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1.
The influence of pH on the rate of dissolution of various carbonates (calcite, aragonite, witherite, magnesite and dolomite) has been investigated at 25°C using a continuous fluidized bed reactor. The general rate dependence on pH observed for the simple carbonates is very similar and is in agreement with the results observed for calcite and aragonite by L.N. Plummer and coworkers. However, the rate of dissolution of magnesite is approximately four orders of magnitude lower than calcite. For simple carbonates, the elementary steps involved in the dissolution reaction are: where M represents the metal ion which can be Ca, Mg and Ba. According to the stoichiometry of the three reaction steps and the thermodynamic constraints, the total forward and backward rates can be expressed as: rb=k-1aM2+aHCO3-+k-2aHCO3-+k-3aM2+aCO32- The rate constants (k1, k2, k3 and k−3) determined with our experimental results for calcite, aragonite and witherite show that the dissolution rates are similar for these three minerals and that the nature of the cations does not play a significant role. The good agreement between the Ksp calculated from the measured k3/k−3 ratio and the theromodynamic value suggests that our dissolution mechanism is coherent. The rate dependence on pH of the dissolution of dolomite obeys a fractional order at low pH's and confirms previously published observations therein. However, the two-step reaction mechanism proposed does not explain the fractional reaction order observed, which is likely due to a more complex surface reaction. 相似文献
2.
Dissolution rates of single calcite crystals were determined from sample weight loss using free-drift rotating disk techniques. Experiments were performed at 25 °C in aqueous HCl solutions over the bulk solution pH range −1 to 3 and in the presence of trace concentrations of aqueous NaPO 3 and MgCl 2. These salts were chosen for this study because aqueous magnesium and phosphate are known to strongly inhibit calcite dissolution at neutral to basic pH. Reactive solutions were undersaturated with respect to possible secondary phases. Neither an inhibition or enhancement of calcite dissolution rates was observed in the presence of aqueous MgCl 2 at pH 1 and 3. The presence of trace quantities of NaPO 3, which dissociates in solution to Na + and H 2PO 4−, decreased the overall calcite dissolution rate at pH≤2. This contrasting behavior could be attributed to the different adsorption behavior of these dissolved species. As calcite surfaces are positively charged in acidic solutions, aqueous Mg 2+ may not adsorb, whereas aqueous phosphate, present as either the anion H 2PO 4− or the neutral species H 3PO 40, readily adsorbs on calcite surfaces leading to significant dissolution inhibition. 相似文献
3.
The hydrochemical interaction between groundwater and lakewater influences the composition of water that percolates downward from the surficial aquifer system through the underlying intermediate confining unit and recharges the Upper Floridan aquifer along highlands in Florida. The 87Sr/ 86Sr ratio along with the stable isotopes, D, 18O, and 13C were used as tracers to study the interaction between groundwater, lakewater, and aquifer minerals near Lake Barco, a seepage lake in the mantled karst terrane of northern Florida. Upgradient from the lake, the 87Sr/ 86Sr ratio of groundwater decreases with depth (mean values of 0.71004, 0.70890, and 0.70852 for water from the surficial aquifer system, intermediate confining unit, and Upper Floridan aquifer, respectively), resulting from the interaction of dilute oxygenated recharge water with aquifer minerals that are less radiogenic with depth. The concentrations of Sr 2+ generally increase with depth, and higher concentrations of Sr 2+ in water from the Upper Floridan aquifer (20–35 μg/L), relative to water from the surficial aquifer system and the intermediate confining unit, result from the dissolution of Sr-bearing calcite and dolomite in the Eocene limestone. Dissolution of calcite [δ 13C = −1.6 permil (% o)] is also indicated by an enriched δ 13C DIC(-8.8 to -11.4% o) in water from the Upper Floridan aquifer, relative to the overlying hydrogeologic units (δ 13C DIC < -16% o). Groundwater downgradient from Lake Barco was enriched in 18O and D relative to groundwater upgradient from the lake, indicating mixing of lakewater leakage and groundwater. Downgradient from the lake, the 87Sr/86Sr ratio of groundwater and aquifer material become less radiogenic and the Sr2+ concentrations generally increase with depth. However, Sr2+ concentrations are substantially less than in upgradient groundwaters at similar depths. The lower Sr2+ concentrations result from the influence of anoxic lakewater leakage on the mobility of Sr2+ from clays. Based on results from mass-balance modeling, it is probable that cation exchange plays the dominant role in controlling the 87Sr/86Sr ratio of groundwater, both upgradient and downgradient from Lake Barco. Even though groundwater from the three distinct hydrogeologic units displays considerable variability in Sr concentration and isotopic composition, the dominant processes associated with the mixing of lakewater leakage with groundwater, as well as the effects of mineral-water interaction, can be ascertained by integrating the use of stable and radiogenic isotopic measurements of groundwater, lakewater, and aquifer minerals. 相似文献
4.
The playa Areg el Makrzene is situated in the north of the escarpment of the Djebel Rehach in southern Tunisia. It is characterised by more than 70 spring mounds which are bound to faults in the Triassic sandstone, and by (sub-) recent calcareous and iron hydroxide precipitations. The artesian spring water contains high amounts of Na +, Ca 2+, Mg 2+ and Cl −, SO 42−, and HCO 3, shows slightly alkaline character and a temperature of 25 °C. The spring mounds consist of porous travertine (calcite), goethite, gypsum and of Na–Mg evaporites and are up to 10 m high. Few metres away from the springs the amorphous iron hydroxides have altered to badly ordered goethite and ferrihydrite and finally to well ordered goethite. The muddy precipitate has altered to hard crusts (calcrete, ferricrete). The source of the precipitated material is discussed. The faults in the sandstone are filled with (hydr-)oxides of iron and manganese, e.g. with goethite, hollandite and pyrolusite. The amount of Mn-oxides may reach 60 mass%. 相似文献
5.
Independent lines of geological evidence suggest that fluctuations in the Mg/Ca ratio of seawater between 1.0 and 5.2 have caused the oceans to alternate between favouring the precipitation of the aragonite and high-Mg calcite polymorphs of calcium carbonate ( m Mg/Ca > 2; aragonite seas) and the low-Mg calcite polymorph ( m Mg/Ca < 2; calcite seas) throughout Phanerozoic time. The rise of aragonite-secreting bryopsidalean algae as major producers of carbonate sediments in middle Palaeogene time, a role that they maintained through to the present, has been attributed to a transition from calcite-to-aragonite seas in early Cenozoic time. Recent experiments on the modern, carbonate-sediment-producing bryopsidales Halimeda , Penicillus and Udotea reveal that their rates of calcification, linear extension and primary production decline when reared in experimental calcite seawaters ( m Mg/Ca < 2). These normally aragonite-secreting algae also began producing at least one-quarter of their CaCO 3 as calcite under calcite sea conditions, indicating that their biomineralogical control can be partially overridden by ambient seawater chemistry. The observation that primary production and linear extension declined along with calcification in the mineralogically unfavourable seawater suggests that photosynthesis within these algae is enhanced by calcification via liberation of CO 2 and/or H +. Thus, the reduced fitness of these algae associated with their low rates of calcification in calcite seas may have been exacerbated by concomitant reductions in tissue mass and algal height. 相似文献
6.
Multiple regression analysis of a compilation of the Fe 2+–Mg distribution between garnet and hornblende from experimental runs on basaltic to intermediate compositions ( n=22) and coexisting garnet–clinopyroxene–hornblende from natural (intermediate to basaltic) rocks ( n=43) has been performed to define ln KD(Fe2+/Mg)Grt–Hbl as a function of temperature and garnet composition. The regression of data covering a large span in pressure (5–16 kbar), temperature (515–1025°C) and composition yields the ln KD(Fe2+/Mg)Grt–Hbl– P– T compositional relationship ( r2=0.93): where Application of this expression to natural garnet–hornblende pairs in intermediate to basaltic and semipelitic rock types from various settings gives temperatures that are consistent with other methods. 相似文献
7.
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. 相似文献
8.
X-ray difffaction and differential thermal (DTA) techniques were applied to evaluate the semi-quantitative mineralogical composition of a deep black soil profile from India. X-ray investigations revealed the predominance fo a smectic mineral throughout the profile. The mineral gave its main dehydroxylation peak between 532°C (Mg-sat.) and 550° (K-sat.), indicating that it belonged to the nontronite-beidellite series. The concentration of this mineral decreased with increasing particle size, i.e. increasing concentration of feldspars and amphiboles. In addition, illite, iron-rich chlorite, quartz, attapulgite, sepiolite and some mixed-layer minerals were detected. The effect of cation (Mg++, Ca++, K+) saturation on the intensity, symmetry and temperature of the DTA peaks is discussed. Abnormal behaviour of double dehydroxylation in two clay fractions was found to be due to the abundance of Mg++ cations in the exchangeble positions K+ and Ca++-saturation of the clays did not produce this effect. 相似文献
9.
本文应用化学热力学的观点分析讨论了具有正磷酸盐、方解石和文石三种矿物成分的介壳生物化石的形成顺序.从理论上清楚地解释了在介壳生物的演化过程中,磷酸盐介壳形成在先,方解石介壳形成在次,文石介壳形成在后这一地质事实。在此基础上根据活度-pH图解,定性分析了具不同矿物组合的介壳生物化石所处地质时代的海水pH条件,指出元古代末磷酸盐介壳发育时,海水的pH可能接近于6,而古生代碳酸盐介壳广泛发育时,海水的pH可能己接近或超过6.45。 相似文献
10.
Acidithiobacillus ferrooxidans are commonly present in acid mine drainage (AMD). A. ferrooxidans derive metabolic energy from oxidation of Fe 2+ present in natural acid solutions and also may be able to utilize Fe 2+ released by dissolution of silicate minerals during acid neutralization reactions. Natural and synthetic fayalites were reacted in solutions with initial pH values of 2.0, 3.0 and 4.0 in the presence of A. ferrooxidans and in abiotic solutions in order to determine whether these chemolithotrophic bacteria can be sustained by acid-promoted fayalite dissolution and to measure the impact of their metabolism on acid neutralization rates. The production of almost the maximum Fe 3+ from the available Fe in solution in microbial experiments (compared to no production of Fe 3+ in abiotic controls) confirms A. ferrooxidans metabolism. Furthermore, cell division was detected and the total cell numbers increased over the duration of experiments. Thus, over the pH range 2–4, fayalite dissolution can sustain growth of A. ferrooxidans. However, ferric iron released by A. ferrooxidans metabolism dramatically inhibited dissolution rates by 50–98% compared to the abiotic controls. Two sets of abiotic experiments were conducted to determine why microbial iron oxidation suppressed fayalite dissolution. Firstly, fayalite was dissolved at pH 2 in fully oxygenated and anoxic solutions. No significant difference was observed between rates in these experiments, as expected, due to extremely slow inorganic ferrous iron oxidation rates at pH 2. Experiments were also carried out to determine the effects of the concentrations of Fe2+, Mg2+ and Fe3+ on fayalite dissolution. Neither Fe2+ nor Mg2+ had an effect on the dissolution reaction. However, Fe3+, in the solution, inhibited both silica and iron release in the control, very similar to the biologically mediated fayalite dissolution reaction. Because ferric iron produced in microbial experiments was partitioned into nanocrystalline goethite (with very low Si) that was loosely associated with fayalite surfaces or coated the A. ferrooxidans cells, the decreased rates of accumulation of Fe and Si in solution cannot be attributed to diffusion inhibition by goethite or to precipitation of Fe–Si-rich minerals. The magnitude of the effect of Fe3+ addition (or enzymatic iron oxidation) on fayalite dissolution rates, especially at low extents of fayalite reaction, is most consistent with suppression of dissolution by interaction between Fe3+ and surface sites. These results suggest that microorganisms can significantly reduce the rate at which silicate hydrolysis reactions can neutralize acidic solutions in the environment. 相似文献
11.
海水入侵是沿海地区主要环境地质问题,分析沿海地下水和河水水化学特征,对圈定海水入侵范围及判断影响程度具有重要意义。通过在福建长乐市海水入侵含水层和闽江口海水上溯区采取23件水样进行室内常规离子测试,获得了海水入侵(上溯)区水中主要离子含量。利用海水稀释线分析主要离子与Cl离子之间的相对变化,对比离子实际浓度与理想浓度的差异,分析海水入侵对水化学变化的影响。研究结果显示,随着海水与淡水混合,水化学类型从海水到淡水依次为Na-Cl型水-Na-Cl·HCO 3型水-Na·Ca-HCO 3·Cl型水-Ca-HCO 3型水;引起水化学类型和TDS变化的主要因素为Na +和Cl -的增加;Ca 2+、Mg 2+高于海水稀释线和理想浓度线,Na +、K +在海水稀释线和理想浓度线上下跳跃：Br -/Cl -与海水稀释线吻合较好,可以作为判断海水入侵范围的依据。 相似文献
12.
研究海水体系(即Na +,K +,Mg 2+,Ca 2+∥Cl -,$SO_{4}^{2-}$-H 2O六元体系)中杂卤石的形成条件不仅有助于理解海相蒸发盐成因,对开发杂卤石钾资源利用技术也具有重要的指导作用。但杂卤石以及其他含有硫酸钙矿物(如二水石膏、半水石膏、无水石膏、钾石膏、多钙钾石膏、钙芒硝和水钙芒硝)的相平衡,无论是在实验研究方面还是在热力学模拟方面都仍然存在很多争议。由于缺乏杂卤石在复杂水溶液体系中可靠的相平衡数据,使人们对认识杂卤石成因和利用杂卤石钾资源带来巨大障碍。本工作对海水体系中杂卤石的形成条件进行了热力学模拟和实验研究。超过一年的长时间固液平衡实验表明25 ℃下Na +,K +,Mg 2+,Ca 2+∥Cl -,$SO_{4}^{2-}$-H 2O六元体系中杂卤石的形成区域极为可观,且较前人实验结果均大数倍;同时证实了热力学模型预测结果的可靠性。这些结果为讨论盐矿床中杂卤石的形成条件提供了物理化学依据。25 ℃下可靠的热力学信息表明:杂卤石与其他盐类矿物的共生情况丰富多样,并且与前人看法不同,杂卤石的形成并不需要极高的钾、镁浓度。这给以杂卤石为指示寻找可溶性固体钾盐带来了挑战,但却指示了以杂卤石为线索更容易找到钾、镁盐未饱和的富钾卤水。 相似文献
13.
浅层地下水是任丘市重要的水资源之一,为研究其水化学特征及其形成机制,本文在实地调查取样分析化验的基础上,以水文地球化学理论为指导,借助多元数理统计的方法,从多个角度揭示了研究区浅层地下水的形成演化过程:①通过离散分析,认为研究区各主要离子变异系数较大,说明研究区浅层地下水受人为影响明显,水化学特征复杂.②通过相关分析,... 相似文献
14.
在分析南极乔治王岛冰帽大冰穹顶部降水和成冰条件的基础上,利用冰芯上部层物理特征参数确定的5个年层及其附近气象站相应的降水记录,结合多年降水资料将大冰穹45m冰芯划分为15个年层.应用此年层剖面,证实了微粒含量的两个异常峰值分别对应于1987年Deception岛和1980年的SealNunataks两次火山喷发.乔治王岛冰帽属于温性冰帽,大、小冰穹冰芯阴阳离子受沉积后融水渗浸淋溶作用的影响.对冰芯阴阳离子的淋溶次序分析显示,大冰穹为SO 42->Mg 2+>Ca 2+>K +>Cl ->Na +>NO 3->Br -,而小冰穹为Mg 2+>Ca 2+>SO 42->K +>Cl ->Br ->Na +. 相似文献
15.
The dissolved constituents being carried to the oceans by rivers cannot all be removed by sedimentary processes, including authigenesis. Direct introduction of formation waters to the oceans has no significant effect. Reaction of seawater with basaltic rocks is, however, potentially capable of removing the excess cations by a combination of low-temperature weathering (removing K +), and higher temperature hydrothermal reaction (removing Na + and Mg 2+), although these processes seem to release more silica than can be conveniently accounted for. Although these are essentially kinetic rather than equilibrium buffer mechanisms, they appear to be sufficient to have maintained a constant seawater composition (except for SiO 2) during the Phanerozoic. 相似文献
16.
The concentrations of Mg 2+ and Sr 2+ incorporated within calcite overgrowths precipitated from seawater and related solutions, determined at 25°C, were independent of the precipitation rate over approximately an order of magnitude. The saturation states used to produce this range of precipitation rates varied from 3 to 17 depending on the composition of the solution.The amount of Mg 2+ incorporated in the overgrowths was not directly proportional to in solution over the entire range (1–20) of ratios studied. Below a ratio of 7.5, the overgrowth was enriched in MgCO 3 relative to what is predicted by the constant distribution coefficient measured above a ratio of 7.5. This increased MgCO 3 correlates with the relative enrichment of adsorbed Mg 2+. Above a ratio of 7.5 the concentration of MgCO 3 in the calcite overgrowths followed a classical thermodynamic behavior characterized by a constant distribution coefficient of 0.0123 (±0.008 std dev).The concentration of SrCO 3 incorporated in the overgrowths was linearly related to the MgCO 3 content of the overgrowths, and is attributed to increased solubility of SrCO 3 in calcite due to the incorporation of the smaller Mg 2+ ions.The kinetic data indicate that the growth mechanism involves the adsorption of the cations on the surface of the calcite prior to dehydration and final incorporation. It is suggested that dehydration of cations at the surface is the rate controlling step. 相似文献
17.
The formation and subsequent reactions of magnesiancalcite overgrowths on calcite were investigated bymeans of closed system seeded precipitationexperiments. These experiments demonstrated that(1) thin overgrowths of magnesian calcite are precipitatedon calcite seeds suspended in seawater;(2) the solubilities of the coatings increase outward from theseed crystals as a linear function of the log ofrelative coating thickness;(3) during the period ofthese experiments (up to 5.5 months), the magnesiancalcite coatings continued to increase in thickness,but became less soluble in composition. Thestabilization reaction, referred to asrecrystallization, can be described by the followingequation:Cax Mg(1-x) CO3 + [z + y(x + z)]Ca2++ 2yHCO3- ]= (1 + y)Ca(x + z)Mg(1 - x -z)CO3 + [z + y(x + z - 1)]Mg2++ y CO2 + yH20;]4) recrystallization rate is dependent on solutionsaturation state, with a reaction order of 3.2 forartificial seawater and 4.0 for natural seawater; and(5) by the cessation of the closed system experiments,overgrowth compositions approached that of the stablecalcite (a few mol % MgCO3).Armoring of suspended carbonate particles in thesurface oceans with magnesian calcite overgrowthswould provide an effective barrier to release of theoceanic supersaturation with respect to calcite. Thicknesses of such coatings would be limited by therecrystallization rate of the magnesian calcite. Estimates based on the recrystallization ratesdetermined in this work indicate coatings on the orderof 0.02 µm in thickness could form on particles asthey sink through the mixed layer. According to thesecalculations, the total amount of carbon precipitatedannually in magnesian calcite overgrowths iscomparable to the riverine flux of dissolved carbon tothe oceans. Field observations of severalinvestigators indicate the likely presence ofmagnesian calcite coatings on planktonic particles,and provide evidence for possible recrystallization ofbiogenic magnesian particles in the marineenvironment. 相似文献
18.
The exchange of Fe 2+ and Mg 2+ between orthopyroxene and sapphirine has been investigated at pressures 7-16 kbar and temperatures 850-1300°C using a piston cylinder apparatus for the synthetic and natural systems. This reaction is temperature-dependent and would be a good geothermometer. The equilibration temperature T is approximately expressed by the distribution coefficient as follows: T(°C)=1515/(ln KD+0.943)-273. This empirical equation was applied to some Antarctic granulites and associated rocks. The new orthopyroxene-sapphirine geothermometer gives consistent results with those estimated from the Fe-Mg orthopyroxene-garnet geothermometer. 相似文献
19.
白云石化是碳酸盐典型的成岩作用类型之一,中-下奥陶统鹰山组浅海碳酸盐岩是塔河地区重要的含油气储层,普遍发育多种类型的白云石化作用。本文针对塔河地区鹰山组灰岩中沿缝合线分布这一特定类型的白云石化进行了研究。岩石学基础上的阴极发光分析、 86Sr/ 87Sr比值以及δ 13C-δ 18O 的研究表明,这种类型的白云石化发育于相对还原的浅埋藏成岩环境,孔隙中的残留海水是主要的白云石化流体来源,碳酸盐矿物(主要是高镁方解石)稳定化过程中释放的Mg 2+ 可能是白云石化主要的物质来源,而埋藏过程中逐渐升高的温度一定程度上也促进了白云石化的发生。成岩流体及Mg 2+ 有限的供给量限制了白云石化作用的整体规模。显微结构与岩石物性分析表明,该类白云石化对储层物性参数的绝对贡献相对有限,但可能成为小规模油气运移以及深部热流体活动的潜在通道。 相似文献
20.
通过对沾化凹陷古近系1 160条数据体的试油资料,内容包含矿化度、水型、各离子含量(氯离子、钠离子、钙离子、镁离子、碳酸氢根离子、硫酸根离子等)、原油物性(原油密度、粘度、凝固点及含蜡量等)的分析,对沾化凹陷古近系的水化学场特征进行了研究,研究结果表明,与东营凹陷古近系沙河街组三段与四段封闭性滞留型水化学场特征明显不同,沾化凹陷古近系在宏观上呈现一系列开放性敞流湖盆水化学场的重要特征:矿化度及各离子含量较低(矿化度平均在10 g/L 左右),平面上水化学场环带状特征及剖面上的分带性不明显,而主要呈现平面的分区性及剖面的旋回性; 主要发育NaHCO 3型地层水(比例达到80%),变质系数、碳酸盐平衡系数高(分别在1.0和50以上),显示地层水变质作用及交替活动能力强; 不同类型地层水Cl --HCO 3-响应有明显差异,低矿化度NaHCO 3型地层水rCl -/r(HCO 3-)比值基本小于10,表明研究区溶解、溶蚀作用明显; 少量Ca 2+ 和Mg 2+ 负相关性显示,在研究区这种白云岩化作用主要发生在CaCl 2型地层水中; Na +-Ca 2+ 关系显示,Na相对亏损、Ca相对富集特征不明显,代表Ca的相对富集数量的流体线(Ca excess=0.997 4(Na deficit)＋29.355(R 2=0.859 6))远低于世界平均盆地流体线; 原油物性响应明显,研究区大多次生稠油分布在低矿化度型地层水中,显示了原油在开放性敞流型湖盆地层水载体中发生运移、聚集时的稠化作用。受湖盆中各次级洼陷的不均衡性发育和演化,研究区这种总体开放性敞流湖盆水化学场特征并不排除局部(如渤南洼陷)有封闭性滞留型湖盆水化学场特征。 相似文献
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