方解石在不同水环境中的溶解与沉淀作用

方解石的溶解与沉淀是各种岩溶地质作用的基础,但对其在不同水环境条件下的溶解过程和溶解度有待深入研究。文章通过实验研究了天然方解石(CaCO₃)在不同水环境中的溶解作用。结果表明,方解石在纯净水、空气饱和水、CO₂饱和水、初始pH=3的溶液和初始pH=9的溶液中溶解时,Ca浓度随着溶解时间的增加呈现缓慢升高并趋于稳定,在溶解4 080 h后达到0.4444～0.4696 mmol·L^-1、0.402 0～0.415 4 mmol·L^-1、0.573 9-0.659 7 mmol·L^-1、1.098 1 mmol·L^-1和0.448 9 mmol·L^-1;方解石(CaCO₃)在纯净水中溶解时溶度积(K_sp)为10^-8.48±0.08～10^-8.48±0.13,吉布斯生成自由能ΔG_f^o[CaCO₃     

不同有机酸对矿物溶解的动力学实验研究

用石英、微斜长石和方解石混合颗粒模拟碎屑组分分别与不同有机酸水溶液进行溶蚀实验,以比较储集层内不同矿物在含低分子量有机酸地层水中溶解的速率,并试图探讨矿物溶蚀的微观机理。结果表明：①所有矿物颗粒都发生了不同程度的溶解,表现为颗粒失重,溶液中SiO2和金属阳离子含量增加,pH值上升。②优先溶解的是方解石,其次是硅酸盐矿物。③温度增加,硅酸盐矿物在水中的溶解度明显增加,而方解石的溶解度基本不变。④由于不同有机酸与二氧化硅和金属阳离子生成的络合物稳定性不同,因此,在不同有机酸水溶液中,矿物的溶蚀速率有较大差别。多官能团有机酸的水溶液中,不同矿物有更大的溶解;但在含有丰富Ca2＋的草酸水溶液中,由于矿物颗粒表面难溶草酸钙的沉淀,方解石的溶解变得更加困难。⑤多官能团有机酸与SiO2形成的多环螯合物由于完全取代了硅氧四面体的氧原子,在水中具有高度稳定性,可能有助于(铝)硅酸盐的溶蚀和硅元素的迁移     

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.     

靖宇县玄武岩区矿泉水特征组分H2SiO3成因实验——以王大山泉为例

以靖宇县典型泉岩样为实验材料,结合野外实际情况,考虑pH值和CO₂影响因素设计了矿泉水中H₂SiO₃实验,对实验结果进行了化学动力学分析,并利用matlab建立数学模型分析了矿物反应的机理。结果表明:1)仅考虑pH值的情况下:初始pH值近中性(pH=7.25)时,实验溶液中H₂SiO₃释放量较小,反应难以发生;初始pH值为碱性(pH=8.10)时,实验溶液中H₂SiO₃缓慢增加,平均释放速率为3.08 mg/(kg·d)。2)在考虑pH值和CO₂情况下:初始pH值为碱性条件时,通入CO₂能够较快促进H₂SiO₃产生,平均释放速率可由4.29 mg/(kg·d)升高为12.00 mg/(kg·d);初始pH值为弱酸性(pH=6.64)时,实验溶液中H₂SiO₃增加较快,通入CO₂,溶液中H₂SiO₃释放速率稍微增加。3)实验溶液中H₂SiO₃释放规律符合Stanford一阶反应动力学模型。靖宇县矿泉水中H₂SiO₃主要来自偏硅酸矿物(斜长石、镁橄榄石、辉石)的反应。在中性条件下,玄武岩矿物很难反应;在碱性条件时,主要是玄武岩矿物的水解,反应缓慢;在弱酸性条件下,主要是玄武岩矿物与H⁺和CO₂的反应,反应强度较大。     

H+和有机酸对可变电荷土壤铝释放的动力学研究

利用流动搅动法研究了在模拟酸雨和低分子量有机酸条件下可变电荷土壤铝释放的动力学特征,结果表明,在pH3.5的模拟酸雨作用下,红壤和黄壤中流出液铝的浓度范围约为15～40μmol/L,铝的释放快反应来源于土壤交换性铝和有机络合态铝,铝的释放慢反应对应于含铝矿物的溶解。赤红壤和砖红壤上在0～300min内流出液铝的浓度范围约为1～5μmol/L,流出液pH值大于4.5,对H 的缓冲作用表现为阳离子交换、SO24-的专性吸附释放OH-和矿物表面的质子化;当流出液pH值小于4.5时,H 开始溶解土壤中的含铝固相,铝释放的最后浓度为20～30μmol/L。用相近pH值的有机酸溶出土壤铝的浓度比pH3.5的模拟酸雨要高,特别是在砖红壤上,开始就有大量铝的释放,其浓度为20～75μmol/L,红壤上是70～150μmol/L,随时间延长,流出液中的铝浓度分别为10～20μmol/L和20～30μmol/L。有机酸作用下铝的释放机制主要是有机酸被土壤吸附后,有机酸与位于表面晶格中的铝原子形成络合体,促进了铝的溶解;其次是有机酸的吸附掩盖了土壤表面的质子化过程,增强了酸的溶解,以及有机配体对铝的络合作用,增加了铝的释放量。不同有机酸对铝的溶出能力也有不同,其释放铝能力的大小为:柠檬酸>酒石酸>苹果酸,这取决于有机配体与铝的络合能力。     

鄂尔多斯盆地奥陶系不同组构碳酸盐岩埋藏溶蚀实验

鄂尔多斯盆地奥陶系碳酸盐岩储层受埋藏溶蚀作用控制明显,而地层深部复杂的水-岩反应造成埋藏溶蚀研究难度较大,并进而影响了储层的评价与预测。分别利用CO₂溶液和乙酸溶液为流体介质进行溶蚀模拟实验,探讨埋藏条件下温度、压力、流体等因素对不同矿物及组构碳酸盐岩溶蚀作用的影响。结果表明:1）随着温度与压力升高,碳酸盐岩样品在乙酸溶液中的溶解速率均相应提高,在CO₂溶液中的溶解速率则先增加后减小,且在110℃~130℃区间内溶蚀速率最大;深埋藏环境下,各岩类溶蚀速率差异减小,并趋于一致;2）岩石矿物成分和组构,原岩初始孔隙度的大小及其连通关系,以及晶体的产状对成岩后期的埋藏溶蚀作用也具有重要的影响。不溶组分含量低、颗粒/灰泥比高、矿物成分复杂的碳酸盐岩由于组构选择性溶蚀作用而更易被溶蚀;碳酸盐岩的溶蚀速率随方解石含量的增加而增加,但深埋藏环境下,矿物成分含量差异对溶蚀速率的影响作用减弱;硬石膏与白云岩相伴生时,可优先溶蚀形成膏模孔,并促进白云石的溶解,改善储层效果。不同岩性,总体上灰岩较白云岩及过渡岩类更易发生埋藏溶蚀作用。结合研究区实际地质条件分析,砂屑灰岩、膏质白云岩等埋藏溶蚀强度较大,通过对原岩早期组构选择性溶蚀形成孔隙的继承和调整,叠加埋藏期岩溶作用后,可形成规模优质储层。     

莺歌海盆地乐东区储层碳酸盐胶结物成因机理及与流体活动的关系

乐东A区中新统黄流组是南海北部莺歌海盆地高温超高压天然气勘探的主力层系,发育重力流水道-海底扇沉积的细、中、粗粒砂岩,中、低、特低渗物性特征,多期次、多类型碳酸盐胶结。研究碳酸盐胶结物类型、期次、成因机理及其与流体活动的关系,对于储层评价预测有重要意义。研究结果表明,碳酸盐胶结物表现为早、中、晚三期方解石与早、晚两期白云石,由早期到晚期,方解石及白云石的δ¹³C、δ¹⁸O值负偏增大,MnO、BaO、SrO等含量增高,早—中期方解石的形成与生物碎屑、碳酸盐矿物溶解再沉淀有关;晚期铁方解石、(铁)白云石的形成与深部热流体、无机CO₂、有机酸脱羧有关。方解石的溶解-沉淀受地层压力及CO₂含量共同控制,地层压力与天然气组分中CO₂含量相对较高,溶解作用较强,(铁)白云石发育;反之则溶解作用较弱,(铁)方解石发育。     

硫酸根离子对方解石和白云石溶解度的影响

在无CO2和有P_CO2条件下,利用目前成熟的水文地球化学模拟软件——PHREEQC,分别对方解石、白云石在Na2SO4、CaSO4和MgSO4溶液中的溶解度进行了模拟计算。结果显示:溶液中SO₄2-的存在对方解石、白云石溶解度的提高作用很大。如在Pco2、浓度为1200mmol／L的Na2SO4溶液中,方解石和白云石溶解度分别为纯水中溶解度的9．544和9．897倍。其作用机理是:在无同离子效应时,SO₄2-等所产生的盐效应和SO₄2-与各种阳离子形成的离子对起重要作用;而有同离子效应时,将发生白云石化或去白云石化反应,从而促使不全等溶解继续发生。与此同时,即使存在同离子效应的条件下,特别是在较高浓度条件下,盐效应的作用也是不容忽视的。      

CO2分压条件下煤中矿物质溶解度数值模拟

查明煤中矿物质在不同温度和CO₂分压条件下溶解度变化规律,能为注入CO₂过程中煤储层渗透率分析提供重要依据。借助水文地球化学模拟软件PHREEQC对在不同温度和CO₂分压条件下煤中各矿物的溶解度进行了水化学模拟,得出不同温度和CO₂分压条件下矿物质溶解度的变化规律。结果表明:在无CO₂分压时,随着温度的升高各矿物的溶解度增加;当溶液中CO₂分压增加到一定程度时,随着温度的升高各矿物的溶解度降低（石英除外）;在温度相同时,随着CO₂分压的增加,所有矿物（石英除外）溶解度均增加,方解石的溶解度随着CO₂分压的升高呈现出迅速增加的趋势,其他矿物随着CO₂分压的升高,溶解度增加的速率较为缓慢。      

矿物-水反应的地球化学动力学研究进展

回顾了地球化学动力学这门新兴学科的产生与发展，评述了国内外矿物-水反应的地球化学动力学研究的新进展，介绍了矿物-水反应的溶解动力学及地球化学动力学模拟的新成果及应用领域。低温条件下硅酸盐和碳酸盐矿物与水的反应得到高度重视。硅酸盐矿物的溶解速率与溶液的pH值、离子强度、温度及有机酸的含量等密切相关。碳酸盐类矿物的溶解速率主要取决于温度、GO2分压、酸碱度及相关离子的活度等因素。氧化物、硫化物、及氟化物等的溶解沉淀的动力学研究开始得到关注。矿物-水反应的地球化学动力学模拟已成为一个很有前景的方向。     

Silicate and carbonate mineral weathering in soil profiles developed on Pleistocene glacial drift (Michigan, USA): Mass balances based on soil water geochemistry

Geochemistry of soil, soil water, and soil gas was characterized in representative soil profiles of three Michigan watersheds. Because of differences in source regions, parent materials in the Upper Peninsula of Michigan (the Tahquamenon watershed) contain only silicates, while those in the Lower Peninsula (the Cheboygan and the Huron watersheds) have significant mixtures of silicate and carbonate minerals. These differences in soil mineralogy and climate conditions permit us to examine controls on carbonate and silicate mineral weathering rates and to better define the importance of silicate versus carbonate dissolution in the early stage of soil-water cation acquisition.Soil waters of the Tahquamenon watershed are the most dilute; solutes reflect amphibole and plagioclase dissolution along with significant contributions from atmospheric precipitation sources. Soil waters in the Cheboygan and the Huron watersheds begin their evolution as relatively dilute solutions dominated by silicate weathering in shallow carbonate-free soil horizons. Here, silicate dissolution is rapid and reaction rates dominantly are controlled by mineral abundances. In the deeper soil horizons, silicate dissolution slows down and soil-water chemistry is dominated by calcite and dolomite weathering, where solutions reach equilibrium with carbonate minerals within the soil profile. Thus, carbonate weathering intensities are dominantly controlled by annual precipitation, temperature and soil pCO₂. Results of a conceptual model support these field observations, implying that dolomite and calcite are dissolving at a similar rate, and further dissolution of more soluble dolomite after calcite equilibrium produces higher dissolved inorganic carbon concentrations and a Mg²⁺/Ca²⁺ ratio of 0.4.Mass balance calculations show that overall, silicate minerals and atmospheric inputs generally contribute <10% of Ca²⁺ and Mg²⁺ in natural waters. Dolomite dissolution appears to be a major process, rivaling calcite dissolution as a control on divalent cation and inorganic carbon contents of soil waters. Furthermore, the fraction of Mg²⁺ derived from silicate mineral weathering is much smaller than most of the values previously estimated from riverine chemistry.     

黄骅坳陷三马地区中-深部储层成岩作用及主控因素分析

黄骅坳陷三马地区储集岩样品的显微特征及成岩矿物的组合关系分析结果表明，三马地区下第三系中深层储层主要处于晚成岩A期，成岩现象包括石英、长石的次生加大、碳酸盐矿物胶结作用、矿物交代作用、溶解作用和粘土矿物转化作用等。其中石英次生加大于2700m左右开始出现，随埋深增大，石英增生加强；长石次生加大现象不十分普遍；碳酸盐胶结作用包括早期自生泥晶方解石胶结作用、连晶方解石和晚期白云石(或铁方解石)的胶结作用。在扫描电镜下可见到方解石与含铁方解石集合体充填在粒间孔隙中或与石英、钠长石及粘土矿物共生，白云岩多呈菱形粒状分布于粒间；常见的交代现象主要有方解石交代长石、石英及粘土矿物，粘土矿物交代长石、石英等；溶解作用主要有长石的溶解、碳酸盐颗粒的溶解和方解石胶结物的溶解等，粘土矿物的转化主要为蒙脱石、高岭石向伊利石(或绿泥石)转化。还讨论了储层岩相、岩性特征、孔隙水中有机酸含量、早期方解石的充填、烃类早期注入等因素对储层成岩演化的控制作用。     

Carbonate dissolution in the guts of benthic deposit feeders: A numerical model

We present a numerical model to quantify calcite dissolution in the guts of deposit feeding invertebrates. Deposit feeder guts were modeled as constantly stirred reactors (CSTRs) following terminology from digestion theory. Saturation state and dissolution of calcium carbonate were calculated from changes in total dissolved carbon dioxide and alkalinity resulting from sediment passage through the digestive tract, while accounting for dissolution of calcite and respiration of organic carbon. Typical dissolution rates for a gut volume of 1 ml ranged between 0.5-4 mg calcite d⁻¹. Sensitivity analysis revealed gut pH, sediment organic matter (OM) content and OM reactivity to be the critical parameters determining calcite dissolution rate. Carbonate dissolution rate was inversely related to gut pH. However, calcite dissolution was found to be possible even at alkaline gut pH due to respiration by intestinal microbes. The kinetics of calcite dissolution had only marginal influence on daily calcite dissolution rates: Varying the calcite dissolution rate constant κ by six orders of magnitude affected calcite dissolution rates by less than a factor of 10. Calcite dissolution rates were calculated for 4 different hydrographic regimes that differed in their content of sedimentary calcite and OM and furthermore in their OM reactivity. Highest dissolution rates were calculated for the shallow water setting, where relatively high OM content facilitated high microbial respiration rates depressing gut pH. However, dissolution rates for the deep sea setting were only slightly lower, due to greatly elevated ingestion rates resulting from low OM content. As a consequence of much higher faunal abundances, shallow-water benthos is likely to contribute the vast majority of gut-mediated carbonate dissolution. Nevertheless, the fraction of sedimentary calcite that dissolves during one gut passage is probably too small to be observable by simple gravimetric analysis. This may explain the notable scarcity of evidence for gut-mediated carbonate dissolution in the literature to date. Assuming depth-dependent calcite dissolution rates and deposit feeder abundances, we estimate gut-mediated carbonate dissolution to contribute approximately 5% of the annual global sedimentary carbonate dissolution rate, which corresponds to an average calcite dissolution rate of approximately 0.5 mg m⁻² d⁻¹ for the entire ocean floor.     

Dissolution kinetics and the weathering of mafic minerals

Fayalite, hypersthene, basalt, and obsidian were dissolved in buffered solutions (25°C; pH 4.5 and 5.5) under air, N₂ or O₂ atmospheres, in order to follow the kinetics of dissolution. Each dissolved more rapidly at lower pH values, dissolving most rapidly in the initial few days, followed by slower dissolution for periods up to six months. Dissolution was more rapid when air was excluded. In oxygen atmospheres an Fe(OH)₃ precipitate armors mineral surfaces, thus inhibiting further dissolution, and further affects the solution by scavenging dissolved silica and cations. Dissolution reactions include initial exchange between cations and H⁺, incongruent dissolution of silicate structures, oxidation of Fe²⁺ in solution, precipitation of Fe(OH)₃, and scavenging of dissolved silica and cations by Fe(OH)₃. Dissolution kinetics may explain weathering of mafic rocks and minerals at the Earth's surface, the formation of Fe-oxide coatings on mineral grains, weathering of submarine mafic rocks and intrastratal solution of mafic minerals in buried sandstones. Early Precambrian weathering would have been more rapid before the appearance of large amounts of oxygen in the atmosphere, and continental denudation rates may have been higher than at present because of this effect and the predominance of mafic igneous rocks at an early stage of continent formation and growth.     

Controlling factors for dawsonite diagenesis: a case study of the Binnan Region in Dongying Sag,Bohai Bay Basin,China

Authigenic minerals and the diagenetic sequence of the dawsonite-bearing sandstones from the Binnan Region of the Dongying Sag, Bohai Bay Basin, China were studied to understand the formation of dawsonite, as a possible mechanism for mineral trapping of CO₂ in carbon capture and storage (CCS) programmes. Authigenic minerals include quartz overgrowth, dawsonite (5–15 vol%), calcite, ferrocalcite and ankerite. The major rock types are medium- to fine-grained arkose, feldspathic litharenite and lithic arkose. Quantitative analysis suggests that the burial depth and feldspar content are the two dominant controlling factors of the growth of dawsonite. The dawsonite content increases initially before decreasing with burial depth, with the peak dawsonite content occurring at approximately 1500 m depth. This trend is probably due to increases in temperature and pCO₂ with the burial depth and contributes to the formation of dawsonite. However, the pCO₂ content and stability of dawsonite decrease with increasing distance from the centre of the gas reservoir. When the formation temperature exceeds the upper limit of the preservation temperature of dawsonite, the dawsonite is suppressed, while the dissolution of dawsonite is promoted. Overall, the dawsonite content exhibits a positive correlation with the feldspar content. The dissolution of feldspar makes both Na⁺ and Al³⁺ available and creates the accommodation space necessary for dawsonite growth. In addition, feldspar dissolution also neutralises the acidity of the thermal fluid present, which again facilitates the growth and preservation of the dawsonite.     

Dissolution rates of phyllosilicates as a function of bacterial metabolic diversity

Weathering experiments using biotite and phlogopite in the presence of bacteria were conducted to better understand biotic dissolution kinetics and processes (proton- and ligand-promoted dissolution) under aerobic conditions. Miniature batch reactors (300 μl in microplate wells) were used at 24 °C for 3 days with and without bacterial strains. Abiotic experiments were performed with organic and nitric acids in order to calibrate the biotite-phlogopite chemical dissolution. An empirical model was used to fit the pH dependence for iron release rate (r_Fe) considering the influence of both protons and ligands from acidic to neutral conditions (pH ranging from 3 to 7): r_Fe=k_H(a_H+)^m+k_L(a_L)¹ where k is the apparent rate constant, a_H+ and a_L are the activities of protons and ligands, and m and l are the reaction orders. For both minerals in most cases at a given pH, the iron release rates in the presence of bacteria were in good agreement with rates determined by the chemical model and could be explained by a combination of proton- and ligand-promoted processes. Bacteria affect mineral dissolution and iron release rates through the quantities and nature of the organic acids they produce. Three domains were differentiated and proposed as biochemical models of mica dissolution: (1) below pH 3, only proton-promoted dissolution occurred, (2) in weakly acidic solutions both ligand- and proton-promoted mechanisms were involved, and (3) iron immobilization occured, at pH values greater than 4 for biotite and greater than 5 for phlogopite. This model allows us to distinguish the “weathering pattern phenotypes” of strains. Bacteria that are isolated from horizons poor in carbon appear more efficient at weathering micas than bacterial strains isolated from environments rich in carbon. Moreover, our results suggest that the mineral could exert a control on the release of organic acids and the “weathering pattern phenotypes” of bacteria.     

Hydro-chemical analysis and ionic flux of meltwater runoff from Khangri Glacier,West Kameng,Arunachal Himalaya,India

The detailed hydro-chemical study of meltwater draining from Khangri glacier Arunachal Pradesh has been carried out to evaluate the major ion chemistry and weathering processes in the drainage basin. The investigative results shows that the meltwater is almost neutral to slightly acidic in nature with Mg–HCO₃-dominated hydro-chemical facies. In glacial meltwater, Ca^+?2 is the most dominated cation followed by Mg⁺², Na⁺, and K⁺, while HCO₃^? is the most dominant anion followed by SO₄^2?, NO₃^?, and Cl^?. The dominant cations such as Ca⁺² and Mg⁺² show a good relation with the minerals abundance of the rocks. Calcite (CaCO₃) and biotite [K(Mg,Fe)₃AlSi₃O₁₀(F,OH)₂] are the most abundant minerals in the deformed carbonate-rich metasedimentary rocks near to the snout with some K feldspar (KAlSi₃O₈) and quartz (SiO₂). This suggests Ca⁺² have definitely entered into the water due to the dissolution of calcite and Ca feldspar (CaAl₂Si₂O₈), while one of the source of Mg⁺² is biotite. Na feldspar (NaAlSi₃O₈) has contributed towards the availability of sodium ion, while potassium ion is derived from the chemical weathering of K feldspar and biotite. The chemical weathering is the foremost mechanism controlling the hydro-chemistry of the Khangri glacier because of the least anthropogenic interferences. The mineralogy of surrounding rocks is studied to understand better, the rock–water interaction processes, and their contribution towards ionic concentration of meltwater. The meltwater discharge and individual ion flux of the catchment area have also been calculated, to determine the ionic denudation rate for the ablation season. The high elemental ratio of (Ca?+?Mg)/(Na?+?K) (7.91?±?0.39 mg/l) and low elemental ratio of (Na?+?K)/total cations (0.11?±?0.004) indicate that the chemical composition of meltwater is mainly controlled by carbonate weathering and moderately by silicate weathering. The scatter plot result between (Ca?+?Mg) and total cations confirms that carbonate weathering is a major source of dissolved ions in Khangri glacier meltwater. In addition, the statistical analysis was also used to determine the correlation between physical parameters of glacier meltwater which controlled the solute dynamics.     

The role of reaction affinity and secondary minerals in regulating chemical weathering rates at the Santa Cruz Soil Chronosequence, California

In order to explore the reasons for the apparent discrepancy between laboratory and field weathering rates and to determine the extent to which weathering rates are controlled by the approach to thermodynamic equilibrium, secondary mineral precipitation, and flow rates, a multicomponent reactive transport model (CrunchFlow) was used to interpret soil profile development and mineral precipitation and dissolution rates at the 226 ka Marine Terrace Chronosequence near Santa Cruz, CA. Aqueous compositions, fluid chemistry, transport, and mineral abundances are well characterized [White A. F., Schulz M. S., Vivit D. V., Blum A., Stonestrom D. A. and Anderson S. P. (2008) Chemical weathering of a Marine Terrace Chronosequence, Santa Cruz, California. I: interpreting the long-term controls on chemical weathering based on spatial and temporal element and mineral distributions. Geochim. Cosmochim. Acta72 (1), 36-68] and were used to constrain the reaction rates for the weathering and precipitating minerals in the reactive transport modeling. When primary mineral weathering rates are calculated with either of two experimentally determined rate constants, the nonlinear, parallel rate law formulation of Hellmann and Tisserand [Hellmann R. and Tisserand D. (2006) Dissolution kinetics as a function of the Gibbs free energy of reaction: An experimental study based on albite feldspar. Geochim. Cosmochim. Acta70 (2), 364-383] or the aluminum inhibition model proposed by Oelkers et al. [Oelkers E. H., Schott J. and Devidal J. L. (1994) The effect of aluminum, pH, and chemical affinity on the rates of aluminosilicate dissolution reactions. Geochim. Cosmochim. Acta58 (9), 2011-2024], modeling results are consistent with field-scale observations when independently constrained clay precipitation rates are accounted for. Experimental and field rates, therefore, can be reconciled at the Santa Cruz site.Additionally, observed maximum clay abundances in the argillic horizons occur at the depth and time where the reaction fronts of the primary minerals overlap. The modeling indicates that the argillic horizon at Santa Cruz can be explained almost entirely by weathering of primary minerals and in situ clay precipitation accompanied by undersaturation of kaolinite at the top of the profile. The rate constant for kaolinite precipitation was also determined based on model simulations of mineral abundances and dissolved Al, SiO₂(aq) and pH in pore waters. Changes in the rate of kaolinite precipitation or the flow rate do not affect the gradient of the primary mineral weathering profiles, but instead control the rate of propagation of the primary mineral weathering fronts and thus total mass removed from the weathering profile. Our analysis suggests that secondary clay precipitation is as important as aqueous transport in governing the amount of dissolution that occurs within a profile because clay minerals exert a strong control over the reaction affinity of the dissolving primary minerals. The modeling also indicates that the weathering advance rate and the total mass of mineral dissolved is controlled by the thermodynamic saturation of the primary dissolving phases plagioclase and K-feldspar, as is evident from the difference in propagation rates of the reaction fronts for the two minerals despite their very similar kinetic rate laws.     

Coupled alkali feldspar dissolution and secondary mineral precipitation in batch systems – 2: New experiments with supercritical CO2 and implications for carbon sequestration

In order to evaluate the extent of CO₂–water–rock interactions in geological formations for C sequestration, three batch experiments were conducted on alkali feldspars–CO₂–brine interactions at 150–200 °C and 300 bars. The elevated temperatures were necessary to accelerate the reactions to facilitate attainable laboratory measurements. Temporal evolution of fluid chemistry was monitored by major element analysis of in situ fluid samples. SEM, TEM and XRD analysis of reaction products showed extensive dissolution features (etch pits, channels, kinks and steps) on feldspars and precipitation of secondary minerals (boehmite, kaolinite, muscovite and paragonite) on feldspar surfaces. Therefore, these experiments have generated both solution chemistry and secondary mineral identity. The experimental results show that partial equilibrium was not attained between secondary minerals and aqueous solutions for the feldspar hydrolysis batch systems. Evidence came from both solution chemistry (supersaturation of the secondary minerals during the entire experimental duration) and metastable co-existence of secondary minerals. The slow precipitation of secondary minerals results in a negative feedback in the dissolution–precipitation loop, reducing the overall feldspar dissolution rates by orders of magnitude. Furthermore, the experimental data indicate the form of rate laws greatly influence the steady state rates under which feldspar dissolution took place. Negligence of both the mitigating effects of secondary mineral precipitation and the sigmoidal shape of rate–ΔG_r relationship can overestimate the extent of feldspar dissolution during CO₂ storage. Finally, the literature on feldspar dissolution in CO₂-charged systems has been reviewed. The data available are insufficient and new experiments are urgently needed to establish a database on feldspar dissolution mechanism, rates and rate laws, as well as secondary mineral information at CO₂ storage conditions.     

Geochemical characteristics and controlling factors of chemical composition of groundwater in a part of Guntur district,Andhra Pradesh,India

A survey on quality of groundwater was carried out for assessing the geochemical characteristics and controlling factors of chemical composition of groundwater in a part of Guntur district, Andhra Pradesh, India, where the area is underlain by Peninsular Gneissic Complex. The results of the groundwater chemistry show a variation in pH, EC, TDS, Ca²⁺, Mg²⁺, Na⁺, K⁺, HCO₃ ^?, Cl^?, SO₄ ^2?, NO₃ ^? and F^?. The chemical composition of groundwater is mainly characterized by Na⁺?HCO₃ ^? facies. Hydrogeochemical type transits from Na⁺–Cl^?–HCO₃ ^? to Na⁺–HCO₃ ^?–Cl^? along the flow path. Graphical and binary diagrams, correlation coefficients and saturation indices clearly explain that the chemical composition of groundwater is mainly controlled by geogenic processes (rock weathering, mineral dissolution, ion exchange and evaporation) and anthropogenic sources (irrigation return flow, wastewater, agrochemicals and constructional activities). The principal component (PC) analysis transforms the chemical variables into four PCs, which account for 87% of the total variance of the groundwater chemistry. The PC I has high positive loadings of pH, HCO₃ ^?, NO₃ ^?, K⁺, Mg²⁺ and F^?, attributing to mineral weathering and dissolution, and agrochemicals (nitrogen, phosphate and potash fertilizers). The PC II loadings are highly positive for Na⁺, TDS, Cl^? and F^?, representing the rock weathering, mineral dissolution, ion exchange, evaporation, irrigation return flow and phosphate fertilizers. The PC III shows high loading of Ca²⁺, which is caused by mineral weathering and dissolution, and constructional activities. The PC IV has high positive loading of Mg²⁺ and SO₄ ^2?, measuring the mineral weathering and dissolution, and soil amendments. The spatial distribution of PC scores explains that the geogenic processes are the primary contributors and man-made activities are the secondary factors responsible for modifications of groundwater chemistry. Further, geochemical modeling of groundwater also clearly confirms the water–rock interactions with respect to the phases of calcite, dolomite, fluorite, halite, gypsum, K-feldspar, albite and CO₂, which are the prime factors controlling the chemistry of groundwater, while the rate of reaction and intensity are influenced by climate and anthropogenic activities. The study helps as baseline information to assess the sources of factors controlling the chemical composition of groundwater and also in enhancing the groundwater quality management.