沉积物孔隙水地球化学异常:天然气水合物存在的指标

沉积物孔隙水氯度、氧同位素和硫酸盐浓度梯度是指示天然气水合物存在的指标之一，成功的实例 表明：孔隙水氯度明显降低，而δ^18OSMOW向深部升高，线性的，陡的硫酸盐梯度和浅的硫酸盐－甲烷界面（SMI），都是天然气水合物可能存在的标志。     

海水中挥发性卤代烃产生机制研究进展

挥发性卤代烃ＶＨＣ（Ｖｏｌａｔｉｌｅｈａｌｏｈｙｄｒｏｃａｒｂｏｎ）是一类重要的卤代有机物，通常包括卤代甲烷、乙烷和乙烯等挥发性卤代有机物ＶＨＯＣ（Ｖｏｌａｔｉｌｅ ｈａｌｏｇｅｎａｔｅｄ　ｏｒｇａｎｉｃ　ｃｏｍ－ｐｏｕｎｄｓ）。自从人们发现氯氟烃对平流层臭氧有破坏作用以来，挥发性卤代烃（ＶＨＣ）的天然来源及其产生机制引起了广泛兴趣，并开展了大量研究。１９９３年在荷兰召开了首届有机卤化物夭然产生国际学术会议。研究表明，海水中挥发性卤代烃的天然释放对大气中它们的源与汇的影响是显著的［ｌ，２］。如Ｃ…     

南海东北部及吕宋海峡邻近海域海水和大气中挥发性卤代烃的浓度分布与海-气通量

挥发性卤代烃(VHCs)是大气中一类重要的挥发性有机污染物。本文于2020年9月对南海东北部及吕宋海峡邻近海域海水及大气中的二氯二氟甲烷(CFC-12)、三氯氟甲烷(CFC-11)、溴甲烷(CH₃Br)和碘甲烷(CH₃I)的浓度进行了同步测量,探讨了4种VHCs浓度的水平分布及其影响因素,并估算了CH₃Br和CH₃I的海-气通量。结果表明,调查海域海水中CFC-12、CFC-11、CH₃Br和CH₃I的浓度平均值分别为(1.96±0.84)、(5.35±4.86)、(1.26±0.57)和(2.58±0.88)pmol·L^-1。海水中CH₃Br和CH₃I的分布是生物生产释放、陆源输入和光化学等多种因素共同作用的结果。大气中CFC-12、CFC-11、CH₃Br和CH₃I的浓度平均值分别为(480.65±68.55)、(184.07±31.22)、(...     

研究海水交换的示踪剂——氯氟甲烷

最近研究表明,氯氟甲烷(CFM_s)对海洋表面和海洋内部之间的水交换可以起到定量的示踪作用,因而把它作为海水运动和交换的示踪剂。利用CFM_s进行示踪有一个独特的优点是,它在海洋中的扩散性质与CO_2和热的扩散性质完全类似。据在东北太平洋中的测量表明,在深度为100米左右的这层水中CFM_s     

珠江口淇澳岛海岸带沉积物中硫酸盐还原和不同形态硫的分布

对珠江口淇澳岛海岸带3个站位(QA-11,QA-9和QA-14)的沉积物中不同形态的还原硫(酸可挥发性硫,黄铁矿和有机硫)、总有机碳(TOC)和孔隙水中SO42-,甲烷浓度进行了测定,并且利用稳态扩散模型计算其中2个站位(QA-9和QA-14)硫酸盐还原通量[1.74和1.14 mmol/(m2.d)]和甲烷厌氧氧化通量[0.34和0.29 mmol/(m2.d)]。研究结果表明由于潮间带沉积物受到SO42-供给的限制,因此位于潮间带的QA-11站位硫酸盐还原带较浅(约16 cm);在潮下带的QA-9和QA-14站位,随离海岸距离和水深的增加,硫酸盐还原通量呈现减小的趋势,并且硫酸还原逐渐受到可利用活性有机质的限制;甲烷厌氧氧化对硫酸盐还原的贡献表现出增加的趋势,由19.2%增加至25.5%。三个站位沉积物中按不同形态还原硫含量由大到小列出,它们是有机硫(OS)、黄铁矿(DS)、酸可挥发性硫(AVS)。沉积物中AVS的空间分布与硫酸盐还原通量有正相关性。QA-11和QA-14站位的黄铁矿与AVS硫的含量比值大于3,分别为7.9和3.6,表明两个站位的黄铁矿形成可能受硫酸盐还原作用的控制;QA-9站位黄铁矿与AVS硫的含量比值为2.2,暗示AVS向黄铁矿转化受到可利用活性铁的限制。     

台湾地区湖泊甲烷释放量

本研究首次对台湾湖泊的甲烷释放量化评估,以期了解湖泊在台湾地区甲烷总释出量,研究主要利用两种方式进行,一是收集箱实测法,大多运用在交通便利地区,使用甲烷收集箱,定时收集甲烷气,进行浓度分析后,进而估算释放量,另一是利用水汽浓度差估算法,大多运用在交通不便地区,以水体内及接近水体的空气甲烷浓度差,考虑风速及利用理论方程式估算甲烷释放通量,两方法所得到的甲烷释放通量误差在一次方左右。     

海底沉积物-水界面溶解甲烷渗漏通量原位观测研究进展

海底沉积物-水界面溶解甲烷渗漏不仅是海底天然气水合物的存在标志和分解释放途径,也是冷泉生物群落的物质和能量来源,因其对海洋环境乃至全球变化的可能重要影响而日益引起人们关注,而海底原位观测及渗漏甲烷通量估算是理解上述问题的关键。目前国际上有两种较为成熟的海底甲烷通量观测方法:1流体渗漏速率原位测量配以室内甲烷浓度分析;2底栖室流体连续取样配以室内甲烷浓度分析,前者能灵敏反应冷泉渗漏速率的时序变化,而后者具有较高的甲烷通量测量准确度。随着甲烷传感器技术的发展,原位测量方法将大大提高甲烷通量测量精度、时间和分辨率。在可移动式观测平台上搭载甲烷传感器,同时进行近海底界面微尺度甲烷浓度梯度测量和湍流观测,不仅能够精细刻画近海底甲烷浓度变化、渗漏通量变化,并且非封闭环境能够最大限度地避免沉积物-水界面遭受扰动,使观测数据更接近海底真实环境,这成为未来海底原位观测的主要发展方向之一。除此之外,特征冷泉生物群落的分布已被广泛应用于将个别测量站位的观测结果扩展到整个区域的甲烷渗漏流量估算。目前,国外学者已经对部分典型海底冷泉区进行了渗漏甲烷通量估算,发现每个渗漏系统每年通过溶解形式向海水释放甲烷量约为6×103~1.35×107 mol,并且甲烷渗漏在时间上和空间上都是多变的,但还没能将单个冷泉系统的通量估算延伸到更大的时空尺度,这成为深入研究海底甲烷储库及其在全球碳循环和气候变化中的作用的瓶颈之一。     

南海北部陆坡天然气水合物的沉积物孔隙水地球化学研究进展

孔隙水地球化学异常是天然气水合物勘探的重要工具之一,南海北部陆坡地区拥有良好的天然气水合物成藏潜力,孔隙水地球化学异常在南海的天然气水合物勘探中发挥了重要作用。其中与水合物直接相关的氯离子含量异常被用于识别神狐及东沙海域钻探区的水合物层和计算水合物饱和度。除直接指标外,浅表层沉积物中的硫酸盐含量及其他与早期成岩作用有关的地球化学异常作为间接指标可用于水合物的找矿预测,研究者们通过对硫酸盐还原过程的判别、硫酸盐甲烷接触界面的计算等方面对南海北部陆坡不同海域的沉积物甲烷通量进行了评估,预测出水合物可能的成藏区域。其他如碘含量、氧化还原敏感元素、氯同位素、地球化学模型等新的地球化学指标和计算机手段也被应用于南海北部陆坡区水合物成藏研究并取得了不错的成效。     

深海热液喷口金属硫化物中甲烷菌的多样性研究

对两个来自太平洋洋脊胡安·德富卡的两个热液烟囱的金属硫化物4136-2和4148-B1进行甲烷菌甲基辅酶 M 还原酶的编码基因 mcrA 的序列扩增,构建克隆文库并进行分子进化分析.结果表明在这个甲烷富集的热液喷口周围含有丰富的甲烷产生菌,没有任何甲烷氧化菌存在.两个硫化物样品的甲烷产生菌种类完全不同.在4136-2硫化物中的甲烷产生菌都与热液口的高温环境有关系,主要属于甲烷球菌目的甲烷暖球菌(Methanocaldococcus),少部分属于甲烷火菌目甲烷嗜高热菌属的坎氏甲烷嗜高热菌(Methanopyrus kandleri).与这两个属的可分离菌株的氨基酸同源性为89%~97%,核苷酸同源性高达92%~100%.4148-B1硫化物中发现的一类疑似甲基辅酶 M 还原酶的编码序列,它们与已知的甲烷菌 mcrA 序列核苷酸同源性为69%~72%,氨基酸同源性仅为43%~47%.这可能是由于4148-B1来自于正在喷发的超高温热液喷口相关.由于与已发表的甲烷菌克隆子或菌株同源性较低,有可能是热液口特有的以前未发现的甲烷菌     

海洋环境中甲烷好氧氧化过程的研究进展

海洋环境中微生物驱动的甲烷好氧氧化作用是甲烷迁移转化过程的关键环节之一,在降解甲烷方面的贡献不容忽视,能够有效降低甲烷大气通量、影响海洋碳循环。本文系统调研了国内外文献资料,认识到海洋环境中甲烷好氧氧化的赋存范围十分广泛,可赋存于超过3 000 m水深的深海环境、热液喷口等极端环境,其中海底高压、渗漏甲烷的动态运移等是甲烷好氧氧化所面临的特殊环境,在该赋存环境下,好氧甲烷氧化菌主要以Ⅰ型氧化菌为主。Ⅰ型与Ⅱ型氧化菌对甲烷、微量金属元素等环境条件具有一定偏向性,并且在水体和沉积物两种赋存环境下氧化菌的类型也不尽相同。同时,在该赋存环境下甲烷好氧氧化强度存在时间或空间上的差异,受温度、甲烷浓度、氧浓度、微量金属元素等环境因子影响显著,但目前对压力以及甲烷渗漏运移状态对好氧氧化过程的影响规律认识不清。随着深海科研探索不断发展,甲烷氧化菌菌群多样性研究将更加丰富。此外,还需进一步针对海底高压渗漏状态下的好氧氧化过程开展精细研究工作,进一步理解海洋环境中甲烷的好氧氧化规律,这对深刻揭示甲烷迁移转化机制、科学评估甲烷生态环境效应具有重要意义。     

北黄海海水中挥发性卤代烃的分布和海-气通量研究

用吹扫-捕集气相色谱法对北黄海常见的4种挥发性卤代烃(VHC)的研究表明,秋季北黄海表层海水中CHCl3,C2HCl3,CHBr2Cl和CHBr3的浓度和平均值分别为9.9~63.4(14.1±8.1),7.1~29.4(15.4±6.2),0.1~30.3(8.8±10.0)和4.2~56.4(21.6±12.2)pmol/dm3。这4种VHC在水平分布上呈现一定的空间变化,其浓度可能是陆地径流、人为活动和生物产生的影响程度不同造成的。VHC在垂直分布上受到地理位置和水文条件的不同影响,在不同站位有较大差异。周日变化研究表明,VHC具有一定的周日变化特征,受光照和潮汐等因素的共同影响最大值均出现在13:00—16:00。采用Liss和Slater双层模型理论对北黄海表层海水和大气之间CHCl3,C2HCl3和CHBr3的海-气通量进行估算,得到这3种物质在北黄海的海-气通量平均值和范围分别为14.8(0.2~104.4),23.2(1.8~93.0)和15.6(0.7~55.1)nmol/(m2.d)。结果表明,在秋季该研究海域是大气CHCl3,C2HCl3和CHBr3的源。     

Monitoring the carbon dioxide mixing ratio in the troposphere and the methane total column over Siberia according to the data of the AIRS and IASI IR sounders

The development of the AIRS (EOS/Aqua) and IASI (MetOp) satellite hyperspectral IR sounders opens new opportunities for determining the average tropospheric carbon dioxide concentration (X_CO2 X_{CO_2 } ) and total methane content (Q_CH4 Q_{CH_4 } ) in the atmosphere from large distances, which is important in climatic studies and since the ground network for CO₂ and CH₄ observations is scarce. The improved scheme for X_CO2 X_{CO_2 } retrieval from the AIRS data, which was used to construct the X_CO2 X_{CO_2 } spatial distribution based on the AIRS data for July 2003 and 2010 covering Siberia, is presented. A similar methodology was also used to retrieve instantaneous X_CO2 X_{CO_2 } values from the cloud-cleared IASI data for July 7, 2008 and the YAK-AEROSIB experimental region. A comparison of the satellite data with quasi-synchronous aircraft observations gives an error of about 2.2 million⁻¹. The iterative physical algorithm was developed in order to retrieve Q_CH4 Q_{CH_4 } . The efficiency of the proposed algorithm was estimated during the experiments with actual IASI data covering the Siberian region during several days in July 2008. The Q_CH4 Q_{CH_4 } estimates were validated by comparing them with the spatially superimposed and quasi-synchronous Q_CH4 Q_{CH_4 } , estimates based on the AIRS data. The standard deviations of both types of estimates are not more than 3%.     

珠江口表层水中主要常量离子的研究

９９４年９月采集了珠江口表层海水水样,并对其溶解态的Ｋ＋、Ｎａ＋、Ｃａ２＋、Ｍｇ２＋、ＳＯ２－４、Ｃｌ等化学要素进行了测定。结果表明,珠江口调查海域表层水中溶解态的Ｋ＋、Ｎａ＋、Ｃａ２＋、Ｍｇ２＋、ＳＯ２－４主要受陆源淡水与外海水物理混合稀释的影响,与Ｃｌ具有良好的直线正相关;Ｃａ２＋／Ｃｌ、ＳＯ２－４／Ｃｌ明显高于大洋水相应比值,Ｎａ＋／Ｃｌ、Ｍｇ２＋／Ｃｌ略高,而Ｋ＋／Ｃｌ比大洋比值低;在与中国其它各主要河口表层水对应Ｃｌ比较中,珠江口的ＳＯ２－４／Ｃｌ较高,而Ｃａ２＋／Ｃｌ,Ｍｇ２＋／Ｃｌ比值居低;上述各主要常量离子和Ｃｌ的等值线均沿自北向南走向递增。     

天然气水合物的地球化学识别标志及探测技术

介绍了天然气水合物地球化学识别标志及相关的分析测试技术,包括海底沉积物空隙水中阴离子和同位素地球化学异常、标型矿物、海底底层水中CH4异常等。应用地球化学、地球物理、地质方法对天然气水合物进行综合研究,可提高天然气水合物勘探的精确度。     

利用孔隙水Br/Cl、I/Cl比和氯同位素组成来示踪南海北部东沙海域浅层流体来源

The Dongsha area is one of the most promising target areas for gas hydrate exploration in the South China Sea(SCS).The study of pore water geochemistry has played a key role in Chinese gas hydrate exploration.Br/Cl,I/Cl and δ37Cl in pore water were applied here in tracing gas hydrate occurrence,chemical evolution of pore fluids and water/rock interactions in low temperature sediment environments.The samples were collected from Sites HD255 PC and HD309 PC in the Dongsha area in 2004.At Site HD255 PC,we found the elevated Br/Cl,I/Cl and decreased SO_4/Cl at the depth of 4–5 m,suggestive of a laterally migrated fluid probably generated from the gas hydrate occurrence.The range of δ37Cl is –0.54‰ to +0.96‰,and positive δ~(37)Cl at 4–5 m interval should be related with different diffusion rates between ~(35)Cl and ~(37)Cl.At Site HD309 PC,a laterally migrated fluid was also found at the depth of 3–4 m,with the Br/Cl two times to that of the seawater and decreased I/Cl,indicating the fluid has no relationship with the gas hydrate.In this site,the chlorine isotopic composition varies from –0.7‰ to+1.9‰.Extra high Br/Cl might relate with the deep generated fluid.At higher temperature and pressure,the Br/Cl of the fluid is elevated during the hydrous silicate formation,while positive δ37Cl is also associated with the same mechanism.     

Fluid escape structures in the north Sicily continental margin

High resolution and multichannel seismic profiles coupled with multibeam echosounder (seafloor relief) data, acquired along the northern Sicily continental margin (southern Tyrrhenian Sea), document the occurrence of mound and pockmark features, revealing fluid escape processes. Along this margin, morphology of the high-gradient continental slope is irregular due to the presence of structural highs, slope failures and canyons, and is interrupted by flat areas at a mean depth of 1500 m.Seismostratigraphic analysis tools and methods were used to identify fluid escape structures and to work out a classification on the basis of their morpho-acoustic characteristics. The detailed 3D bathymetric chart was used to define the top view morphologic features and their areal distribution. With the aim to evaluate the geochemical content of fluids, we collected a 2.3 m long sediment core in correspondence of a pockmark at a depth of 414 m. Pore waters were sampled every 10 cm and analysed in relation to their conductivity (EC) and composition (δ¹⁸O, δD, Li, Na, K, Mg, F, Cl, Br, NO₃, SO₄).The new data show the occurrence of different types of structures with highly contrasting seismic and morphologic signatures, both dome-type and concave-upward structures. The latter have a characteristic circular shape and are known as pockmarks. Morphobathymetric, stratigraphic and structural data suggest that these structures occur along fault planes, mainly associated with diagenetic carbonates and fluid venting activity. Pockmarks could be the result of both fault and landslide structures, as they appear aligned along a straight direction and occur in proximity of the slope, and are associated with slope instabilities. The structural features are possibly associated with the recent tectonics mapped on-land as well as the widespread seismicity of the margin.Geochemical features reveal that pore water is slightly enriched in heavy isotopes with respect to Mediterranean seawater, while the distribution profiles of EC, ion concentration (Cl, SO₄, Na, K, Mg, Ca), ion/Chloride ratios (Na/Cl, K/Cl, Ca/Cl, Mg/Cl and Alk/Cl) seem to indicate the existence of an external source of fluids and the occurrence of sediment-fluids interaction processes. A possible mechanism causing pore water freshening could be the destabilisation of gas hydrates.     

Production of methyl bromide and methyl chloride in laboratory cultures of marine phytoplankton II

Methyl halides (monohalomethanes), especially methyl bromide, are known to contribute significantly to ozone destruction in the stratosphere. Budgets of natural and anthropogenic methyl bromide suggest that marine organisms may be the source of a significant proportion of the total global production. Since phytoplankton are abundant in surface waters, they are obvious candidates. Cultures of nine phytoplankton species were grown in CO₂-enriched, nitrate-limited medium in sealed glass vessels. Species tested include Chaetoceros calcitrans, Isochrysis sp., Porphyridium sp., Synechococcus sp., Phaeodactylum tricornutum, Tetraselmis sp., Prorocentrum sp., Emiliania huxleyi and Phaeocystis sp. Methyl bromide (CH₃Br) and methyl chloride (CH₃Cl) concentrations were determined by bubbling the cultures with high-purity air, cryotrapping the effluent and analyzing it on a gas chromatograph with an electron capture detector. The Phaeocystis sp. samples were monitored with GCMS. Cell population, bacterial population, Chl a, pH, and nitrate concentration were monitored for periods of at least two weeks. CH₃Cl was produced by all cultures. CH₃Br was absent in Tetraselmis sp. and Isochrysis sp. cultures, but present in all the others. Methyl iodide (CH₃I) was present in most cultures but could not be quantified due to analytical limitations. CH₃I and CH₃Br production was fastest in stationary phase and continued long after cell division had ceased. Axeic cultures of Phaeocystis sp. achieved almost identical production rates of CH₃Cl and CH₃Br as xenic cultures of the same species. Species from tropical waters had faster CH₃Cl and CH₃Br production rates than temperate species. Scaling the observed production rates using global standing stock estimates for Chl a and particulate nitrogen indicate that phytoplankton can account for only a fraction of the CH₃Cl and CH₃Br believed to be produced in the ocean. Calculations based on the estimated global biomass of Phaeocystis sp. and E. huxleyi blooms show that their contribution is insignificantly small.     

印度洋卡尔斯伯格脊6°48′N附近热液羽状流水化学参数异常和颗粒物成分特征

2015年中国大洋33航次在西北印度洋卡尔斯伯格脊6°48′N附近进行了热液异常探测,成功发现了大糦热液区。本文对该热液区附近采集的CTD水样开展了水化学与颗粒物分析。结果表明,在3 150~3 400 m水深范围内水体存在Cl、Br、Mg负异常以及DFe和DMn正异常。其中Cl、Br、Mg的浓度较研究区海水背景值分别亏损2.87%~5.27%、3.21%~4.53%和2.52%~3.82%,Cl和Br的亏损指示海底释放的热液流体曾经发生了相分离。根据Mg的亏损情况,可以估算热液羽状流中热液流体的贡献约3.90%。DFe和DMn的浓度峰值分别为127 nmol/L和29.0 nmol/L,均出现在水深3 150 m层位。颗粒物的电镜观察和能谱分析结果显示,在2 900~3 400 m深度范围内存在热液成因的富铁氧化物(FeO占49.1%~95.2%),与海水样品中发现的高浓度DFe和DMn相印证。根据实测底层流流速与Fe(Ⅱ)扩散半径对研究区的Fe(Ⅱ)氧化半衰期进行了估算,得到大糦热液区Fe(Ⅱ)氧化半衰期为0.56~2.22 h。     

用化学平衡常数判断台湾岛东北部龟山岛附近海域海底热液活动形成自然硫的化学反应

由龟山岛热液气体推断几个可能化学反应方程式的存在,根据相关的假设条件,尽量接近于真实的龟山岛热液环境情况,通过计算、比较这些可能存在的化学反应在标况和龟山岛热液条件下的平衡常数,得出龟山岛热液活动区自然硫的形成可能反应式2H2S(g) O2(g)=2S(s) 2H2O(l)和CH4(g) SO2(g)=3S(s) 2H2O(l) CO2(g)起到了较大的作用。这与龟山岛热液活动所具有的水深浅,周围氧气含量高的事实以及采集的热液气体中含有大量CO2气体等情况十分一致。     

杭州湾溶解态的Ca2+,Mg2+,SO42-

为研究杭州湾河口海水地区性水化学特征,于１９９４年５月和１９９３年８月在杭州湾１４个大面站和两个连续站采集表层海水水样,对Ｃａ＾２＋、Ｍｇ＾２＋、ＳＯ４＾２－及Ｓ,Ｃｌ等化学要素进行了测定。研究结果表明,与黄河口长江口一样,杭州湾中溶解态Ｃａ＾２＋、Ｍｇ＾２＋、ＳＯ４＾２－主要受陆源径流与外海水物理混合稀释的影响,与Ｃｌ具有良好的线性关系。由于受北岸工业排废水的影响,Ｃａ＾２＋与Ｃｌ线性相关比Ｍｇ