Chemical evolution of seawater during the Phanerozoic: Implications from the record of marine evaporites

The chemical evolution of seawater during the Phanerozoic is still a matter of debate. We have assembled and critically analyzed the available data for the composition of fluid inclusions in marine halite and for the mineralogy of marine evaporites. The composition of fluid inclusions in primary marine halite reveals two major long-term cycles in the chemistry of seawater during the past 600 myr. The concentration of Mg²⁺, Ca²⁺, and SO₄²⁻ has varied quite dramatically. The Mg²⁺ concentration in seawater during most of the early Paleozoic and Jurassic to Cretaceous was as low as 30 to 40 mmol/kg H₂O; it reached maximum values ≥50 mmol/kg H₂O during the Late Neoproterozoic and Permian. The Ca²⁺ concentration in seawater during the Phanerozoic has reached maximum values two to three times greater than the concentration in seawater today (10.6 mmol/kg H₂O), whereas SO₄²⁻ concentrations may have been as low as 5 to 10 mmol/kg H₂O (a third to a fifth of the modern value) during the Jurassic and Early Paleozoic. The Mg²⁺/Ca²⁺ ratio in seawater ranged from 1 to 1.5 during the early to middle Paleozoic and Jurassic-Cretaceous to a near-modern value of 5.2 during the Late Neoproterozoic and Permian. This change in seawater Mg²⁺/Ca²⁺ ratio is consistent with the notion of alternating “calcite-aragonite seas” recorded in oölites and marine carbonate cements.Several models have been proposed to explain the chemical evolution of seawater. These have invoked significant changes in one or more of the major geochemical processes that control the composition of seawater. The pattern and magnitude of the variations in the composition of seawater proposed in this study are similar to those proposed elsewhere that suggest that seawater fluxes through midocean ridges have played a major role in the evolution of seawater during the past 600 myr. Two Phanerozoic supercycles of the Earth’s exogenic processes were recognized in the literature that are caused by mantle convection and plate activity. The composition of seawater has apparently undergone dramatic secular changes in phase with these supercycles and as a consequence of biological evolution. Analyses of fluid inclusions containing unevaporated seawater and a better understanding of the processes that affect the composition of seawater are needed to refine our understanding of the history of Phanerozoic seawater.     

Stoichiometric saturation tests of NaCl1−xBrx and KCl1−xBrx

Stoichiometric saturation is examined as a possible control on Br contents of halite and sylvite during precipitation from binary salt solutions of NaCl-NaBr and KCl-KBr, respectively. Experimental data at 25°C, assumed to represent Stoichiometric saturation, were used to predict mole fractions of NaBr in halite and KBr in sylvite in thermodynamic equilibrium with fluids as a function of aqueous activity ratios of Br⁻:Cl⁻. The predictions are based on the additional assumption that the aqueous activity product of the major salt component in the precipitated salt was independent of the trace Br content in the salt lattice. The extension of the predictions to diagenetic pressures and temperatures is discussed.The predicted equilibrium Br content of halite at initial halite saturation of evaporating seawater is in close agreement with that computed from the distribution coefficient of Lutz (1975), measured in slowgrowth single crystal experiments. Fluid recrystallization of halite and sylvite at near-surface temperatures is predicted to generally deplete the Br contents in the solids. Bulk Br contents in halite in cap-rock of Gulf Coast salt domes generally agree with those predicted by the recrystallization of halite in the presence of evaporative-concentrated seawater. At a constant solution composition, increasing temperature results in increasing the equilibrium Br content of halite, making less efficient Br depletion in halite by recrystallization.     

Chemical composition of seawater in Neoproterozoic: Results of fluid inclusion study of halite from Salt Range (Pakistan) and Amadeus Basin (Australia)

Data on chemical composition of brines in primary inclusions of marine halites and on mineralogy of marine evaporites and carbonates lead to the conclusion that during the Phanerozoic two long-term cycles of chemical composition of seawater existed. During each of those cycles, seawater dominantly a Na-K-Mg-Ca-Cl (Ca-rich) type changed to a Na-K-Mg-Cl-SO₄ (SO₄-rich) type. Recrystallised halite from the uppermost Neoproterozoic Salt Range Formation (ca. 545 Ma) in Pakistan, contains solitary inclusions indicating SO₄-rich brines. This supports the concept derived from the study on primary fluid inclusions from the Neoproterozoic Ara Formation of Oman; SO₄-rich seawater existed during latest Neoproterozoic time (ca. 545 Ma). In contrast, samples of recrystallised halite from the Bitter Springs Formation (840–830 Ma) in Australia contain inclusion brines that are entirely Ca-rich, indicating that basin brines and seawater were Ca-rich during deposition of central Australian evaporites. These combined data supported by the timing of aragonite and calcite seas suggest that during the Proterozoic, significant oscillations of the chemical composition of marine brines, and seawater, occurred, which are similar to those known to exist during the Phanerozoic. It is suggested that Ca-rich seawater dominated for a substantial period of time (more than 200 Ma), at 650 Ma, this was replaced by SO₄-rich seawater, finally returning to Ca-rich seawater at 530 Ma.     

四川盆地三叠纪古盐湖已达钾石盐析出阶段——来自石盐流体包裹体化学组成的约束

石盐的流体包裹体成分可提供古流体组成的物理化学信息,用以探查卤水组成变化及环境演化规律等。四川盆地位于上扬子地台,其中的早-中三叠纪沉积建造是中国海相找钾的有利层位之一。获取石盐沉积时期的卤水成分信息,是深刻认识四川盆地古海水蒸发浓缩程度的重要途径。文章利用激光剥蚀电感耦合等离子体质谱法,对采自川东地区长平3井嘉陵江组的石盐流体包裹体开展了化学组成分析,结果显示古卤水化学类型为Mg_SO4型;流体包裹体中的ρ(K~+)与现代海水浓缩到钾石盐析出阶段的ρ(K~+)基本一致,可能揭示了盆地三叠纪时期古卤水已达到钾石盐析出阶段,对四川盆地沉积环境演化及钾盐成矿规律研究等具有重要的理论意义。     

显生宙全球海水化学成分演化及其对蒸发岩沉积的约束

通过搜集显生宙以来不同地质时期内海相碳酸盐岩鲕粒及胶结物矿物成分、钾盐矿床矿物种类及组合特征、蒸发岩盆地中石盐流体包裹体成分,并利用这些资料与人工海水模拟实验得到的石盐中Br分配特征的对比,得出海水成分在5.5亿年以来的显生宙期间,经历了五个阶段:其中晚元古代至寒武纪早期、二叠纪早期至中生代早期、新生代早期至现今,这些时期的原始海水组成特征系数m(SO_4~(2-))+m(HCO_3~-)/2m(Ca~(2+)),为Na-Mg-K-SO_4-Cl型海水,此期间沉积的钾盐矿床的钾镁盐矿物主要为钾盐镁矾、无水钾镁矾、杂卤石、硫酸镁石等含MgSO_4矿物,海相鲕粒和碳酸盐胶结物矿物成分为文石;而寒武纪早期至石炭纪、中生代早期至新生代早期,原始海水组成特征系数m(Ca~(2+))m(SO_4~(2-))+m(HCO_3~-)/2,为Na-Mg-KCa-Cl型海水,此期间沉积的钾镁盐矿物主要为光卤石和钾石盐,甚至含有溢晶石,海相鲕粒和碳酸盐胶结物矿物成分为方解石。根据石盐流体包裹体成分计算得出:显生宙期间,海水K+含量大部分时间变化幅度较小,为9.3～11.5mmol/kg H_2O(除了石炭纪和晚元古代),平均为10.55mmol/kg H_2O。Mg~(2+)含量在早寒武世≥67mmol/kg H_2O、晚志留世至中泥盆世31～41mmol/kg H_2O、晚古生代≥48mmol/kg H22O、晚白垩世34mmol/kg H_2O和现代55.1mmol/kg H_2O。Ca~+含量在晚元古代至古生代早期≤11mmol/kg H_2O、古生代早期至石炭纪22～35mmol/kg H_2O、石炭纪至中生代早期≤17mmol/kg H_2O、中生代早期至新生代早期19～39mmol/kg H_2O及新生代早期至今7～21mmol/kg H_2O。SO_4~(2-)含量在晚元古代至古生代早期≥23mmol/kg H_2O、古生代早期至石炭纪5～17mmol/kg H_2O、石炭纪至中生代早期13～22mmol/kg H_2O、中生代早期至新生代早期5～19mmol/kg H_2O及新生代早期至今12～29.2mmol/kg H_2O。海水Ca~(2+)与SO_4~(2-)含量的相对变化是控制海相钾盐矿床钾镁盐矿物类型的基本因素。同时,利用以上数据计算得到的显生宙各时期海水[m(Mg~(2+))+m(SO_4~(2-))]/[m(K~+)+m(Ca~(2+))]的变化与各时期海相蒸发岩系石盐层底部的Br含量变化具有同步性,进一步验证了显生宙期间海水成分是不断变化的,是约束海相蒸发岩钾盐矿物类型的主要因素。海水成分变化的控制因素为洋中脊热液和陆地水,其中洋中脊热液起主要作用,而控制这些因素变化的根本原因为板块构造运动。     

Are secular variations in seawater chemistry reflected in the compositions of basinal brines?

It has been proposed that brines in Phanerozoic sedimentary basins inherited their chemistries and salinities from evaporated paleoseawaters during times when the world oceans were Ca-rich and SO₄-poor, such as the Silurian and Devonian. However, the compositions of typical Silurian and Devonian-hosted brines in the Illinois and Michigan basins show significant deviations from calculated Silurian seawater evaporation trends, reflecting instead, diagenetic control of compositions. In addition, brines in many basins show evidence for the dissolution of halite being an important source of salinity in addition to, or instead of, evaporated seawater. As long as there is halite present, generation of salinity could continue to occur long after the deposition of evaporites and the influx of evaporated seawater. Thus, even the concept of assigning an age to a basinal brine is problematic given the dynamics of fluid flow, mixing, and solute transport which can occur in sedimentary sequences.     

基于相化学研究老挝万象钾镁盐矿床形成的机制

老挝万象钾镁盐矿床是一个典型的海相碎屑盐缺硫酸盐型钾盐矿床, 该矿床形成于古近纪, 是古海水蒸发浓缩沉积形成。老挝万象钾镁盐矿床中缺乏硫酸盐和碳酸盐沉积物, 因此深入研究该矿床的形成机制很重要。本文研究探讨了该矿床形成时的古海水特点, 根据相化学, 分析成钾原始卤水的物理化学特性, 从矿体形成的化学基础来研究老挝钾镁盐矿床形成的机制。结果表明: 显生宙以来海水组分发生变化, 经海相非骨骼灰岩和钾盐蒸发岩矿物学研究, 发现这两种沉积岩长期以来连续变化, 在“文石海”是MgSO4型蒸发盐, 在“方解石海”是KCl型蒸发盐, 从白垩纪晚期、第三纪早期的底部石盐溴含量及矿物学特征表明, 此时处于“方解石海”, 古海水组分的特点是造成缺硫酸盐型钾盐矿床形成的物化基础; 通过NaCl-KCl-MgCl2-H2O和NaCl-KCl-MgCl2-CaCl2-H2O两个体系相图的分析认为, 当时所形成的成钾原始体系母液是高镁、低钾氯化物型的卤水, 在母液蒸发过程中, 由于原始海侵母液与残余高镁母液的掺杂作用, 致使结晶路线直接从氯化钠区到E点母液或光卤石与氯化钠共饱线上, 而没有通过氯化钠和氯化钾的共饱线, 因而在矿体中氯化钾相很少或几乎不存在, 由于外界CaCl2型水体的掺杂, 使成钾母液进入光卤石相区, 随着蒸发的进行, 最终形成溢晶石矿物。     

显生宙海水成分、碳酸盐沉积和生物演化系统研究进展

简述了显生宙海水成分演化的特征、识别标志和成因解释模型以及存在的问题和今后研究的方向.不同时期海水的成分的差异,特别是海水的x(Mg)/x(Ca)值,导致了文石海、方解石海时期的碳酸盐沉积和早期成岩作用均存在差异,甚至影响了盆地深部成岩流体的特征.显生宙海生生物的演替和盛衰,特别是简单生物(如钙藻和海绵)和高产率生物(如造礁生物和碳酸盐沉积物主要生产者),明显体现了海水的x(Mg)/x(Ca)值周期性变化对海生生物的影响.这种影响也同样体现在古生代末期的生物大绝灭及随后的生物复苏样式上,在生物更替事件研究中应引起重视.因此,生物与环境的协同演化研究必须从地球系统科学的角度展开.     

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.     

Dolomite Controls on Phanerozoic Seawater Chemistry

We investigate the potential role of dolomite as a long-term buffer on Phanerozoic seawater composition. Using a comprehensive model of Phanerozoic geochemical cycling, we show how variations in the formation rate of sedimentary marine dolomite have buffered seawater saturation state. The total inventory of inorganic carbon reflects the sum of fluxes derived from continental weathering, basalt-seawater exchange, alumino-silicate diagenesis (reverse weathering), and global deposition of calcium carbonate. Although these fluxes are approximately balanced, model results indicate that seawater saturation state is sensitive to the marine dolomite depositional flux. This conclusion is consistent with and constrained by independent proxy data for seawater ion ratios, paleo-atmospheric CO₂ concentrations, and paleo-pH data, and dolomite mass-age distribution through Phanerozoic time. Abundant research indicates that dolomite’s occurrence in marine sediments is sensitive to many factors: temperature, seawater composition, paleogeographic setting, continental organization, etc. Although the complexity of the process of dolomite formation prevents a complete understanding of the relative role of these factors, our model results clearly underscore the importance of this mineral in the chemical history of Phanerozoic seawater.     

An evaporated seawater origin for the ore-forming brines in unconformity-related uranium deposits (Athabasca Basin, Canada): Cl/Br and δCl analysis of fluid inclusions

Analyses of halogen concentration and stable chlorine isotope composition of fluid inclusions from hydrothermal quartz and carbonate veins spatially and temporally associated with giant unconformity-related uranium deposits from the Paleoproterozoic Athabasca Basin (Canada) were performed in order to determine the origin of chloride in the ore-forming brines. Microthermometric analyses show that samples contain variable amounts of a NaCl-rich brine (Cl concentration between 120,000 and 180,000 ppm) and a CaCl₂-rich brine (Cl concentration between 160,000 and 220,000 ppm). Molar Cl/Br ratios of fluid inclusion leachates range from ∼100 to ∼900, with most values between 150 and 350. Cl/Br ratios below 650 (seawater value) indicate that the high salinities were acquired by evaporation of seawater. Most δ³⁷Cl values are between −0.6‰ and 0‰ (seawater value) which is also compatible with a common evaporated seawater origin for both NaCl- and CaCl₂-rich brines.Slight discrepancies between the Cl concentration, Cl/Br, δ³⁷Cl data and seawater evaporation trends, indicate that the evaporated seawater underwent secondary minor modification of its composition by: (i) mixing with a minor amount of halite-dissolution brine or re-equilibration with halite during burial; (ii) dilution in a maximum of 30% of connate and/or formation waters during its migration towards the base of the Athabasca sandstones; (iii) leaching of chloride from biotites within basement rocks and (iv) water loss by hydration reactions in alteration haloes linked to uranium deposition.The chloride in uranium ore-forming brines of the Athabasca Basin has an unambiguous dominantly marine origin and has required large-scale seawater evaporation and evaporite deposition. Although the direct evidence for evaporative environments in the Athabasca Basin are lacking due to the erosion of ∼80% of the sedimentary pile, Cl/Br ratios and δ³⁷Cl values of brines have behaved conservatively at the basin scale and throughout basin history.     

An Review of the Strontium Isotopic Vomposition of Phanerozoic Seawater

Strontium isotopic evolution of the Phanerozoic seawater is an emerging research field of the material cycle in the Earth’s outer-spheres. It is greatly significant for the research of the environmental change on the Earth’s surface during the geological history. The researches of the strontium isotopic evolution of the Phanerozoic seawater have gone through three stages: The early stage, the accumulated stage, and the integrated stage. In the early stage, the primitive evaluation of the diagenetic alteration and the low precision of the analytical instruments resulted in most strontium isotope data without stratigraphic significance. Most researches were only at the initially exploratory stage. In the accumulated stage, the gradually mature evaluation of the diagenetic alteration and higher precision of the analytical instruments made ongoing progress in the researches, especially the establishment and development of the high-resolution strontium isotopic evolution curves of the Cenozoic seawater had spawned a new interdisciplinary branch: Strontium isotope stratigraphy. In the integrated stage, the accumulated high-quality strontium isotope data had been integrated into some strontium isotope database of Phanerozoic seawater. These databases are becoming one of the effective tools to solve the problems in the stratigraphy, petrology, ore deposit, hydrology, and other related applications. Currently, many problems still have not been satisfactorily resolved in the researches of the strontium isotopic evolution of the Phanerozoic seawater, such as the preservation differences of the original seawater information in a sample, the age of uncertainty of samples, lower dating accuracy of more ancient samples, the materials and stratigraphic questions of the Cambrian samples, trace rubidium contamination of samples, the isotope fractionation between ⁸⁶Sr and ⁸⁸Sr, the interlaboratory bias, the uncertainty of the data fitting, etc. These problems are the difficulties to possess more practicability and applicability of strontium isotope stratigraphy. Based on the summary of the research progress, we attempted to systematically summarize the stages and differences of the researches of strontium isotopic composition of Phanerozoic seawater at different periods. We wish this paper offer some perspective to the researches of strontium isotopic composition of Phanerozoic seawater in future.     

Evolution of saline waters and brines in the Benue-Trough,Nigeria

Hydrogeochemical assessment of 40 saline waters and brines from 20 locations within the lower (southern) and middle regions of the Benue-Trough, Nigeria are presented and discussed in terms of genesis of the primary salinity and subsequent hydrochemical evolution. The total dissolved ions range from 5263 to 88,800 mg/L and 5148 to 47,145 mg/L in the lower and middle region, respectively.The saline waters and brines are characteristically Na–Cl type enriched in Ca and Sr on the one hand and depleted in Mg and SO₄ on the other, relative to the seawater evaporation trend. Ionic ratios, Na–Cl–Br systematic and divalent cations suggest two likely sources of primary salinity: a fossil seawater source and dissolution of halite. However, water–rock interaction involving Mg uptake by clay minerals and possibly dolomitization during diagenesis appear to be responsible for further modification of the primary chemistry. A conceptualized hydrogeological/flow model for the brines is presented.     

Geochemistry of modern seawater and brines from salt pans: Main components and bromine distribution

Seawater at different stages of evaporation from the salt works of Seovlje near Portoro (Yugoslavia) was analyzed geochemically. The seawater there passes through 20 stages of concentration until the first halite crystallizes. All important parameters were determined at all stages: concentrations of Cl, SO₄, Na, K, Ca, Mg, and Br, temperature, pH, Eh, oxygen content and titration alkalinity. With increasing evaporation calcium carbonate crystallizes first followed by calcium sulphate as gypsum and after these halite. All three components crystallize from supersaturated solutions. The pH of the initial seawater is 8.32; it falls abruptly to 6.65 when the first calcium carbonate precipitates. Eh in the original seawater is +393 mv; negative values were found in the halite crystallization pans, which contain an anaerobic mud as a reducing agent. The oxygen content of the solution decreases parallel to the drop in Eh. In the pans in which NaCl crystallizes Eh is zero. Apparently the mud also adsorbs K, as can be inferred from a change in the Mg/K ratio.The bromine partition between crystallizing halite and the brine in the salt pans of Seovlje is discussed with regard to some genetic problems of marine salt deposits. In the conditions in the salt pans the bromine partition coefficient at the beginning of NaCl crystallization from seawater—expressed as b=wt.-% Br (mineral)/wt.-% Br (solution)—is 0.12 to 0.14 or—expressed as D=Br/Cl(mineral)/Br/Cl(solution)—0.030 to 0.034 at temperatures between 33° C and 42° C. The conclusion is that a Br content of about 60 to 75 ppm is to be expected for the first halite that crystallizes from evaporating seawater.     

海水化学演化对生物矿化的影响综述

显生宙非骨屑碳酸盐矿物经历了文石海和方解石海的交替,主要造礁生物和沉积物生产者的骨骼矿物与非骨屑碳酸盐矿物具有同步变化的趋势。这种长期的变化趋势可以用海水化学Mg/Ca摩尔比的变化来解释。流体包裹体、同位素和微量元素等证据也证实了海水化学在地质历史中经历过剧烈的变化。虽然生物诱导矿化和生物控制矿化的相对重要性一直存在争议,但古生物地层记录和人工海水养殖实验结果都表明,海水化学演化对生物矿化有重要的影响,体现在造礁生物群落的兴衰、生物起源时对骨骼矿物类型的选择以及微生物碳酸盐岩在地质历史中的分布等。这些为研究前寒武纪海水化学演化、古气候和古环境的重建、同位素地层对比以及碳酸盐的沉积和成岩等问题提供了新的思路。     

87Sr/86Sr in Precambrian carbonates as an index of crustal evolution

The Sr isotopic composition of ‘seawater’, as measured on carbonate rocks, shows a composite pattern during geologic history. All known Archaean data are compatible with contemporaneous upper mantle ⁸⁷Sr/⁸⁶Sr values. This is followed by a strong increase in the radiogenic component during the 2.5–2.1 b.y. period, a less pronounced increase during the remaining portion of the Proterozoic and a decrease during the Phanerozoic. The trend closely resembles the K₂O/Na₂O secular variations in composition of igneous and sedimentary rocks (Engelet al, Bull. Geol. Soc. Amer. 85, 843–858, 1974) and probably reflects the fractionation state of the contemporary crust. The data are compatible with recent suggestions of three major tectonic regimes during geologic history: greenstone belts during the Archaean, mobile belts during the Proterozoic and plate tectonics during the Phanerozoic. They also indicate that continental crust during the Archaean contributed only subordinate Sr into the meteoric cycle.     

钾盐矿床中Br的地球化学特征及研究进展

本文概述了Br的地球化学行为及其在钾盐矿床中的应用,重点论述了Br的分配系数和热力学模型的新发展。指出近年来用海相蒸发岩盐中的溴来评价显生宙海水组分变化行为,对于重新认识贫硫酸盐型的钾盐矿床有十分重要的意义。由于大洋中脊热液流体组分改变和海底扩张作用,使古海水组分发生变化,这种作用比碳酸盐白云石化或硫酸镁缺损使古海水组分发生变化更为重要。指出研究老挝贫硫酸盐型钾盐矿床对在我国兰坪一思茅盆地寻找钾盐矿床有重要的指导意义。     

Origin of Ore-Forming Fluids of Mississippi Valley-Type （MVT） Pb-Zn Deposits in Kangdian Area, China

Analyses of fluid-inclusion leachates from ore deposits show that Na/Br ratios are within the range of 75 - 358 and Cl/Br 67 - 394, respectively, and this variation trend coincides with the seawater evaporation trajectory on the basis of the Na/Br and Cl/Br ratios. The average Cl/Br and Na/Br ratios of mineralizing fluids are 185 and 173 respectively, which are very close to the ratios ( 120 and 233 ) of the residual evaporated seawater past the point of halite precipitation. It is suggested that the original mineralizing brine was derived from highly evapo-rated seawater with a high salinity. However, the inclusion fluids have absolute Na values of 69.9—2606.2 mmol kg^-1 and Cl values of 106.7 — 1995.5 mmol kg^-1. Most of the values are much less than those of seawater: Na, 485 mmol kg^-1 and Cl, 566 mmol kg^-1 , respectively; the salinity measured from fluid inclusions of the deposits ranges from 2.47 wt% to 15.78 wt% NaCl equiv. The mineralizing brine has been diluted. The δ ^18O and δD values of ore-forming fluids vary from -8.21‰ to 9.51‰ and from -40.3‰ to -94.3‰, respectively. The δD values of meteoric water in this region varied from - 80‰ to - 100‰ during the Jurassic. This evidenced that the ore-forming fluids are the mixture of seawater and meteoric water. Highly evaporated seawater was responsible for leaching and extracting Pb, Zn and Fe, and mixed with and diluted by descending meteoric water, which resulted in the formation of ores.     

海相钾盐矿床溶滤卤水找钾指标体系: 以川东北天星桥构造寒武系深部地下卤水为例

长期工作成果显示我国现阶段常用的找钾指标Br×103/Cl值偏低.创新性地应用"以古验古"的溶滤实验与地质统计法厘清了海相蒸发盐盆地找钾指标体系,充分考虑了不同地质年代海水成分的变化,也可克服"将今论古"应用于现代海水在等温等压条件下实验数据的不足.通过对世界上典型钾盐矿床的石盐、含钾石盐及钾盐(含光卤石)进行溶滤实验...     

Ediacaran seawater temperature: Evidence from inclusions of Sinian halite

Seawater temperatures throughout Earth's history have been suggested to illustrate a long-term cooling trend from nearly 70 °C at ～3500 Ma to around 20 °C at ～800 Ma. The terminal Neoproterozoic prior to the “Cambrian Explosion” is a key interval in evolutionary history, as complex multicellularity appeared with the advent of the Ediacara fauna. These organisms were likely the first that required higher levels of atmospheric and dissolved marine oxygen for their sustainability. It is known that most modern macroinvertebrates are intolerant of temperatures in excess of 45 °C. Perhaps more importantly, these high seawater temperatures limit the potential of dissolved oxygen, and therefore become an integral part of this evolutionary story. Previously, our understanding of seawater temperature during the terminal Neoproterozoic comes only from ¹⁸O/¹⁶O and ³⁰Si/²⁸Si ratios ascertained from a limited number of cherts. Isotopic ratio methods for assessing seawater temperatures are inherently indirect and have a wide range of oscillation. However, maximum homogenization temperatures (Th_max) of primary fluid inclusions in halite provide a direct means of assessing brine temperature, and have been shown to correlate well with average maximum air temperatures. The oldest halites date to the Neoproterozoic–lower Paleozoic (～700–500 Ma), and Ediacaran representatives can be found in Sichuan Province, China, which do preserve primary fluid inclusions for analysis via cooling nucleation methods. We utilized halite samples from the Changning-2 well, correlative to the Dengying Formation (551–542 Ma), to provide a direct assessment of terminal Neoproterozoic seawater temperature. Our measurements indicate that seawater temperatures where these halites formed are highly similar to tropical Phanerozoic seawater temperature estimates. From compiled paleotemperature data, the decline in seawater temperatures over the course of the Proterozoic, accompanied by the reduction of seawater salinity with the sequestration of salt in massive halite deposits in the Neoproterozoic, allowed the ocean system to accumulate more dissolved oxygen, and potentially paved the way for the evolutionary innovation of complex multicellularity.