生物壳体Sr／Ca、Mg／Ca、^87Sr／^86Sr比值在恢复古气候、古环境中的应用—以小渡口剖面为例

生物壳体的Sr/Ca、Mg/Ca比值能反映其沉积水体的Sr/Ca、Mg/Ca比值，在一定条件下反映水体的盐度、温度，并分别与宿生水体的盐度、温度呈正比关系。生物壳体的^87Sr/^86Sr比值是恢复盆地古水文条件的一种重要手段。本文以著名的泥河湾盆地小渡口剖面的第28层为实例，力图通过对有孔虫、介形虫、腹足类生物壳体Sr/Ca、Mg/Ca比值与^87Sr/^86Sr比值的对比研究，并结合前人所作的中更新世古地理特征研究，来恢复生物壳体沉积时泥河古湖水的温度、盐度，进而进行古气候、古环境的恢复。研究结果表明：在0.97-0.94Ma间，古泥河湾湖为一陆相湖泊，湖水的温度、盐度变化趋势相吻合，均呈低－高－低的演化特征，可能对应着盆地水体的扩展－退缩－扩展变化。其中，在0.96-0.95Ma间，古泥河湾湖具有较高的温度、盐度特征。     

印尼海区浮游有孔虫壳体Mg/Ca值的LA-ICP-MS原位微区分析

激光剥蚀电感耦合等离子质谱仪(Laser Ablation-Inductively Coupled Plasma-Mass Spectrometer,LA-ICP-MS)为更详细地探索微量元素在有孔虫方解石壳体中的分布提供了可能,也为有孔虫壳体Mg/Ca值测试提供了一种新的方法。利用LA-ICP-MS技术对擭取自印尼海区的11个钻孔顶部沉积样品中的多枚Globigerinoides ruber壳体进行了共173点位的激光剥蚀Mg/Ca值原位微区和深度分析,发现不同壳体、同一壳体不同房室以及同一房室不同部位之间,从壳壁外部到内部Mg/Ca值的变化是不同的。随后,将利用LA-ICP-MS获得的Mg/Ca值与利用常规测试手段获得的Mg/Ca值进行对比,结果表明利用LA-ICP-MS测试浮游有孔虫壳体Mg/Ca值,不但可以避免常规测试复杂的前处理过程,减少化学药品对实验人员健康的危害,也具有较好的准确度和可靠性。     

青藏高原湖泊水化学与盐度的相关性初步研究

本文综合分析了青藏高原地区400多个湖泊的水化学成分(Mg2+、Ca2+、Sr2+、Sr/Ca和Mg/Ca)与湖水盐度的相关关系,以及这种关系随着湖水变化(不同采样时间和采样点以及蒸发实验)而产生的变化规律。认为:在青藏高原湖泊中,Mg2+与盐度具有较为稳定的正相关关系,而Ca2+、Sr2+、Sr/Ca以及Mg/Ca与盐度的相关性较弱且不稳定。而在特定的水化学类型的湖泊中,碳酸盐型湖泊的Mg2+、Ca2+以及Mg/Ca与盐度均没有明显的相关性。硫酸盐型湖泊中Mg2+和盐度呈现较高的正相关关系,而Ca2+以及Mg/Ca与盐度的相关性仍很弱。而在氯化物型湖泊中,Mg2+与盐度呈更强的正相关关系,Ca2+与盐度也呈一定的正相关关系,而Mg/Ca与盐度的相关性依然很弱。在特定的单个湖泊中,Ca2+以及Mg/Ca与盐度的相关性仍然不稳定或很弱,而Mg2+与盐度仍然保持明显的正相关关系。在青藏高原利用湖相沉积恢复特定湖区古环境演化序列的时候,Mg2+浓度是湖水古盐度一个较好的转换指标,而在应用Mg/Ca这一指标时应谨慎。     

有孔虫壳体的Mg/Ca比值在古环境研究中的应用

有孔虫壳体的Mg/Ca比值测定是目前估算海水古温度最受重视的方法,适用于低纬和高纬、表层和深层海水古温度的测定。该方法理论误差仅为±1.1℃,考虑到盐度以及海水pH值的影响,其误差为±1.3℃。运用此法推算出的热带海区表层海水温度领先于全球冰盖的变化,是热带过程调控冰期旋回最强有力的证据之一;与氧同位素相结合,还成功地运用于全球冰量的估算,是目前古环境研究中较常用的古温度测试手段。     

腕足化石古温度研究

温度变化研究是理解地球气候系统变化的关键环节之一.通过对海水温度变化的了解,可以系统地了解全球气候演化规律及其驱动机制.由于腕足化石具有保存完好以及分布年限长等优势,提取腕足化石中氧同位素信息进行古生代海水温度变化研究,已成为常用手段,但利用其Mg/Ca比值进行古温度变化的探讨却很少报道.通过对四川龙门山泥盆纪腕足化石中氧同位素以及Fe、Mn、Sr、Mg、Ca等微量元素的提取,结合微体结构观察、阴极发光等实验,在判定腕足化石保存良好的前提下,发现根据腕足化石中Mg/Ca(mmol/mol,下同)比值计算的温度相比氧同位素推算的温度,同生物学、古地理学证据显示的温度更为接近.此结果可能是由于利用氧同位素计算温度时古海水氧同位素未知及其不稳定性造成的.尽管腕足化石Mg/Ca比值温度计同样受海水的盐度以及pH等因素的影响,但计算结果显示,其反演的古温度比较接近真实的温度变化.      

壳体大小对浮游有孔虫生物地球化学记录的影响

在浮游有孔虫壳体稳定同位素及Mg/Ca和Sr/Ca值的相关研究中,人们常因各种原因而选择不同粒径的壳体进行分析测试,而很少注意壳体大小可能导致研究结果的分歧。针对这一问题,本文分析了位于低纬度海区钻孔中不同粒径的Glo-bigerinoides ruber(白色,sensu stricto)和Pulleniatinaobliquiloculata壳体,结果表明G.ruber壳体的δ13C值受壳体大小的影响最为强烈,表现为正相关关系,不同粒径壳体的δ13C绝对平均差值可达0.48‰±0.12‰和0.25‰±0.09‰;P.obliquiloc-ulata400μm与315~400μm和250~315μm壳体Mg/Ca值的差异相当于1.8℃的海水温度;相对而言,G.ruberδ18O和Mg/Ca值以及P.obliquiloculataδ13C受壳体大小的影响较小,但它们的Sr/Ca值与壳体大小的关系不显著。本文推测,壳体大小相同时厚重的壳体可能成壳速度较快,相对优先吸收轻的同位素,且壳体Mg/Ca值可能更接近周围海水的水平。据此,本文认为较大个体P.obliquiloculata的壳体分泌可能与周围海水达到了平衡分馏。     

近800a来内蒙古岱海湖水的盐度定量及其气候意义

在干旱半干旱地区 ,封闭湖泊的湖水盐度对气候变化反应敏感。首先通过现生介形类 (Lim nocytherecf.inopinata)壳体与湖水Sr/Ca比值的测定确定了Sr/Ca的分配系数 ;然后测试现代岱海湖水盐度与湖水Sr/Ca比值 ,建立湖水盐度与湖水Sr/Ca比值的函数关系 ;最后利用湖泊沉积剖面中介形类壳体的Sr/Ca比值定量恢复了岱海湖水近 80 0a来的盐度。通过分析岱海湖水盐度变化过程 ,揭示了研究区小冰期前期降水增加的冷湿气候 ,这明显不同于东部其它地区的冷干气候 ;研究区在小冰期中后期以偏干旱气候为主 ,这与东部其它地区干冷气候相一致 ;推测了 2 1世纪初 10～ 2 0a ,岱海地区降水将有所增加 ,干旱趋于缓和。     

青藏高原中部色林错中晚全新世以来古气候变化特征

色林错位于青藏高原中部印度季风和西风环流的过渡地带,同时受西风环流和印度季风系统控制,是研究二者进退变化特征的理想场所。本文利用色林错SL-1钻孔中介形虫Limnocythere inopinata的丰度及其壳体微量元素Mg/Ca和Mn/Ca比值重建了色林错5.3 ka BP以来的古气候环境变化特征。5.3～2.9 ka BP,L.inopinata丰度较小,壳体的低Mg/Ca比值和高Mn/Ca比值表明此阶段气候偏冷湿;2.9～1.8 ka BP,L.inopinata丰度较前一阶段增加,壳体Mg/Ca比值略有增长但仍为低值表明气温虽然有所回升但仍然较低,Mn/Ca比值较前一阶段明显降低,指示湖泊水位下降;1.8 ka BP至今,L.inopinata丰度达到最大,壳体的高Mg/Ca和Mn/Ca比值指示湖泊温度和水位均呈显著的上升趋势。通过与西风区、过渡区以及印度季风区其他湖泊的环境沉积记录对比,本文认为青藏高原中部地区在中全新世晚期主要受西风环流影响,气温较低,西风带来大量水汽使得湖面呈扩张趋势;而到晚全新世西风环流逐渐北撤,色林错受季风影响更大,季风带来的降水和气温升高导致的冰川融...     

青海湖冰后期以来古气候波动模式的研究

本文根据青海湖QH-16A近代沉积物岩芯中介形虫壳体的δ¹⁸O、δ¹³C、Mg/Ca和Sr/Ca值分析,讨论了青海湖区12,000年以来的气候特征。利用氧、碳同位素的相关性和相对温度、盐度变化曲线建立了青海湖区冰后期以来的气候波动模式,划分出5个气候期和23个气候阶。通过与布列特-谢尔南德冰后期气候方案对比,证实该气候波动模式具有世界性。     

浮游有孔虫壳体Mg/Ca值--SST的替代性指标

通过对东北印度洋区MD77181和MD81349两支岩心中Globigerinoides sacculifer壳体极为精细的清洗和溶样后,由ICP—MS测试获得了近260ka以来Mg／Ca值．结果表明Mg／Ca值与δ^18O值变化趋势较为吻合,随温度的增加而升高,浮游有孔虫G．sacculifer壳体Mg／Ca值是海洋表层水温(SST)良好的替代性指标．运用函数式Mg／Ca=0．4717exp(0．0825*SST)计算表明,包括印度洋在内的中、低纬地区,LGM时期的SST与全新世的温差大于最初CLIMAP推测的2℃,很可能达到4℃．     

Messinian Ca–Cl Brines from Mediterranean Basins: Tracing Diagenetic Effects by Ca/Mg Versus Ca/Sr Diagram

In natural resource exploration, Ca–Cl basinal brines are important for understanding the origin and spatial and temporal distribution of hydrocarbons and sedimentary ore deposits. Little attention has been paid to the possible connection between fossil basinal brines and paleo-seawaters and to the implications for reconstructing paleo-seawater compositions. Secular variations of Ca/Mg and Ca/Sr ratios in seawater have been documented mainly using fluid inclusions in halite, calcareous fossils and mineral analyses. However, brines and other sedimentary records connected to paleo-seawater or its evaporated residues may be chemically affected by burial diagenesis or the effects of continental waters of meteoric origin, thus complicating interpretations of the analytical results. To investigate these effects on fluids and minerals related to the Messinian salinity crisis of the Mediterranean basin, we re-evaluate published data from: (1) brackish-to-brine waters from onshore (Northern Apennine foredeep; Levantine basin) and offshore (porewaters from the Deep Sea Drilling Project); (2) Messinian parental seawater deduced from calcareous fossils, fluid inclusions and sulfate minerals; (3) meteoric waters dissolving evaporites. The compositional trends related to seawater evaporation, diagenesis and mixing that affect the Ca/Mg and Ca/Sr molar ratios of the basinal brines are effectively discriminated on a binary plot depicting the proper fields for seawater and meteoric-derived fluids. Brines showing stronger dolomitization start from Ca/Mg and Ca/Sr molar ratios of Messinian seawater deduced from the published analysis of fluid inclusions and open ocean fossils, that are therefore here validated ex post.     

普光气田长兴组白云岩地球化学特征及其成因意义

普光气田区长兴组白云岩的矿物组成与地球化学特征研究表明,自东南向西北方向,由普光8井至普光5井至普光6井,长兴组白云岩白云石颗粒的结晶程度和有序度总体上逐渐变高,其Fe、Mn、AI、K、Na、Sr含量及Mg^2＋／Ca^2＋比值总体呈降低的趋势;而氧同位素值逐渐降低,碳同位素值略增高,两者具负相关关系,这反映出白云石化作用与混合水无关;普光6井结晶白云岩87Sr／86Sr比值高于晚二叠世末古海水,说明白云石化流体并非长兴期古海水。研究认为长兴组泥-微晶白云岩由长兴期蒸发浓缩形成的高镁卤水交代灰泥丘而形成,属准同生白云石化作用成因,为非-差储层;结晶白云岩及碎裂化白云岩的白云石化流体应来自二叠纪高盐度海源地层水。属埋藏成因,可为优质储层。     

蒸发岩非传统稳定同位素研究综述

蒸发岩是海水/卤水蒸发浓缩的产物,不同的水化学环境下析出的蒸发岩类型不同,其在不同的地质历史时期都有分布,是重要的古海水和古环境记录载体。蒸发岩研究的主要问题包括:蒸发岩的物质来源、形成时代、蒸发盆地和卤水的演化历史、蒸发岩矿物所记录的环境变化。一些矿物、元素及同位素指标可用于解决这些问题,其中稳定同位素对于示踪蒸发岩的物质来源与形成过程具有不可替代的作用。近20年来,非传统稳定同位素地球化学获得快速发展,并在蒸发岩研究中获得成功应用,这些同位素体系包括阴离子元素B、Cl和Br,以及阳离子元素Mg、K和Ca。本文综述了多个非传统稳定同位素在蒸发岩领域的研究,主要包括:蒸发岩矿物与溶液之间的同位素分馏系数、蒸发岩的同位素信息重建古海水同位素组成及示踪蒸发岩成因和时代等。     

The impact of salinity on the Mg/Ca and Sr/Ca ratio in the benthic foraminifera Ammonia tepida: Results from culture experiments

Over the last decade, sea surface temperature (SST) reconstructed from the Mg/Ca ratio of foraminiferal calcite has increasingly been used, in combination with the δ¹⁸O signal measured on the same material, to calculate the δ¹⁸O_w, a proxy for sea surface salinity (SSS). A number of studies, however, have shown that the Mg/Ca ratio is also sensitive to other parameters, such as pH or , and salinity. To increase the reliability of foraminiferal Mg/Ca ratios as temperature proxies, these effects should be quantified in isolation. Individuals of the benthic foraminifera Ammonia tepida were cultured at three different salinities (20, 33 and 40 psu) and two temperatures (10-15 °C). The Mg/Ca and Sr/Ca ratios of newly formed calcite were analyzed by Laser Ablation ICP-MS and demonstrate that the Mg concentration in A. tepida is overall relatively low (mean value per experimental condition between 0.5 and 1.3 mmol/mol) when compared to other foraminiferal species, Sr being similar to other foraminiferal species. The Mg and Sr incorporation are both enhanced with increasing temperatures. However, the temperature dependency for Sr disappears when the distribution factor D_Sr is plotted as a function of calcite saturation state (Ω). This suggests that a kinetic process related to Ω is responsible for the observed dependency of Sr incorporation on sea water temperature. The inferred relative increase in D_Mg per unit salinity is 2.8% at 10 °C and 3.3% at 15 °C, for the salinity interval 20-40 psu. This implies that a salinity increase of 2 psu results in enhanced Mg incorporation equivalent to 1 °C temperature increase. The D_Sr increase per unit salinity is 0.8% at 10 °C and 1.3% at 15 °C, for the salinity interval 20-40 psu.     

山西平朔矿区上石炭统太原组11号煤层沉积地球化学特征及其成煤微环境?

山西平朔矿区上石炭统太原组11号煤层具有中硫、高灰、较高有机硫的特征，但其中各煤分层的基本性质差异较大，指示其成煤微环境显著变化。地球化学研究表明，Ca/（Ca＋Fe）、Th/U、Al/Ti、V/Zn、δEu、δCe可作为指示11号煤层沉积水介质盐度的标志，St,d、So,d/Sp,d可分别作为指示水介质氧化还原程度和酸碱度的标志，Ad、V/I、ΣREE可作为指示水介质动力条件的标志。在此基础上，分析了该煤层成煤微环境特征及其演化历程，认为11号煤层形成于波动式海进的半咸水-咸水沉积环境。在此过程中，海水对泥炭沼泽的影响经历了3个发展阶段：第1阶段，泥炭形成于微咸-半咸水条件，水动力条件逐渐增强；第2阶段，泥炭形成于半咸水-咸水条件，水动力条件总体上相对较强，沼泽水体从逐渐加深演化为显著变浅；第3阶段，泥炭形成于半咸水环境，海水影响再次逐渐增强，在泥炭沼泽演化末期水体显著变深，动力条件明显减弱，还原性显著增强。     

Origin of brine in the Kangan gasfield: isotopic and hydrogeochemical approaches

The Kangan Permo-Triassic brine aquifer and the overlying gas reservoir in the southern Iran are located in Kangan and Dalan Formations, consisting dominantly of limestone, dolomite, and to a lesser extent, shale and anhydrite. The gasfield, 2,900 m in depth and is exploited by 36 wells, some of which produce high salinity water. The produced water gradually changed from fresh to saline, causing severe corrosion in the pipelines and well head facilities. The present research aims to identify the origin of this saline water (brine), as a vital step to manage saline water issues. The major and minor ions, as well as δ²H, δ¹⁸O and δ³⁷Cl isotopes were measured in the Kangan aquifer water and/or the saline produced waters. The potential processes causing salinity can be halite dissolution, membrane filtration, and evaporation of water. The potential sources of water may be meteoric, present or paleo-seawater. The Na/Cl and I/Cl ratios versus Cl^? concentration preclude halite dissolution. Concentrations of Cl, Na, and total dissolved solid were compared with Br concentration, indicating that the evaporated ancient seawater trapped in the structure is the cause of salinization. δ¹⁸O isotope enrichment in the Kangan aquifer water is due to both seawater evaporation and interaction with carbonate rocks. The δ³⁷Cl isotope content also supports the idea of evaporated ancient seawater as the origin of salinity. Membrane filtration is rejected as a possible source of salinity based on the hydrochemistry data, the δ¹⁸O value, and incapability of this process to dramatically enhance salinity up to the observed value of 330,000 mg/L. The overlaying impermeable formations, high pressure in the gas reservoir, and the presence of a cap rock above the Kangan gasfield, all prevent the downward flow of meteoric and Persian Gulf waters into the Kangan aquifer. The evaporated ancient seawater is autochthonous, because the Kangan brine aquifer was formed by entrapment of brine seawater during the deposition of carbonates, gypsum, and minor clastic rocks in a lagoon and sabkha environment. The reliability of determining the source of salinity in a deep complicated inaccessible high-pressure aquifer can be improved by combining various methods of hydrochemistry, isotope, hydrodynamics, hydrogeology and geological settings.     

Evolution of saline waters and brines in the Benue-Trough,Nigeria

Hydrogeochemical assessment of 40 saline waters and brines from 20 locations within the lower (southern) and middle regions of the Benue-Trough, Nigeria are presented and discussed in terms of genesis of the primary salinity and subsequent hydrochemical evolution. The total dissolved ions range from 5263 to 88,800 mg/L and 5148 to 47,145 mg/L in the lower and middle region, respectively.The saline waters and brines are characteristically Na–Cl type enriched in Ca and Sr on the one hand and depleted in Mg and SO₄ on the other, relative to the seawater evaporation trend. Ionic ratios, Na–Cl–Br systematic and divalent cations suggest two likely sources of primary salinity: a fossil seawater source and dissolution of halite. However, water–rock interaction involving Mg uptake by clay minerals and possibly dolomitization during diagenesis appear to be responsible for further modification of the primary chemistry. A conceptualized hydrogeological/flow model for the brines is presented.     

鲁西南浅层高氟地下水成因的水文地球化学研究

鲁西南京杭运河以西的大部分地区浅层地下水氟含量普遍偏高,最高达6.0 7mg/L,是地方性氟中毒症高发区。根据巨野煤田勘探期间在巨野、郓城、嘉祥等地进行的浅层地下水(埋深<2 0m)水文地球化学调查资料,结合本区地形、地貌、气候、岩性等因素,对浅层地下水的水文地球化学特征及高氟地下水的成因机理进行了研究,指出本区地下水氟的富集主要与pH值、矿化度、HCO₃-、Ca2+、Mg2+含量有关,计算了F、Ca、Mg 3种元素的组分浓度以及几种固相沉积物的饱和指数,并提出了相应的预防和治理措施。