海南岛南岸三亚湾海水Sr/Ca、Mg/Ca变化及对珊瑚微量元素温度计的响应

本文对海南岛南岸三亚湾2008~2009年海水的周间隔取样,用全谱直读等离子体原子发射光谱(ICP-AES)分析方法对其Sr/Ca、Mg/Ca比值进行了测定。结果显示其比值（Sr/Ca=8.558~9.227mmol/mol,Mg/Ca=4.924~5.403 mol/mol）与全球各大洋和主要珊瑚礁区有明显地高异常偏差,而且在春末夏初和秋末冬初两个过渡期,三亚湾海水Sr/Ca比值波动幅度比Mg/Ca相对较大,且体现了一定的差异性。在此基础上,结合海水的Sr/Ca、Mg/Ca比值在时间和地域空间上的变化对珊瑚温度计标定的影响,及对不同站点建立的珊瑚Sr/Ca温度计进行了重新校正,并与分配系数法对比分析,我们认为利用珊瑚的Sr/Ca、Mg/Ca比值重建古SST记录时必须综合考虑包括海水微量元素比值变化在内的各种影响因素对温度计标定的干扰。     

南黄海牡蛎壳元素组成的原位微区分析及环境指示

碳酸盐生物壳体的周期性生长纹层是记录气候环境变化的天然材料。随着原位微区测试技术的快速发展,高分辨率的同位素和化学元素组成的快速分析显著推动了古气候环境变化及生物地球化学研究。应用激光剥蚀等离子体质谱仪(LAICP-MS)对南黄海现代牡蛎Crassostrea gigas壳体韧带部的元素组成进行原位微区测试,利用内标元素43Ca进行元素比值的校正,探讨了牡蛎壳中化学元素特征及其环境意义。研究的长牡蛎壳体中Mg/Ca、Sr/Ca、Na/Ca比值具有显著的季节性周期变化。环境水体物理化学性质的变化对壳体生长速率影响较大,壳中白垩质方解石和叶片方解石生长层分别对应较高和较低的环境温度,白垩方解石层具有较高的Mg/Ca、Sr/Ca和较低的Na/Ca比值。Mg/Ca比值可指示牡蛎壳体生长环境水体温度,利用前人Mg/Ca比值公式计算可以恢复与器测资料相符的近岸海水温度结果。本研究对应用LA-ICP-MS分析技术开展高分辨率的生物壳体元素组成和环境示踪研究具有借鉴意义。     

三亚湾海水中Sr/Ca、Mg/Ca 变化及对珊瑚微量元素温度计的响应

对海南岛南岸三亚湾海水2008~2009年周间隔取样,用全谱直读等离子体原子发射光谱(ICP-AES)分析方法对其Sr、Mg、Ca的含量m(Sr)、m(Mg)、m(Ca)进行了测定。结果显示,m(Sr)/m(Ca)=8.558×10-3~9.227×10-3、m(Mg)/m(Ca)=4.924~5.403,与全球各大洋和主要珊瑚礁区有明显的高异常偏差,而且在春末夏初和秋末冬初两个过渡期,三亚湾海水m(Sr)/m(Ca)波动幅度比m(Mg)/m(Ca)相对较大,且体现了一定的差异性。在此基础上,结合海水的m(Sr)/m(Ca)、m(Mg)/m(Ca)在时间和地域空间上的变化对珊瑚温度计标定的影响,对不同站点建立的珊瑚m(Sr)/m(Ca)温度计进行了重新校正,并与分配系数法对比分析,我们认为利用珊瑚的m(Sr)/m(Ca)、m(Mg)/m(Ca)重建古海水表面温度(SST)记录时必须综合考虑包括海水微量元素比值变化在内的各种影响因素对温度计标定的干扰,为进一步了解气候环境演变具有重要意义。     

琼东南盆地与甲烷渗漏有关的早期成岩作用和孔隙水化学组分异常

X-射线衍射和扫描电镜观察表明,采自南海北部琼东南盆地的沉积物样品中有天然气水合物和甲烷渗漏指示意义的自生碳酸盐、硫酸盐和草莓状framboids黄铁矿,自生矿物组合和显微结构特征与冷泉沉积物类似,属微生物成因。沉积物孔隙水化学组分分析结果显示,随着埋藏深度加深,SO₄2-,Ca2+,Mg2+和Sr2+浓度明显降低,Mg2+浓度与Ca2+浓度和Sr2+浓度与Ca2+浓度的比值急剧增加,这些地球化学特征与世界上天然气水合物产区的浅表层沉积物孔隙水中离子浓度异常吻合较好,暗示采样站位深部可能有油气或天然气水合物藏。     

南海东北部GMGS2-16站位自生矿物特征及对水合物藏演化的指示意义

硫酸盐-甲烷转换带(SMTZ)是海洋富甲烷沉积环境中重要的生物地球化学分带,其内发生的甲烷厌氧氧化反应(AOM)通常能影响多种自生矿物(碳酸盐类、黄铁矿、重晶石和石膏等)的形成过程。本文选取南海东北部天然气水合物赋存区GMGS2-16站位的58个沉积物样品,对其中发育的自生矿物进行了类型、含量、分布、显微形貌和稳定同位素研究。GMGS2-16站位岩心沉积物中主要发育碳酸盐类、黄铁矿和石膏3类自生矿物,亦发现单质硫颗粒的存在。自生矿物含量分布变化较大,存在多个富集层位。自生碳酸盐类均为块状,具极负的δ~(13 )C值(-37.3‰~-51.7‰VPDB)和较重的δ~(18 )O值(3.13‰~4.95‰VPDB),指示其为甲烷碳源,即AOM成因。自生黄铁矿主要呈不规则块状、棒状-管状和生物充填状,δ~(34 )S值变化范围为-41.7‰~27.1‰VCDT,其中δ~(34)S值异常正偏很可能与大量甲烷流体上涌至SMTZ内加强AOM反应有关。多层AOM成因的自生碳酸盐类与δ~(34)S值异常的自生黄铁矿产出层位基本吻合,共同指示了研究站位曾发生过多期次甲烷渗漏事件,可能与研究站位天然气水合物藏失稳存在一定联系。自生石膏主要呈棱柱状和透镜状,偶见黄铁矿-石膏共生体,初步推测自生石膏可能与水合物形成过程中的排离子效应和(或)沉积环境氧化还原条件改变导致的黄铁矿氧化有关。因此,海洋沉积物中碳酸盐类-黄铁矿-石膏自生矿物组合对探讨古海洋甲烷渗漏事件和天然气水合物藏的演化具有重要指示意义。     

浮游有孔虫表层水种不同形态类型壳体的Sr/Ca记录

浮游有孔虫表层水种Globigerinoides ruber （白色）和Trilobatus sacculifer壳体是过去海洋环境信息的重要载体,其壳体Sr/Ca比值在重建古海洋环境变化中具有较大潜力,因此本文旨在探讨G. ruber（白色）和T. sacculifer的不同形态类型Sr/Ca比的差异及其影响因素。对取自西菲律宾海的MD06-3047B沉积物岩芯中G. ruber的两种形态类型,即G. ruber(sensu stricto, s.s.)和G. ruber(sensu lato, s.l.),以及T. sacculifer的两种形态类型,即T. sacculifer (with sac)和T. sacculifer (without sac)壳体的Sr/Ca进行了测试分析。结果显示,MIS 3期（～48 ka）以来,MD06-3047B岩芯中G. ruber s.s.和G. ruber s.l.的Sr/Ca差异较小;而T. sacculifer (with sac)和T. sacculifer (without sac)的Sr/Ca存在显著差异,且前者显著高于后者。通...     

南黄海表层沉积物碳酸盐及Ca、Sr、Ba分布特征

依据表层沉积物碳酸盐及元素Ca、Sr、Ba特征,探讨了南黄海表层沉积物的来源及其动力成因。现代黄河物质及老黄河三角洲物质以高钙、高碳酸盐和高Ca/Sr比值为特征;海区东北部物质以低钙、低碳酸盐、低Ca/Sr与Sr/Ba比值为特征,长江物质以碳酸盐及CaO含量、Ca/Sr与Sr/Ba比值中等为特征。表层沉积物碳酸盐、CaO含量及Ca/Sr、Sr/Ba比值的分布对不同特征沉积物的搬运和沉积具有很好的指示意义,南黄海北部Sr/Ba低值带沿NE－SW向延伸大体反映了黄海暖流的入侵路线。     

天然气水合物赋存区甲烷渗漏活动的地球化学响应特征

综述了天然气水合物赋存区甲烷渗漏活动的地球化学响应指标的研究进展,分析了应用单一指标识别甲烷渗漏活动各自所存在的问题,包括浅表层沉积物孔隙水中CH_4、SO_4~(2–)、Cl~–等离子浓度随深度的变化;浅层沉积物全岩W_(TOC)(W表示质量分数,TOC表示总有机碳)和W_(TS)(TS表示总硫)之间的相关性及比值;自生碳酸盐岩δ~(13)C和δ~(18)O;自生矿物重晶石、黄铁矿、自生石膏的δ~(34)S;有孔虫壳体和生物标志化合物的δ~(13)C等。结果表明孔隙水中的CH_4、SO4_~(2–)浓度及溶解无机碳的碳同位素组成可以用来识别目前正在发生的甲烷渗漏活动;而沉积物中的WTS、自生矿物的δ~(34)S、钡含量及其异常峰值和生物标志化合物的δ~(13)C等指标的联合使用可以更真实准确地反映地质历史时期天然气水合物赋存区的甲烷渗漏活动。因此,在实际研究过程中,可将孔隙水和沉积物两种介质的多种指标相结合。随着非传统稳定同位素(Fe、Ca、Mg等)和沉积物氧化还原敏感元素(Mo、V、U等)等研究的发展,甲烷渗漏活动地球化学响应指标的研究也将得到拓展,而多种地球化学指标的联合使用将为天然气水合物勘探及其形成分解过程识别研究提供重要的科学依据。     

有孔虫的高精度Mg/Ca比值的ICP-AES分析

利用等离子体光谱(ICP AES)建立了测量高精度有孔虫Mg/Ca比值的分析方法,并分别对仪器分析误差、残留的铁锰氧化物盖层的影响、有孔虫清洗过程以及有孔虫个体差异等因素对最终结果可能产生的误差进行评估。结果显示:Mg/Ca比值的ICP AES测量的外部精度可达0.3%左右,其引起的温度误差小于±0.1℃;清洗后残留的铁锰氧化物覆盖层中Mg、Ca引起的Mg/Ca比值误差为0.2%～2.7%,引起的温度偏高约0.2℃;有孔虫个体的Mg/Ca比值的差异为0.2%～3.6%,这种差异引起的温度误差为±(0.2～0.4)℃。综合考虑这些因素,利用有孔虫Mg/Ca比值重建表层海水温度(SST)记录时,获得的温度结果的误差在±0.5℃之内,可以满足冰期/间冰期气候变化过程中SST变化研究的要求。     

南海北部东沙海域水合物区浅表层沉积物的地球化学特征

对采自南海北部陆坡东沙海域水合物区HD319、HD196A和GC10站位的浅表层沉积物进行了地球化学特征研究。X射线衍射分析和扫描电镜观察表明,沉积物中存在具有天然气水合物和甲烷渗漏指示意义的自生碳酸盐、硫酸盐和黄铁矿。沉积物孔隙水化学组分分析显示,随着埋藏深度加深,SO42-、Ca2+、Mg2+和Sr2+浓度明显降低,CH4、H2S浓度的增加,以及Mg2+/Ca2+和Sr2+/Ca2+比值急剧增加,与世界上水合物区浅表层沉积物孔隙水中离子浓度异常特征吻合。沉积物顶空气游离烃分析结果和孔隙水化学组分变化,特别是SO42-、H2S和甲烷含量的急剧变化,说明研究区有丰富的气源,赋存水合物的可能性非常大,同时指示了研究区硫酸盐-甲烷界面(SMI)较浅,位于海底之下8m左右。     

A contribution to the reconstruction of Miocene seepage from authigenic carbonates of the northern Apennines (Italy)

Authigenic carbonates from outcrops of the northern Apennines consist of small and irregular lenses and exhibit numerous features indicative of cold-seep settings. Detailed petrographic, mineralogical and geochemical studies from two Miocene deposits are presented. The first carbonate outcrop, named Fosso Riconi, is located in the foredeep basin of the Apenninic chain, whereas the second deposit represents a satellite basin called Sarsetta. The stable isotope data from specific carbonate minerals show a wide range of values well known from other palaeoseeps of the Apennine Mountains. The majority of seep carbonates are formed by low-Mg calcite and ankerite. Those minerals have δ¹³C values between ?7 and ?23‰ V-PDB, suggesting variable amounts of carbonate derived from oxidized methane, seawater (dissolved inorganic carbon) and sedimentary organic matter. Dolomite samples have the lowest δ¹³C values (?30.8 to ?39.0‰ V-PDB), indicating methane as the main carbon source. The findings suggest an evolutionary formation of the seeps and development of authigenic carbonates influenced by the activity of chemosynthetic organisms, of which large lucinid clams are preserved. Bioirrigation by the clams controlled the sediment–water exchange, and is here considered as an explanation for the anomalous Mg content of the calcite. We hypothesize that the seep carbonates were formed during periods of active methane-rich seepage, whereas during periods of slow seepage carbonate formation was reduced. Despite different geological settings, the two examined deposits of Sarsetta and Fosso Riconi show similar features, suggesting that a common pattern of fluid circulation played a major role in carbonate formation at both seep sites.     

热带印度-太平洋浮游有孔虫Pulleniatina obliquiloculata的B/Ca和Cd/Ca指标：次表层海水碳化学参数计算的应用

Pulleniatina obliquiloculata shells from 16 core-top samples from the tropical Indo-Pacific Oceans are analyzed for the ratios of boron and cadmium to calcium(B/Ca and Cd/Ca). The B/Ca ratios show a very weak positive relationship with [B(OH)_4~-] and the dissolved carbonate species at the apparent calcification depth of P.obliquiloculata. The boron partition coefficients(K_D) between P. obliquiloculata B/Ca and seawater[B(OH)_4~-]/[HCO_3~-] distribute around 1.1×10~(-3)-1.3×10~(-3) with a mean value of(1.19±0.12)×10~(-3),and are significantly related to the nutrient concentration, especially phosphate. The lack of any clear correlation between the P. obliquiloculata B/Ca and seawater carbonate chemical parameters suggests that the physiochemical controls on boron incorporation are masked by the complexity of natural seawater condition. But the significant dependence of Ku on nutrient may likely be explained by a nutrient related growth-rate effect. Cd/Ca of P.obliquiloculata shows significant correlation with seawater phosphate concentration, and its partition coefficients(D_(cd)) are significantly related to temperature. A first-principle methodology of P. obliquiloculata B/Ca is applied;with the aid of Cd/Ca as a phosphate proxy and a constraint on K_D, to estimating sea water carbonate chemistry(e.g., pH). The results are fairly promising and allow us to propose the possibility to apply the combination of B/Ca and Cd/Ca proxies(and also Mg/Ca and δ~(18)O for estimating temperature and salinity) for the paleoreconstruction of seawater carbonate chemistry.     

Experimentally determined Mg/Ca and Sr/Ca ratios in juvenile bivalve calcite for Mytilus edulis: implications for paleotemperature reconstructions

To further evaluate the potential use of Mg/Ca and Sr/Ca ratios as a paleothermometer in the shell carbonate of the blue mussel Mytilus edulis, we grew juvenile mussels (～15 mm shell height; <2 years old) collected from Maine, USA, in controlled environments for 4 months. The four-by-three factorial design consisted of four circulating temperature baths (7, 11, 15 and 19°C), and three salinity ranges (23, 28, and 32). During the experiment, water Mg/Ca and Sr/Ca molar ratios were monitored weekly, and showed little variation across all salinity and temperature ranges. Data from sampled shells including all salinity treatments yielded relatively poor relationships between shell elemental chemistry and water temperatures. However, if only the low salinity treatment data (23) are used, the relationships between shell elemental chemistry and water temperature improve moderately. Based on the data presented here, it may be possible to use Mg/Ca and Sr/Ca ratios from the shell carbonate of juvenile M. edulis to reconstruct paleotemperatures in estuarine settings (salinity below 24) with a corresponding RMSE (root mean squared error; 95% confidence interval) of ±2.4°C and ±2.8°C, respectively. In order for this methodology to be statistically meaningful, water temperature changes must be rather large, as the errors associated with using Mg/Ca and Sr/Ca ratios from the shell material of M. edulis are substantial. Further work is required to determine if the findings presented here can be duplicated, and if the potential salinity effect is pervasive.     

胶州湾双壳类壳体中的Ca,Mg,Mn,Sr元素组成及影响因素

探讨影响双壳类元素组成的可能因素,从胶州湾沿岸不同取样点采集黄海近海常见的菲律宾蛤仔(Ruditapesphilippinarum)、褶牡蛎(Oystrea denselamellosa)和紫贻贝(Mytilus galloprovincialis),分别测量了3种壳体的矿物物相类型和壳体中的Ca,Mg,Mn,Sr元素组成。研究表明:3种壳体分别属于文石质、方解石质和混合质壳;Ca,Mn元素含量在菲律宾蛤仔、褶牡蛎和紫贻贝壳体中没有差别,而Mg元素含量在菲律宾蛤仔壳体中含量较低,在褶牡蛎壳体和紫贻贝壳体中含量较高,Sr元素恰好与Mg元素相反。双壳类壳体中元素组成主要受壳体矿物物相类型的制约,而与水体环境要素之间的关系弱。     

滨珊瑚Sr/Ca的种间和种内差异性*

滨珊瑚骨骼的锶和钙元素的比值(Sr/Ca)是重建热带海区海水表面温度(sea surface temperature, SST)变化最常用的地球化学代用指标之一。但是, 珊瑚作为生物体, 其生理活动会对骨骼内的Sr/Ca产生干扰从而影响重建的准确度。文章采用全谱直读等离子体原子发射光谱(Inductively Coupled Plasma Optical Emission Spectrometer, ICP-OES)技术对南海北部涠洲岛两块滨珊瑚的Sr/Ca比值进行测量, 并结合卫星观测的SST值分别建立各个珊瑚个体的Sr/Ca-SST温度计方程。结果显示: 1) 该研究采集的两种滨珊瑚(澄黄滨珊瑚和普哥滨珊瑚)的Sr/Ca值和温度计具有显著的种间差异。因此在古气候重建时, 建议古珊瑚和现代珊瑚严格使用同一种滨珊瑚; 2) 同种滨珊瑚不同个体之间的Sr/Ca也存在差异性, 一方面是由于冬、夏季的极端低、高温对珊瑚生理产生胁迫, 从而造成Sr/Ca出现异常值; 另一方面则是取样误差导致, 尤其是夏季高温和冬季低温时期; 3) 同一珊瑚个体内的不同生长轴的生长率存在显著差异, 然而Sr/Ca却没有显著的差异性, 说明不同生长轴的取样对骨骼Sr/Ca没有显著影响。最后, 文章用多样品的平均值建立Sr/Ca温度计方程, 用于减小个体之间的差异性带来的误差, 得到Sr/Ca(mmol·mol^-1)= -0.04027×SST(℃)+9.623的方程。用该温度计对涠洲岛海域的SST后报的误差为±0.6℃(1σ), 达到了古海温重建的精度需求。     

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‰.     

微量生物碳酸盐ICP-OES元素分析中的仪器优化

为优化电感耦合等离子体发射光谱仪（ICP-OES）测试微量生物碳酸盐中元素含量的工作条件,在Thermo—Fisher公司生产的iCAP6300 Radial型ICP—OES上,对1050组仪器条件、32种不同组成的标准溶液、36个谱线对和两种仪器校正工作曲线进行了测试;借助开源科学计算软件Scilab数据插值和可视化...