梭菌SN-1菌株参与下形成的碳酸盐矿物组合及其主要矿物成分的动态变化

在Mg/Ca比值为6的Lagoa Vermelha改良培养基中,对分离自青海湖湖底沉积物的梭菌(Clostridiumsp.)进行了为期100 d的碳酸盐矿物培养实验,同时还完成了一组无菌对照实验。利用X射线衍射仪(XRD)和扫描电子显微镜(SEM)分别对矿物成分和形态进行了测定和观察。实验结果表明:细菌培养实验的沉淀物数量始终多于无菌对照实验;在梭菌SN-1菌株作用下形成的碳酸盐矿物组合的变化趋势是方解石→方解石+单水碳钙石→单水碳钙石+方解石→单水碳钙石,而无菌对照实验产物中矿物的演化方向是单水碳钙石+方解石→方解石+单水碳钙石;在综合分析SEM和XRD观测结果的基础上,推测哑铃状矿物可能是高镁方解石,而球状矿物可能是单水碳钙石。     

梭菌对含镁方解石形态的控制及其可能机理

在 Mg/Ca 摩尔比为 4∶1 的 Lagoa Vermelha 培养基中对一株分离自青海湖底沉积物的梭菌 SN-1（Clostridium sp.）进行了为期 55 d 的碳酸盐矿物培养实验,同时还完成了一组无菌对照实验。利用扫描电子显微镜对沉淀物进行了系统的观察,用 X- 射线衍射仪对沉淀物的矿物成分进行了测定。结果表明：（1）SN-1 可以促进特殊形态含镁方解石的形成,而无菌对照实验产物中仅见不规则状的碳酸盐矿物;（2）特殊形态的含镁方解石可能是在细菌表面成核和生长的结果,它们的演化趋势是（杆状）→哑铃形→花菜状→球形。作者认为这是因为梭菌两端的带负电基团比菌体中间丰富,易聚集更多的 Ca²⁺和 Mg²⁺,Ca²⁺和 Mg²⁺离子作为“阳离子桥”吸引 CO32-,其结果是两端的晶体生长相对较快、中间生长相对较慢,进而形成哑铃形含镁方解石;“哑铃”继续生长,其两端会长成两个“花菜”或半球;若两个半球相接并闭合则发展为球状矿物。     

利用小半径粉晶相机测定钙镁碳酸盐矿物的含镁量

白云石和方解石是分布很普遍的造岩矿物,尤其在沉积地层中更属常见。镁方解石是现代碳酸盐沉积物和某些海洋生物介壳的一种常见矿物。一般说来,区分白云石与方解石是比较容易做到的。但是,要确切地回答一块白云岩样品是由典型的白云石(Ca/Mg克分子比值接近于1)还是由富钙白云石矿物(Ca/Mg克分子比值大于1)构成的,则比较困难。     

石笋矿物类型、成因及其对气候和环境的指示

洞穴石笋的矿物组成分为方解石、文石和文石-方解石三种类型。本文总结了国内外已有的研究成果,并结合野外观测现象和数据,讨论了影响石笋矿物形成和转变的因素,分析了利用石笋矿物类型特征研究古气候和古环境变化的可行性。洞内滴水饱和度和滴水中Mg/Ca比值是影响石笋矿物类型的主要因素:当滴水Mg/Ca 比值较低（Mg/Ca＜1或<<1）时,滴水饱和度较低易形成方解石,而文石沉积则需要更高的滴水饱和度;当滴水Mg/Ca 比值较高（Mg/Ca≥1）时,方解石相对文石沉积需要更高的滴水饱和度。洞穴围岩镁含量高且滴水多而稳定的洞内环境是我国南方大量文石笋发育的主要原因。长期处于滴水淋滤环境的文石笋容易向方解石转变,但若滴水中Mg2+浓度较大,此转变过程会受到抑制。在围岩镁含量较低的洞穴中,干旱时期渗流水滞留时间长、滴水速率变慢,会造成滴水中Mg/Ca比值升高并引起文石沉积。因此,石笋矿物类型及矿物相转变可指示气候和环境的变化。      

南海北部甲烷渗漏的沉积地球化学指标(Sr/Ca和Mg/Ca)识别

自生碳酸盐矿物是揭示甲烷渗漏过程及其周期性变化的重要指标。为了方便、快速地识别出自生碳酸盐矿物,在探讨了前人建立的端元组分模型(文石、高镁方解石、生物成因方解石和碎屑)在我国南海北部适用性的基础上,利用沉积物全样中Sr/Ca和Mg/Ca值计算了南海北部神狐海域两支沉积物柱状样中自生碳酸盐矿物的质量分数,计算结果表明,在不同沉积深度均有含量不等的自生碳酸盐矿物。这一结果被X射线衍射结果和沉积物中存在晶形完好的自生高镁方解石和文石矿物所验证,表明利用前人建立的端元组分模型计算的结果具有可靠性。自生碳酸盐矿物的出现显示该海域深受甲烷渗漏作用影响。利用地球化学指标(Sr/Ca和Mg/Ca)获得的自生碳酸盐矿物含量垂向变化显示该区域甲烷渗漏具有强弱交替的周期变化。运用端元组分模型来获取沉积物柱状样中自生碳酸盐矿物的高分辨率剖面,从而识别甲烷渗漏信息非常方便,在大范围寻找甲烷渗漏和天然气水合物方面具有较大潜力。     

广州火烧岗垃圾填埋场自生碳酸盐岩的微生物成因特征

为探讨垃圾填埋场自生碳酸盐岩的生物地球化学过程和机制,对广州火烧岗垃圾填埋场渗滤液收集管道发育的纹层状碳酸盐结壳进行了岩石学和地球化学研究。结果显示,碳酸盐岩主要为低镁和高镁方解石,保存了叠层石、鲕粒、团粒、凝块、草莓状黄铁矿和球状、丝状和杆状体等与微生物活动有关的组构;碳酸盐矿物的δ~(13)CV-PDB值为+7.34‰~+18.21‰,表明碳主要来自产CH_4作用残余的CO_2;稀土元素组成显示其形成于还原环境。研究表明,厌氧微生物将垃圾有机质逐渐降解为CH_4和CO_2,提高渗滤液的碱度和p H值,降低SO_4~(2-)浓度,使得方解石晶体在细胞表面成核和沉淀;较晚形成的高镁方解石具有较高的δ~(13)C值,可能指示流体的Mg/Ca值和溶解无机碳δ~(13)C值在封闭的填埋场稳定化过程中逐渐上升。     

Mg2+调控低温环境下单水方解石的合成

在4℃的低温条件下,通过模拟纳木错湖水中主要离子种类,控制反应体系中的Mg/Ca摩尔比,探究纳木错单水方解石(MHC)的无机成因,并利用X-射线衍射(XRD)、傅里叶变换红外光谱(FTIR)和电感耦合等离子体发射光谱(ICP-OES)对实验沉淀产物进行了分析。结果表明,单水方解石是通过无定形碳酸钙(ACC)转化而来的,且单水方解石的形成和稳定受溶液中的Mg2+调控。当反应溶液中Mg/Ca 2时,生成方解石和镁方解石;当反应溶液中Mg/Ca 2时,单水方解石生成,并且在溶液中的存在时间随着Mg/Ca摩尔比的增加而增加。Mg/Ca=2时,单水方解石在溶液中仅存在48 h,随后转化为文石和少量镁方解石。单水方解石形成过程中Mg2+的作用主要是抑制方解石成核和生长,使单水方解石能够在溶液中形成并稳定存在。此结果为纳木错单水方解石无机成因提供一定的研究基础。     

西藏纳木错沉积物单水方解石出现前后的环境变化

2005年在西藏纳木错水下60m处钻取一支332cm的湖芯,沉积物皆为灰黑-黑色碳酸盐粘土。对湖芯1cm间隔取样并进行X射线、扫描电镜、Sr/Ca和碳酸盐含量的分析。研究发现,纳木错湖底0～258cm沉积物中出现了单水方解石,扫描电镜下该矿物晶形完好,这是个亚稳定矿物,具有重要环境意义。利用碳酸盐含量（24.12%～54.52%）、Sr/Ca比值（<0.006）、方解石中Mg含量（MgCO₃mol%<3.325%）、石膏、粘土矿物（伊利石和镁绿泥石）、单水方解石成因和沉积速率讨论了单水方解石形成前后湖泊环境的变化。2.1cal.kaB.P.单水方解石开始出现,此时纳木错湖水性质推断为pH>8.6,mol Mg/Ca>6.5,Ca²⁺和SO^2-₄离子浓度足以沉淀少量石膏,演化至现代,表层湖水性质为pH=9.4,mol Mg/Ca=10.03～15.03,SO^2-₄浓度较高,Ca²⁺含量低,不足以沉淀石膏。单水方解石出现之前的3.0～2.1cal.kaB.P.时期,沉积速率低（0.134mm/a）,蒸发作用强度不稳定,湖水温度低,矿化度呈上升趋势。该矿物出现后的2.1～1.7cal.kaB.P.时期,沉积速率快（1.639mm/a）,矿化度稳定,气温低,1.8cal.kaB.P.温度达到最低值,为气候冷事件的表现。较快的沉积速率（>1.168mm/a）是纳木错单水方解石形成的重要原因之一,碳酸盐沉积加快和入湖碎屑物质增加是沉积速率加快的主要原因。     

关于生物矿物的某些问题

生物矿物的形成阶段可分非晶质、过渡、成熟和石化4个阶段。生物矿物在门类由低到高,时代由新到老的分布上存在着一种演化趋向,硫化物→硫酸盐→铁锰氧化物→非晶硅→钙白云石→碳磷灰石→镁方解石→文石→方解石这种演化趋向也重演于个体发育阶段,反映在示序接触关系中。古代原始镁方解石可以根据现实主义原则、铁方解石交代作用、微量元素和同位素成分加以识别。     

安哥拉Bonga铌矿床成矿碳酸岩岩石地球化学和C-O同位素研究

安哥拉Bonga碳酸岩型铌矿床位于Parana'-Angola-Etendeka碱性岩-碳酸岩火成岩省东部,是一个孤立产出的中心式岩栓,侵入于元古宙花岗岩基底中。岩石地球化学研究表明,Bonga岩体由钙碳酸岩和少量的镁碳酸岩组成,岩体成分从钙碳酸岩向镁碳酸岩演化。矿物组合上,钙碳酸岩以方解石为主,副矿物有磷灰石、磁铁矿、烧绿石和少量稀土矿物;镁碳酸岩以白云石为主,烧绿石含量降低,稀土矿物含量增高。富钙碳酸岩(摩尔比值Ca O/Ca O+Mg O+Fe O+Mn O0.83)中Nb含量较高,变化于148.1×10~(-6)~8394×10~(-6),平均为2127×10~(-6),∑REE变化于1441×10~(-6)~9452×10~(-6),平均为2791×10~(-6),LREE/HREE变化于16.7~58.3,平均为25.0;富镁碳酸岩(摩尔比值Ca O/Ca O+Mg O+Fe O+Mn O0.83)Nb含量降低,变化于300.9×10~(-6)~3910×10~(-6),平均为1502×10~(-6),∑REE升高,变化于1659×10~(-6)~18849×10~(-6),平均为7111×10~(-6),轻稀土更加富集,LREE/HREE增大,变化于19.1~114,平均为57.6。铌在碳酸岩浆演化的早期富集,铌矿化主要与富钙碳酸岩有关;稀土元素的富集相对较晚,主要与富镁碳酸岩有关。对碳酸岩碳氧同位素的瑞利分馏模拟计算(RIFMS模型)结果表明,Bonga碳酸岩的铌矿化(烧绿石沉淀)主要受岩浆作用控制,其温度不低于600℃。     

洞穴次生碳酸盐沉积的Mg/Ca与Sr/Ca比值研究进展——兼论洞穴次生沉积物Mg/Ca与Sr/Ca的影响机制

微量元素是岩溶洞穴沉积中非常重要的一类古气候环境替代指标,为近20年来国内外的一个研究热点。总结前人的研究,主要取得了以下一些重要认识:（1）洞穴上覆土壤 和围岩是洞穴次生碳酸盐沉积Mg、Sr的主要来源;（2）Mg/Ca与Sr/Ca能够指示气候环境变化,但需结合其它指标综合考虑。（3）洞穴次生碳酸盐沉积Mg/Ca与Sr/Ca受多种气候环境因素（包括土壤和围岩的组成和性质、水-岩相互作用、先期碳酸盐沉积、分配系数等）影响,其古气候环境指示意义具有多解性;（4）矿物结晶作用对Mg/Ca与Sr/Ca有一定的影响,特别是文石在向方解石转变的过程中容易丢失Mg、Sr,此外,杂质的混入也将抑制Mg、Sr进入方解石,从而引起洞穴次生碳酸盐沉积Mg/Ca与Sr/Ca比值的变化。今后应进一步加强对石笋中这些微量元素的影响机制研究,尤其是对一些影响因素与微量元素含量变化之间的定量关系进行探讨。      

A strong temperature effect on U/Ca in planktonic foraminiferal carbonates

Three planktonic foraminiferal species Globigerina bulloides, Neogloboquadrina pachyderma (d), and Globorotalia inflata collected from core-tops spanning 35° to 65°N in the North Atlantic were used for U/Ca and Mg/Ca and foraminiferal shell weight analyses. Except for U/Ca in G. bulloides calcified under warm conditions (>∼13 °C), U/Ca ratios in all three studied species increase with decreasing latitude and show strong positive correlations with Mg/Ca ratios. A dissolution effect on planktonic U/Ca is suggested by decreased shell weight and U/Ca and Mg/Ca ratios for shells from very deep water depth (>4.4 km) along the latitudinal transect. G. bulloides from down core samples in the North Atlantic show low U/Ca ratios during the last glacial and high ratios during the Holocene, similar to the Mg/Ca evolution trend. In general, our data indicate that the U incorporation into planktonic foraminiferal carbonates is strongly influenced by calcification temperature, although U/Ca in G. bulloides may be affected by seawater carbonate ion concentration under warm conditions and/or other factors.     

The impact of solution chemistry on Mytilus edulis calcite and aragonite

Magnesium/calcium, Sr/Ca, and Na/Ca atom ratios were determined in the calcite and aragonite regions of Mytilus edulis shells which were grown in semi-artificial ‘seawater’ solutions having varying Mg/Ca, Sr/Ca, and Na/Ca ratios. These ratios were measured by instrumental neutron activation, atomic absorption, and electron microprobe analytical techniques. Strontium/calcium ratios in both calcite and aragonite were linearly proportional to solution Sr/Ca ratios. Magnesium/calcium ratios in calcite increased exponentially when solution Mg/Ca ratios were raised above the normal seawater ratio; whereas in aragonite, Mg/Ca ratios increased linearly with increases in solution Mg/Ca ratios. Sodium/calcium and sulfur/calcium ratios in calcite covaried with Mg/Ga solution ratios. Conversely, in aragonite, Na/Ca ratios varied linearly with solution Na/Ca ratios.Magnesium is known to inhibit calcite precipitation at its normal seawater concentration. We infer from the results of the work reported here that Mytilus edulis controls the Mg activity of the outer extrapallial fluid, thus facilitating the precipitation of calcitic shell. Increases in sulfur content suggest that changes in shell organic matrix content occur as a result of environmental stress. Certain increases in Mg content may also be correlated to stress. Sodium/calcium variations, and their absolute amounts in calcite and aragonite, are best explained by assuming that a substantial amount of Na is adsorbed on the calcium carbonate crystal surface. Strontium/calcium ratios show more promise than either Mg/Ca or Na/Ca ratios as seawater paleochemistry indicators, because the Sr/Ca distribution coefficients for both aragonite and calcite are independent of seawater Ca and Sr concentrations.     

利用富钴结壳碳酸盐基岩有孔虫矿物标型重建古海洋温度

重建古海洋海表温度(SST),是研究地质历史时期气候变化控制过程的关键。组成有孔虫化石的矿物Mg/Ca值是海水温度的可靠代用指标,是重建古海洋SST的一个非常好的手段。麦哲伦海山区的富钴结壳和基岩中普遍存在有孔虫化石,这对重建该区的SST有重要意义。利用LA-ICP-MS测得西太平洋麦哲伦海山区富钴结壳碳酸盐基岩中8颗浮游有孔虫化石Globigerinoides sacculifer的Mg/Ca值为3.84±0.36(mmol/mol),通过线性公式:T(℃)=2.898Mg/Ca(mmol/mol)+13.76及已有的定年数据,得到0.91Ma±西太平洋麦哲伦海山区海表温度为24.9+1.1/-1.0℃,未能检索到前人关于该区0.91Ma±前海表温度数据。     

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。     

Li/Ca ratios of ostracod shells at Lake Qinghai, NE Tibetan Plateau, China: a potential temperature indicator

Acquiring continuous and high-resolution natural records in recent 2,000?years is the hot issue in the palaeoclimate research. Recent studies revealed that Li/Ca and Mg/Li ratio of carbonate is a potential tracer of past environmental changes in the oceans, and is seldom applied for palaeoclimate reconstruction in lakes. To make full understanding of the potential of Li/Ca ratios of carbonates in lakes, Li/Ca ratios of monospecific ostracod shell Eucypris inflate with similar size in the lacustrine sediment core from Lake Qinghai, NE Tibetan Plateau have been analysed for the first time. Single species can effectively avoid the interspecies effects. In combination with the sedimentation rate that existed, data derived from ²¹⁰Pb and ¹³⁷Cs, downcore variations of Li/Ca ratios of ostracod shells during the past 800?years in Lake Qinghai have been reconstructed successfully. By comparing Li/Ca ratios and temperature inferred from meteorological records and tree ring widths in Dulan and Qilianshan in adjacent regions, Li/Ca ratios of ostracod shells negatively correlate with temperature. Higher temperature corresponds with lower Li/Ca ratios, and vice versa, indicating that Li/Ca ratio of ostracod shells is an effective indicator for temperature variations. Therefore, ongoing in-depth investigation using Li/Ca ratios of carbonates in more lakes to further reveal its palaeotemperature implications would be deserved.     

雪玉洞岩溶地下水、地表水Ca2+、Mg2+、Sr2+变化特征研究

通过2011年对重庆丰都雪玉洞洞内滴水和地下河河水,上覆岩层中出露的表层岩溶泉水和雪玉洞附近龙河河水等不同类型水中Ca2+、Mg2+、Sr2+浓度及Mg/Ca、Sr/Ca值的研究,发现不同水的Ca2+、Mg2+、Sr2+随外界降水条件的改变而出现明显变化。表层岩溶泉水Ca2+变化能够敏感反应外界降水条件改变,滴水对外界降雨的反应滞后接近1个月,地下河Ca2+可以反应雨季和旱季的变化,地表河水Ca2+全年比较稳定,但是对特殊干旱天气有显著响应。2011年不同类型水的Mg2+、Sr2+全年变化趋势基本一致,在降水较多的3、5、10月呈低值,在其他降水较少的月份浓度相对较高。各离子的这种变化特征主要是受到稀释效应、CO2效应以及所在地层的岩性的影响。雪玉洞不同类型水的Mg/Ca、Sr/Ca值呈现出滴水>地表河>地下河>表层岩溶泉的特点,反映出不同类型水在含水介质中滞留时间的长短,并且Mg/Ca、Sr/Ca值在降水较多的月份降低,在降水较少的月份升高;受碳酸钙的前期沉淀和运移路径差异的影响,不同类型水的Mg/Ca、Sr/Ca值变化稍有不同。因此,不同类型水的离子变化及其比值对外界降水条件变化的响应特征和时间的不同,决定了在利用元素及其比值反映外界环境变化时也要区别对待。      

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.     

An Isotope Dilution ICP‐MS Method for the Determination of Mg/Ca and Sr/Ca Ratios in Calcium Carbonate

Mg/Ca and Sr/Ca ratios in calcium carbonate are important components of many palaeoclimate studies. We present an isotope dilution method relying on a single mixed spike containing ²⁵Mg, ⁴³Ca and ⁸⁷Sr. Dozens of samples per day, as small as 10 μg of carbonate, could be dissolved, spiked and run in an ICP‐MS with a precision of 0.8% (2 RSD). Two instruments types, a sector field and a quadrupole ICP‐MS, were compared. The best long term precision found was 0.4% (2 RSD), although this increased by up to a factor of two when samples of very different Mg or Sr content were run together in the same sequence. Long term averages for the two instruments concurred. No matrix effects were detected for a range of Ca concentrations between 0.2 and 2 mmol l^‐1. Accuracy, tested by measuring synthetic standard solutions, was 0.8% with some systematic trends. We demonstrate the strength of this isotope dilution method for (a) obtaining accurate results for sample sets that present a broad Mg and Sr range and (b) testing solid carbonates as candidate reference materials for interlaboratory consistency. Mg/Ca and Sr/Ca results for reference materials were in good agreement with values from the literature.