Shale basins,sulfur-deficient ore brines and the formation of exhalative base metal deposits

The massive sulfide deposits of the Iberian Pyrite Belt are interbedded with felsic volcanic rocks and shale, and underlain by several thousand meters of siliciclastic sedimentary rocks known as the PQ Group. Isotope geochemistry and regional geology are both consistent with equilibration of the ore-forming fluids with the PQ Group, prior to ore deposition near the former seafloor. The average Cu:Zn:Pb ratio of the PQ Group rocks (ca. 26:55:19) is similar to the weighted average of all the massive sulfide orebodies combined (ca. 25:52:23).The genetic relationship between massive sulfide deposits and a siliciclastic sedimentary metal source is explained here by a thermodynamic model, proposing that mildly reducing redox conditions imposed by equilibration with the sedimentary rocks are most critical for the formation of an effective ore-forming fluid. Relatively metal-rich but organic-poor pyrite-bearing shale undergoing dewatering of saline pore fluids is an effective source for the generation of sulfur-deficient but relatively iron and base metal-rich brines. Thus, we propose that the giant deposits of the Iberian Pyrite Belt owe their existence not to exceptionally metal-enriched (e.g., magmatic) fluids, but to the existence of a fairly ordinary but large metal source in reactive siliciclastic sediments, combined with an underlying igneous heat source and a particularly efficient mechanism of sulfide precipitation by mixing with H₂S-rich fluids at or near the seafloor.Essentially similar mineral equilibria are imposed when saline fluids are buffered by typical continental basement rocks. Leaching of retrograde minerals and possibly residual salts from their magmatic or metamorphic prehistory is expected to generate similar, variably metal-rich but relatively sulfide-deficient fluids. Thus, the existence of mildly reducing rocks can be the dominant chemical control in the source of fluids generating many volcanogenic, Irish-type or sedex deposits, many of which are known to precipitate their metal load in response to biogenic sulfide addition at the ore deposition site.     

Chemical composition of natural waters and brines as a result of hydrogeochemical processes in water-rock-gas systems

Thermodynamic computer modeling was carried out to evaluate the formation of the chemical composition of main geochemical types of groundwaters. An explanation was proposed for the geochemical evolution of underground saline waters and brines along the calcic and sodic trends, the inversion of groundwater in the deep horizons of sedimentation structures, and the geochemical diversity of CO₂-rich waters in crystalline rocks. The occurrence of hydrogeochemical processes is controlled by the physicochemical conditions of the state of the water-rock-gas system. The following parameters (boundary conditions) are critical in natural hydrogeologic environments: the mass ratio of interacting rock and water (R/W), the openness (closeness) of hydrogeochemical systems with respect to CO₂ and O₂, the chemical and mineral composition of rocks, and temperature-pressure conditions. The estimation of boundary conditions showed the following.

1. The petrochemical type of rock affects the composition of the aqueous phase through the dissolution rates of minerals, especially volatile-bearing ones. A decrease in water exchange and an increase in R/W (10^?6??10²) are accompanied by an increase in the salinity of the aqueous phase and an increase in the fraction of Cl, Na, and Ca (in a closed system) or HCO₃, Cl, and Na (in a system open to CO₂).
2. The composition of the aqueous phase of water-rock systems is most strongly affected by the abundance in the rock of extractable Cl and reactive organic matter, which controls the geochemical type of the aqueous phase and its position in the Hardie-Eugster diagram.
3. The composition of the aqueous phase is shifted into the calcic field of the Hardie-Eugster diagram at the closure of the water-rock system and into the carbonate field at the opening of the water-rock system to CO₂. Waters showing pH ?? 8.5 are formed in feldspathic rocks with low contents of extractable volatiles. Alkaline waters with pH > 9 are formed in water-rock systems (a) under the influence of organic matter and (b) by the evaporative concentration waters under surface conditions.
4. The higher the degree of seawater concentration and the lower the R/W value, the more significant the effect of seawater composition on the aqueous phase chemistry of the water-rock system. With increasing degree of seawater concentration, the composition of the aqueous phase changes in the sequence Cl-SO₄-Na-Mg- ?? Cl-SO₄-Mg-Na?? Cl-Mg (at low R/W) and Cl-Na ?? Cl-Na-Mg (at high R/W). The influence of the petrochemical type of rock and CO₂ partial pressure, on the geochemical type of the aqueous phase in the seawater-rock system is more significant at high R/W.
5. A temperature increase shifts the acid-base state of the aqueous phase into the alkaline region and its redox state into the reducing region.

     

Basinal brines and groundwaters as possible metal carriers in the formation of sandstone-hosted lead-zinc deposits

Features of the two best-documented worldclass sandstone-hosted Pb-Zn deposits (Laisvall, Sweden; Yava, Nova Scotia, Canada) and a few similar but smaller deposits (SE Missouri, Quebec Appalachians) are compared with the purpose of contributing to the debate on the problem of the aqueous medium of metal transport: basinal brines or groundwaters? For the dolostone-sandstone-hosted deposits in SE Missouri, it is concluded that basinal brines formed this medium in both host rocks. The paleotopographic control of these Missouri deposits is pronounced and leads to the conclusion that such control is insufficient evidence to establish the groundwater hypothesis for the Yava deposit. In the Quebec Appalachian deposits, basinal brines, expelled tectonically, were the most likely metal carriers; these deposits constitute an ore type that differs from other known sandstone-hosted lead deposits.     

地下咸水中Ca~(2+)和Mg~(2+)对CO_2溶解度的影响

获得CO2在地下咸水中的溶解度是CO2地质储存研究中亟待解决的问题,然而不同离子对CO2溶解度的影响却鲜有文献提及。为了填补实验数据的空缺,本研究设计了一套高压条件下CO2溶解度测量装置,克服了传统高压釜取样不便和实验重现性差的缺点;通过测定纯水中CO2的溶解度验证了实验装置和方法的精准性;测定了地质埋存条件下0.1 mol/L、0.2 mol/L和0.5 mol/L Ca Cl2、Mg Cl2溶液中CO2的溶解度。与文献结果不同,实验发现Ca2+对超临界CO2溶解度的影响小于Mg2+,并且CO2在两种溶液中的溶解度差异会受到温度和压力的影响。在本实验范围内,不同离子溶液中溶解度的最大差别高达18.53%,而几乎所有CO2溶解度模型文献都没有提及此变化。最后对溶解度随温度、压力以及离子种类变化的现象进行了理论分析。     

The role of brines in high-temperature metamorphism and granitization

The paper discusses petrological effects related to interaction between rocks and concentrated aqueous salt fluids (brines) at lower crustal metamorphism. These effects arise mainly from the low H₂O activity typical of brines, while preserving and even increasing transport properties relative to pure H₂O or H₂O–nonpolar gas fluids. The paper presents thermodynamic properties of the halogen-bearing end members of the biotite solid solution based on experimental data, and examples illustrating how they can be employed to calculate the activities (concentrations) of alkali halides in the fluid. Action of brines significantly changes conventional views on the solubility of several minerals and on the distribution of elements (including trace elements) between minerals, melts, and fluids. The specific role of brines is also in bringing to interaction zones not only water but also alkali metals and Ca, which results in numerous metasomatic net-transfer reactions involving mafic minerals and/or exchange reactions with feldspars that produce new mineral assemblages with lower melting temperature, i.e., cause granitization of rocks as defined by D.S. Korzhinskii. Brines also exert fine “tuning” of metasomatic and melting processes: even at equal pressure, temperature, and water activity values metasomatism may or may not trigger melting depending on the Na/K/Ca ratio in the fluid phase.     

天然与风干状态下冷生亚黏土的崩解形态特征

土的崩解形态是描述土的崩解过程及探讨其崩解机理重要的必要条件之一,选取了一种高孔隙率、粉黏粒含量较高,且不具有湿陷性的原状冷生轻质亚黏土作为研究对象,对其天然含水量及风干含水量状态下的土样品进行崩解试验. 结果表明：天然状态的土样呈块状崩解,而风干状态下的呈鳞片状崩解,且鳞片状崩解的强度及平均速率都大于块状崩解;块状崩解的速率随时间变化较为缓和,而鳞片状崩解的速率随时间变化起伏较大. 崩解形态与崩解速率有着紧密的对应关系,与崩解形态相对比,发现崩解速率降低的过程是水侵入土样,且土样中空气压力增大的过程,而速率上升的过程则是土样崩解的过程.     

Incipient charnockites from southern India:The role of brines

Southern India and Sri-Lanka are the places where "incipient charnockites",i.e.the local transformation of amphibolite-facies gneisses into orthopyroxene-bearing,igneous looking charnockites,have been discovered in the early sixties.The fact that some incipient charnockites occur along a network of brittle fractures,together with CO_2 remnants preserved in mineral inclusions,had called for the role of fluids during charnockite alteration.The present work presents new observations on fluid inclusions and microtextures of incipient charnockites from type localities in southern India.In addition to CO_2-rich fluid inclusions in quartz and feldspar,all of the occurrences have disrupted remnants of concentrated aqueous alkali chloride solutions.CO_2 inclusions are more abundant in paragneiss(Kerala)than in orthogneiss(Karnataka/Tamil Nadu).The finding of disrupted brine inclusions in the Kabbal charnockite is a key link between closely associated massive charnockites and Closepet Granite,both of which also share the brine remnants.All of the occurrences studied here have feldspar or feldspar-quartz microvein networks along grain boundaries of recrystallized quartz,feldspar and orthopyroxene.These metasomatic veins again indicate the action of alkali-exchanging fluids(i.e.,saline solutions).Feldspar microveins,which have been found in most "massive" charnockites,along with the CO_2-rich fluid inclusions,suggest a commonality of incipient charnockite and massive charnockite,both types differing in intensity of interaction with metasomatizing pore fluids.     

The use of bromide and chloride mass ratios to differentiate salt-dissolution and formation brines in shallow groundwaters of the Western Canadian Sedimentary Basin

In the Western Canadian Sedimentary Basin, the petroleum industry handles two geochemically distinctive brines that are traceable in the environment: formation brines extracted along with hydrocarbons from the basin, and salt-dissolution brines, produced by dissolving deep halite formations to create caverns for petroleum product storage. The concentrations of the conservative ions chloride (Cl) and bromide (Br) in many formation brines plot closely to the seawater evaporation trajectory of previous studies. These brines contain Cl/Br mass ratios of around 300, while salt-dissolution brines are relatively Br depleted, having Cl/Br mass ratios in excess of 20,000. An oilfield site in central Alberta had experienced nearby releases of both salt-dissolution and formation brines. Geochemical mixing trends were defined by theoretically mixing samples of local salt-dissolution and formation brine sources with background shallow groundwater. Most site monitoring wells and local surface water samples plotted directly on a salt-dissolution brine dilution trend, while results from four monitoring wells, all located directly downgradient of formation brine spills, suggested the mixing of formation brines into shallow groundwater. This work indicates that there is a large-scale salt-dissolution brine plume beneath the site and reinforces the use of Cl and Br concentrations and mass ratios as environmental tracers.     

The role of dense brines in the formation of vent-distal sedimentary-exhalative (SEDEX) lead–zinc deposits: field and laboratory evidence

A majority of the world's sediment-hosted exhalative (SEDEX) lead-zinc deposits are vent-distal. They are not underlain by a discordant alteration zone or stockwork vent complex that would indicate the path by which ore fluids reached the seafloor. The absence of a vent complex, together with sulfide mineral replacement of host rock mineral assemblages has led several investigators to suggest that, in spite of the well-layered nature of these deposits, mineralization was formed by sub-seafloor lateral migration of ore fluids along permeable strata. Field observations, supported by simple laboratory experiments, however, suggest an alternative process for characterizing the genesis of vent-distal SEDEX deposits. Cool, saline brines (e.g., ~120 °C and >15 wt% NaCl equiv.) are denser than seawater and, upon discharging into the sea, would flow away from the discharge vent as bottom-hugging fluids, similar to the behavior of turbidity currents. Their high densities and velocities prevent them from mixing with overlying seawater, thereby precluding significant cooling and dilution of the ore fluid. Upon coming to rest in a seafloor depression, the addition of H₂S and/or dilution of the ore fluids to lower salinities result in the eventual precipitation of a vent-distal SEDEX deposit. Furthermore, the dense ore-forming fluid can sink into permeable sediments beneath the brine pool by displacing less dense pore water. The ore fluids are thus capable of effectively overprinting and/or replacing pre-existing minerals in the consolidating sediment pile.     

The tempo-spatial characteristics and forming mechanism of Lithium-rich brines in China

With the technological development of exploitation and separation, the primary sources of lithium have gradually changed from ore to brine, which has become the main raw material, accounting for more than 80% of the total production. Resources of lithium-bearing brine are abundant in China. This paper has summarized the spatial and temporal distribution, characteristics, and formation mechanism of the lithium-rich brine in China, aiming to provide a comprehensive set of guidelines for future lithium exploitation from brines. Lithium-rich brines usually exist in modern saline lakes and deep underground sedimentary rocks as subsurface brines. The metallogenic epoch of China’s lithium-rich brine spans from the Triassic to the Quaternary, and these brines exhibit obvious regional distribution characteristics. Modern lithium-rich saline lakes are predominately located in the Qinghai-Tibet Plateau. In comparison, the subsurface lithium-rich brines are mainly distributed in the sedimentary basins of Sichuan, Hubei, Jiangxi provinces and so on in south Block of China, and some are in the western part of the Qaidam Basin in Qinghai province in northwestern China. Lithium-rich saline lakes are belonging to chloride-enriched, sulfate-enriched, and carbonate-enriched, while the deep lithium-rich brines are mainly chloride-enriched in classification. On the whole, the value of Mg/Li in deep brine is generally lower than that of brine in saline lakes. The genesis of lithium-rich brines in China is not uniform, generally there are two processes, which are respectively suitable for salt lakes and deep brine.     

Trace-metal content of Mississippi oil field brines

Lead-and zinc-rich oil field brines from lowermost Cretaceous formations in central Mississippi locally contain geochemically significant levels of trace metals that are found in several types of sediment-hosted metallic mineral deposits, providing additional support for the genetic link between sedimentary formation waters and these deposits. Copper content of brine samples from Lower Cretaceous formations ranges from < 0.02 mg 1⁻¹ to 0.37 mg 1⁻¹, and silver was detected in 2 samples with a maximum value of 0.021 mg 1⁻¹. Cobalt values range from <0.04 mg 1⁻¹ to 0.22 mg 1⁻¹, and molybdenum is present in the range of <0.03 mg 1⁻¹ to 0.05 mg 1⁻¹. Gold, platinum, and palladium were not found at levels above their respective lower detection limits of 0.0001 mg 1⁻¹, 0.003 mg 1⁻¹, and 0.002 mg 1⁻¹ for the graphite furnace AA procedure used. Comparison of the results from this study to recent published studies of trace-metal solubilities in chloride-rich hydrothermal solutions suggests that the brines are approximately saturated with respect to Pb, Zn and Fe, and apparently are undersaturated with respect to Au, Pt, Pd, Sb, Co and probably Ag. The composite effects of the reduced sulfur content and physicochemical characteristics of the brines (i.e., salinity, temperature, redox state and pH), along with formation metal sources and brine migration history, apparently control the observed present-day concentrations of trace metals in Mississippi oil field brines.     

Calcite dissolution kinetics in Na-Ca-Mg-Cl brines

Sedimentary basins can contain close to 20% by volume of pore fluids commonly classified as brines. These fluids can become undersaturated with respect to calcite as a result of migration, dispersive mixing, or anthropogenic injection of CO₂. This study measured calcite dissolution rates in geologically relevant Na-Ca-Mg-Cl synthetic brines (50-200 g L⁻¹ TDS). The dissolution rate dependency on brine composition, pCO₂ (0.1-1 bar), and temperature (25.0-82.5 °C) was modeled using the empirical rate equation

R=k(1-Ω)ⁿ     

A possible mechanism for natural graphite formation

By extrapolating the Arrhenius plots for carbonization and experimental thermal progressive graphitization, it is shown that carbonization can go to completion in nature (ΔH ≈ 65 kcal/mole), whereas progressive graphitization is thermodynamically improbable (ΔH ≈ 260 kcal/mole). The mechanism of formation of natural graphite has thus to be determined. Since the geothermal gradient is not strong enough for producing graphite, the existence of shear stresses has to be taken into account. Metamorphism and tectonics create suitable conditions for this transformation. Series of samples of increasing rank from anthracites to metaanthracites, semigraphite and graphite (some of them from the same parent rocks) were compared with carbon, heat-treated experimentally under pressure (5 kbar). Anthracites are microporous materials. Their pores are flattened parallel to the bedding by a pressure effect which is responsible for a long-range statistical preferred orientation. They are anisotropic in texture but only biperiodically crystallized (turbostratic). Metaanthracites differ from anthracites only by an increasing coalescence between adjacent pores. They are thus either mesoporous or even macroporous. They are still turbostratic. Semi-graphites are suddenly obtained as a new phase by an increase in temperature, pressure and shear stresses. They are formed by single macropores, i.e. hollow distorted polyhedral shells. They are partially graphitized. Graphite is suddenly produced by a second phase change also due to an increase in temperature, pressure and shear stresses. The lamellar shape represents the limit of a flattened macropore.     

Modeling acid-gas generation from boiling chloride brines

Background  

This study investigates the generation of HCl and other acid gases from boiling calcium chloride dominated waters at atmospheric pressure, primarily using numerical modeling. The main focus of this investigation relates to the long-term geologic disposal of nuclear waste at Yucca Mountain, Nevada, where pore waters around waste-emplacement tunnels are expected to undergo boiling and evaporative concentration as a result of the heat released by spent nuclear fuel. Processes that are modeled include boiling of highly concentrated solutions, gas transport, and gas condensation accompanied by the dissociation of acid gases, causing low-pH condensate.     

The evolution of marine evaporitic brines in inland basins: The Jordan-Dead Sea Rift valley

Marine-evaporitic brines frequently display Na, Cl and Br concentrations that significantly deviate from seawater evaporation paths, yielding markedly conflicting degrees of evaporation calculated for a specific brine. Here we present 493 new and 33 previously reported analyses of Ca-chloridic waters of Neogene age from the Dead Sea Rift (DSR) valley to explain such offsets. The DSR brines plot along an almost perfect mixing line (R² = 0.990) on a Br/Cl-Na/Cl diagram, extending between two end members A and B. Points A and B are located at Na/Cl = 0.804 and Br/Cl = 0.00193, and at Na/Cl = 0.00773 and Br/Cl = 0.0155, respectively, within the halite and bischofite stability fields.Brines A and B originated in a dual-mode evaporation basin. Brine A formed under the classic lagoon scenario (mode A), with seawater inflow and brine outflow at steady state. Occasional drops in water level, imposed by climatic or tectonic causes, resulted in outflow cutoff and in rapid concentration buildup. The second mode (B) initiated upon equilibration of the activity of water in the brine with the overlying relative humidity, resulting in composition and salinity approaching that of brine B, sustaining it until the next reversal to mode A.Thick evaporite deposits inhibited infiltration of brines A and B into the subsurface terrain, a process that was enabled only when the brine reached the permeable carbonate rock rim and border faults of the basin. Hence, brines that formed during the relatively short shifts from mode A to mode B could not penetrate into the deep subsurface, and bittern minerals that were formed during the frequent mode shifts were dissolved and flushed out into the sea upon the next resumption of outflow.The proposed model accounts for the deviations of brines from the marine evaporitic evolution curve by brine mixing, rather than due to a change in ocean chemistry. It also explains the absence of bittern minerals in the thick halite and gypsum/anhydrite succession, and the compositional gap between the widely different end member hypersaline fluids. This model applies directly to the studied DSR brines and evaporites, but it may be relevant to other inland evaporitic basins.     

The role of sedimentary and tectonic brines in the Damara Orogen, Namibia

Along the southern margin of the Upper Proterozoic Damara Orogen, Namibia, an accumulation of extraordinarily large megacrystalline quartz-dolomite bodies occur. They were emplaced in tectonically controlled positions during an early deformational phase of the Damara Orogeny, where hot nappes were thrust over a fluvial-lacustrine and evaporitic metaplaya sequence (Kamtsas and Duruchaus Formations) which was deposited on the faulted EW-trending continental margin of the Kalahari craton. Individual occurrences of the quartz-dolomite bodies often cover several hundred square meters. Characteristic for the quartz-dolomite bodies is zoning with an outer shell of giant milky quartz crystals, some more than 15 m long along the c-axis, tightly intergrown or twinned (Brazilian twins) with a perfect cleavage parallel to the positive rhombohedral faces {1011}; there is an inner shell of crystalline dolomite and a central pipe of dolomitic breccia. Based on fluid inclusions studies the formation fluids of quartz-dolomite bodies can be related to the mobilization of interstitial fluids and to dehydration and leaching of evaporitic hydrate minerals of the metaplaya sequence. The fluids are characterized by extremely high salinities of up to 68 wt % total salt content. Minimum temperatures of formation, as determined in fluid inclusion studies, ranged from 150 to 250°C. At a later stage CO₂ derived from decarbonatization reactions was dissolved in the fluids. Changes in pressure and temperature led to effervescence and the formation of a quartz stockwork in the surrounding country rock. During the main phase of the progressive Damara Orogeny, the southward advancing accretionary nappe pile of the Khomas trough drove ahead large amounts of tectonometamorphic fluids, characterized by intermediate salinity and high CO₂ contents. When these fluids met with the previously established hypersaline fluid system, large amounts of CO₂ were released due to the mixing of the two fluids; if there is no mixing, each fluid then maintains its salinity and there is no CO₂ degassing. The CO₂ from this mixing is now present as secondary, high-density inclusions not only in the quartz-dolomite bodies but also in the surrounding country rock. Pressure estimations indicate at least 100–600 MPa as a minimum pressure of formation for these inclusions. The remaining aqueous fluid phase has produced local alterations and Cu, Pb, and Au mineralization.