Geochemical studies of pore fluid in surface sediment on the Daini Atsumi Knoll

We collected sediment samples and pore water samples from the surface sediment on the Daini Atsumi Knoll, and analyzed the sediments for CH₄, C₂H₆, and δ¹³C_CH4, and the pore fluids for CH₄, C₂H₆, δ¹³C_CH4, Cl⁻, SO₄²⁻, δ¹⁸O_H2O, and δD_H2O, respectively. A comparison of the measured concentration and isotopic composition of methane in pore water samples with those in sediment samples revealed that methane was present in the sediment samples at a higher concentration and was isotopically heavier than those in the pore water samples. It suggests that the effect of the release of a sorbed gas bound to organic particles when heated prior to analysis of hydrocarbons was larger than that of the degassing process. A large amount of a sorbed gas would be a significant source of natural gas. Two striking features are the chemical and isotopic composition of the pore water samples taken from the different sites around the Daini Atsumi Knoll. In the KL09, KL10, and KP07 samples, Cl⁻ concentrations in the pore water samples showed depletion to a minimum of 460 mmol/kg, correspond to  17% dilution of seawater, however the latter was not enriched in CH₄. The isotopic compositions of pore water samples suggested the low-Cl⁻ fluids in the pore water were not derived from dissociation of methane hydrate, but were derived from input of meteoric water. In contrast, in the KP05 samples from the north flank of the Daini Atsumi Knoll, pore water were characterized by CH₄ enrichment more than 370 μmol/kg, but not depleted in Cl⁻ concentrations. The observed methane concentration in the KP05 samples is not sufficient for methane hydrate to form in situ, indicating that the existence of methane hydrate in the surface sediment is negligible, as supported by Cl⁻ concentration. Based on the stable carbon isotope ratio of methane in the pore fluid from the KP05 site (δ¹³C_CH4 < − 50‰PDB), methane is thought to be of microbial origin. The pore waters in the surface sediments in the north flank of the Daini Atsumi Knoll were not directly influenced by upward fluid bearing methane of thermogenic origin from a deeper part of the sedimentary layer. However, extremely high methane concentration in the north flank site as compared with the concentration of pore water taken from the normal seafloor suggests that the north flank site is not the normal seafloor. We hypothesize that upward migration of chemically-reduced fluids from a deeper zone of the sedimentary layer reduces chemically-oxidized solutes in the surface sediment. As a consequence methane production replaced sulfate reduction as the microbial metabolism in the reduced environment of the surface sediment.     

Rising methane gas bubbles form massive hydrate layers at the seafloor

Extensive methane hydrate layers are formed in the near-surface sediments of the Cascadia margin. An undissociated section of such a layer was recovered at the base of a gravity core (i.e. at a sediment depth of 120 cm) at the southern summit of Hydrate Ridge. As a result of salt exclusion during methane hydrate formation, the associated pore waters show a highly elevated chloride concentration of 809 mM. In comparison, the average background value is 543 mM.A simple transport-reaction model was developed to reproduce the Cl⁻ observations and quantify processes such as hydrate formation, methane demand, and fluid flow. From this first field observation of a positive Cl⁻ anomaly, high hydrate formation rates (0.15-1.08 mol cm⁻² a⁻¹) were calculated. Our model results also suggest that the fluid flow rate at the Cascadia accretionary margin is constrained to 45-300 cm a⁻¹. The amount of methane needed to build up enough methane hydrate to produce the observed chloride enrichment exceeds the methane solubility in pore water. Thus, most of the gas hydrate was most likely formed from ascending methane gas bubbles rather than solely from CH₄ dissolved in the pore water.     

南海北部陆坡西沙海槽XS-01站位沉积物孔隙水的 地球化学特征及其对天然气水合物的指示意义*

天然气水合物是近年来国际上发现的一种新型能源,大量赋存在海底沉积物中。西沙海槽位于南海北部陆坡区,周边有多个大型深水油气田区。对该区地形地貌、地质构造和沉积条件分析以及地球物理BSR分布表明,西沙海槽是我国海洋天然气水合物资源勘查的一个有利远景区。文章主要研究了位于西沙海槽最大BSR区内的XS-01站位沉积物孔隙水的地球化学特征,发现该站位孔隙水阴阳离子浓度和微量元素组成特征变化显示出可能与天然气水合物有关的明显地球化学异常,与国际上己发现有天然气水合物地区的异常相类似。因此,认为该站位是西沙海槽区最有利的天然气水合物赋存区,值得进一步的勘查工作。     

Geochemical characteristics of sediment pore water from Site XS-01 in the Xisha trough of South China Sea and their significance for gas hydrate occurrence

Gas hydrate is a recently-found new source of energy that mostly exists in marine sediments. In recent years, we have conducted gas hydrate exploration in the South China Sea. The Xisha trough, one of the promising target areas for gas hydrate, is located in the northern margin of the South China Sea, adjacent to several large oil and gas fields. The Xisha trough extends 420 km long with the water depth of 1 500 m in the west part and 3 400 m in the east part and deposits thick sediments with organic matter content of 0.41%–1.02%. Previous studies on topographical features, geological P-T conditions, structural geology, sedimentary geology and geophysical bottom simulating reflectors (BSR) in the Xisha trough suggest that this area is favorable for the formation and accumulation of gas hydrate. In this paper, we present geochemical analyses for the sediment and pore water from a piston core at Site XS-01 in the Xisha trough. Seven pore water samples were analyzed for their anion (Cl⁻, SO₄ ²⁻, Br⁻, I⁻) contents, cation (Na, K, Ca, Mg) contents and trace element (Li, B, Sr, Ba, Rb, Mn) contents. Eight sediment samples were analyzed for stable carbon and oxygen isotopic compositions. A number of geochemical anomalies such as anions (e.g. Cl⁻, SO₄ ²⁻), cations (e.g. Ca, Mg) and trace elements (e.g. Sr, Ba, B) were found in this study. For example, the concentrations of Cl⁻ and SO₄ ²⁻ in pore water show a decreasing trend with depth. The estimated sulfate/methane interface (SMI) is only 18 m, which is quite similar to the SMI value of 23 m in the ODP164 Leg 997 at Blake Ridge. The Ca, Mg and Sr concentrations of pore water also decrease with depth, but concentrations of Ba, and Mg/Ca and Sr/Ca ratios increase with depth. These geochemical anomalies are quite similar to those found in gas hydrate locations in the world such as the Blake Ridge and may be related to the formation and dissociation of gas hydrates. The salt exclusion effect during the gas hydrate formation will cause an increase in major ion concentrations in the pore waters that diffused upward such as Cl. The anaerobic methane oxidation (AMO) may lead to the change of SO₄ ²⁻ and other cations such as Ca, Mg, Sr and Ba in pore water. Low δ ¹³C value of authigenic carbonates is a good indicator for gas hydrate occurrence. However, the bulk sediment samples we analyzed all show normal δ ¹³C values similar to biogenic marine carbonates, and this may also suggest that no gas hydrate-related authigenic carbonates exist or their amount is so small that they are not detectable by using this bulk analytical method. In conclusion, we suggest that the Site XS-01 in the Xisha trough of the northern margin of the South China Sea is a potential target for further gas hydrate exploration. Translated from Quaternary Sciences, 2006, 26(3): 442–448 [译自: 第四纪研究]     

The origin of high sulfate concentrations in a coastal plain aquifer,Long Island,New York

Ion-exchange batch experiments were run on Cretaceous (Magothy aquifer) clay cores from a nearshore borehole and an inland borehole on Long Island, NY, to determine the origin of high SO₄²⁻ concentrations in ground water. Desorption batch tests indicate that the amounts of SO₄²⁻ released from the core samples are much greater (980–4700 μg/g of sediment) than the concentrations in ground-water samples. The locally high SO₄²⁻ concentrations in pore water extracted from cores are consistent with the overall increase in SO₄²⁻ concentrations in ground water along Magothy flow paths. Results of the sorption batch tests indicate that SO₄²⁻ sorption onto clay is small but significant (40–120 μg/g of sediment) in the low-pH (<5) pore water of clays, and a significant part of the SO₄²⁻ in Magothy pore water may result from the oxidation of FeS₂ by dissolved Fe(III). The acidic conditions that result from FeS₂ oxidation in acidic pore water should result in greater sorption of SO₄²⁻ and other anions onto protonated surfaces than in neutral-pH pore water. Comparison of the amounts of Cl⁻ released from a clay core sample in desorption batch tests (4 μg/g of sediment) with the amounts of Cl⁻ sorbed to the same clay in sorption tests (3.7–5 μg/g) indicates that the high concentrations of Cl⁻ in pore water did not originate from connate seawater but were desorbed from sediment that was previously in contact with seawater. Furthermore, a hypothetical seawater transgression in the past is consistent with the observed pattern of sorbed cation complexes in the Magothy cores and could be a significant source of high SO₄²⁻ concentrations in Magothy ground water.     

Dating of Dissolved Iodine in Pore Waters from the Gas Hydrate Occurrence Offshore Shimokita Peninsula,Japan: 129I Results from the D/V Chikyu Shakedown Cruise

Iodine concentration and radioisotopic composition (¹²⁹I/I) were measured in the pore waters from the gas hydrate occurrence in the forearc basin offshore Shimokita Peninsula, north-eastern Japan, to determine the source formation of I and accompanying hydrocarbons. Iodine concentrations correlate well with the alkalinity and SO₄ patterns, reflecting degradation stages of I-rich buried organic matter, rapidly increasing in the sulfate reduction interval, and becoming constant below 250 meters below the seafloor with an upwelling flux of 1.5 × 10⁻¹¹ µmol cm⁻² year⁻¹. The ¹²⁹I/I ratios of 300 × 10⁻¹⁵–400 × 10⁻¹⁵ in deep pore waters suggest ages for iodine and hydrocarbon sources as old as 40 Ma. These ages correlate well with the coaly source formations of the Eocene age thought to be responsible for the conventional natural gas deposits underlying the gas hydrate stability zone. Similar profiles are observed in ¹²⁹I/I ratios of pore waters in the gas hydrate stability zone from the forearc basin in the eastern Nankai Trough, offshore central Japan, where pore waters are enriched in I and reach ages as old as ∼50 Ma through the sediment column. At the outer ridge site along the trough, on the other hand, relatively younger I are more frequently delivered probably through thrusts/faults associated with subduction. The nature of source formations of I and hydrocarbons in the offshore Shimokita Peninsula has a more terrestrial contribution compared with those in the Nankai Trough, but these formations are also considerably older than the host sediments, suggesting long-term transport of I and hydrocarbons for the accumulation of gas hydrates in both locations.     

Halogen systematics in the Mallik 5L-38 gas hydrate production research well,Northwest Territories,Canada: Implications for the origin of gas hydrates under terrestrial permafrost conditions

The authors report here halogen concentrations in pore waters and sediments collected from the Mallik 5L-38 gas hydrate production research well, a permafrost location in the Mackenzie Delta, Northwest Territories, Canada. Iodine and Br are commonly enriched in waters associated with CH₄, reflecting the close association between these halogens and source organic materials. Pore waters collected from the Mallik well show I enrichment, by one order of magnitude above that of seawater, particularly in sandy layers below the gas hydrate stability zone (GHSZ). Although Cl and Br concentrations increase with depth similar to the I profile, they remain below seawater values. The increase in I concentrations observed below the GHSZ suggests that I-rich fluids responsible for the accumulation of CH₄ in gas hydrates are preferentially transported through the sandy permeable layers below the GHSZ. The Br and I concentrations and I/Br ratios in Mallik are considerably lower than those in marine gas hydrate locations, demonstrating a terrestrial nature for the organic materials responsible for the CH₄ at the Mallik site. Halogen systematics in Mallik suggest that they are the result of mixing between seawater, freshwater and an I-rich source fluid. The comparison between I/Br ratios in pore waters and sediments speaks against the origin of the source fluids within the host formations of gas hydrates, a finding compatible with the results from a limited set of ¹²⁹I/I ratios determined in pore waters, which gives a minimum age of 29 Ma for the source material, i.e. at the lower end of the age range of the host formations. The likely scenario for the gas hydrate formation in Mallik is the derivation of CH₄ together with I from the terrestrial source materials in formations other than the host layers through sandy permeable layers into the present gas hydrate zones.     

Geochemical relation between gas hydrates and water venting in the seismic blanking zone on the northern Cascadia continental margin offshore Vancouver Island, Canada

The isotopic composition (δD and δ¹⁸O) and chloride concentration (Cl⁻) of pore waters from the northern Cascadia continental margin offshore Vancouver Island were measured to characterize the relations between the water flow regime and the distribution, formation and dissociation of gas hydrates. The δD values of pore waters in gas hydrate-bearing sediments are slightly higher ( 1‰) than those of seawater as the result of gas hydrate dissociation during core recovery and handling. Within the seismic blanking zone, the δD values were slightly lower (− 1‰) than values measured from sites outside the blanking area (0‰). We attribute these differences to 1) distillation of D-rich water during hydrate formation in the center of the blanking zone and 2) limited migration of pore water between inside and outside of the blanking zone due to different fluid fluxes. In contrast, the δ¹⁸O values and Cl⁻ concentrations do not show significant spatial variation due to decreased isotopic fractionation of oxygen and small fraction of chloride relative to hydrogen isotope during gas hydrate formation. The δD value of pore water, therefore, appears to be a sensitive indicator of gas hydrate occurrence. We estimate that gas hydrate occupied at least 2.0 to 6.3% of sediment pore space using δD distribution in this area.     

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

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

Halogen concentrations in pore waters and sediments of the Nankai Trough,Japan: Implications for the origin of gas hydrates

Presented here are halogen concentrations (Cl, Br and I) in pore waters and sediments from three deep cores in gas hydrate fields of the Nankai Trough area. The three cores were drilled between 1999 and 2004 in different geologic regions of the northeastern Nankai Trough hydrate zone. Iodine concentrations in all three cores increase rapidly with depth from seawater concentrations (0.00043 mmol/L) to values of up to 0.45 mmol/L. The chemical form of I was identified as I⁻, in accordance with the anaerobic conditions in marine sediments below the SO₄ reduction depth. The increase in I is accompanied by a parallel, although lesser increase in Br concentrations, while Cl concentrations are close to seawater values throughout most of the profiles. Large concentration fluctuations of the three halogens in pore waters were found close to the lower boundary of the hydrate stability zone, related to processes of formation and dissociation of hydrates in this zone. Generally low concentrations of I and Br in sediments and the lack of correlation between sediment and pore water profiles speak against derivation of I and Br from local sediments and suggest transport of halogen rich fluids into the gas hydrate fields. Differences in the concentration profiles between the three cores indicate that modes of transportation shifted from an essentially vertical pattern in a sedimentary basin location to more horizontal patterns in accretionary ridge settings. Because of the close association between organic material and I and the similarity of transport behavior for I⁻ and CH₄, the results suggest that the CH₄ in the gas hydrates also was transported by aqueous fluids from older sediments into the present layers.     

甲烷水合物生成过程中海水常量离子浓度的变化规律

本文自行研制了一套甲烷水合物合成装置,模拟海洋环境甲烷水合物的生成过程,对该过程水合物生成位置、形态、反应时间、环境温压条件进行观测,同时连续测试体系海水中常量离子K+、Na+、Ca2+、Mg2+、C1-、SO42-的浓度及海水盐度,探讨水合物生成过程的温压变化及离子浓度变化之间的关系和离子浓度的变化规律.结果表明,海水中甲烷水合物生成具有很大的随机性,在相同的初始条件下可能有不同的水合物成核、聚集过程;甲烷水合物在生成过程中,耗气量不断增加,孔隙水的盐度和海水中常量阴阳离子的浓度也在不断增加,这种变化具有较高的线性相关性(相关系数为0.9848～0.9950),且不受甲烷水合物生成位置及状态的影响;在水合物生成过程的微环境下耗气量相同时,离子浓度存在细微的差异.这些特征为通过测定海底水合物周围孔隙水中常量离子的浓度初步推算水合物的甲烷耗气量提供了依据.     

我国海洋地质分析测试技术

21世纪是海洋开发和利用的新世纪,随着国家对海洋地质调查工作的日益重视,海洋地质分析测试技术迎来了快速发展时期。本文对我国海洋地质分析测试技术的最新进展进行了简要评述:为满足海洋区域调查、海岸带地质调查的需要,建立了以大型分析仪器为主的多元素同时分析海洋地质样品的快速高效分析方法体系;针对新能源天然气水合物样品,开展了异常识别测试技术和应用测试技术研究,建立了用离子色谱法快速测定孔隙水中阴离子Cl^-、Br^-、SO₄^2-和阳离子Na⁺、NH₄⁺、K⁺、Ca²⁺、Mg²⁺ 的方法,开发出了以声学、电阻、时域反射(Time Domain Reflectometry, 简称为TDR)三种探测技术为主的适用于天然气水合物模拟实验的探测新技术;对于海洋沉积物中有机污染物样品,采用复合固相萃取净化柱,对海洋沉积物萃取液样品进行净化分离,依次选用正己烷和正己烷－二氯甲烷混合液淋洗固相萃取净化柱,可有效保留基体杂质,实现了海洋环境地质调查中基质复杂沉积物样品的同时净化、分离与测试,可显著提高实验效率;同时在大洋矿产样品分析技术、海洋地质标准物质研制、船载与原位化学探测技术等方面也取得了重要进展。本文还提出在海洋调查和监测的应用中,船载及原位测试技术将愈趋重要,加强海洋化学传感器的性能和检测集成化技术是今后的一个重要发展方向。     

Experimental study on characteristics of pore water conversion during methane hydrates formation in unsaturated sand

Understanding the pore water conversion characteristics during hydrate formation in porous media is important to study the accumulation mechanism of marine gas hydrate. In this study, low-field NMR was used to study the pore water conversion characteristics during methane hydrate formation in unsaturated sand samples. Results show that the signal intensity of T₂ distribution isn’t affected by sediment type and pore pressure, but is affected by temperature. The increase in the pressure of hydrogen-containing gas can cause the increase in the signal intensity of T₂ distribution. The heterogeneity of pore structure is aggravated due to the hydrate formation in porous media. The water conversion rate fluctuates during the hydrate formation. The sand size affects the water conversion ratio and rate by affecting the specific surface of sand in unsaturated porous media. For the fine sand sample, the large specific surface causes a large gas-water contact area resulting in a higher water conversion rate, but causes a large water-sand contact area resulting in a low water conversion ratio (C_w=96.2%). The clay can reduce the water conversion rate and ratio, especially montmorillonite (C_w=95.8%). The crystal layer of montmorillonite affects the pore water conversion characteristics by hindering the conversion of interlayer water.©2022 China Geology Editorial Office.     

盐类对甲烷水合物稳定性影响研究进展

甲烷水合物稳定性主要控制着甲烷水合物稳定带的厚度,温度、压力、孔隙水盐度和气体组分等因素影响着水合物稳定带的厚度。甲烷水合物的形成与地层水关系密切,而地层水中的各种盐离子(Cl~-、Na~+、Mg~(2+)、SO_4(~2-)、Ca~(2+))以及过渡金属(Fe、Mn、Cu、Co、Ni等)会影响天然气水合物的形成和分解条件。因此,研究盐类对甲烷水合物的稳定性认识有助于更加深入了解天然气水合物的成藏条件。本文分析了氯化物、硫酸盐、碳酸盐三大盐类对甲烷水合物稳定性的影响:同一盐类不同盐度条件下,随着盐度的增加,甲烷水合物相平衡曲线向低温高压偏移。总结了不同盐类和阴阳离子对甲烷水合物的抑制作用大小:在相同浓度、不同盐类条件下,盐类浓度在1.0~1.5 mol/L时盐类对甲烷水合物的抑制作用大小为MgCl_2CaCl_2Na ClKCl,盐类浓度大于1.5 mol/L时CaCl_2的抑制作用较强;阴离子对甲烷水合物的抑制作用大小争议较大,阳离子中Mg~(2+)对甲烷水合物的抑制作用最强。从目前的研究成果来看,已有数据与实际地质条件还存在一定差距,需要在真实实验条件下加强氯化物-硫酸盐-碳酸盐-甲烷-水体系的详细研究。本文提出,将高压可视反应腔与显微激光拉曼技术相结合,有望准确获取天然气水合物稳定形成时的温压条件,明确盐类和阴阳离子的抑制作用大小,以及盐类和离子特性如何影响水合物的形成和稳定,以便为未来的水合物勘探开发提供参考。     

Chemical and isotope compositions of shallow groundwater in areas impacted by hydraulic fracturing and surface mining in the Central Appalachian Basin,Eastern United States

Hydraulic fracturing of shale deposits has greatly increased the productivity of the natural gas industry by allowing it to exploit previously inaccessible reservoirs. Previous research has demonstrated that this practice has the potential to contaminate shallow aquifers with methane (CH₄) from deeper formations. This study compares concentrations and isotopic compositions of CH₄ sampled from domestic groundwater wells in Letcher County, Eastern Kentucky in order to characterize its occurrence and origins in relation to both neighboring hydraulically fractured natural gas wells and surface coal mines. The studied groundwater showed concentrations of CH₄ ranging from 0.05 mg/L to 10 mg/L, thus, no immediate remediation is required. The δ¹³C values of CH₄ ranged from −66‰ to −16‰, and δ²H values ranged from −286‰ to −86‰, suggesting an immature thermogenic and mixed biogenic/thermogenic origin. The occurrence of CH₄ was not correlated with proximity to hydraulically fractured natural gas wells. Generally, CH₄ occurrence corresponded with groundwater abundant in Na⁺, Cl⁻, and HCO₃⁻, and with low concentrations of SO₄²⁻. The CH₄ and SO₄²⁻concentrations were best predicted by the oxidation/reduction potential of the studied groundwater. CH₄ was abundant in more reducing waters, and SO₄²⁻ was abundant in more oxidizing waters. Additionally, groundwater in greater proximity to surface mining was more likely to be oxidized. This, in turn, might have increased the likelihood of CH₄ oxidation in shallow groundwater.     

Solute transport in formations of very low permeability: profiles of stable isotope and dissolved noble gas contents of pore water in the Opalinus Clay, Mont Terri, Switzerland

Pore water profiles of water, stable isotope, and dissolved noble gas content have been determined across the Opalinus Clay and adjacent formations at the rock laboratory at Mont Terri. We have found enhanced helium contents (up to [⁴He] = 1 × 10⁻⁴ cubic centimeters at standard pressure and temperature per gram of pore water) and argon isotope ratios (⁴⁰Ar/³⁶Ar ratios up to 334) due to accumulation of ⁴He and ⁴⁰Ar produced in situ. The helium profile was found to be in steady state with respect to in situ production and diffusive loss into the adjacent limestones where groundwater circulates. From this profile a representative mean value of the apparent diffusion coefficient for helium in the pore water of the whole formation was derived for the first time to be D_a = 3.5 × 10⁻¹¹ m² · s⁻¹, which is more than two orders of magnitude lower than the diffusion coefficient D₀ in free water. The stable isotope profile, however, indicates a component of fossil marine pore water, which has not yet been replaced by molecular diffusion of meteoric water from the adjacent limestone and shale formations over the past 10 million years.     

Methane flux from mangrove sediments along the Southwestern coast of Puerto Rico

Although the sediments of coastal marine mangrove forests have been considered a minor source of atmospheric methane, these estimates have been based on sparse data from similar areas. We have gathered evidence that shows that external nutrient and freshwater loading in mangrove sediments may have a significant effect on methane flux. Experiments were performed to examine methane fluxes from anaerobic sediments in a mangrove forest subjected to secondary sewage effluents on the southwestern coast of Puerto Rico. Emission rates were measured in situ using a static chamber technique, and subsequent laboratory analysis of samples was by gas chromatography using a flame ionization detector. Results indicate that methane flux rates were lowest at the landward fringe nearest to the effluent discharge, higher in the seaward fringe occupied by red mangroves, and highest in the transition zone between black and red mangrove communities, with average values of 4 mg CH₄ m^?2 d^?1, 42 mg CH₄ m^?2 d^?1, and 82 mg CH₄ m^?2 d^?1, respectively. Overall mean values show these sediments may emit as much as 40 times more methane than unimpacted pristine areas. Pneumatophores ofAviciennia germinans have been found to serve as conduits to the atmosphere for this gas. Fluctuating water level overlying the mangrove sediment is an important environmental factor controlling seasonal and interannual CH₄ flux variations. Environmental controls such as freshwater inputs and increased nutrient loading influence in situ methane emissions from these environments.     

Calcite dissolution driven by benthic mineralization in the deep-sea: in situ measurements of Ca2+, pH,pCO2 and O2

In situ measured microprofiles of Ca²⁺, pCO₂, pH and O₂ were performed to quantify the CaCO₃ dissolution and organic matter mineralization in marine sediments in the eastern South Atlantic. A numerical model simulating the organic matter decay with oxygen was used to estimate the calcite dissolution rate. From the oxygen microprofiles measured at four stations along a 1300-m isobath of the eastern African margin and one in front of the river Niger at a water depth of 2200 m the diffusive oxygen uptake (DOU) and oxygen penetration depth (OPD) was calculated. DOU rates were in the range of 0.3 to 3 mmol m⁻² d⁻¹ and showed a decrease with increasing water depth, corresponding to an increase in OPD. The calculated amount of degradated organic matter is in the range of 1 to 8.5 gC m⁻² a⁻¹. The metabolic CO₂, released from mineralization of the organic matter drives calcite dissolution in these sediments overlain by calcite-supersaturated water. Fluxes across the sediment water interface calculated from the in situ Ca²⁺ microprofiles were 0.6 mmol m⁻² d⁻¹ for two stations at a water depth of 1300 m. The ratio of calcite dissolution flux and organic C degradation is 0.53 and 0.97, respectively. The microprofiles indicate that CO₂ produced within the upper oxic sediment layer dissolves up to 85% of the calcite rain to the seafloor. Modeling our O₂, pH and Ca²⁺ profiles from one station predicted a calcite dissolution rate constant for this calcite-poor site of 1000 mol kgw⁻¹ a⁻¹ (mol per kg water and year), which equals 95% d⁻¹. This rate constant is at the upper end of reported in situ values.     

Geochemical interactions resulting from carbon dioxide disposal on the seafloor

The storage of CO_2(liquid) on the seafloor has been proposed as a method of mitigating the accumulation of greenhouse gases in the Earth's atmosphere. Storage is possible below 3000 m water depth because the density of CO_2(liquid) exceeds that of seawater and, thus, injected CO_2(liquid) will remain as a stable, density stratified layer on the seafloor. The geochemical consequences of the storage of CO_2(liquid) on the seafloor have been investigated using calculations of chemical equilibrium among complex aqueous solutions, gases, and minerals. At 3000 m water depth and 4°C, the stable phases are CO_2(hydrate) and a brine. The hydrate composition is CO₂·6.3H₂O. The equilibrium composition of the brine is a 1.3 molal sodium-calcium-carbonate solution with pH ranging from 3.5 to 5.0. This acidified brine has a density of 1.04 g cm⁻³ and will displace normal seawater and react with underlying sediments. Seafloor sediment has an intrinsic capacity to neutralize the acid brine by dissolution of calcite and clay minerals and by incorporation of CO₂ into carbonates including magnesite and dawsonite. Large volumes of acidified brine, however, can deplete the sediments buffer capacity, resulting in growth of additional CO_2(hydrates) in the sediment. Volcanic sediments have the greatest buffer capacity whereas calcareous and siliceous oozes have the least capacity. The conditions that favor carbonate mineral stability and CO_2(hydrates) stability are, in general, mutually exclusive although the two phases may coexist under restricted conditions.The brine is likely to cause mortality in both plant and animal comunities: it is acidic, it does not resemble seawater in composition, and it will have reduced capacity to hold oxygen because of the high solute content. Lack of oxygen will, consequently, produce anoxic conditions, however, the reduction of CO₂ to CH₄ is slow and redox disequilibrium mixtures of CO₂ and CH₄ are likely. Seismic or volcanic activity may cause conversion of CO_2(liquid) to gas with potentially catastrophic release in a Lake Nyos-like event. The long term stability of the CO_2(hydrate) may be limited: once isolated from the CO_2(liquid) pool, either through burial or through depletion of the CO₂ pool, the hydrate will decopose, releasing CO₂ back into the sediment-water system.     

天然气水合物成因探讨

天然气水合物是未来的能源资源。其分布于极地地区、深海地区及深水湖泊中。在海洋里,天然气水合物主要分布于外大陆边缘和洋岛的周围,其分布与近代火山的分布范围具有一致性。同位素组成表明天然气水合物甲烷主要是由自养产甲烷菌还原CO₂形成的。典型的大陆边缘沉积物有机碳含量低（＜0．5％～1．0％）,不足以产生天然气水合物带高含量的甲烷。赋存天然气水合物的沉积物时代主要为晚中新世-晚上新世,具有一定的时限性,并且天然气水合物与火山灰或火山砂共存,表明其形成与火山-热液体系有一定联系。火山与天然气水合物空间上的一致性表明,天然气水合物甲烷的底物可能主要是由洋底火山喷发带来的CO2。由前人研究结果推断 HCO^－₃在脱去两个O原子的同时,可能发生了亲核重排,羟基 H原子迁移到 C原子上,形成了甲酰基（HCO^－）,使甲烷的第一个 H原子来源于水。探讨了甲烷及其水合物的形成机制,提出了天然气水合物成因模型。