动态式抽取,气相色谱法测定海水中的甲烷

本文报道了用动态技术，经抽取、气相色谱法测定海水中溶存甲烷浓度的方法。     

海湾区海水中的溶存甲烷 Ⅰ.分布特征及成因

本文基于日本东京湾、伊势湾和浜名湖的调查资料，详细地讨论了海湾区海水中溶存甲烷的分布特征、成因及其来源。溶存甲烷在海湾中的分布主要受物理混合过程所控制；由河流携入和沉积物中产生是海湾区海水中溶存甲烷的两个主要来源。     

海湾区海水中的溶存甲烷 Ⅱ.浓度、海气交换通量

本文基于日本东京湾、伊势湾和浜名湖的调查资料，详细地比较了这3个海湾海水中的溶存甲烷浓度、饱和度。表层海水中，溶存甲烷浓度以供名湖最高，达95nmol／dm3，伊势湾和东京湾相近，分别为41nmol／dm3和37nmol／dm3；其表层测定浓度是其平衡浓度的13～78倍，并分别计算了这3个海湾中甲烷的海气交换通量；用平均值外推法得出全球海洋环境中总的甲烷海气交换通量为6．3Tg／a。     

海湾区海水中的溶存甲烷I.分布特征及成因

本文基于日本东京湾，伊势湾和滨名湖的调查资料，详细地讨论了海湾区海水中溶存甲烷的分布特征，成因及其来源，溶存甲烷在海湾中的分布主要受物理混合过程所控制，由河流携入和沉积物中产生是海湾区海水溶存甲烷的两种主要来源。     

海湾区海水中的溶存甲烷：Ⅱ.浓度,海气交换通量

本文基于日本东京湾，伊势湾和浜名湖的调查资料，详细地比较了这３个海湾海水中的溶存甲烷浓度，饱和度，表层海水中，溶存甲烷浓度以滨名湖最高，达９５ｎｍｏｌ／ｄｍ＾３，伊势湾和东京湾相近，分别为４１ｎｍｏｌ／ｄｍ＾３和３７ｎｍｏｌ／ｄｍ＾３；其表层测定浓度是其平衡深度的１３－７８倍，并分别计算了这３个海湾中甲烷的海气交换通量；用平均值外推法得出全球海洋环境中总的甲烷海气交换通量为６．３Ｔｇ／ｇ。     

南海中部和北部上层海水中溶存甲烷浓度及海气交换通量*

根据2010年4—5月国家基金委南海多学科综合航次在南海中部和北部的调查资料,利用抽真空气相色谱法测定海水中溶存甲烷浓度,分析了该海区上层海水中溶存甲烷的浓度、饱和度及海气交换通量。南海中部和北部表层海水中溶存甲烷浓度范围为1.15—5.6nmol·L?1,平均值为2.2nmol·L?1,饱和度范围为59.7%—298.8%,59%站位的溶存甲烷处于过饱和状态。甲烷海气交换通量范围分别为?17.7—61.3μmol·m?2·d?1(根据 LM-86方程计算)和?27.9—119.6μmol·m?2·d?1(根据 W-92方程计算)。南海是大气中甲烷的来源之一,年甲烷辐射量估算值为2.7×10?2—4.0×10?2Tg·a?1。     

微分电位溶出法测定生物样品中的镉

电位溶出分析（ＰＳＡ）是７０年代发展起来的一种新颖的分析方法。该方法一问世便在测定海水中痕量元素方面表现出很大优越性。微分电位溶出分析（ＤＰＳＡ）较单纯的电位溶出分析其灵敏度和分析速度得到进一步提高，已应用于海水中痕量金属元素的常规测定。但对于测定生物样品中的痕量元素，方法目前报道不多。 本文采用国产微机化电位溶出仪介绍了动态富集──静态微分溶出分析方法，对摄食了Ｃｄ污染的配合饵料的鲈鱼体内所积累的Ｃｄ进行了测定。该法灵敏度高，操作简便、快速，数据准确可靠，结果令人满意。１材料与方法１．１主要试…     

海水中铋(Ⅲ)的微分电位溶出分析

利用微分电位溶出分析法研究了海水中痕量铋（III）的最适测定条件。结果表明，实验条件选择电解电位（E）为-1．10V，溶出上限电位（E上）为-0.70V，溶出下限电位（E下）为-0．00V，工作电极旋转速度2500rpm.洗电极时间和富集时间分别为30s和600s。适宜的盐度和酸度为5．8－29．0×10-2mol／L和1．00-2.00×10-mol／LHNO3。对在海水中加入5μg／L铋（III）的样品8次测定的相对标准偏差为53％。校正曲线方程为Y=4.77＋55X,相关系数（γ）为0．9993。对青岛沿岸海水测定的加入回收率为96．5％。1994年利用该方法测定青岛沿岸海水中铋（III）的浓度为0．017－0．103μg／L。     

一种改进的温克勒海水溶氧分析方法

本文推荐了一种改进的温克勒（Winkler1888)海水溶解氧的分析方法，并介绍了该方法的基本原理、仪器设备、分析和计算方法等。由于这种改进的分析方法在六个方面作了较大的技术改进，其分析精密度与分析准确度都有了较大的提高。大量的实验数据表明，改进方法的海水溶氧测定精密度约为经典方法精密度的3－5倍，溶氧测量准确度也比经典方法提高了0．8％。本方法可以作为海水溶氧观测仪器计量校准的标准分析方法使用。     

西太平洋雅浦海沟区海水中CH4和DMSP的垂直变化特征

本研究首次探究了西太平洋雅浦海沟北段从表层到超深渊海水中甲烷（CH₄）及二甲基硫（DMS）的前体物质二甲基巯基丙酸内盐（DMSP）的浓度变化情况。结果表明:雅浦海沟海水甲烷浓度变化范围为1.49~3.87 nmol/L。其上层海水甲烷平均浓度最高,有明显的次表层极大现象。雅浦海沟氧最小层海水的甲烷平均浓度最低;在500~1 000 m中层水中甲烷浓度有一定程度的增大,1 000 m以下至底层甲烷浓度继续升高。研究海区溶解态DMSP（DMSPd）和总DMSP（DMSPt）平均浓度的垂直变化随深度呈先增大后减小趋势,颗粒态DMSP（DMSPp）的平均浓度随深度呈波动式变化,在中层达到最大。雅浦海沟CH₄和DMSP浓度垂直变化受浮游生物、微生物、光照、温度、压力、大洋环流等的复杂影响。在真光层海水中,CH₄浓度与DMSPd、DMSPp和DMSPt浓度表现为负相关关系,在200 m至底层海水中,CH₄浓度与DMSPd、DMSPp和DMSPt浓度表现为正相关关系,显示光照条件是造成雅浦海沟不同深度海水CH₄和DMSP浓度相关性差异的关键因素。     

Automatic determination of dissolved organic carbon in seawater in the sub-ppm range

The improvement of a dissolved organic carbon (DOC) analysis technique is described. This continuous flow system, based on both persulfate and UV oxidations, allows the automatic determination of DOC in sea and estuarine waters. The use of FID detection gives a very high sensitivity, permitting the detection of small variations in carbon content. The efficiency of the method and its sensitivity are tested, together with the influence of initial pH and duration of nitrogen bubbling. The system can also be used to determine total or inorganic carbon.     

Pore-water geochemistry in methane-seep sediments of the Makran accretionary wedge off Pakistan: Possible link to subsurface methane hydrate

Cold seeps are pervasive along the continental margin worldwide,and are recognized as hotspots for elemental cycling pathway on Earth.In this study,analyses of pore water geochemical compositions of one-400 cm piston core(S3) and the application of a mass balance model are conducted to assess methane-associated biogeochemical reactions and uncover the relationship of methane in shallow sediment with gas hydrate reservoir at the Makran accretionary wedge off Pakistan.The results revealed that approximately 77% of sulfate is consumed by the predominant biogeochemical process of anaerobic oxidation of methane.However,the estimated sulfate-methane interface depth is-400 cm below sea floor with the methane diffusive flux of 0.039 mol/(m~2·a),suggesting the activity of methane seepage.Based on the δ~(13)C_(DIC) mass balance model combined with the contribution proportion of different dissolved inorganic carbon sources,this study calculated the δ~(13)C of the exogenous methane to be-57.9‰,indicating that the exogenous methane may be a mixture source,including thermogenic and biogenic methane.The study of pore water geochemistry at Makran accretionary wedge off Pakistan may have considerable implications for understanding the specific details on the dynamics of methane in cold seeps and provide important evidence for the potential occurrence of subsurface gas hydrate in this area.     

Influx of Streaming Methane into Anoxic Waters of the Black Sea Basin

Oceanology - Based on long-term data on the spatial distribution and fluxes of streaming (bubbling) methane in the Black Sea, the study considers various types of streaming gas emissions...     

耦合碳、硫同位素及其它地球化学指征研究海底甲烷渗漏

Methane seepage is the signal of the deep hydrocarbon reservoir. The determination of seepage is significant to the exploration of petroleum, gas and gas hydrate. The seepage habits microbial and macrofaunal life which is fueled by the hydrocarbons, the metabolic byproducts facilitate the precipitation of authigenic minerals. The study of methane seepage is also important to understand the oceanographic condition and local ecosystem. The seepage could be active or quiescent at different times. The geophysical surveys and the geochemical determinations reveal the existence of seepage. Among these methods, only geochemical determination could expose message of the dormant seepages. The active seepage demonstrates high porewater methane concentration with rapid SO_4~(2–) depleted, low H_2S and dissolved inorganic carbon(DIC), higher rates of sulfate reduction(SR) and anaerobic oxidation of methane(AOM). The quiescent seepage typically develops authigenic carbonates with specific biomarkers, with extremely depleted ~13C in gas, DIC and carbonates and with enriched ~34S sulfate and depleted ~34S pyrite. The origin of methane, minerals precipitation, the scenario of seepage and the possible method of immigration could be determined by the integration of solutes concentration, mineral composition and isotopic fractionation of carbon, sulfur. Numerical models with the integrated results provide useful insight into the nature and intensity of methane seepage occurring in the sediment and paleooceanographic conditions. Unfortunately, the intensive investigation of a specific area with dormant seep is still limit. Most seepage and modeling studies are site-specific and little attempt has been made to extrapolate the results to larger scales. Further research is thus needed to foster our understanding of the methane seepage.     

海水中微量无机离子的气相色谱测定的研究

本文讨论了介绍了用气相色谱法测定海水中无机离子Ｓｅ（－Ⅱ，Ｏ，Ⅳ，Ⅵ）；Ｂｅ（Ⅱ）；Ｃｒ（Ⅲ，Ⅳ）；ＣＨ３Ｈｇ＾＋，ＮＯ３，ＮＯ２，Ｂｒ，Ｉ，ＣＮ的测定方法和色谱条件。     

Isotopic composition of gas hydrates in subsurface sediments from offshore Sakhalin Island, Sea of Okhotsk

Hydrate-bearing sediment cores were retrieved from recently discovered seepage sites located offshore Sakhalin Island in the Sea of Okhotsk. We obtained samples of natural gas hydrates and dissolved gas in pore water using a headspace gas method for determining their molecular and isotopic compositions. Molecular composition ratios C₁/_C2+ from all the seepage sites were in the range of 1,500–50,000, while δ¹³C and δD values of methane ranged from ?66.0 to ?63.2‰ VPDB and ?204.6 to ?196.7‰ VSMOW, respectively. These results indicate that the methane was produced by microbial reduction of CO₂. δ¹³C values of ethane and propane (i.e., ?40.8 to ?27.4‰ VPDB and ?41.3 to ?30.6‰ VPDB, respectively) showed that small amounts of thermogenic gas were mixed with microbial methane. We also analyzed the isotopic difference between hydrate-bound and dissolved gases, and discovered that the magnitude by which the δD hydrate gas was smaller than that of dissolved gas was in the range 4.3–16.6‰, while there were no differences in δ¹³C values. Based on isotopic fractionation of guest gas during the formation of gas hydrate, we conclude that the current gas in the pore water is the source of the gas hydrate at the VNIIOkeangeologia and Giselle Flare sites, but not the source of the gas hydrate at the Hieroglyph and KOPRI sites.     

南海北部甲烷渗漏活动存在的证据:近底层海水甲烷高浓度异常

用吹扫-捕集法对东沙群岛西南和西沙海槽附近海域5个站位水柱中的甲烷浓度进行了测定,在其中的3个站位发现了甲烷高浓度异常。在东沙群岛西南海域的E105A和E106两站位近底层海水中甲烷浓度均出现异常增加,其值分别为4.25和10.64 nmol/dm3。在西沙海槽附近的E413站位甲烷异常出现在1 750,1 900和2 050 m深的近底层水中,浓度分别达5.17,8.48和8.70 nmol/dm3。在近底层海水中出现的甲烷高浓度异常是由于沉积物下部甲烷渗漏活动造成的,结合前人在这两个海域沉积物的地球物理和化学调查资料,认为可能是与冷泉渗漏或天然气水合物分解有关。2007年5月在探测到甲烷高浓度明显异常的东沙群岛西南神弧海域,获得了天然气水合物的实物样品,但是西沙海槽附近海域近底层水的甲烷高浓度异常是来源于天然气水合物还是来源于冷泉需要进一步加以确认。     

东海海水中的溶存甲烷

基于1994年秋季航次在东海的调查资料,较详细地分析了溶存甲烷在水体中的分布规律、成因和来源.表层水中溶存甲烷呈过饱和状态,饱和度127%～254%,温跃层以上水体中,甲烷的断面分布不同于营养盐的分布,各站测值相近,没有显示出受长江冲淡水的影响,而呈现的舌状分布,在陆架底层水中有明显的高浓度甲烷水体,表明甲烷从沉积物中迅速扩散进入底层水.黑潮次表层水的涌升过程稀释了陆架边缘底层水中的甲烷.在陆架和大洋区测站上,甲烷的垂直分布不同,前者主要受物理混合过程所控制;后者呈大洋区分布特征,在温跃层附近出现甲烷的次表层最大,这可能是陆架底层高浓度甲烷沿等密度面的输送所致.     

Modeling of rising methane bubbles during production leaks from the gas hydrate sites of India

Natural gas hydrates is considered as a strategic unconventional clean hydrocarbon resource in the energy sector. Understanding the behavior of the rising methane gas bubbles during production leaks from the deep marine gas hydrate reservoirs well head is essential for environmental impact studies and to design environmental monitoring systems. Numerical model for quantitatively characterizing the vertical dissolution pattern of the wellhead released methane gas bubbles is analyzed for three potential gas hydrate locations in India. Simulation results indicate that the methane bubbles with diameter of 10?mm can transport methane gas till 650, 800, and 750?m from the seabed in the Krishna–Godavari(KG), Mahanadi and Andaman basins respectively. Results brought out that potential well head damage during methane hydrate production at 1050?m water depth could release up to 28?m³ of methane gas, in which 50% of the molar mass shall get dissolved within 40?m of water column from the seafloor.     

Variations of methane induced pyrite formation in the accretionary wedge sediments offshore southwestern Taiwan

The accretionary wedge of offshore southwestern Taiwan contains abundant deposits of gas hydrate beneath the sea floor. High concentrations of methane in pore waters are observed at several locations with little data concerning historical methane venting available. To understand temporal variation of methane venting in sediments over geologic time, a 23-m-long Calypso piston core (MD05-2911) was collected on the flank of the Yung-An Ridge. Pore water sulfate, dissolved sulfide, dissolved iron, methane, sedimentary pyrite, acid volatile sulfide, reactive iron, organic carbon and nitrogen as well as carbonate δ¹³C were analyzed.Three zones with markedly different pyrite concentration were found at the study site. Unit I sediments (>20 mbsf) were characterized with a high amount of pyrite (251–380 μmol/g) and a δ¹³C-depleted carbonate, Unit II sediments (15–20 mbsf) with a low pyrite (15–43 μmol/g) and a high content of iron oxide mineral and Unit III sediments (<10 mbsf) by a present-day sulfate–methane interface (SMI) at 5 m with a high amount of pyrite (84–221 μmol/g) and a high concentration of dissolved sulfide.The oscillation records of pyrite concentrations are controlled by temporal variations of methane flux. With an abundant supply of methane to Unit I and III, anaerobic methane oxidation and associated sulfate reduction favor diagenetic conditions conducive for significant pyrite formation. No AOM signal was found in Unit II, characterized by typical organically-limited normal marine sediments with little pyrite formation. The AOM induced pyrite formation near the SMI generates a marked pyrite signature, rendering such formation of pyrite as a useful proxy in identifying methane flux oscillation in a methane flux fluctuate environment.