NaCl-X-H2O三元体系25℃等温蒸发石盐流体包裹体均一温度实验研究

复杂卤水组分对于石盐流体包裹体均一温度的影响尚不明确,文章基于NaCl-X-H_2O(X=KCl, MgCl_2,CaCl_2, Na_2SO_4)三元卤水体系,尝试探讨K~+、Mg~(2+)、Ca~(2+)、SO_4~(2-)对石盐流体包裹体均一温度测试结果的影响。不同卤水体系最大均一温度分析结果表明,K~+、Mg~(2+)、Ca~(2+)的存在总体上会导致石盐流体包裹体均一温度偏大,SO_4~(2-)的存在对均一温度的影响很小。以NaCl-H_2O体系为参照,NaCl-Na_2SO_4-H_2O体系平均均一温度较之要低,而NaCl-KCl-H_2O、NaCl-MgCl_2-H_2O和NaCl-CaCl_2-H_2O体系与其相反。NaCl-KCl-H_2O体系中的KCl浓度与平均均一温度呈现负相关关系,NaCl-MgCl_2-H_2O、NaCl-CaCl_2-H_2O、NaCl-Na_2SO_4-H_2O体系中的w(MgCl_2)、w(CaCl_2)和w(Na_2SO_4)与平均均一温度则呈现正相关关系。平均和最大均一温度分析结果都显示出复杂卤水体系中不同离子及其浓度对石盐流体包裹体均一温度会产生影响。本研究对于具有复杂化学组分卤水结晶析出石盐均一温度的研究具有重要的参考价值。     

浅海Mg~(2+)和SO_4~(2-)对微生物诱导形成锰碳酸盐的影响

为了模拟浅海环境下锰氧化物微生物还原作用诱导碳酸盐沉淀的过程,选取最常见的锰氧化物-水钠锰矿(K_(0.33)Mn_7O_(14)·7H_2O)为研究对象,在不同种类与浓度盐离子(Mg~(2+)、SO_4~(2-))存在条件下开展异化锰还原菌Dietzia cercidiphylli 45-1b好氧还原水钠锰矿的实验研究.通过测试体系蛋白、Mn~(2+)等离子浓度变化,利用X射线衍射(XRD)和X射线吸收谱(XAS)表征反应前后矿物结构变化,来探讨不同初始Mg~(2+)和SO_4~(2-)浓度对于菌株45-1b还原水钠锰矿及诱导碳酸盐矿物沉淀的影响.结果显示体系pH值在4天内从7.0迅速上升至9.3,Mn~(2+)浓度在2天内迅速上升至166μmol/L,随后迅速下降至8μmol/L(第4天),其好氧还原产物为菱锰矿(MnCO3),且其产生量随Mg~(2+)浓度的升高而降低,随SO_4~(2-)浓度的升高而升高.上述实验结果表明好氧环境下菌株45-1b能够利用乙酸为电子供体,水钠锰矿为电子受体还原水钠锰矿释放Mn~(2+),最终转化有机碳为无机碳酸盐矿物菱锰矿.Mg~(2+)通过影响微生物生长和菱锰矿成核对水钠锰矿的还原及菱锰矿沉淀产生抑制作用,而SO_4~(2-)可以缓解Mg~(2+)的抑制作用并促进水钠锰矿的还原及菱锰矿沉淀.     

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。     

新生碳酸钙沉积矿物形态的影响因素分析

石笋是古气候重建的重要地质载体,文石与方解石是石笋碳酸钙晶体的常见矿物形态。根据现代洞穴监测数据分析洞穴新生碳酸钙沉积物 (Active Speleothem: AS)的矿物形态的研究较少。本文在重庆武隆芙蓉洞三个滴水点 (MP2、MP5、MP9)下放置玻璃片,收集新生碳酸钙沉积物和滴水样品,监测新生碳酸钙沉积物矿物形态、滴水的Mg/Ca比值、pH、滴率和洞穴环境等指标,分析玻璃片正面和反面新生碳酸钙沉积物的δ18O、δ13C和Mg/Ca比值。研究发现:(1) MP2滴水点下的玻璃片正反面新生碳酸钙沉积物的矿物形态均为方解石;MP5和MP9滴水点的正面沉积方解石和文石-方解石混合两种情况,反面沉积文石-方解石,且反面文石多于正面。 (2) MP2滴水Mg/Ca比值小于MP5和MP9,说明滴水Mg/Ca比值是影响新生碳酸钙沉积物矿物形态的重要因素;而滴水pH值对AS矿物形态的影响在不同滴水点有差异。(3) 不论是玻璃片正面还是反面,文石-方解石混合的新生碳酸钙沉积物δ18O和δ13C比以方解石为主的沉积物偏正,说明AS矿物形态的变化会导致δ18O和δ13C发生变化。通过在芙蓉洞的系统监测和分析,发现新生碳酸钙沉积物的矿物形态与地表环境、洞穴上部岩溶水文地质条件密切相关,并验证了洞穴新生碳酸钙沉积物的矿物形态对石笋δ18O和δ13C具有重要影响。      

法国罗瓦尔河口悬移质中的石膏颗粒及表面新生方解石霰石晶体描述

本文介绍在暖温带河口悬移质中发现的石膏颗粒及其表面的新生方解石和霰石晶体。石膏颗粒经受了不同程度的化学和生物化学风化。在一部分风化石膏表面,存在大量的数微米到数十微米大小的方解石和霰石晶体,某些晶体还呈现出亲岩生物遗留的生长纹。由于河口水的溶蚀作用,一部分石膏颗粒已充分碳酸钙化。     

16ka以来青海湖湖相自生碳酸盐沉积记录的古气候

研究了青海湖沉积物碳酸盐的组成、来源及其同湖水物理化学性质的关系,建立了文石饱和指数同温度和湖水Mg/Ca比值（可指示盐度）的关系,利用碳酸盐的组成探讨了青海湖16ka B.P.以来的古气候环境演化过程。结果表明,青海湖沉积碳酸盐大都是自生的,16ka B.P.以来沉积碳酸盐以文石为主。文石的高含量时段同暖湿气候相对应,低含量则同冷干气候相对应。15.2ka B.P.为末次冰期盛冰阶进入晚冰期的界限,晚冰期气候的冷暖波动频繁,幅度较小,13.4-13ka B.P.,11.6-12ka B.P.和11-10.4ka B.P.之间的冷颤动分别相当于老仙女木、中仙女木和新仙女木事件,12－13ka B.P.和11.6-11ka B.P.之间的暖期则分别对应于博令和阿勒罗得暖期。全新世初期（10.4-10ka B.P.)白云石含量的突然增高和文石的消失,可能同淡水快速补给前期盐度较高的湖水有关,反映了全新世开始时气温和降水的增加具有突变性的特点。全新世大暖期的鼎盛期,即6.7ka B.P.左右时湖水的盐度较低。6.7-4ka B.P.为气候转型过程中的冷暖和干湿的快速波动期。4ka B.P.以后碳酸盐含量急剧降低,气候逐步向冷干化方向发展。     

结构矿物学的新成果

五、无水碳酸盐矿物结构中阳离子有序—无序问题本文讨论与CaCO_3的各种同质多相变体(方解石、文石、球方解石)结构相关的无水碳酸盐矿物.近年来,在我国找到了几乎所有的已知的这类矿物,并且发现了几种新矿物(黄河矿、氟碳钸钡矿、中华镁矿、大青山矿)和新变种(富锶的文石、富锶的本斯顿石、富镍的菱镁矿(河西矿).对这些矿物都作过X射线研究,测定了钡解石、大青山矿、黄河矿、氟碳钸钡矿、碳钸钠石、Doverite的晶     

盐类对甲烷水合物稳定性影响研究进展

甲烷水合物稳定性主要控制着甲烷水合物稳定带的厚度,温度、压力、孔隙水盐度和气体组分等因素影响着水合物稳定带的厚度。甲烷水合物的形成与地层水关系密切,而地层水中的各种盐离子(Cl~-、Na~+、Mg~(2+)、SO_4(~2-)、Ca~(2+))以及过渡金属(Fe、Mn、Cu、Co、Ni等)会影响天然气水合物的形成和分解条件。因此,研究盐类对甲烷水合物的稳定性认识有助于更加深入了解天然气水合物的成藏条件。本文分析了氯化物、硫酸盐、碳酸盐三大盐类对甲烷水合物稳定性的影响:同一盐类不同盐度条件下,随着盐度的增加,甲烷水合物相平衡曲线向低温高压偏移。总结了不同盐类和阴阳离子对甲烷水合物的抑制作用大小:在相同浓度、不同盐类条件下,盐类浓度在1.0~1.5 mol/L时盐类对甲烷水合物的抑制作用大小为MgCl_2CaCl_2Na ClKCl,盐类浓度大于1.5 mol/L时CaCl_2的抑制作用较强;阴离子对甲烷水合物的抑制作用大小争议较大,阳离子中Mg~(2+)对甲烷水合物的抑制作用最强。从目前的研究成果来看,已有数据与实际地质条件还存在一定差距,需要在真实实验条件下加强氯化物-硫酸盐-碳酸盐-甲烷-水体系的详细研究。本文提出,将高压可视反应腔与显微激光拉曼技术相结合,有望准确获取天然气水合物稳定形成时的温压条件,明确盐类和阴阳离子的抑制作用大小,以及盐类和离子特性如何影响水合物的形成和稳定,以便为未来的水合物勘探开发提供参考。     

典型华北型煤矿区主要充水含水层水文地球化学特征及控制因素

地下水形成、演化过程中控制因素不同所造成的水化学组分的差异性是矿井涌水水源识别的基础,为揭示矿井主要充水含水层水化学作用及控制因素,以位于太行山东麓的典型华北型煤矿区——鹤壁矿区为研究对象,采用统计分析、Piper三线图、Gibbs图、离子相关性分析与主成分分析法对矿区122个地下水水化学资料进行了分析研究。结果表明鹤壁矿区主要充水含水层中地下水的化学组分主要受岩石的风化作用控制。奥灰水主要水化学类型为HCO_3-Ca·Mg型,水中Ca~(2+)、Mg~(2+)主要来自碳酸盐岩(方解石和白云石)的溶解。二灰水主要水化学类型为HCO_3·SO_4-Ca·Mg型或SO_4·HCO_3-Ca·Mg型,其中Ca~(2+)、Mg~(2+)、HCO_3~-的主要来源于碳酸盐岩的溶解,SO_4~(2-)来自硫酸盐岩的溶解作用和黄铁矿的氧化作用。砂岩水主要水化学类型为HCO_3-Na型,Na~+、Cl~-与HCO_3~-主要来自盐岩的溶解和硅酸盐矿物的风化作用。八灰水既有HCO_3-Ca·Mg型和HCO_3·SO_4-Ca·Mg型,也有HCO_3-Na型,Ca~(2+)、Mg~(2+)、HCO_~3-和SO_4~(2-)的来源与二灰水一致,Na~+和Cl~-可能来自盐岩的溶解作用以及砂岩水与八灰水的混合作用。     

兖州煤田奥陶系灰岩地下水水化学特征及其形成机理

鲁西南兖州煤田的奥陶系灰岩地下水对煤田深部煤炭开采具有潜在的水害威胁,且为研究区的主要供水水源之一,其水化学特征及形成机理分析,可为该区深部煤炭开采水害防治和地下水资源利用提供依据。经过目的层水样的采集与测试可知,地下水水化学类型以SO_4-Ca-Mg型为主,SO_4~(2-)含量为537~2 296 mg/L,Ca~(2+)和Mg~(2+)的平均含量分别为455.7 mg/L和116.6 mg/L,TDS的范围为961~3 555 mg/L,pH值为6.9~8.0。Ca~(2+)和SO_4~(2-)随TDS的增加而增加,呈良好线性关系,推断TDS的增加主要来自Ca~(2+)和SO_4~(2-)的贡献。由饱和指数(SI)可知,地下水中的白云石和方解石均处于过饱和状态,而绝大部分的水样的石膏饱和指数均小于0,处于不饱和状态。石膏的饱和指数与地下水中TDS呈正相关关系。这些结果表明,在该含水层中地下水运移过程中不断发生水岩相互作用,主要包括石膏溶解、白云石和方解石沉淀或溶解、离子交换等反应。     

碳酸钙矿物低温化学合成及其同质多象转变矿物学机理研究

通过缓慢分解Ca²⁺-Mg²⁺-HCO₃^--Cl^--H₂O溶液和以菱锶矿(或碳钡矿、白铅矿)为晶种的附晶生长法,在0-90℃温度范围内定向合成了碳酸钙同质多象变体.矿物合成实验结果表明,随着温度升高,有利于亚稳态文石和不稳定六方方解石的生成;随着溶液中Mg²⁺离子浓度增大和Ca(HCO₃)₃溶液浓度减小,均有利于亚稳态文石的形成.以XRD和SEM技术为实验手段,详细研究了碳酸钙同质多象转变过程.结果显示:在流体参与的情况下,文石→方解石和六方方解石→方解石的同质多象转变速率很快,并且其转变的矿物学机理为溶解/再沉淀.     

The effect of cobalt ion on nucleation of calcium-carbonate polymorphs

Cobalt, like Mg, may cause the precipitation of aragonite rather than calcite in aqueous solutions due to the adsorption and crystal poisoning of calcite by a hydrated ion. Solutions containing NaCl and CaCl₂, having the ionic strength and Ca content of seawater (35‰ salinity), were spiked with known amounts of CoCl₂. Calcium carbonate was precipitated by the addition of 0.7 ml of 1 M Na₂CO₃. All experimental runs were made at 25°C, and all products were examined by X-ray diffraction. At low concentrations of Co (< 5·^?4M) calcite and vaterite formed. At concentrations from 5·10^?4 M to 2·10^?3M, the products consisted of combinations of calcite and vaterite; aragonite and calcite; aragonite and vaterite; calcite, vaterite and aragonite. In solutions of 3·10^?3M CoCl₂, most precipitates were aragonite with only one sample containing a small amount of calcite. All precipitates from 5·10^?3M CoCl₂ solutions either contained aragonite or were amorphous. Solutions with concentrations of 1 · 10^?2M CoCl₂ produced only amorphous precipitates. All precipitates contained an amorphous violet phase, assumed to be basic cobaltous carbonate (2CoCO₃·Co(OH)₂·H₂O).     

Carbon and Oxygen Isotopic Composition of Surface‐Sediment Carbonate in Bosten Lake (Xinjiang,China) and its Controlling Factors

Bosten Lake is a mid-latitude lake with water mainly supplied by melting ice and snow in the Tianshan Mountains. The depositional environment of the lake is spatially not uniform due to the proximity of the major inlet and the single outlet in the western part of the lake. The analytical results show that the carbon and oxygen isotopic composition of recent lake sediments is related to this specific lacustrine depositional environment and to the resulting carbonate mineralogy. In the southwestern lake region between the Kaidu River inlet and the Kongqi River outlet, carbon isotope composition (δ13C) values of the carbonate sediment (?1‰ to ?2‰) have no relation to the oxygen isotope composition of the carbonate (δ18O) values (?7‰ to ?8‰), with both isotopes showing a low variability. The carbonate content is low (<20%). Carbonate minerals analyzed by X-ray diffraction are mainly composed of calcite, while aragonite was not recorded. The salinity of the lake water is low in the estuary region as a result of the Kaidu River inflow. In comparison, the carbon and oxygen isotope values are higher in the middle and eastern parts of the lake, with δ13C values between approximately +0.5‰ and +3‰, and δ18O values between ?1‰ and ?5‰. There is a moderate correlation between the stable oxygen and carbon isotopes, with a coefficient of correlation r of approximately 0.63. This implies that the lake water has a relatively short residence time. Carbonate minerals constitute calcite and aragonite in the middle and eastern region of the lake. Aragonite and Mg–calcite are formed at higher lake water salinity and temperatures, and larger evaporation effects. More saline lake water in the middle and eastern region of the lake and the enhanced isotopic equilibrium between water and atmospheric CO2 cause the correlating carbon and oxygen isotope values determined for aragonite and Mg–calcite. Evaporation and biological processes are the main reasons for the salinity and carbonate mineralogy influence of the surface-sediment carbonate in Bosten Lake. The lake water residence time and the CO2 exchange between the atmosphere and the water body control the carbon and oxygen isotope composition of the carbonate sediment. In addition, organic matter pollution and decomposition result in the abnormally low carbon isotope values of the lake surface-sediment carbonate.     

Adsorption and Desorption of Phosphate on Calcite and Aragonite in Seawater

The adsorption and desorption of phosphate on calcite and aragonite were investigated as a function of temperature (5–45 °C)and salinity (0–40) in seawater pre-equilibrated with CaCO₃. An increase in temperature increased the equilibrium adsorption; whereas an increase in salinity decreased the adsorption. Adsorption measurements made in NaCl were lower than the results in seawater. The higher values in seawater were due to the presence of Mg²⁺ and Ca²⁺ ions. The increase was 5 times greater for Ca²⁺ than Mg²⁺. The effects ofCa²⁺ and Mg²⁺ are diminished with the addition of SO₄ ^2- apparently due to the formation of MgSO₄ and CaSO₄ complexes in solution and/or SO₄ ^2- adsorption on the surface of CaCO₃. The adsorbed Ca²⁺ and Mg²⁺ on CaCO₃ (at carbonate sites) may act as bridges to PO₄ ^3- ions. The bridging effect of Ca²⁺is greater than Mg²⁺ apparently due to the stronger interactions of Ca²⁺ with PO₄ ^3-.The apparent effect of salinity on the adsorption of PO₄ was largely due to changes in the concentration of HCO₃ ^- in the solutions. An increase in the concentration of HCO₃ ^- caused the adsorption of phosphate to decrease, especially at low salinities. The adsorption at the same level of HCO₃ ^- (2 mM) was nearly independent of salinity. All of the adsorption measurements were modeled empirically using a Langmuir-type adsorption isotherm[ [PO₄]_ad = K_mC_m[PO₄]_T/(1 +K_m [PO₄]_T) , ]where [PO₄]_ad and [PO₄]_T are the adsorbed and total dissolved phosphate concentrations, respectively. The values of C_m (the maximum monolayer adsorption capacity, (mol/g) and K_m (the adsorption equilibrium constant, g/(mol) over the entire temperature (t, °C) and salinity (S) range were fitted to[ C_m = 17.067 + 0.1707t - 0.4693S + 0.0082S² ( = 0.7) ][ ln K_m = - 2.412 + 0.0165t - 0.0004St - 0.0008S² ( = 0.1) ]These empirical equations reproduce all of our measurements of[PO₄]_ad up to 14 mol/g and within ±0.7 mol/g.The kinetic data showed that the phosphate uptake on carbonate minerals appears to be a multi-step process. Both the adsorption and desorption were quite fast in the first stage (less than 30 min) followed by a much slower process (lasting more than 1 week). Our results indicate that within 24 hours aragonite has a higher sorption capacity than calcite. The differences between calcite and aragonite become smaller with time. Consequently, the mineral composition of the sediments may affect the short-term phosphate adsorption and desorption on calcium carbonate. Up to 80 % of the adsorbed phosphate is released from calcium carbonate over one day. The amount of PO₄ left on the CaCO₃ is close to the equilibrium adsorption. The release of PO₄ from calcite is faster than from aragonite. Measurements with Florida Bay sediments produced results between those for calcite and aragonite. Our results indicate that the calcium carbonate can be both a sink and source of phosphate in natural waters.     

Carbonate weathering and connate seawater influencing karst groundwaters in the Gevas–Gurpinar–Güzelsu basins,Turkey

There are 59 springs at the Gevas–Gurp?nar–Güzelsu basins, 38 of these springs emerge from the fractured karst aquifers (recrystallized limestone and travertine) and 21 emerge from the Yuksekova ophiolites, K?rkgeçit formation and alluvium. The groundwater samples collected from 38 out of the total of 59 springs, two streams, one lake and 12 wells were analyzed physico-chemically in the year 2002. EC and TDS values of groundwater increased from the marble (high altitude) to the ophiolites and alluvium (toward Lake Van) as a result of carbonate dissolution and connate seawater. Five chemical types of groundwater are identified: Ca–Mg–HCO₃, Mg–Ca–HCO₃, Mg–Na–HCO₃, Na–Ca–HCO₃ and Mg–Ca–Na–HCO₃. The calculations and hydrochemical interpretations show that the high concentrations of Ca²⁺, Mg²⁺ and HCO₃ ^? as predominant ions in the waters are mainly attributed to carbonate rocks and high pCO₂ in soil. Most of the karst springs are oversaturated in calcite, aragonite and dolomite and undersaturated in gypsum, halite and anhydrite. The water–rock interaction processes that singly or in combination influence the chemical composition of each water type include dissolution of carbonate (calcite and dolomite), calcite precipitation, cation exchange and freshening of connate seawater. These processes contribute considerably to the concentration of major ions in the groundwater. Stable isotope contents of the groundwater suggest mainly direct integrative recharge.     

Shoreline tufa and tufaglomerate from Pleistocene Lake Bonneville,Utah, USA: stable isotopic and mineralogical records of lake conditions,processes, and climate

Shoreline carbonate deposits of Pleistocene Lake Bonneville record the conditions and processes within the lake, including the evaporative balance as well as vertical and lateral chemical and isotopic gradients. Tufas (swash‐zone) and tufaglomerates (cemented, subaqueous colluvium or beachrock) on multiple, well‐developed shorelines near the Silver Island Range, Utah, also present an opportunity to examine physicochemical lake processes through time. Three shorelines are represented by carbonate deposits, including the 23–20 ka Stansbury stage, 15–14.5 ka Bonneville stage, and 14.5–14 ka Provo stage. Mean δ¹⁸O_VSMOW values of all three shorelines are statistically indistinguishable ( ～ 27 ± 1‰), when a few Bonneville samples of unusual composition are neglected. However, differences in primary carbonate mineralogy indicate that the correspondence is an artefact of the different fractionation factors between calcite or aragonite and water. Second, in order to sustain a much smaller, shallower lake during the colder Stansbury stage, the climate must have also been relatively dry. Third, δ¹⁸O values in tufa are higher than tufaglomerate by ～ 0.5‰, consistent with greater evaporative enrichment of lake water in the swash zone. Fourth, mean δ¹³C values for the Provo, Stansbury and Bonneville shorelines (4.4, 5.0 and 5.2‰, respectively) show that carbon species were dominated by atmospheric exchange, with the variations produced by differences in the oxidation of organic matter. Comparisons of shoreline carbonates with deep‐lake marls of the same approximate age indicate that shoreline carbonate was much higher in δ¹³C and δ¹⁸O values (both ～ 2.5‰) during Bonneville time, whereas isotopic differences were minor (both ～ 1‰) in Stansbury time. In particular, the Bonneville stage may have sustained large vertical or lateral isotopic gradients due to evaporative enrichment effects on δ¹⁸O values. In contrast, the lake during the much shallower Stansbury stage may have been well mixed. Differences in the primary mineralogy (Stansbury and Bonneville, aragonite > calcite; Provo, calcite > aragonite) reflect profound differences in lake chemistry in terms of open versus closed‐basin lakes. The establishment of a continuous outlet during Provo time probably reduced the Mg²⁺/Ca²⁺ ratio of lake water. Curiously, regardless of primary mineralogy, tufaglomerate cements are enriched in Na⁺ and Cl^? and depleted in Mg²⁺ relative to capping tufa of the same age. This probably reflects vital or kinetic effects in the swash zone (tufa). We suspect that ‘abiotic’ effects may have been important in the dark pore space of developing tufaglomerate, where the absence of light suppressed photosynthesis. Copyright © 2005 John Wiley & Sons, Ltd.     

Hydromagnesite replacement of biomineralized aragonite in a new location of Holocene stromatolites, Lake Walyungup, Western Australia

Holocene stromatolites are described from Lake Walyungup, a coastal hyposaline lake in south-western Australia. At summer low water, this groundwater-fed depression comprises two permanent shallow water bodies and an ephemeral southern pool, set within an areally extensive littoral zone of variably cemented carbonate crust. Up to 5 m of organic-rich carbonate mud has been deposited within each of these basins in less than 7000 years. Stromatolites rim the water bodies with individual columns up to 2 m tall. Stromatolite-capped tepee structures in subparallel alignment are widespread in the littoral crust, suggesting a linkage between stromatolite growth and zones of groundwater discharge. Lake Walyungup stromatolites, regardless of external morphology and setting, are coarsely laminated and have aragonitic mesoclot microfabrics. These microfabrics are similar to those from lithified portions of active thrombolitic microbialites from nearby Lake Clifton. Hydromagnesite is a minor to subdominant phase (up to 47 wt%) of the carbonate mineral assemblage in Lake Walyungup. It occurs mainly in the littoral zone as a diagenetic replacement of precursor aragonite, particularly within the mesoclot fabric of stromatolites, but also in sediments (strandline and dune sand, crusts) derived mainly from erosion of stromatolites. In contrast with nonreplaced and impermeable inorganic aragonitic cements, stromatolite mesoclots are microper- meable. Micropermeability is inferred to facilitate hydromagnesite diagenesis. Dolomite is also present in minor amounts as a pore fill in stromatolites, and as a subdominant to dominant (up to 100 wt%) phase in thin, mudcracked micrite layers within the crust package. The layered dolomite may be precipitated directly from the lake water. Major element abundance of the lake water is: Na⁺ > Mg²⁺ » K⁺ > Ca²⁺ for cations, and Cl^? » SO₄^2? ≈ HCO₃^? > CO₃^2? for anions. Compared to other nearby coastal lakes, Lake Walyungup has a high pH (> 9·0), and an extremely high molar Mg/Ca ratio of > 90. Groundwater in the area has a Mg/Ca ratio generally less than 1. The unusual Mg/Ca ratio in Lake Walyungup is partially a result of in-lake processes with additional minor contribution of Mg²⁺ sourced from basal marine sand because no Mg-rich bedrock source has been found in the region.     

Major ion geochemistry of shallow groundwater in the Qinghai Lake catchment, NE Qinghai-Tibet Plateau

Conventional hydrochemical techniques and statistical analyses were applied to better understand the solute geochemistry and the hydrochemical process of shallow groundwater in the Qinghai Lake catchment. Shallow groundwater in the Qinghai Lake catchment is slightly alkaline, and is characterized by a high ion concentrations and low water temperature. The total dissolved solids (TDS) in most of the samples are <1,000?mg/L, i.e. fresh water and depend mainly on the concentration of SO₄ ^2?, Cl^? and Na⁺. Groundwater table is influenced directly by the residents?? groundwater consumption. Most of the groundwaters in the Qinghai Lake catchment belong to the Ca²⁺(Na⁺) ?CHCO₃ ^? type, while the Qinghai Lake, part of the Buha (BHR) and the Lake Side (LS) samples belong to the Na⁺?CCl^? type. The groundwater is oversaturated with respect to aragonite, calcite and dolomite, but not to magnesite and gypsum. Solutes are mainly derived from strong evaporite dissolution in Daotang, BHR and LS samples and from strong carbonate weathering in Hargai and Shaliu samples. Carbonate weathering is stronger than evaporite dissolution with weak silicate weathering in the Qinghai Lake catchment. Carbonate weathering, ion exchange reaction and precipitation are the major hydrogeochemical processes responsible for the solutes in the groundwater in the Qinghai Lake catchment. Most of the shallow groundwaters are suitable for drinking. More attention should be paid to the potential pollution of nitrate, chloride and sulfide in shallow groundwater in the future.     

The interaction of magnesium with calcite during crystal growth at 25–90°C and one atmosphere

Calcite crystals were grown in a closed system by recrystallization of synthetic and natural aragonite crystals, in the presence of various CaCl2-MgCl2 solutions with and without NaCl.The distribution of Mg2+ between calcite and solution at the entire temperature range is heterogeneous, closely following the Doerner-Hoskins (Doerner and Hoskins, 1925) distribution law. λMg2+C is strongly dependent on temperature, being: 0·0573 ± 0·0017 at 25°C, 0·0681 ± 0·0019 at 35°C, 0·0778 ± 0.0022 at 50°C, 0·0973 ± 0·0021 at 70°C, and 0·1163 ±0 ·0034 at 90°C. λMg2+C is independent of the absolute concentration of Ca2+ in solution as well as of the presence of NaCl.Relatively high λMg2+C values are obtained during the initial reaction stages when too-highly reactive synthetic aragonites are recrystallized. SEM micrographs show that calcite crystals grown from such aragonites are imperfect and that their earlier formed Mg-rich cores redissolve later, resulting in apparently inconsistent λMg2+C values.Calculations applying the new λMg2+C value for 25°C and the solubility data for magnesian calcites (Chaveet al., 1962) demonstrate that although no calcite should be expected to precipate directly from open sea water, its direct precipitation (or recrystallization from aragonite) is possible in closed diagenetic systems which still contain marine solutions, provided a temporary increase in the dissolved calcium concentration takes place.The λMg2+C values obtained allow for a new insight into processes of calcite cementation of reefs and a variety of other carbonate sediments, and for a more precise definition of dedolomitization chemistry.     

Major ion composition and seasonal variation in the Lesser Himalayan lake: case of Begnas Lake of the Pokhara Valley, Nepal

The Begnas Lake in the Pokhara Valley is one of the threatened habitats in Nepal. The major ion chemistry explains the status of most of the inorganic nutrients and their possible sources. However, the earlier studies mostly cover limnological investigations, and phytoplankton and zooplankton diversity. Thus, the present study has been conducted to investigate the geochemical processes and to examine the seasonal variation of chemical composition within Begnas Lake. The results showed that SO ₄ ^2- , PO ₄ ^3- , and NO ₃ ^- increased compared with the previous values. The domination of Ca²⁺, Mg²⁺, and HCO ₃ ^- explains the influence of carbonate weathering on the major ion concentration. In general, pH and dissolved oxygen decreased with the depth of water-column, while electric conductivity, total dissolved solids, HCO ₃ ^- , Cl^-, H₄SiO₄, K⁺, Mg²⁺, Ca²⁺, Mn²⁺, and Fe increased. Among the cations, the predominance of Ca²⁺ and Mg²⁺ as characterized by high (>0.6) (Ca²⁺ + Mg²⁺)/(Tz⁺) and (>0.8) (Ca²⁺ + Mg²⁺)/(Na⁺ + K⁺) equivalent ratios, also suggests prevalence of carbonate weathering. The low value of (Na⁺ + K⁺)/Tz⁺ ratio shows deficiency of Na⁺ and K⁺, suggesting low contribution of cations via aluminosilicate weathering. The C-ratio suggests a proton source derived both from oxidation of sulfide and dissolution and dissociation of atmospheric CO₂ during different seasons. Though the major hydro-chemical parameters are within permissible limit, the increase in trophic state of the lake suggests that inherent biogeochemical processes make the limiting nutrients available, rendering eutrophic effect. Therefore, further comprehensive studies incorporating sediment–water interaction ought to be carried out to explain the ongoing phenomena and curb the eutrophication process in the lake.