数据和水体数据。对多波束数据进行处理,展示了多波束水体数据形成的声学水柱影像。研究表明：在台西南盆地天然气水合物富集区,多波束水柱影像异常,呈现羽状流特点,揭示了台西南盆地的天然气资源,多波束声呐系统为探测海底天然气水合物提供了精确高效的方法。