海水化学演化对生物矿化的影响综述

显生宙非骨屑碳酸盐矿物经历了文石海和方解石海的交替,主要造礁生物和沉积物生产者的骨骼矿物与非骨屑碳酸盐矿物具有同步变化的趋势。这种长期的变化趋势可以用海水化学Mg/Ca摩尔比的变化来解释。流体包裹体、同位素和微量元素等证据也证实了海水化学在地质历史中经历过剧烈的变化。虽然生物诱导矿化和生物控制矿化的相对重要性一直存在争议,但古生物地层记录和人工海水养殖实验结果都表明,海水化学演化对生物矿化有重要的影响,体现在造礁生物群落的兴衰、生物起源时对骨骼矿物类型的选择以及微生物碳酸盐岩在地质历史中的分布等。这些为研究前寒武纪海水化学演化、古气候和古环境的重建、同位素地层对比以及碳酸盐的沉积和成岩等问题提供了新的思路。     

I/(Ca+Mg)作为指示碳酸盐沉积氧化还原条件的重要指标:研究进展与问题评述

海水氧化还原条件显著影响真核生物的起源与早期演化,但以往有关早期海水氧化还原条件研究的对象,主要依赖相对深水的细粒碎屑岩沉积(如黑色页岩),而对真核生物集中分布的浅水环境中的碳酸盐岩关注不够且手段缺乏。这显著制约了对真核生物起源与早期演化机理的认识。近年来,有学者提出碳酸盐岩的I/(Ca+Mg)值可作为反映海洋氧化还原条件的重要指标,并将其广泛应用于海相碳酸盐岩的古氧相研究中。该指标的提出主要基于对现代海洋碘组分的观测以及室内方解石合成实验结果:观测结果表明,海水中的碘主要以氧化态(IO_3~-)和还原态(I~-)2种形式存在,随着氧含量的下降(如在氧极小带),氧化态的碘被逐步转换为还原态的碘,且海水中的IO_3~-浓度与海水氧含量大体呈正相关。实验研究证明,IO_3~-可按一定的分配系数进入到碳酸盐矿物晶格中,但I~-则不能。由于IO_3~-/I-的还原势能与O_2/H_2O的还原势能接近,因此I/(Ca+Mg)值是最早响应海洋氧含量下降的指标之一,可用于表征深时(如前寒武纪)次氧化环境中表层海水的氧含量波动。此外,学者们也尝试建立I/(Ca+Mg)值与氧含量之间的半定量关系,如I/(Ca+Mg)值大于0和2.5μmol/mol这两个临界值所对应的海水氧含量。结合大量现代缺氧水体和氧极小带中碘组分与溶解氧浓度相关关系的研究,作者提出I/(Ca+Mg)=1.5μmol/mol为重要的临界值之一,可用于限定初级生产力在表层海水中所能产生的最大氧浓度值(~10μM),并能进一步区分海水和大气的氧化。此外,对I/(Ca+Mg)值的应用进展及潜在问题进行评述,并对可能的发展方向进行展望。     

I/(Ca+Mg)作为指示碳酸盐沉积氧化还原条件的重要指标: 研究进展与问题评述*

海水氧化还原条件显著影响真核生物的起源与早期演化,但以往有关早期海水氧化还原条件研究的对象,主要依赖相对深水的细粒碎屑岩沉积(如黑色页岩),而对真核生物集中分布的浅水环境中的碳酸盐岩关注不够且手段缺乏。这显著制约了对真核生物起源与早期演化机理的认识。近年来,有学者提出碳酸盐岩的I/(Ca+Mg)值可作为反映海洋氧化还原条件的重要指标,并将其广泛应用于海相碳酸盐岩的古氧相研究中。该指标的提出主要基于对现代海洋碘组分的观测以及室内方解石合成实验结果: 观测结果表明,海水中的碘主要以氧化态(IO₃^-)和还原态(I^-)2种形式存在,随着氧含量的下降(如在氧极小带),氧化态的碘被逐步转换为还原态的碘,且海水中的IO₃^-浓度与海水氧含量大体呈正相关。实验研究证明,IO₃^-可按一定的分配系数进入到碳酸盐矿物晶格中,但I^-则不能。由于IO₃^-/I^-的还原势能与O₂/H₂O的还原势能接近,因此I/(Ca+Mg)值是最早响应海洋氧含量下降的指标之一,可用于表征深时(如前寒武纪)次氧化环境中表层海水的氧含量波动。此外,学者们也尝试建立I/(Ca+Mg)值与氧含量之间的半定量关系,如I/(Ca+Mg)值大于0和2.5μmol/mol这两个临界值所对应的海水氧含量。结合大量现代缺氧水体和氧极小带中碘组分与溶解氧浓度相关关系的研究,作者提出I/(Ca+Mg)=1.5μmol/mol为重要的临界值之一,可用于限定初级生产力在表层海水中所能产生的最大氧浓度值(~10 μM),并能进一步区分海水和大气的氧化。此外,对I/(Ca+Mg)值的应用进展及潜在问题进行评述,并对可能的发展方向进行展望。     

锶同位素地层学在碎屑岩成岩研究中的应用

基于同一地质历史时期海水的锶同位素组成为一定值的锶同位素地层学基本原理,可将锶同位素地层学用于碎屑岩成岩作用研究,以评价海相和非海相对成岩作用的影响.三个不同类型的研究实例说明:1)海相碎屑岩成岩流体的锶同位素组成的演化途径有较好的规律性,陆相影响随成岩作用的进行而增加,相对晚期的碳酸盐胶结物的87Sr/86Sr比值通常高于相对早期的碳酸盐胶结物,变化的本底值即为同期海水的锶同位素组成,该数值为一定值;2)有沉积期深源锶和非同期海相影响的陆相碎屑岩中,碳酸盐胶结物的锶同位素比值可能低于大陆淡水,但埋藏成岩过程中相对晚期的碳酸盐胶结物的87Sr/86Sr比值仍高于相对早期的碳酸盐胶结物;3)当深部流体影响碎屑岩的整个成岩过程时,深源锶的烙印可以抹掉或减少不同成岩阶段不同程度陆相影响造成的各种碳酸盐胶结物之间锶同位素组成的差别,使各种碳酸盐胶结物都具有很低的87Sr/86Sr比值,因而缺乏其它沉积盆地中常见的相对晚期碳酸盐胶结物87Sr/86Sr比值高于早期胶结物的一般模式。     

珠江口盆地白云凹陷深层砂岩储层中碳酸盐胶结作用及成因探讨

通过各类薄片显微镜下鉴定与定量统计,阴极发光、扫描电镜、电子探针、碳、氧及锶同位素、流体包裹体均一温度测试等分析,开展了白云凹陷深水区珠江组和珠海组砂岩储层中碳酸盐胶结物的类型与期次、地球化学特征、成因机制研究。结果显示,存在三期碳酸盐胶结作用,早期主要为方解石,以高Ca、低Fe、低Mg为特征。但珠江组早期碳酸盐胶结物的同位素组成(δ~(13)C_(PDB):-2.43‰~0.29‰,δ~(18)OPDB:-9.79‰~-3.08‰,87 Sr/86Sr:0.7084~0.7109)与珠海组(δ~(13)C_(PDB):-9.37‰~-8.13‰,δ~(18)OPDB:-7.11‰~-7.09‰,87Sr/86Sr:0.7138~0.7142)有一定差异,前者是在浅埋藏阶段从碳酸盐过饱和碱性海水介质中沉淀出的产物;后者与碳酸盐过饱和的碱性淡水有关。中期主要为铁方解石,以高Ca、较高Fe、低Mg、碳和锶同位素组成变化范围较大(δ~(13)C_(PDB):-20.88‰~-5.29‰,δ~(18)OPDB:-11.1‰~-8.99‰,87Sr/86Sr:0.7093~0.7151)为特征,其部分碳源与有机酸脱羧作用产生的CO_2有关,另一部分碳源(δ~(13)C_(PDB):-5.38‰~-5.29‰)可能与深部物质有关。形成碳酸盐胶结物所需的Ca2+、Mg2+、Fe2+等离子来源于砂岩中长石等碎屑的溶蚀、黏土矿物的转化以及深部热液流体。晚期主要为铁白云石(δ~(13)C_(PDB):-2.83‰~-1.83‰,δ~(18)OPDB:-9.45‰~-5.77‰,87Sr/86Sr:0.7101~0.7162),以高Fe、高Mg、较低Ca、碳同位素组成与同期海水基本一致为特征,87Sr/86Sr值低于正常成岩演化形成的碳酸盐,该期碳酸盐胶结物的形成与砂岩中生物碎屑以及先期碳酸盐胶结物的溶蚀再沉淀有关,部分可能受到深部热液流体的影响。     

鲕粒原生矿物识别及对海水化学成分变化的指示意义

鲕粒是碳酸盐沉积过程中一类非常特殊的颗粒类型, 为研究当时的沉积背景、水动力条件、气候环境, 甚至储层特征提供了重要线索。然而, 鲕粒的矿物组成及控制因素问题, 长期受到忽视。组成鲕粒的原生矿物类型在地质历史时期呈周期性变化, 在显生宙表现为三个以文石和高镁方解石占主导的时期以及两个以低镁方解石占主导的时期, 这也被称作“文石海”和“方解石海”时期。原生矿物的组成, 制约着鲕粒的纹层结构、保存程度以及成岩特征, 还蕴含着海水化学成分变化的线索。鲕粒原生矿物识别主要依据:①原生纹层结构;②保存程度;③微量元素浓度, 尤其是Sr-Mg的浓度。文石质鲕粒受文石不稳定性的影响, 原生结构保存程度较差;一般保存有典型的文石残余纹层结构(例如砖砌结构、溶解变形结构以及偏心结构等);在封闭成岩环境下原生矿物为文石质的鲕粒Sr浓度往往大于2 000 ppm;纹层结构主要为切线状(占主导)和放射状。方解石质鲕粒包括低镁方解石和高镁方解石两种类型:低镁方解石为稳定矿物, 原生结构一般保存良好。尽管高镁方解石也为亚稳定矿物, 但成岩转换后的保存程度好于文石。两者Sr含量一般均低于1 000 ppm, Mg含量一般在0~20 mol % MgCO₃(两者以4 mol % MgCO₃为界)。高镁方解石受成岩作用影响, 在纹层中往往保留有微粒白云石包裹体;海相地层中保存的方解石质鲕粒为放射状或同心-放射状结构。另外还存在一类由两种矿物共同构成的双矿物鲕粒, 可以通过分析两类纹层在结构和保存特征上的差异进行区分。鲕粒原生矿物成分随时间的波动变化受到海水化学条件, 尤其是Mg/Ca比值, 大气二氧化碳分压以及碳酸盐饱和度的控制。Mg/Ca比值的波动决定着鲕粒原生矿物类型的长期变化规律。一些突发性事件可能会扰动(区域)短时间尺度下鲕粒原生矿物的组成, 造成鲕粒原生矿物的转换。通过研究碳酸盐鲕粒原生矿物特征以及控制因素进而了解海水的化学特征, 是独立于古生物学和地球化学分析之外的一种较为可靠的沉积学方法。     

镁同位素示踪碳酸盐岩沉积—成岩过程

镁（Mg）作为主要的造岩元素及生物营养元素,是连接大陆、海洋和地球内部循环的重要纽带。碳酸盐岩作为Mg的主要储库,是全球Mg循环的重要组成环节,利用Mg同位素示踪碳酸盐岩沉积—成岩过程是有效反演深时海水Mg同位素组成（δ26Mg_海水）、恢复全球Mg循环的基本前提。近二十年来,Mg同位素在示踪碳酸盐岩沉积—成岩过程研究中取得了较大进展:1）不同类型碳酸盐矿物形成过程中的Mg同位素分馏及其影响因素的研究得到完善;2）建立了Mg同位素地球化学模型,对不同白云石化过程进行半定量—定量模拟;3）初步探索了利用Mg同位素反演早期成岩流体体系的方法。以上研究进展为利用碳酸盐岩恢复δ26Mg_海水奠定了理论基础,在选择有效的碳酸盐岩载体恢复δ26Mg_海水时,需充分考虑碳酸盐岩的沉积—成岩过程及其对Mg同位素组成的影响,并适当结合地球化学模型,消除沉积—成岩因素的影响,进而恢复δ26Mg_海水。     

显生宙全球海水化学成分演化及其对蒸发岩沉积的约束

通过搜集显生宙以来不同地质时期内海相碳酸盐岩鲕粒及胶结物矿物成分、钾盐矿床矿物种类及组合特征、蒸发岩盆地中石盐流体包裹体成分,并利用这些资料与人工海水模拟实验得到的石盐中Br分配特征的对比,得出海水成分在5.5亿年以来的显生宙期间,经历了五个阶段:其中晚元古代至寒武纪早期、二叠纪早期至中生代早期、新生代早期至现今,这些时期的原始海水组成特征系数m(SO_4~(2-))+m(HCO_3~-)/2m(Ca~(2+)),为Na-Mg-K-SO_4-Cl型海水,此期间沉积的钾盐矿床的钾镁盐矿物主要为钾盐镁矾、无水钾镁矾、杂卤石、硫酸镁石等含MgSO_4矿物,海相鲕粒和碳酸盐胶结物矿物成分为文石;而寒武纪早期至石炭纪、中生代早期至新生代早期,原始海水组成特征系数m(Ca~(2+))m(SO_4~(2-))+m(HCO_3~-)/2,为Na-Mg-KCa-Cl型海水,此期间沉积的钾镁盐矿物主要为光卤石和钾石盐,甚至含有溢晶石,海相鲕粒和碳酸盐胶结物矿物成分为方解石。根据石盐流体包裹体成分计算得出:显生宙期间,海水K+含量大部分时间变化幅度较小,为9.3～11.5mmol/kg H_2O(除了石炭纪和晚元古代),平均为10.55mmol/kg H_2O。Mg~(2+)含量在早寒武世≥67mmol/kg H_2O、晚志留世至中泥盆世31～41mmol/kg H_2O、晚古生代≥48mmol/kg H22O、晚白垩世34mmol/kg H_2O和现代55.1mmol/kg H_2O。Ca~+含量在晚元古代至古生代早期≤11mmol/kg H_2O、古生代早期至石炭纪22～35mmol/kg H_2O、石炭纪至中生代早期≤17mmol/kg H_2O、中生代早期至新生代早期19～39mmol/kg H_2O及新生代早期至今7～21mmol/kg H_2O。SO_4~(2-)含量在晚元古代至古生代早期≥23mmol/kg H_2O、古生代早期至石炭纪5～17mmol/kg H_2O、石炭纪至中生代早期13～22mmol/kg H_2O、中生代早期至新生代早期5～19mmol/kg H_2O及新生代早期至今12～29.2mmol/kg H_2O。海水Ca~(2+)与SO_4~(2-)含量的相对变化是控制海相钾盐矿床钾镁盐矿物类型的基本因素。同时,利用以上数据计算得到的显生宙各时期海水[m(Mg~(2+))+m(SO_4~(2-))]/[m(K~+)+m(Ca~(2+))]的变化与各时期海相蒸发岩系石盐层底部的Br含量变化具有同步性,进一步验证了显生宙期间海水成分是不断变化的,是约束海相蒸发岩钾盐矿物类型的主要因素。海水成分变化的控制因素为洋中脊热液和陆地水,其中洋中脊热液起主要作用,而控制这些因素变化的根本原因为板块构造运动。     

杭州湾及其邻近海域沉积物中Fe、Mn、Ca、Mg的地球化学研究

本文通过对杭州湾及其邻近海域29个站位的表层沉积物化学、粘土矿物及碎屑矿物资料的分析,详细研究了开放型海湾沉积物中Fe、Mn、Ca、Mg元素地球化学特征。研究表明,1)与同类型海湾相比,杭州湾显示高Fe、Mn、Mg低Ca的特点。表明物质来源丰富,而生物作用较弱;2)Fe、Mn主要来自长江和钱塘江径流搬运,受粘土控制。Mg主要来自粘土对海水中Mg~(2+)的吸附,同时受上覆水盐度的影响;3)北区元素间关系明显的比南区强烈,表明南区物质来源较北区复杂;4)主断面沉积物中Mg/Ca由河口向海洋增加,并与有机碳呈明显的正相关,显示杭州湾及邻近陆架区可能发生着原始碳酸盐(钙)白云岩化的反应。     

活体珊瑚微量元素对硼同位素组成影响及硼掺入珊瑚的形式

为确定元素 B 掺入进珊瑚的形式、B(OH)与 B(OH)3间的分馏系数及珊瑚中微量元素对硼同位素?4组成的影响,对北海涠洲岛、海南三亚和雷州半岛灯楼角三地活体珊瑚的 Mg、Sr、Na、Ca、B 浓度及硼同位素组成(δ11Bcoral)进行了测定.结果表明,涠洲岛、三亚和灯楼角三地珊瑚的 Mg、Sr、Na 和 Ca 浓度平均值分别为40.1 mmol/L、86.1 mmol/L、449 mmol/L 和12.1 mol/L.珊瑚中 B 浓度的变化范围为4.4~8.4 mmol/L,平均值为5.9 mmol/L.Ca、Sr 在珊瑚中明显富集,而 Mg 在珊瑚中贫化.珊瑚 B 浓度的变化主要反映了珊瑚生长时海水 pH 值的变化.δ11Bcoral 的变化范围为22.8‰~27.9‰,平均为25.2‰.除与 B 浓度呈弱正相关关系外,δ11Bcoral 与其他四种元素不相关.应用珊瑚硼同位素组成恢复古海水 pH 值时选择同属种珊瑚和判别是否有 Mg(OH)2的存在是必要的.涠洲岛、灯楼角和三亚三地珊瑚与海水间的硼同位素分馏系数αcoral-sw 分别为0.9839、0.9847和0.9850.计算得到的珊瑚与海水 B(OH)3间的分馏系数αcoral-3的变化范围为0.9772~0.9800,平均值为0.9788.该新的α4-3值是准确的,可以用来反演古海水 pH 值.αcoral-sw 和αcoral-3随pH 值的升高分别呈现出增大和减小的变化趋势.珊瑚的平均δ11Bcoral 位于理论计算的δ11B4和δ11B3曲线之间,而且都低于原始合成海水的δ11B.这些都表明 B 以 B(OH)3和B(OH)两种形式以变化的比例同时掺入进?4珊瑚,并以B(OH)优先掺入为主.计算得到有0.1%~5.5%(平均值为2.2%)的 B(OH)3掺入进珊瑚中.由于?4 B(OH)3同时掺入进生物碳酸盐,δ11Bcarb=δ11B4的假设不能成立,由所测生物碳酸盐δ11Bcarb 值计算的海水 pH值将产生误差,使δ11B-pH 技术变得更为复杂.通过无机碳酸盐沉积或有孔虫或珊瑚的养殖实验(或者野外观测实验)建立用于重建古海水 pH 值的δ11Bcarb-pH 经验方程是今后的一项重要任务.     

Mg fractionation in crustose coralline algae: Geochemical, biological, and sedimentological implications of secular variation in the Mg/Ca ratio of seawater

The Mg/Ca ratio of seawater has varied significantly throughout the Phanerozoic Eon, primarily as a function of the rate of ocean crust production. Specimens of the crustose coralline alga Neogoniolithon sp. were grown in artificial seawaters encompassing the range of Mg/Ca ratios shown to have existed throughout the Phanerozoic. Significantly, the coralline algae’s skeletal Mg/Ca ratio varied in lockstep with the Mg/Ca ratio of the artificial seawater. Specimens grown in seawater treatments formulated with identical Mg/Ca ratios but differing absolute concentrations of Mg and Ca exhibited no significant differences in skeletal Mg/Ca ratios, thereby emphasizing the importance of the ambient Mg/Ca ratio, and not the absolute concentration of Mg, in determining the Mg/Ca ratio of coralline algal calcite. Specimens grown in seawater of the lowest molar Mg/Ca ratio (mMg/Ca = 1.0) actually changed their skeletal mineralogy from high-Mg (skeletal mMg/Ca > 0.04) to low-Mg calcite (skeletal mMg/Ca < 0.04), suggesting that ancient calcitic red algae, which exhibit morphologies and modes of calcification comparable to Neogoniolithon sp., would have produced low-Mg calcite from the middle Cambrian to middle Mississippian and during the middle to Late Cretaceous, when oceanic mMg/Ca approached unity. By influencing the original Mg content of carbonate facies in which these algae have been ubiquitous, this condition has significant implications for the geochemistry and diagenesis of algal limestones throughout most of the Phanerozoic. The crustose coralline algae’s precipitation of high-Mg calcite from seawater that favors the abiotic precipitation of aragonite indicates that these algae dictate the precipitation of the calcitic polymorph of CaCO₃. However, the algae’s nearly abiotic pattern of Mg fractionation in their skeletal calcite suggests that their biomineralogical control is limited to polymorph specification and is generally ineffectual in the regulation of skeletal Mg incorporation. Therefore, the Mg/Ca ratio of well-preserved fossils of crustose coralline algae, when corrected for the effect of seawater temperature, may be an archive of oceanic Mg/Ca throughout the Phanerozoic. Magnesium fractionation algorithms that model algal skeletal Mg/Ca as a function of seawater Mg/Ca and temperature are presented herein. The results of this study support the empirical fossil evidence that secular variation of oceanic Mg/Ca has caused the mineralogy and skeletal chemistry of many calcifying marine organisms to change significantly over geologic time.     

Application of calcite Mg partitioning functions to the reconstruction of paleocean Mg/Ca

Calcite Mg/Ca is usually assumed to vary linearly with solution Mg/Ca, that a constant partition coefficient describes the relationship between these two ratios. Numerous published empirical datasets suggests that this relationship is better described by a power function. We provide a compilation of these literature data for biotic and abiotic calcite in the form of Calcite Mg/Ca = F(Solution Mg/Ca)^H, where F and H are empirically determined fitting parameters describing the slope and deviation from linearity, respectively, of the function. This is equivalent to Freundlich sorption behavior controlling Mg incorporation in calcite. Using a power function, instead of a partition coefficient, lowers Phanerozoic seawater Mg/Ca estimates based on echinoderm skeletal material by, on average, 0.5 mol/mol from previous estimates.These functions can also be used to model the primary skeletal calcite Mg/Ca of numerous calcite phases through geologic time. Such modeling suggests that the Mg/Ca of all calcite precipitated from seawater has varied through the Phanerozoic in response to changing seawater Mg/Ca and that the overall range in Mg/Ca measured among various calcite phases would be greatest when seawater Mg/Ca was also high (e.g., “aragonite seas”) and lowest when seawater Mg/Ca was low (e.g., “calcite seas”). It follows that, during times of “calcite seas” when the seawater Mg/Ca is presumed to have been lower, deposition of calcite with low Mg contents would have resulted in a depressed drive for diagenetic stabilization of shelfal carbonate and, in turn, lead to greater preservation of crystal and skeletal microfabrics and primary chemistries in biotic and abiotic calcites.     

Dolomite Controls on Phanerozoic Seawater Chemistry

We investigate the potential role of dolomite as a long-term buffer on Phanerozoic seawater composition. Using a comprehensive model of Phanerozoic geochemical cycling, we show how variations in the formation rate of sedimentary marine dolomite have buffered seawater saturation state. The total inventory of inorganic carbon reflects the sum of fluxes derived from continental weathering, basalt-seawater exchange, alumino-silicate diagenesis (reverse weathering), and global deposition of calcium carbonate. Although these fluxes are approximately balanced, model results indicate that seawater saturation state is sensitive to the marine dolomite depositional flux. This conclusion is consistent with and constrained by independent proxy data for seawater ion ratios, paleo-atmospheric CO₂ concentrations, and paleo-pH data, and dolomite mass-age distribution through Phanerozoic time. Abundant research indicates that dolomite’s occurrence in marine sediments is sensitive to many factors: temperature, seawater composition, paleogeographic setting, continental organization, etc. Although the complexity of the process of dolomite formation prevents a complete understanding of the relative role of these factors, our model results clearly underscore the importance of this mineral in the chemical history of Phanerozoic seawater.     

Calcium-isotope fractionation in selected modern and ancient marine carbonates

The calcium-isotope composition (δ^44/42Ca) was analyzed in modern, Cretaceous and Carboniferous marine skeletal carbonates as well as in bioclasts, non-skeletal components, and diagenetic cements of Cretaceous and Carboniferous limestones. In order to gain insight in Ca²⁺_aq-CaCO₃-isotope fractionation mechanisms in marine carbonates, splits of samples were analyzed for Sr, Mg, Fe, and Mn concentrations and for their oxygen and carbon isotopic composition. Biological carbonates generally have lower δ^44/42Ca values than inorganic marine cements, and there appears to be no fractionation between seawater and marine inorganic calcite. A kinetic isotope effect related to precipitation rate is considered to control the overall discrimination against ⁴⁴Ca in biological carbonates when compared to inorganic precipitates. This is supported by a well-defined correlation of the δ^44/42Ca values with Sr concentrations in Cretaceous limestones that contain biological carbonates at various stages of marine diagenetic alteration. No significant temperature dependence of Ca-isotope fractionation was found in shells of Cretaceous rudist bivalves that have recorded large seasonal temperature variations as derived from δ¹⁸O values and Mg concentrations. The reconstruction of secular variations in the δ^44/42Ca value of seawater from well preserved skeletal calcite is compromised by a broad range of variation found in both modern and Cretaceous biological carbonates, independent of chemical composition or mineralogy. Despite these variations that may be due to still unidentified biological fractionation mechanisms, the δ^44/42Ca values of Cretaceous skeletal calcite suggest that the δ^44/42Ca value of Cretaceous seawater was 0.3-0.4‰ lower than that of the modern ocean.     

Chemical evolution of seawater during the Phanerozoic: Implications from the record of marine evaporites

The chemical evolution of seawater during the Phanerozoic is still a matter of debate. We have assembled and critically analyzed the available data for the composition of fluid inclusions in marine halite and for the mineralogy of marine evaporites. The composition of fluid inclusions in primary marine halite reveals two major long-term cycles in the chemistry of seawater during the past 600 myr. The concentration of Mg²⁺, Ca²⁺, and SO₄²⁻ has varied quite dramatically. The Mg²⁺ concentration in seawater during most of the early Paleozoic and Jurassic to Cretaceous was as low as 30 to 40 mmol/kg H₂O; it reached maximum values ≥50 mmol/kg H₂O during the Late Neoproterozoic and Permian. The Ca²⁺ concentration in seawater during the Phanerozoic has reached maximum values two to three times greater than the concentration in seawater today (10.6 mmol/kg H₂O), whereas SO₄²⁻ concentrations may have been as low as 5 to 10 mmol/kg H₂O (a third to a fifth of the modern value) during the Jurassic and Early Paleozoic. The Mg²⁺/Ca²⁺ ratio in seawater ranged from 1 to 1.5 during the early to middle Paleozoic and Jurassic-Cretaceous to a near-modern value of 5.2 during the Late Neoproterozoic and Permian. This change in seawater Mg²⁺/Ca²⁺ ratio is consistent with the notion of alternating “calcite-aragonite seas” recorded in oölites and marine carbonate cements.Several models have been proposed to explain the chemical evolution of seawater. These have invoked significant changes in one or more of the major geochemical processes that control the composition of seawater. The pattern and magnitude of the variations in the composition of seawater proposed in this study are similar to those proposed elsewhere that suggest that seawater fluxes through midocean ridges have played a major role in the evolution of seawater during the past 600 myr. Two Phanerozoic supercycles of the Earth’s exogenic processes were recognized in the literature that are caused by mantle convection and plate activity. The composition of seawater has apparently undergone dramatic secular changes in phase with these supercycles and as a consequence of biological evolution. Analyses of fluid inclusions containing unevaporated seawater and a better understanding of the processes that affect the composition of seawater are needed to refine our understanding of the history of Phanerozoic seawater.     

Heterogeneous Mg isotopic composition of the early Carboniferous limestone: implications for carbonate as a seawater archive

Carbonate precipitation and hydrothermal reaction are the two major processes that remove Mg from seawater. Mg isotopes are significantly (up to 5‰) fractionated during carbonate precipitation by preferential incorporation of ²⁴Mg, while hydrothermal reactions are associated with negligible Mg isotope fractionation by preferential sequestration of ²⁶Mg. Thus, the marine Mg cycle could be reflected by seawater Mg isotopic composition (δ²⁶Mg_sw), which might be recorded in marine carbonate. However, carbonates are both texturally and compositionally heterogeneous, and it is unclear which carbonate component is the most reliable for reconstructing δ²⁶Mg_sw. In this study, we measured Mg isotopic compositions of limestone samples collected from the early Carboniferous Huangjin Formation in South China. Based on petrographic studies, four carbonate components were recognized: micrite, marine cement, brachiopod shell, and mixture. The four components had distinct δ²⁶Mg: (1) micrite samples ranged from ?2.86‰ to ?2.97‰; (2) pure marine cements varied from ?3.40‰ to ?3.54‰, while impure cement samples containing small amount of Rugosa coral skeletons showed a wider range (?3.27‰ to ?3.75‰); (3) values for the mixture component were ?3.17‰ and ?3.49‰; and (4) brachiopod shells ranged from ?2.20‰ to ?3.07‰, with the thickened hinge area enriched in ²⁴Mg. Due to having multiple carbonate sources, neither the micrite nor the mixture component could be used to reconstruct δ²⁶Mg_sw. In addition, the marine cement was homogenous in Mg isotopes, but lacking the fractionation by inorganic carbonate precipitation that is prerequisite for the accurate determination of δ²⁶Mg_sw. Furthermore, brachiopod shells had heterogeneous C and Mg isotopes, suggesting a significant vital effect during growth. Overall, the heterogeneous δ²⁶Mg of the Huangjin limestone makes it difficult to reconstruct δ²⁶Mg_sw using bulk carbonate/calcareous sediments. Finally, δ²⁶Mg_sw was only slightly affected by the faunal composition of carbonate-secreting organisms, even though biogenic carbonate accounts for more than 90% of marine carbonate production in Phanerozoic oceans and there is a wide range (0.2‰–4.8‰) of fractionation during biogenic carbonate formation.     

The Sensitivity of the Phanerozoic Inorganic Carbon System to the Onset of Pelagic Sedimentation

The onset of pelagic sedimentation attending the radiation of pelagic calcifiers during the Mesozoic was an important divide in Earth history, shifting the locus of significant carbonate sedimentation from the shallow shelf environments of the Paleozoic to the deep sea. This shift would have impacted the CO₂ cycle, given that decarbonation of subducted pelagic carbonate is an important return flux of CO₂ to the atmosphere. Coupled with the fact that the mean residence time of continental platform and basin sedimentary carbonate exceeds that of the oceanic crust, it thus becomes unclear whether carbon cycling would have operated on a substantially different footing prior to the pelagic transition. Here, we examine this uncertainty with sensitivity analyses of the timing of this transition using a coupled model of the Phanerozoic atmosphere, ocean, and shallow lithosphere. For purposes of comparison, we establish an age of 250 Ma (i.e., after the Permo-Triassic extinctions) as the earliest opportunity for deposition of extensive biogenic pelagic carbonate on the deep seafloor, an age that predates known occurrences of pelagic calcifiers (and intact seafloor). Although an approximate boundary, we do show that attempts to shift this datum either significantly earlier or later in time produce model results that are inconsistent with observed trends in the mass–age distribution of the rock record and with accepted trends in seawater composition as constrained by proxy data. Significantly, we also conclude that regardless of the timing of the onset of biogenic pelagic carbonate sedimentation, a carbon sink involving seawater-derived dissolved inorganic carbon played a critical role in carbon cycling, particularly in the Paleozoic. This CaCO₃ sink may have been wholly abiogenic, involving calcium derived either directly from seawater (thus manifest as a direct seafloor deposit), or alternatively from basalt–seawater reactions (represented by precipitation of CaCO₃ in veins and fissures within the basalt). Despite the uncertainty in the source and magnitude of this abiogenic CaCO₃ flux, it is likely a basic and permanent feature of global carbon cycling. Subduction of this CaCO₃ would have acted as a basic return circuit for atmospheric CO₂ even in the absence of biogenically derived pelagic carbonate sedimentation. Lastly, model calculations of the ratio of dissolved calcium to carbonate ion (Ca²⁺/CO₃ ^2?) show this quantity underwent significant secular evolution over the Phanerozoic. As there is increasing recognition of this ratio’s role in CaCO₃ growth and dissolution reactions, this evolution, together with progressive increases in nutrient availability and saturation state, may have created a tipping point ultimately conducive to the appearance of pelagic calcifiers in the Mesozoic.     

Mollusc and brachiopod skeletal hard parts: Intricate archives of their marine environment

The biogenic carbonate hard parts of fossil bivalves, cephalopods and brachiopods are among the most widely exploited marine archives of Phanerozoic environmental and climate dynamics research. The advent of novel analytical tools has led many workers to explore non‐traditional geochemical and petrographic proxies, and work performed in neighbouring disciplines sheds light on the complex biomineralization strategies applied by these organisms. These considerations form a strong motivation to review the potential and problems related to the compilation and interpretation of proxy data from bivalve, cephalopod and brachiopod hard parts from the viewpoint of the sedimentologist and palaeoceanographer. Specific focus is on the complex biomineralization pathways of a given dissolved ion or food particle from its aquatic environment via the digestion and biomineralization apparatus in molluscs and brachiopods and its incorporation into a biomineral. Given that molluscs and brachiopods do not secrete their hard parts from seawater but rather from their mantle and periostracum, this paper evaluates differences and similarities of seawater versus that of body fluids. Cephalopods, bivalves and brachiopods exert a strong biological control on biomineralization that, to some degree, may buffer their shell geochemistry against secular changes in seawater chemistry. Disordered (amorphous) calcium carbonate precursor phases, later transformed to crystalline biominerals, may be significant in carbonate archive research due to expected geochemical offset relative to the direct precipitation of stable phases. A reasonable level of understanding of the related mechanisms is thus crucial for those who use these skeletal hard parts as archives of the palaeo‐environment. The impact of what is commonly referred to as ‘biological factors’ on the geochemistry of mollusc and brachiopod hard parts is explored for conventional isotope systems such as carbon, oxygen, strontium and traditionally used element to calcium ratios. In particular, the often used δ¹³C_carb or the Mg/Ca and Sr/Ca elemental proxies are fraught with problems. An interesting new research field represents the analysis, calibration and application of non‐traditional proxies to mollusc and brachiopod hard parts. Examples include the carbonate clumped isotope (Δ₄₇) approach and the analysis of the isotopes of Ca, Mg, N, Li, S or element to Ca ratios such as Li/Ca or B/Ca and rare earth elements. Based on considerations discussed here, a series of “do's and don'ts” in mollusc and brachiopod archive research are proposed and suggestions for future work are presented. In essence, the suggestions proposed here include experimental work (also field experiments) making use of recent archive organisms or, where possible, a reasonable recent analogue in the case of extinct groups. Moreover, the detailed understanding of the architecture of mollusc and brachiopod hard parts and their ultra‐structures must guide sampling strategies for geochemical analyses. Where feasible, a detailed understanding of the diagenetic pathways and the application of multi‐proxy and multi‐archive approaches should form the foundation of fossil carbonate archive research. The uncritical compilation of large data sets from various carbonate‐shelled organisms collected at different locations is not encouraged.