碳酸钙同质多象转变过程中氧同位素分馏的实验研究

本文通过“一步法”和“两步法”的“附晶生长法”分别合成了碳酸钙矿物，对其进行了同质多象转变过程中的氧同位素分馏行为的研究。同时通过真空条件下的同质多象转变实验，对文石和方解石的酸分馏系数的差异进行了实验验证。结果发现：①在50℃和70℃下，如果文石与水之间的氧同位素分馏未达到平衡，由母体文石经过同质多象转变生成的次生方解石完全继承的母体矿物的氧同位素组成。如果文石与水之间的氧同位素分馏达到平衡，由互过同质多象转变生成的次生方解石部分继承母体文石的氧同位素组成，并且次生方解石相对于母体文石富集^18O。②在0℃和25℃下，“一步法”的“附晶生长法”的实验结果表明，由六方方解石经过同质多象转变生成的次生方解石也完全继承母体矿物的氧同位素组成，并且在该温度下，矿物与水之间的氧同位素分馏与温度无关。     

天然Ⅱ型CaCO3矿物的发现

本文报道了天然Ⅱ型CaCO₃ 矿物。该矿物发现于海洋表层沉积物,成分与方解石、文石及六方球方解石相同,但结构完全不同,它们共同组成了天然CaCO₃ 的同质多象变体。天然Ⅱ型CaCO₃ 矿物的空间群为P21/c,单位轴长为a₀= 0.6290±0.0002 nm,b₀= 0.4934±0.0002 nm,c₀= 0.7979±0.0003nm,β= 107.571°±0.002°,Z= 4,单胞体积为0.23605±0.1749nm³;理论密度为2.82 g/cm³,实测值为2.76 g/cm³;实测硬度H= 4.天然Ⅱ型CaCO₃ 矿物是在深水环境中较高静水压力下形成的珊瑚体生物矿物。     

碳酸钙-水体系氧同位素分馏系数的低温实验研究

碳酸钙是古气候和沉积岩稳定同位素地球化学研究中最常用的矿物 ,因此对碳酸钙水体系氧同位素分馏系数的实验校准已成为稳定同位素地球化学诞生以来的热点和前沿课题。但由于碳酸钙在自然界存在 3种同质多象变体 (方解石、文石和六方方解石 ) ,使人们对碳酸钙矿物与水之间氧同位素分馏系数的实验测定结果存在较大差别 ,当应用到同位素地质测温时 ,会给出显著不同的温度值。正确选用合理的方解石水或文石水体系分馏曲线 ,对低温和环境地球化学研究和应用具有重要价值。文章系统总结和评述了碳酸钙水体系氧同位素分馏系数实验校准的历史、方法和结果 ,对前人在表达方式上的不一致进行了统一 ,对氧同位素分馏的盐效应、动力氧同位素分馏效应和同质多象转变过程中的氧同位素继承性进行了讨论。通过对前人大量实验数据的系统处理并与理论计算相比较 ,推荐了热力学上平衡的方解石水体系氧同位素分馏方程 ,而对于文石水体系 ,理论计算结果尚有待于实验证实。     

利用钾长石合成雪硅钙石纳米粉体的反应机理研究

采用CaO为助剂,在水热条件下分解钾长石,进而合成雪硅钙石。影响反应的主要因素为：n(CaO)/n(SiO₂+AlO_1.5)、晶化温度和晶化时间等。在n(CaO)/n(SiO₂+AlO_1.5)为0.75～1.00、晶化温度为230～250 ℃、晶化时间为5～8 h的条件下,可以合成结晶良好的雪硅钙石晶体。反应机理分析表明：在钾长石-氧化钙的水热体系中,钾长石的分解并不是简单的离子交换作用或铝硅酸盐解聚作用,而是在碱金属离子与水作用的基础上,反应物中H⁺与矿物表面的碱金属离子K⁺、Na⁺、Ca²⁺作用,首先形成表面富硅贫铝的前驱聚合体（SiO_2·nH₂O）;然后这些前驱聚合体分解,与溶液中的Ca²⁺作用,生成C-S-H凝胶和水钙铝榴石;随着反应时间的延长,C-S-H凝胶和水钙铝榴石进一步转变为雪硅钙石。     

湘西花垣地区铅锌矿床流体包裹体显微测温与特征元素测定

花垣铅锌矿床的成矿流体演化特点和铅锌矿物沉淀机制存有分歧,为了总结矿床成因并建立成矿模式,指导该地区铅锌矿的下一步找矿勘探工作.对闪锌矿、主成矿期方解石和萤石中的流体包裹体进行岩相学观察、显微测温、拉曼光谱分析以及同步辐射X射线荧光微探针分析,结果显示花垣地区铅锌矿床成矿流体温度主要为150~220℃,总盐度一般为13%~23% NaCl_eqv,多> 15% NaCl_eqv,密度多 > 1 g/cm3,成矿流体为NaCl-CaCl₂-MgCl₂-H₂O卤水体系.成矿流体均一温度具有由北而南降低的趋势.流体液相组分中主要为Ca2+、Mg2+、Na+、Cl-,具有盆地热卤水体系特点.流体包裹体气相中发育CO₂、CH₄,方解石、萤石中流体包裹体均有成矿元素Pb、Zn的存在.花垣矿集区成矿流体属于低温度、中-高盐度、中-高密度,成分以钠和钙氯化物为主的含矿热水溶液,流体运移方向为由北向南,流体来源于封层水、大气降水和少量变质水.铅锌矿物的沉淀与热化学硫酸盐还原作用有关.闪锌矿、方铅矿等矿石矿物与方解石、萤石等脉石矿物应属同一富含Pb、Zn、Mn、Fe、As、Cr等成矿元素的成矿流体在同一成矿期次相同条件下沉淀的产物.      

微生物介导碳酸盐矿物合成过程中溶液pH值及主要阳离子变化及其地质意义

微生物介导碳酸盐矿物沉淀为“白云岩”问题的解决带来了希望。本次研究利用好氧、中度嗜盐细菌,在Mg²⁺/Ca²⁺值分别为3,5和7的溶液中合成碳酸盐,记录了每隔24 h溶液中的pH值,并取样分析了溶液中主要阳离子的变化情况。了解溶液pH值和阳离子变化,有利于我们了解微生物作用下碳酸盐矿物形成的过程,对理解微生物作用下碳酸盐的形成机制具有重要意义。实验结果表明,合成的矿物主要为一水碳酸钙、方解石及原白云石。3种溶液的pH值在前4 d均明显降低,溶液整体呈酸性,4 d后溶液pH值降低的趋势减缓,10 d后溶液pH值缓慢上升,呈近中性或弱碱性。Ca²⁺,Mg²⁺均呈现先下降后略微上升的趋势,Ca²⁺,Mg²⁺后期略微上升可能是由于细菌活性降低后不再消耗Ca²⁺,Mg²⁺,溶液中的H⁺,Na⁺和K⁺等阳离子在阳离子交替吸附的作用下替换出了一部分吸附在培养基上...     

红柱石、蓝晶石和夕线石的相变与变形

红柱石、蓝晶石和夕线石是铝硅酸盐(Al₂SiO₅)的3种同质多像体，其晶体结构、物理性质和温度、压力稳定范围各不相同。研究它们的矿物共生组合、相变和变形，可以解析矿物结晶顺序、变质与变形历史。本文对已有的天然样品和实验岩石学研究成果进行综合分析，发现Al₂SiO₅的多相转变和相平衡关系受化学组成、流体、温度和压力等环境条件的影响；Al₂SiO₅的双相或三相共生组合通常是亚稳态的；矿物结晶顺序记录着区域的温度压力轨迹和构造演化历史。变质岩石中，Al₂SiO₅矿物可以形成不同强度的结晶学优选方位，其中c[001]轴近似平行线理方向，红柱石、蓝晶石和夕线石的主滑移系分别为(110)[001]、(100)[001]和(010)[001]或(100)[001]。目前，红柱石-夕线石转变线位置和三相点的温压条件还存在争议，三相矿物的共生组合是变质过程的亚稳态共存状态，不能代表三相点的温压条件。     

岩溶溪流的脱气作用及碳酸钙沉积--以重庆市南川区柏树湾泉溪流为例

以一定间距监测水体中pH、电导率、溶解氧等水化学参数及HCO₃-、Ca2+等阴阳离子浓度,揭示了重庆市南川区柏树湾泉及其下游溪水的水化学的空间特征。泉水出露地表后,CO₂溢出导致溪流水的水化学特征沿流程发生有规律的变化,并促使溪水达到过饱和状态而产生明显的碳酸钙沉积。研究结果表明,脱气作用导致溪水的HCO₃-浓度、Ca2+浓度、电导率（EC）和CO₂分压沿流程逐渐递减,pH值及常见碳酸盐矿物的饱和指数逐渐升高。泉水出露时水中CO₂浓度与自由大气之间的浓度梯度是影响脱气速率的主要因素,但溪渠的水力坡度也对脱气速率也有一定影响。地下水出露至泉口处的脱气程度,是影响溪流碳酸钙沉积的决定性因素。旱季泉水流量较小,泉口处脱气程度较大,并且溪水的Ca2+浓度含量较高,再加上溪流沿途的水体扰动加速CO₂溢出,以及溪渠内的枯枝落叶和其他物质的吸附等,皆有利于碳酸钙沉积。     

湘西北花垣矿集区铅锌矿床成矿流体来源及矿床成因

湘西北花垣矿集区位于扬子地台东南缘,是湘西-鄂西成矿带上最典型的超大型铅锌矿床所在地.通过对花垣矿集区典型铅锌矿床流体包裹体显微测温、成分分析及C、H、O同位素研究,结果表明,该区铅锌矿床闪锌矿与方解石中流体包裹体的均一温度范围集中在120~200℃,盐度范围集中在8%~20% NaCl_eqv.流体中液相离子成分主要为Ca2+、Na+、Mg2+、SO₄2-、Cl-,气相成分主要为H₂O、N₂和CO₂及少量的CO、CH₄和H₂.流体的δD_SMOW值范围为-60.4‰~-33.0‰,δ18O_流体值范围为3.8‰~9.2‰.以上流体包裹体和稳定同位素分析结果表明,花垣矿集区铅锌矿床的成矿流体具有热卤水的性质,主要来源于建造水和大气降水.成矿期方解石的δ13C_PDB值范围为-4.89‰~0.57‰,δ18O_SMOW值范围为13.37‰~21.73‰,略低于碳酸盐围岩,说明成矿流体中的碳主要来源于碳酸盐围岩的溶解作用.矿石沉淀机制可能为两种流体的混合,即来自深部的富含金属物质的热卤水与富含有机质和硫酸盐的建造水及下渗大气降水的混合导致了铅锌矿石的沉淀.对地质和地球化学资料的综合结果表明,花垣矿集区铅锌矿床属于密西西比河谷型（MVT）铅锌矿床.      

碳酸钙-水体系氧同位素平衡及稳态分馏的低温实验研究

采用“一步”和“两步”的直接沉淀法和附晶生长法在 5 0℃和 70℃分别合成碳钡矿和文石 ,测定不同条件下合成矿物与水之间的氧同位素分馏 ,结果显示 ,文石—水体系氧同位素分馏机理分两步 :(1) [CO3 ]2 - 与H2 O的氧同位素交换和平衡 ,此过程是文石 水氧同位素平衡的决速率步骤 ;(2 )与H2 O平衡以后的 [CO3 ]2 - 与Ca2 +]结合生成文石 ,此过程体现矿物形成过程中氧同位素分馏的结构效应。在此基础上 ,采用缓慢沉淀法和“两步”的附晶生长法获得了 0～ 70℃的文石 水体系氧同位素平衡分馏方程。采用“一步”和“两步”的附晶生长法在 5 0℃和 70℃合成文石 ,文石在溶液中经同质多象转变成次生方解石 ;结合文献数据 ,获得 0～ 70℃范围内的方解石 水体系稳态氧同位素分馏方程。     

室温条件下青海湖水中镁离子浓度对沉淀碳酸钙同质多像类型的调控

青海湖是我国唯一报道过的现代湖底沉积物中白云石、方解石和文石等多种碳酸盐矿物共存的高原内陆咸水湖泊。以青海湖水和除菌青海湖水作为载体,以CaCl_2和MgCl_2·6 H_2O作为反应原料,在实验室常温条件下采取控制变量法制备出不同浓度Mg~(2+)参与下的钙质沉淀物,探讨Mg~(2+)浓度对沉淀物类型的影响。仅添加CaCl_2时,青海湖水中的沉淀物主要是石膏(Ca SO_4·2 H_2O)和球霰石(CaCO_3);在添加CaCl_2的同时添加MgCl_2·6 H_2O,沉淀物的石膏消失,完全转变成碳酸盐矿物,包括方解石和球霰石;当湖水中Mg~(2+)浓度为0.62 mol/L时,球霰石消失,沉淀物变为方解石和文石;随着Mg~(2+)浓度继续升高,文石含量稳步增加,方解石含量则逐渐减少,当Mg~(2+)浓度达到1.22 mol/L或更高时,方解石全部消失,沉淀物仅剩文石。实验结果表明,青海湖水中较高浓度的SO_4~(2-)对碳酸钙晶体生长有抑制作用,而额外加入的Mg~(2+)可以解除SO_4~(2-)的抑制作用,使得Ca~(2+)与HCO_3~-和CO_3~(2-)结合形成碳酸钙。此外,碳酸钙的同质多像类型也明显受到Mg~(2+)浓度的控制,随着湖水中Mg~(2+)浓度增加,方解石、球霰石不再稳定,而文石逐渐占主导地位,当Mg/Ca值达到6.1时,反应产物中仅有文石稳定存在。     

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).     

Experiments on phase transformations and chemical reactions of mechanically activated minerals by grinding: Petrogenetic implications

Prolonged grinding increases the energy of solids by the production of stored energy in the form of new surfaces and internal defects. Moreover, grinding also generates quasi-hydrostatic pressures which can result in polymorphic transformations and mineral decomposition. Here we demonstrate the solid-state transformation of metastable to stable polymorphs (aragonite → calcite, anatase → rutile); the transformation of low-pressure to high-pressure phases (calcite → aragonite); and the lowering of the dehydration and decarbonation temperatures of minerals (siderite → magnetite or hematite, diaspore → corundum).In the presence of a fluid phase, stored energy from grinding can be released, resulting in accelerated reaction rates and, more importantly, phase transformations. In this paper we demonstrate the following transformations: ground calcite → magnesian calcite (at low Mg²⁺ concentration in solution), ground calcite → aragonite (at high Mg²⁺ concentration), ground magnesite → hydromagnesite, and ground dolomite → aragonite + Mg²⁺.Assuming an analogy between laboratory and natural grinding, tectonic activity may have important consequences on the release of hydrothermal fluids, the solubilization of minerals and on solid-state transformations. As examples the possible role of deformation on the formation of metamorphic aragonite and diaspore-bauxites is discussed.     

Effect of pH on boron coprecipitation by calcite: further evidence for nonequilibrium partitioning of trace elements

The influence of pH and concentration on boron coprecipitation by calcite were evaluated under near-equilibrium conditions at 25°C. Calcite was precipitated by adding a metastable polymorph (vaterite or aragonite) to a solution of known boron concentration. This method maintains a nearly constant solution composition during the slow conversion of the metastable polymorph to calcite.Boron uptake in calcite was found to be strongly pH-dependent, increasing two orders of magnitude from pH 8.5 to pH 10.5. Boron incorporation into calcites precipitated from vaterite-saturated solutions was five times greater than in calcites precipitated from aragonite-saturated solutions. Ostensibly, these results suggest that the calcite precipitation rates were not low enough to attain equilibrium partitioning of boron into calcite. However, scanning electron micrograph analyses showed that the prevalent crystal forms of calcite generated from aragonite and those generated from vaterite were distinctly different. The different quantities of boron incorporated into these calcites may reflect different crystal growth mechanisms, consistent with face-dependent, nonequilibrium partitioning of trace elements in calcite.At a constant pH of 9.0, boron uptake increased from less than 15 to over 290 mg/kg CaCO₃ as the solution boron concentration was increased from 5 to 100 mg/kg. Our results agree with those of other investigators, despite differences in solution composition, and calcite precipitation techniques used. The agreement between the studies may be because the crystal growth morphology of the calcite was rhombohedral in both cases.     

The role of sulfate groups in controlling CaCO3 polymorphism

The nucleation and growth of CaCO₃ phases from aqueous solutions with SO₄²⁻:CO₃²⁻ ratios from 0 to 1.62 and a pH of ∼10.9 were studied experimentally in batch reactors at 25 °C. The mineralogy, morphology and composition of the precipitates were characterized by X-ray diffraction, Fourier transform infrared spectroscopy, scanning electron microscopy and microanalyses. The solids recovered after short reaction times (5 min to 1 h) consisted of a mixture of calcite and vaterite, with a S content that linearly correlates with the SO₄²⁻:CO₃²⁻ ratio in the aqueous solution. The solvent-mediated transformation of vaterite to calcite subsequently occurred. After 24 h of equilibration, calcite was the only phase present in the precipitate for aqueous solutions with SO₄²⁻:CO₃²⁻ ? 1. For SO₄²⁻:CO₃²⁻ > 1, vaterite persisted as a major phase for a longer time (>250 h for SO₄²⁻:CO₃²⁻ = 1.62). To study the role of sulfate in stabilizing vaterite, we performed a molecular simulation of the substitution of sulfate for carbonate groups into the crystal structure of vaterite, aragonite and calcite. The results obtained show that the incorporation of small amounts (<3 mole%) of sulfate is energetically favorable in the vaterite structure, unfavorable in calcite and very unfavorable in aragonite. The computer modeling provided thermodynamic information, which, combined with kinetic arguments, allowed us to put forward a plausible explanation for the observed crystallization behavior.     

Origin of anhedral Sr-rich calcite in deep-water mixed sediment, north-east Australia

At burial depths of 800-1000 m, within the epicontinental Queensland Trough of north-east Australia (ODP Site 823), microcrystalline inter- and intraskeletal mosaics of anhedral (loaf-shaped, rounded) calcite have Sr²⁺ values ranging from below microprobe detection limits (<150 ppm) to 8100 ppm. Host rocks are well lithified, fine-grained mixed sediment to clayey wackestone and packstone of Middle and Late Miocene age. Petrography demonstrates that calcite precipitation has spanned shallow to deep burial, overlapping formation of framboidal pyrite in the upper 50 m; shallow-burial dolomitization (<300 m); and dedolomitization during sediment consolidation and incipient chemical compaction at greater (>400–500 m) depths. Petrographic observations illustrate that the calcite microfabric formed through coalescing crystal growth resulting from one or a combination of displacive growth in clay, porphyroid neomorphism of aragonite/vaterite, and clay replacement by calcite. Sr²⁺ mean concentrations in calcite between depths of 800 and 1000 m are similar to an expected equilibrium pore-water concentration, using a D^sr of 0.06, and may indicate active calcite precipitation. However, Sr²⁺ variation (2000–5000 ppm) within and among crystals, and concentrations that range well above predicted equilibrium values for a given depth, illustrate either variable Sr²⁺ retention during recrystallization of shelf-derived aragonite (and authigenic local vaterite) or relative uptake of Sr²⁺ during calcite precipitation with burial. Within the context of calcite formation during burial to 1 km, diagenetic attributes that affect the latter process include increased concentrations of pore-water Sr²⁺ with depth associated with aragonite recrystallization/dissolution; upward migration of Sr-rich pore water; and increased D^Sr related to local variation in precipitation/recrystallization rates, differential crystal sector growth rates and/or microvariation in aragonite distribution.     

The dolomitization of CaCO3: an experimental study at 252–295°C

The results of experiments on the hydrothermal dolomitization of calcite (between 252 and 295°C) and aragonite (at 252°C) by a 2 M CaCl₂-MgCl₂ aqueous solution are reported and discussed. Dolomitization of calcite proceeds via an intermediate high (ca. 35 mole %) magnesian calcite, whereas that of aragonite is carried out through the conversion of the reactant into a low (5.6 mole %) magnesian calcite which in turn transforms into a high (39.6 mole %) magnesian calcite. Both the intermediate phases and dolomite crystallize through a dissolution-precipitation reaction. The intermediate phases form under local equilibrium within a reaction zone surrounding the dissolving reactant grains. The volume of the reaction zone solution can be estimated from Sr²⁺ and Mg²⁺ partitioning equations. In the case of low magnesian calcite growing at the expense of aragonite at 252°C, the total volume of these zones is in the range of 2 × 10^?5 to 2 × 10^?4 1., out of 5 × 10^?3 1., the volume of the bulk solution.The apparent activation energies for the initial crystallization of high magnesian calcite and dolomite are 48 and 49 kcal/mole, respectively.Calcite transforms completely into dolomite within 100 hr at 252°C. The overall reaction time is reduced to approximately 4 hr at 295°C. The transformation of aragonite to dolomite at 252°C occurs within 24 hr. The nature of the reactant dictates the relative rates of crystallization of the intermediate phases and dolomite. With calcite as reactant, dolomite growth is faster than that of magnesian calcite; this situation is reversed when aragonite is dolomitized.Coprecipitation of Sr²⁺ with dolomite is independent of temperature (within analytical error) between 252 and 295°C. Its partitioning, with respect to calcium, between dolomite and solution results in distribution coefficients in the range of 2.31 × 10^?2 to 2.78 × 10^?2.     

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.     

Experimental study of the aragonite to calcite transition in aqueous solution

The experimental replacement of aragonite by calcite was studied under hydrothermal conditions at temperatures between 160 and 200 °C using single inorganic aragonite crystals as a starting material. The initial saturation state and the total [Ca²⁺]:[CO₃²⁻] ratio of the experimental solutions was found to have a determining effect on the amount and abundance of calcite overgrowths as well as the extent of replacement observed within the crystals. The replacement process was accompanied by progressive formation of cracks and pores within the calcite, which led to extended fracturing of the initial aragonite. The overall shape and morphology of the parent aragonite crystal were preserved. The replaced regions were identified with scanning electron microscopy and Raman spectroscopy.Experiments using carbonate solutions prepared with water enriched in ¹⁸O (97%) were also performed in order to trace the course of this replacement process. The incorporation of the heavier oxygen isotope in the carbonate molecule within the calcite replacements was monitored with Raman spectroscopy. The heterogeneous distribution of ¹⁸O in the reaction products required a separate study of the kinetics of isotopic equilibration within the fluid to obtain a better understanding of the ¹⁸O distribution in the calcite replacement. An activation energy of 109 kJ/mol was calculated for the exchange of oxygen isotopes between [C¹⁶O₃²⁻]_aq and [H₂¹⁸O] and the time for oxygen isotope exchange in the fluid at 200 °C was estimated at ∼0.9 s. Given the exchange rate, analyses of the run products imply that the oxygen isotope composition in the calcite product is partly inherited from the oxygen isotope composition of the aragonite parent during the replacement process and is dependent on access of the fluid to the reaction interface rather than equilibration time. The aragonite to calcite fluid-mediated transformation is described by a coupled dissolution-reprecipitation mechanism, where aragonite dissolution is coupled to the precipitation of calcite at an inwardly moving reaction interface.     

Metastable phenomena on calcite {101̄4} surfaces growing from Sr2+–Ca2+–CO32− aqueous solutions

In situ atomic force microscopy (AFM) experiments, scanning electron microscopy (SEM) imaging and composition analysis, and X-ray diffraction have provided information about the growth, dissolution and transformation processes promoted by Sr²⁺–Ca²⁺–CO₃²⁻ aqueous solutions in contact with calcite {101̄4} surfaces. Experiments have shown a wide variety of surface phenomena, such as the influence of the Sr-bearing newly-formed surface on the subsequent growth (template effect), the growth and subsequent dissolution of surfaces and the nucleation of secondary three-dimensional nuclei on calcite surfaces. These phenomena reveal the metastability of the crystallisation system and are a consequence of the interplay between thermodynamics (the relative stability of the two calcite and aragonite structure solid solutions that can be formed), supersaturation of the aqueous solution with respect to the two possible solid solutions, and the crystallographic control of the surfaces on cation incorporation.