Dolomite effect on borosilicate glass alteration

Dolomite (CaMg(CO₃)₂) is one of the common rock-forming minerals in many geological media, in particular in clayey layers that are currently considered as potential host formations for a deep radioactive waste disposal facility. Magnesium in solution is one of the elements known to potentially enhance the alteration of nuclear glasses. The alteration of borosilicate glasses with dolomite as a Mg-bearing mineral source was investigated for 8 months in batch tests at 90 °C. Glass composition effects were investigated through two compositions (SiBNaAlCaZrO and SiBNaAlZrO) differing in their Ca content. The Ca-rich glass alteration is slightly enhanced in the presence of dolomite compared to the alteration observed in pure water. This greater alteration is explained by the precipitation of Mg silicate phases on the dolomite and glass surfaces. In contrast, the Ca-free glass alteration decreases in the presence of dolomite compared to the alteration observed in pure water. This behavior is explained by Ca incorporation in the amorphous layer (formed during glass alteration) coming from dolomite dissolution. Calcium acts as a layer reorganizer and limits glass alteration by reducing the diffusion of reactive species through the altered layer. Modeling was performed using the GRAAL model implemented within the CHESS/HYTEC geochemical code to discriminate and interpret the mechanisms involved in glass/dolomite interactions. Magnesium released by dolomite dissolution reacts with silica provided by glass alteration to form Mg silicates. This reaction leads to a pH decrease. The main mechanism controlling glass alteration is the ability of dolomite to dissolve. During the experiment the quantities of secondary phases formed were very small, but for longer time scales, this mechanism could supply sufficient Mg in solution to form large amounts of Mg silicates and sustain glass alteration. The ability of the GRAAL model to reproduce the concentrations of elements in solution and solid phases regardless of the amount of dolomite and the glass composition strongly supports the basic modeling hypothesis.     

Experimental study on water–rock interactions during CO2 flooding in the Tensleep Formation,Wyoming, USA

The conditions for mineral alteration and formation damage during CO₂ treatment of Tensleep sandstone reservoirs in northern Wyoming, USA, were examined through core-flooding laboratory experiments carried out under simulated reservoir conditions (80°C and 166 bars). Subsurface cores from the Tensleep sandstone, which were cemented by dolomite and anhydrite, and synthetic brines were used. The brines used were (Ca, Mg, Na)SO₄–NaCl solution (9.69 g/l total dissolved solids) for Run 1 and a 0.25 mol/l NaCl solution for Run 2. The solution used in Run 1 was saturated with respect to anhydrite at run conditions, which is characteristic of Tensleep Formation waters.Three major reactions took place during flooding, including (1) dissolution of dolomite, (2) alteration of K-feldspar to form kaolinite, and (3) precipitation (in Run 1) or dissolution (in Run 2) of anhydrite. All sample solutions remained undersaturated with respect to carbonates. The permeability of all the cores (except one used in Run 2) decreased during the experiments despite the dissolution of authigenic cement. Kaolinite crystal growth occurring in pore throats likely reduced the permeability.Application of the experimental results to reservoirs in the Tensleep Formation indicates that an injection solution will obtain saturation with respect to dolomite (and anhydrite) in the immediate vicinity of the injection well. The injection of NaCl-type water, which can be obtained from other formations, causes a greater increase in porosity than the injection of Tensleep Formation waters because of the dissolution of both dolomite and anhydrite cements.     

近地表温压条件下白云岩溶解过程的实验研究

与溶解作用有关的次生孔隙是碳酸盐岩最主要的油气储集空间,从实验模拟角度研究碳酸盐溶解机制具有重要的理论与应用价值。本文在近地表的温度和压力条件下,进行了具相同成分和结构的白云岩在CO2和乙酸介质中的对照溶解实验,两种类型的具相同成分和不同结构的白云岩在CO2介质中添加和不添加硬石膏的对照溶解实验,以及方解石含量50%的岩石在CO2介质中添加和不添加硬石膏的对照溶解实验。实验结果表明:(1)近地表温压条件的酸性环境中,乙酸对碳酸盐矿物的溶解能力显著大于CO2流体,乙酸对白云石的溶解是接近化学计量的,而CO2流体则是非化学计量的,白云石中Ca优先溶出而Mg滞留;(2)溶解CaSO4的加入会显著改善近地表温压条件下CO2流体对白云石的溶解效果,使得白云石溶解接近化学计量组成,该过程是通过抑制Ca的溶出和加速Mg的溶出来实现的;(3)对于白云石含量大于90%的较纯的白云岩来说,溶解CaSO4的加入会使得白云岩溶出离子的Ca、Mg合量增加,因而总体上有利于白云岩溶解,与之相反,溶液中CaSO4的沉淀可能导致白云石的沉淀。实验结果可以帮助我们更深刻理解近地表环境白云岩的溶解过程,尤其是与膏盐伴生的白云岩的溶解及相应岩溶过程和次生孔隙的形成机制。      

Chemical exchange during hydrothermal alteration of basalt by seawater—I. Experimental results for major and minor components of seawater

Fresh mid-ocean ridge basalt of varying crystallinity has been powdered and reacted with seawater and an artificial Na-K-Ca-Cl solution at 200–500°C and 500–1000 bar in sealed gold capsules. Water/rock mass ratios of 1–3 were used and durations ranged from 2 to 20 months.These time periods were sufficient for most elements to approach a steady-state concentration in solution which was determined by equilibrium with alteration minerals (Mg, SiO₂, SO₄), by rate of formation of these minerals (Na, Ca), or by depletion from the rock (K, B, Ba). The resulting solutions closely resemble the brines from the basalt-seawater geothermal system at Reykjanes, Iceland. Mg was almost completely removed from seawater into the alteration products smectite, tremolite-actinolite, or talc. Sulfate also was removed to low concentrations, both by precipitation of anyhydrite and by reduction to sulfide. Net transfer of Na from seawater into solids occurred in most experiments by formation of sodic feldspar and possibly analcime. Sr was removed from seawater in some experiments but showed no change or a small gain in others. SiO₂, Ca, K, Ba, B and CO₂ were leached from basalt and enriched in solution. SiO₂ concentrations were controlled by saturation with quartz at 300°C and above. The principal Ca-bearing phases which formed were anhydrite, the hydrated Ca-silicate truscottite, tremolite-actinolite, and possibly wairakite. No K-rich phases formed. For some minerals the crystallinity of the starting basalt affected the amount which formed.Removal of Mg from seawater into solid alteration products occurred rapidly and was balanced largely by leaching of Ca from basalt. Net transfer of Na from seawater into solids occurred more slowly and was balanced mainly by leaching of additional Ca from basalt. Thus, reaction between seawater and basalt at low water/rock ratios can be considered to consist of two exchanges: Mg for Ca, and Na for Ca.     

Secular variations in seawater chemistry controlling dolomitization in shallow reflux systems: insights from reactive transport modelling

Dolomitization often plays a critical role in the pore network development of platform carbonates, with implications for reservoir quality distribution. Understanding both the hydrological system driving dolomitization and the chemistry of the fluids involved is fundamental to constrain predictions of the geometry and the petrophysical properties of dolomite bodies. Here, the role of secular variations in seawater Mg/Ca as a control on dolomitization and early porosity modification was evaluated using one‐dimensional reactive transport models and fluids based on modern (aragonite sea), Mississippian and Aptian (calcite sea) seawaters. The sensitivity of dolomitization to a range of extrinsic controls (brine salinity, temperature, fluid flow rate and pCO₂) and to intrinsic reactivity of the sediments (effective reactive surface area) was also explored. Simulations suggest faster calcite replacement by dolomite for seawaters with higher Mg/Ca, indicating that dolomitization potential is determined more by Mg/Ca rather than saturation index. Increasing evaporative concentration enhances reaction rate independent of the effect of enhanced density‐driven fluid flux. In addition to brine composition, effective surface area of precursor sediments and temperature exert a critical control on replacement rate, while secular variations of pH and carbonate alkalinity associated with changes in pCO₂ are only secondary controls. Above flow rates of 0·01 m yr^?1 replacive dolomitization is reaction‐limited rather than flux limited, favouring alteration of fine‐grained carbonates and suggesting that preferential alteration of grainstone units is rare unless head gradients are low. Post‐replacement dolomite cementation is flux dependent, and thus favoured in areas of high head gradient and high permeability sediments and, contrary to replacement, supersaturation is a more important driver than Mg/Ca. While uncertainties remain regarding low‐temperature dolomitization kinetics, the capability of numerical simulations to decouple individual controls provides new insights which can be used, in conjunction with traditional comparative sedimentology, to generate more rigorous conceptual models for individual reservoir settings.     

Diagenesis of Ordovician carbonates from the north-east Michigan Basin, Manitoulin Island area, Ontario: evidence from petrography, stable isotopes and fluid inclusions

Middle to Late Ordovician subtidal carbonates in the Manitoulin Island area of Ontario are predominantly limestone in composition, but non-ferroan and ferroan dolomite is a common cement as well as a selective or locally pervasive replacement phase. Integration of field, petrographic, geochemical (δ¹³C, δ¹⁸O) and fluid inclusion data indicates that lithification of these carbonates occurred during burial diagenesis, with much of the alteration controlled by regional fracturing and hydrothermal influences. Aqueous (type 1) fluid inclusions in early calcite (pre-dolomite) and dolomite are saline (> 29 wt% NaCl eq.) solutions with Ca and/or Mg in excess of Na and display homogenization temperatures with modes of 95 and 101°C, respectively. These temperatures can be explained by significantly more burial than can be accounted for either by the available stratigraphic information or by an unusually high palaeogeothermal gradient, which also is not well supported. The fluid inclusion temperatures are interpreted to have resulted from hydrothermal fluids which circulated during the burial diagenesis of these strata. Type 1 inclusions in late (post-dolomite) calcite are less saline (<19 wt% NaCl eq.) and have a bimodal distribution of homogenization temperatures with a relatively well defined low temperature peak similar to those in early calcite and dolomite and a broad higher temperature grouping with a mode at 183°C. A small proportion of methane and light hydrocarbon-bearing fluid inclusions (type 2) are present in all stages of carbonate. Dolomitizing fluids were derived from burial compaction of argillaceous sediments in the more central parts of the Michigan Basin and the updip migration of these brines along fractures to the basin margin where the carbonates of the Manitoulin Island area were dolomitized. Alternatively, migration of dolomitizing brines downward from the overlying pervasively dolomitized Silurian sequence into fractures in the Ordovician carbonates may have occurred. Integration of the aqueous fluid inclusion data into the diagenetic history of these carbonates remains equivocal because most of the inclusions are secondary or indeterminate in origin. Nevertheless, high salinities resulting from interaction with evaporitic strata and hydrothermal effects are clearly implicated although the origin of the latter remains unclear. The alteration styles of the Ordovician carbonates in the Manitoulin area are similar to those of Ordovician hydrocarbon reservoirs described from other parts of the Michigan Basin. They indicate that fracture-related diagenesis occurred on a basin-wide scale and that hydrothermal effects were important.     

Regional-scale fluid flow and element mobility in Barrow’s metamorphic zones,Stonehaven, Scotland

The geochemistry of metamorphic quartz vein formation in Barrow’s index mineral zones north of Stonehaven, Scotland, was investigated in order to assess regional fluid flow and mass transfer. Metamorphic grade in the Dalradian metasediments increases to the north–northwest away from the Highland Boundary Fault (HBF) and associated ophiolitic rocks of the Highland Border Complex (HBC), passing through the Chlorite (Chl), Biotite (Bt), Garnet (Grt), Chloritoid (Cld), and Staurolite (St) zones. Syn-metamorphic fluid infiltration at 462±8.8 Ma (Breeding et al. in Am Mineral 89:1067, 2004) produced considerable quartz veining. Vein abundance varies from about 5 to 15 volume percent of the outcrops; veins tend to be more abundant in metapelitic layers than in metapsammitic ones. Metamorphic veins are surrounded by centimeter- to decimeter-wide zones of chemical and mineralogical alteration (selvages). Porphyroblasts, particularly Bt, Grt, Cld, and St, are typically larger in selvages than in wallrocks distal to veins. The altered selvages underwent fluid-driven addition of Na, Ca, and Sr, and loss of K, Rb, and Ba. Alteration is most intense within ∼750 m of the HBF, but is still very significant at the northern end of the field area some 2 km away. Mg/Fe^T (Fe^T=total iron) was either unchanged or increased due to alteration. Silica was added at some Chl and Bt zone localities near the HBF. Pb mass transfer was variable although Pb was added at a number of locations. Rare Earth elements (REE) were generally immobile, but light REE and possibly heavy REE were lost at one field site. The gain of Na and Ca and loss of K promoted the growth of plagioclase at the expense of micas (particularly muscovite) in selvages and wallrock inclusions throughout the field area and, probably, some calcite and/or dolomite growth directly adjacent to the HBF. The Ca gains were also critical for epidote production in the Bt zone. Gains of Ca and increases in Mg/Fe^T helped to stabilize Grt at the expense of Cld and St in some selvages. Hornblende and cummingtonite were discovered in strongly altered metapelitic rocks at one Cld zone locality. The metasomatism puts important constraints on the processes of mass transfer and suggests two models for regional fluid flow. In the first model, fluid flow in a direction of increasing temperature downward along the HBF added Na and Ca, and removed K from the Dalradian. In the second model, fluid flow upward from the HBC transported Na and Ca into the overlying Dalradian and, at the same time, stripped out K. The latter model is favored because it can most readily account for silica addition near the HBF, but neither model can be ruled out at present. In either case, the veins represent fractures that transmitted very large time-integrated fluid fluxes of at least ∼10⁴ m³ (fluid)/m² (rock). Consequently, the veins were conduits for regional fluid flow that caused considerable open-system chemical and mineralogical alteration during metamorphism. Electronic Supplementary Material Supplementary material is available for this article at     

A model for the distribution of trace elements between calcite and dolomite

A crystal-growth model is proposed, which allows ions of a trace element to enter the Ca and Mg sites of dolomite in proportion to the size of the ions relative to that of Ca and Mg ions, and which assigns equal portions of the trace element to the Ca site of dolomite and the Ca site of associated calcite. The model produces calcite/dolomite distribution coefficients of 0.79 for Mn and 0.43 for Fe, which may be compared with 0.85 and 0.28 as observed in marble, and a distribution coefficient of 2.0 for Sr and Ba, which may be compared with observed values of 2.3 for Sr and 1.8 for Ba.     

Origin of CaCl2 brines by basalt-seawater interaction: Insights provided by some simple mass balance calculations

Modern rift zone hydrothermal brines are typically CaCl₂-bearing brines, an unusual chemical signature they share with certain oil field brines, fluid inclusions in ore minerals and a few uncommon saline lakes. Many origins have been suggested for such CaCl₂ brines but in the Reykjanes, Iceland, geothermal system a strong empirical case can be made for a basalt-seawater interaction origin. To examine this mechanism of CaCl₂ brine evolution some simple mass balance calculations were carried out. Average Reykjanes olivine tholeiite was “reacted” with average North Atlantic seawater to make an albite-chlorite-epidotesphene rock using Al₂O₃ as the conservative rock component and Cl as the conservative fluid component. The excess components released by the basalt to the fluid were “precipitated” at 275° C as quartz, calcite, anhydrite, magnetite and pyrite to complete the conversion to greenstone. The resulting fluid was a CaCl₂ brine of seawater chlorinity with a composition remarkably similar to the actual Reykjanes brine at 1750 m depth. Thus, the calculations strongly support the idea that the Reykjanes CaCl₂ brines result from “closed system” oceanic basalt-seawater interaction (albitization — chloritization mechanism) at greenschist facies temperatures. The calculation gives a seawater: basalt mass ratio of 3∶1 to 4∶1 (vol. ratio of 9∶1 to 12∶1), in keeping with experimental results, submarine vent data and with ocean crust cooling calculations. The brine becomes anoxic because there is insufficient dissolved or combined oxygen to balance all the Fe released from the basalt during alteration. Large excesses of Ca are released to the fluid and precipitate out in the form of anhydrite which essentially sweeps the brine free of sulfate leaving an elevated Ca concentration. The calculated rock-water interaction basically involves Na + Mg + SO₄ ? Ca + K, simulating chemical differences observed between oceanic basalts and greenstones from many mid-ocean ridges.     

Recent dolomitization of quaternary biocalcarenites from fuerteventura (Canary Islands)

Quaternary marine and eolian biocalcarenites in the supratidal breaker and spray zone along the Barlovento coast of the peninsula Jandía, Fuerteventura (Canary Islands) are dolomitized by percolating brines with a high Mg/Ca ratio resulting from evaporation of seawater on the sediment's surface. Only fragments of calcareous algae primarily consisting of high-magnesian calcite are replaced by a cryptocrystalline variety of dolomite. Dolomite also occurs in large euhedral crystals in intraparticle and interparticle pore spaces. In the marine biocalcarenite dolomite has a composition of Ca₅₆Mg₄₄(CO₃)₂. It is well ordered.     

煤矿酸性“老窑水”低Ca/Mg成因机制

山西省阳泉市山底河煤矿“老窑水”循环系统多年水质监测数据计算结果显示,煤矿酸性“老窑水”的Ca/Mg值普遍偏低,且存在Ca/Mg值随酸化程度的增强（SO₄2?含量增加或pH减小）而减小的规律。针对这一问题,结合研究区的地球化学物源条件,通过室内试验以及野外监测水样的石膏、方解石、白云石矿物饱和指数与pH变化关系,分析煤矿酸性“老窑水”低Ca/Mg值的成因机制。研究表明:区内石炭系－二叠系的煤系地层中碳酸盐岩夹层、分散状态分布的菱镁矿、黄铁矿是“老窑水”中Ca2+、Mg2+、SO₄2?的物质来源;在黄铁矿氧化水解形成的以硫酸根为主导的酸性溶液中（pH为2.0~4.5）,代表硫酸对石膏、方解石、白云石可溶解性的饱和指数排序为石膏>方解石>白云石,受石膏在高浓度硫酸活性降低并发生沉淀、方解石溶解受Ca2+同离子效应抑制和饱和状态的平衡调节的综合影响,使Ca2+相对含量减少,由于MgSO₄溶度积大于CaSO₄,故Mg2+含量未受上述约束（或较低）,脱白云岩化反应可因Ca2+含量随石膏沉淀而继续进行,加之区内有菱镁矿的溶解,使得Mg2+相对含量增加,最终出现了镁矿酸性“老窑水” Ca/Mg值低的结果。Ca/Mg值可作为煤矿酸性“老窑水”的污染特征指标,应用于环境影响评价。      

Origin of components in Chilean thermal waters

Thermal waters of northern (18°–27°S) and southern (37°–45°S) Chile occur in two very different climatic, geologic and hydrologic environments: arid closed basins with abundant evaporites in the north; humid climate and well drained valleys in the south. The origin and behavior of the main components of the two groups of waters are examined and compared to each other. The modeling of the alteration of volcanic rocks leads to water compositions very different from those observed both in the north and south. In addition to hydrothermal alteration and deep emanations, the Cl/Br ratio reveals a major contribution of saline waters to the two groups: infiltrating brines from salt lakes in the north; seawater in the south.In the north, concentrations of Cl, Br, Na, K, Ca, SO₄, Li, B, Si result from the mixing of alteration waters with recycled brines. Hydrothermal alteration is obscured by this massive saline input, except for Mg. δ³⁴S values are consistent with an origin of sulfate from salar brines, which are themselves derived from deep Tertiary gypsum. In the south, two processes account for the composition of thermal waters: mixing of alteration waters with seawater and deep magmatic contribution. The mixing process controls the concentration of Cl, Br, Na, Alk, Si, K, Ca, Mg. Magmatic inputs are detectable for SO₄, Li and B. δ³⁴S suggests that sulfate stems from the mixing of alteration waters with either marine SO₄ in coastal waters or with deep SO₂ in inland waters. In both the north and south, the Mg concentration is drastically lowered (<1 μmol/L) by the probable formation of a chlorite-type mineral. In the south, very small amounts of seawater (<1% in volume) are sufficient to imprint a clear signature on thermal waters. Not only coastal springs are affected by seawater mixing, but also remote inland springs, as far as 150 km from the sea. Subduction of marine sediments in the accretive margin could be the source of the marine imprint in thermal waters of southern Chile. Seawater may be expelled from the subducted lithosphere and incorporated into the mantle source.     

Carbonate dissolution in Mesozoic sand- and claystones as a response to CO2 exposure at 70 °C and 20 MPa

The response to CO₂ exposure of a variety of carbonate cemented rocks has been investigated using pressurised batch experiments conducted under simulated reservoir conditions, 70 °C and 20 MPa, and with a durations of up to14 months. Calcite, dolomite, ankerite and siderite cement were present in the unreacted reservoir rocks and caprocks. Core plugs of the reservoir rocks were used in order to investigate the alterations in situ. Crushing of the caprock samples was necessary to maximise reactions within the relatively short duration of the laboratory experiments. Synthetic brines were constructed for each batch experiment to match the specific formation water composition known from the reservoir and caprock formations in each well. Chemical matched synthetic brines proved crucial in order to avoid reactions due to non-equilibra of the fluids with the rock samples, for example observations of the dissolution of anhydrite, which were not associated with the CO₂ injection, but rather caused by mismatched brines.Carbonate dissolution as a response to CO₂ injection was confirmed in all batch experiments by both petrographical observations and geochemical changes in the brines. Increased Ca and Mg concentrations after 1 month reaction with CO₂ and crushed caprocks are ascribed to calcite and dolomite dissolution, respectively, though not verified petrographically. Ankerite and possible siderite dissolution in the sandstone plugs are observed petrographically after 7 months reaction with CO₂; and are accompanied by increased Fe and Mn contents in the reacted fluids. Clear evidence for calcite dissolution in sandstone plugs is observed petrographically after 14 months of reaction with CO₂, and is associated with increased amounts of Ca (and Mg) in the reacted fluid. Dolomite in sandstones shows only minor dissolution features, which are not clearly supported by increased Mg content in the reacted fluid.Silicate dissolution cannot be demonstrated, either by chemical changes in the fluids, as Si and Al concentrations remain below the analytical detection limits, nor by petrographical changes, as partly dissolved feldspar grains and authigenic analcime are present in the sediments prior to the experiments. It is noteworthy, that authigenic K-feldspar and authigenic albite in sandstones show no signs of dissolution and consequently seem to be stable under the experimental conditions.     

Inorganic synthesis of Fe–Ca–Mg carbonates at low temperature

A set of free-drift experiments was undertaken to synthesize carbonates of mixed cation content (Fe, Ca, Mg) from solution at 25 and 70 °C to better understand the relationship between the mineralogy and composition of these phases and the solutions from which they precipitate. Metastable solid solutions formed at 25 °C which are not predicted from the extrapolation of higher temperature equilibrium assemblages; instead, solids formed that were intermediary in chemical composition to known magnesite–siderite and dolomite solid solutions. A calcite–siderite solid solution precipitated at 25 °C, with the percentage of CaCO₃ in the solid being proportional to the aqueous Ca/Fe ratio of the solution, while Mg was excluded from the crystal structure except at relatively high aqueous Mg/Ca and Mg/Fe ratios and a low Ca content. Alternatively, at 70 °C Mg was the predominant cation of the solid solutions. These results are compatible with the hypothesis that the relative dehydration energies of Fe, Ca and Mg play an important role in the formation of mixed cation carbonates in nature.     

Chemical evolution of saline waters in the Jordan-Dead Sea transform and in adjoining areas

The Ca–Mg relationship in groundwaters strongly points to the overall dolomitization and local albitization. The Mg/Ca ratios reveal two trends by which saline waters develop: increase of Mg/Ca ratio by evaporation and decreasing Mg/Ca ratios due to dolomitization and albitization. Br/Cl vs. Na/Cl ratios demonstrate that albitization does not play a major role which leaves dolomitization to be the main source for decreasing Mg/Ca ratios in saline waters. In the eastern and southern Region of Lake Kinneret, salinization occurs by mixing with a Ca/Mg molar ratio <1 brine (Ha’On type). Along the western shoreline of the Lake, a Ca/Mg > 1 dominates, which developed by the albitization of plagioclase in abundant mafic volcanics and the dolomitization of limestones. The most saline groundwater of the Tabgha-, Fuliya-, and Tiberias clusters could be regional derivatives of at least two mother brines: in diluted form one is represented by Ha’On water, the other is a Na-rich brine of the Zemah type. Additionally, a deep-seated Ca-dominant brine may ascend along the fractures on the western side of Lake Kinneret, which is absent on the eastern side. Groundwaters of the Lower Jordan Valley are chemically different on both sides of the Jordan River, indicating that the exchange of water is insignificant. All saline waters from the Dead Sea and its surroundings represent a complex mixture of brines, and precipitation and local dissolution of halite and gypsum. Many wells of the Arava/Araba Valley pump groundwater from the Upper Cretaceous limestone aquifer, the origin of the water is actually from the Lower Cretaceous Kurnub Group sandstones. Groundwater drawn from the Quaternary alluvial fill either originates from Kurnub Group sandstones (Eilat 108, Yaalon 117) or from altered limestones of the Judea Group. The origin of these waters is from floods flowing through wadis incised into calcareous formations of the Judea Group. On the other hand, as a result of step-faulting, hydraulic contact is locally established between the Kurnub- and the Judea Groups aquifers facilitating the inter-aquifer flow of the confined Kurnub paleowater into the karstic formations of the Judea Group. Two periods of Neogene brine formation are considered: the post-Messinan inland lagoon resulting in drying up of the Sdom Sea and the evaporation of the Pleistocene Samra Lake, which went further through the stage of Lake Lisan to the present Dead Sea. For the first period, major element hydrochemistry suggests that the saline waters and brines in the Jordan-Dead Sea–Arava Valley transform evolved from the gradual evaporation of an accumulating mixture of sea-, ground-, and surface water. Due to the precipitation of carbonates, gypsum, and halite, such an evaporating primary water body was strongly enriched in Mg, Br, and B and shows high molar ratios of Br/Cl, B/Cl, and Mg/Ca but low Na/Cl ratios. The development of the Br/Cl ratio is chemically modelled, showing that indeed brine development is explicable that way. Along with the evaporation brine, evaporites formed which are leached by infiltrating fresh water yielding secondary brines with Na/Cl ratios of 1. When primary brines infiltrated the sub-surface, they were subjected to Mg–Ca exchange in limestones (dolomitization) and to chloritization and albitization in basic igneous rocks turning them into Ca-Cl brines. These tertiary brines are omnipresent in the Rift. The brines of the late Lisan and Dead Sea were generated by evaporating drainage waters, which leached halite, gypsum, and carbonates from the soil and from the sub-surface. All these brines are still being flushed out by meteoric water, resulting in saline groundwaters. This flushing is regionally enhanced by intensive groundwater exploitation. In variable proportions, the Neogene and late Lisan Lake and Recent Dead Sea brines have to be considered as the most serious sources of salinization of groundwaters in the Rift. Deep-seated pre-Sdom brines cannot strictly be excluded, but if active they play a negligible role only. An erratum to this article can be found at     

Elemental composition of concentrated brines in subduction zones and the deep continental crust

It has been well established that fluids played an important part in determining chemical characteristics in many crustal terranes. Studies of fluid inclusions in eclogites have established that brines coexisted with the primary mineral assemblages during their metamorphic crystallization. These brines are currently multiply saturated in halide salts, carbonates, oxides, and sulfides. As a first step in quantitatively bounding the composition of the brines during metamorphism, the equilibrium compositions of the brines at room temperature were computed using the aqueous speciation codes EQ3/6. The results demonstrate that the brines are high density solutions (ca. 1.4 g/cm³) that have ionic strengths of approximately 8 mol, and are approximately 40% dissolved solids, by weight. These are predominately Na- and K-rich brines, with subordinate Ca and Mg. The approximate Na:K:Ca:Mg molar ratios are 4:2:0.5:0.2, but are sensitive to the assumed HCO₃⁻ concentrations. Charge balance is primarily maintained by the very high Cl concentrations. These brines bear resemblance to brines analyzed from fluid inclusions in metamorphic rocks reported by Roedder (Roedder, E., 1972. Composition of fluid inclusions. US Geol. Surv. Prof. Paper 440JJ, p. 164). Although these fluids have the potential of acting as significant metasomatic agents in subduction zones and deep crustal environments, their impact will be mineralogically discernible only if the fluid release and movement is channelized.     

Saddle-Dolomite-Bearing Fracture Fillings and Records of Hot Brine Activity in the Jialingjiang Formation, Libixia Section, Hechuan Area of Chongqing City

Most vein minerals deposited in fractures of the Jialingjiang Formation from Libixia section,Hechan area include a large amount of saddle dolomite and accompanying celestite,calcite and fluorite.This study analyzed the nature,source,evolution of the fluids by plane-light petrography,fluid-inclusion methods,cathodoluminescence images,and stable isotopic compositions.The homogenization temperatures of two-phase aqueous fluid inclusions in dolomite range between100 and 270℃.Combined with theδ~(18)O data,it is suggested that the fluid responsible for the precipitation of fracture fillings haveδ~(18)O values between 10‰and 18‰(relative to SMOW).The saddle dolomite and the accompanying minerals were the result of activity of dense brines at elevated temperatures.Moreover,analysis shows that the fluid was derived from a mixture of marine-derived brine and deeper circulating flow.This fluid was enriched in Sr during diagenesis and formed celestite in fracture and for regional mineralization.Dissolution of saddle dolomite was attributed to the cooling of Mg/Ca-decreased fluids,which may relate to a leaching of gypsum to celestite in surrounding carbonates.     

Geochemistry of hydrothermal alteration at the Roosevelt hot springs thermal area,Utah

Hot spring deposits in the Roosevelt thermal area consist of opaline sinter and sintercemented alluvium. Alluvium, plutonic rocks, and amphibolite-facies gneiss have been altered by acidsulfate water to alunite and opal at the surface, and alunite, kaolinite, montmorillonite, and muscovite to a depth of 70 m. Marcasite, pyrite, chlorite, and calcite occur below the water table at about 30 m.The thermal water is dilute (ionic strength 0.1–0.2) sodium-chloride brine. The spring water now contains 10 times as much Ca, 100 times as much Mg, and up to 2.5 times as much SO₄ as the deep water. Although the present day spring temperature is 25°C, the temperature was 85°C in 1950.A model for development of the observed alteration is supported by observation and irreversible mass transfer calculations. Hydrothermal fluid convectively rises along major fractures. Water cools by conduction and steam separation, and the pH rises due to carbon dioxide escape. At the surface, hydrogen and sulfate ions are produced by oxidation of H₂S. The low pH water percolates downward and reacts with feldspar in the rocks to produce alunite, kaolinite, montmorillonite, and muscovite as hydrogen ion is consumed.     

Mineral Surface after Reaction with Aqueous Solution at High Temperatures and Pressures

This work presents new experimental results on surface chemistry of reacting minerals and interface kinetics between mineral and aqueous solutions. These experiments were carried out using a flow reactor (packed bed reactor) of an open system as well as a continuous stirred tank reactor, CSTR. The authors measured reaction rates of such minerals as zeolite, albite and carbonate (rhodochrosite, dolomite) in various solutions, and tested corresponding mineral surface by using SEM, XPS, SIMS, etc. This paper mainly presents the experimental results of zeolite dissolution in water and in low pH solutions at room temperature, and dolomite dissolution at elevated temperatures. The results show that the release rates of Si, Al and Na of zeolite are different in most cases. The incongruent dissolution of zeolite is related to surface chemical modifications. The Na, Al and Si release rates for dissolution of albite and zeolite in water and various solutions were measured as a function of temperature, flow veloci     

Hydrothermal carbonates in altered wall rocks at the Uwamuki Kuroko deposits, Japan

Magnesite, siderite and dolomite are characteristic alteration minerals occurring in Miocene hanging wall rocks of dacitic composition which host the Kuroko orebodies. These carbonates generally occur in a more stratigraphically upper horizon than chlorite alteration zone surrounding the orebodies. The Mg/(Mg+Fe) ratios of the carbonates decrease from the central alteration zone to marginal zone. The Mg/(Mg+Fe) ratios of carbonates and chlorite positively correlate. The δ¹⁸O and δ¹³C values of magnesite, siderite and dolomite positively correlate with each other and lie between the igneous and marine carbonate values. The petrographic, isotopic and fluid inclusion characteristics and thermochemical modelling calculations indicate that magnesite and dolomite formed in the central zone close to the orebodies due to the interaction of hydrothermal solutions with the biogenic marine carbonates. Calcite formed further from the orebodies from hydrothermal fluids which did not contain a biogenic marine carbon component. The compositional and textural relationships indicate that superimposed alterations (chlorite alteration and carbonate alteration) occurred in hanging wall rocks. The mode of occurrences and the Mg/(Mg+Fe) ratios of magnesite and dolomite occurring in hanging wallrocks are useful in the exploration for concealed volcanogenic massive sulfide-sulfate deposits. Received: 9 September 1997 / Accepted: 23 September 1997