Paleotemperatures from fluid inclusions in halite: method verification and a 100,000 year paleotemperature record, Death Valley, CA

Maximum homogenization temperatures of fluid inclusions (Th_max) in halite (laboratory-grown crystals and modern samples, Death Valley, CA) match maximum brine temperatures during halite precipitation. Maximum brine temperatures during halite precipitation in Death Valley, late April, 1993 (34.4°C) agree with Th_max (34°C) and correlate well with average maximum air temperatures in April (31.3°C) and May (37.6°C). Th_max may be used for paleoclimate interpretations based on the close relationship between saline lake temperatures and average air temperatures from modern settings. Lower homogenization temperatures, demonstrably below the temperatures at which halite grew, are interpreted to reflect collapse of some fluid inclusion walls due to the pressure difference between the inside and outside of inclusions. By only using Th_max, the problems of anomalously low homogenization temperatures due to possible collapse of fluid inclusions are avoided. Halite samples from 30 stratigraphic intervals, 90 to 0 m (100 to 0 ka), Core DV93-1, Death Valley, CA, were used to measure homogenization temperatures of fluid inclusions. Virtually all homogenization temperatures from Core DV93-1 are below the modern Th_max of 34°C (halite precipitation late April, 1993). Lacustrine halites, deposited in a perennial saline lake 35 to 10 ka, have Th_max between 19°C and 30°C, which suggests brine temperatures approximately 4°C to 15°C below modern late April values. Ephemeral saline lake halites precipitated 60 to 35 ka have Th_max between 23°C and 28°C, 6 to 11°C below modern values. The highest Th_max value in the 100 ka record (up to 35°C) is from a halite sample formed approximately 100 ka in a climate regime somewhat colder than the modern.     

古盐湖卤水温度对钾盐沉积的控制作用探讨

古盐湖卤水的温度对钾盐沉积的控制作用的定量研究是钾盐成矿机理分析的重点和难点。本文分析和测试陕北盐盆奥陶系马家沟组、四川盆地三叠系嘉陵江组、云南兰坪-思茅盆地白垩系及老挝沙空那空盆地白垩系等八个含盐系的石盐岩中的流体包裹体,并利用均一温度计算了古盐湖的蒸发速率。若以老挝白垩纪时盐湖的蒸发速率为标准值100,陕北奥陶纪、四川三叠纪、云南白垩纪的蒸发速率标准值分别为54、68和90,而目前在老挝和云南白垩系都找到了一定规模的钾盐矿,因此高温(气温及水温)是盐湖成钾的有利条件,在卤水演化成钾的过程中可以起到重要的"催化"作用。     

Precipitation of dolomite using sulphate-reducing bacteria from the Coorong Region, South Australia: significance and implications

Dolomite was successfully precipitated in culture experiments that simulated microbiogeochemical conditions prevailing during late stages of evaporation in ephemeral, hypersaline dolomitic lakes of the Coorong region, South Australia. Analyses of lake- and pore-water samples document rapid geochemical changes with time and depth in both dolomitic and non-dolomitic lakes. Extremely high sulphate and magnesium ion concentrations in lake waters decline rapidly with depth in pore waters throughout the sulphate-reduction zone, whereas carbonate concentrations in pore waters reach levels up to 100 times those of normal sea water. Ultimately, sulphate is totally consumed and no solid sulphate is recorded in the dolomitic lake sediments. ‘Most probable number’ calculations of lake sediment samples record the presence of large populations of sulphate-reducing bacteria, whereas sulphur-isotope analyses of lake-water samples indicate microbial fractionation in all the lakes studied. Viable populations of microbes from the lake sediments were cultured in anoxic conditions in the laboratory. Samples were then injected into vials containing sterilized clastic or carbonate grains, or glass beads, immersed in a solution that simulated the lake water. Falls in the levels of sulphate and rising pH in positive vials were interpreted as indicating active bacterial sulphate reduction accompanied by increased concentrations of carbonate. Within 2 months, sub-spherical, sub-micron-size crystals of dolomite identical to those of lake sediments were precipitated. It is concluded that bacterial sulphate reduction overcomes kinetic constraints on dolomite formation by removing sulphate and releasing magnesium and calcium ions from neutral ion pairs, and by generating elevated carbonate concentrations, in a hypersaline, strongly electrolytic solution. The results demonstrate that bacterial sulphate reduction controls dolomite precipitation in both the laboratory experiments and lake sediments. It is proposed that dolomite formation, through bacterial sulphate reduction, provides a process analogue applicable to thick platformal dolostones of the past, where benthic microbial communities were the sole or dominant colonizers of shallow marine environments.     

察尔汗盐湖石盐的流质包裹体氢氧稳定同位素分析及其地球化学意义

本文是在建立了盐酸胍法制备样品用于氧同位素分析方法研究的基础上,测定了察尔汗湖区各类天然水及ZK88-01占孔岩心的原生石盐流质包裹体氢氧稳定同位素组成。该方法适用于高盐度卤水微量δ18O分析,具有成本低、操作简便和定量转化的优点,值得在国内推广。 根据原生石盐包体水δD、δ18O的分布特征,论述了察尔汗盐湖距今5万年来湖水的演化历程。划分出三种不同成盐环境下的演化期,各期中古湖水体具有波动的继承性,各期间可能存在成盐环境的突变.根据天然水δD、δ18O关系初步获得该区蒸发线为:δD=2.5δ18O-45.3;证实了剖面上部淤泥水与达布逊湖水下渗有关;下部明显地有侧向水补给.     

Features of acid–saline systems of Southern Australia

The discovery of layered, SO₄-rich sediments on the Meridiani Planum on Mars has focused attention on understanding the formation of acid–saline lakes. Many salt lakes have formed in southern Australia where regional groundwaters are characterized by acidity and high salinity and show features that might be expected in the Meridiani sediments. Many (but not all) of the acid–saline Australian groundwaters are found where underlying Tertiary sediments are sulfide-rich. When waters from the formations come to the surface or interact with oxidised meteoric water, acid groundwaters result. In this paper examples of such waters around Lake Tyrrell, Victoria, and Lake Dey-Dey, South Australia, are reviewed. The acid–saline groundwaters typically have dissolved solids of 30–60 g/L and pH commonly <4.5. Many contain high concentrations of Fe and other metals, leached from local sediments. The combination of acidity and salinity also releases Ra. Around salt-lakes, these acidic waters often emerge at the surface in marginal spring zones where the low density (ρ ∼ 1.04) regional water flows out over the denser (ρ ∼ 1.16) lake brines. In the spring zones examined, large amounts of Fe are commonly precipitated. In a few places minerals of the alunite-jarosite family are formed which can trap many other metals, including Ra. The studied groundwater systems were discovered by U exploration programs following up radiometric anomalies related to this Ra. Evaporation concentrates the lesser soluble salts (gypsum and some halite) on the surface of the lakes. The lake brines contain most of the more soluble salts and form a column within the porous sediments which is held in place by hydrostatic forces around the salt-lake. These brines are near-neutral in pH.     

Ancient Microorganisms and Carotenoids Preserved in Fluid Inclusions in Halite from Chaka Salt Lake,Western China: Evidence from Micro-observation and in situ Raman Spectroscopy

Trapped ancient microorganisms in halite fluid inclusions are of special interest to the understanding of biology and ecology in salt lake systems.With the integration of petrologic,microthermometric,and Raman spectroscopic analyses,this study utilizes fluid inclusions from Chaka Salt Lake,eastern Qaidam Basin,NW China,to assess the possibility of microorganism-trapping by fluid inclusions.Here,we report that the solid phase of some primary fluid inclusions contains carotenoids,which is interpreted as evidence of Dunaliella algae,and that the coexisting liquid phase comprises SO_4~(2-).The homogenization temperatures of single-phase primary fluid inclusions indicate that the precipitation temperature of the Holocene halite in Chaka Salt Lake ranges from 13.5°C to 36.4°C.This suggests that fluid inclusions in halite are a good medium for trapping and preserving ancient microorganisms and organic matter in salt lakes,and that Raman spectroscopy has good potential to identify halophilic archaea.     

塔西南坳陷中新生代蒸发岩沉积初探

通过资料搜集、蒸发岩野外露头地质调查、石盐岩沉积特征分析及盐类矿物学研究,对塔里木盆地塔西南坳陷中新生代蒸发岩的分布、层位、盐类矿物组合、成因进行了初步探讨。塔西南坳陷石盐岩沉积呈透镜体状,主要沿西昆仑山前分布,常含有褐红色、灰绿色泥砾,泥砾岩性与吐依洛克组下段岩性一致,推测应为吐依洛克组沉积晚期海退期成盐,其层位应归属于吐依洛克组上段。石盐岩透镜体在横向分布上不连续,反映了当时塔西南坳陷内部可能存在多个古盐湖次级凹地,其在干旱气候条件下经浓缩蒸发成盐。蒸发岩矿物除石盐、石膏外,还见有杂卤石、钙芒硝等,其中杂卤石可能为后期富钾卤水交代原生石膏的产物,而乌泊1井石盐表面大量的次生钙芒硝可能为盐湖后期石盐析出阶段含钙地下水缓慢持续补给盐湖的产物。     

Evaporites and siliciclastics of the Permian Nippewalla Group of Kansas, USA: a case for non-marine deposition in saline lakes and saline pans

The mid‐Permian Nippewalla Group of Kansas consists of bedded evaporites, red‐bed siliciclastics and grey siliciclastics deposited in a non‐marine environment. Lithologies and sedimentary features indicate lacustrine and aeolian deposition, subaerial exposure and palaeosol formation. Grey siliciclastic mudstones characterized by planar and convolute laminations, ostracods, peloids and plant material represent a freshwater‐brackish perennial lake facies. Bedded anhydrites containing gypsum‐crystal pseudomorphs, clastic anhydrite grains and grey mud drapes and partings suggest deposition in saline lakes. Bedded halites consist of chevron and cumulate crystals, dissolution surfaces and pipes and mudcracked microcrystalline salt crusts, which were deposited in saline pans dominated by flooding, evaporative concentration and desiccation. Chaotic halite, composed of red‐bed mudstone and siltstone with displacive halite crystals, formed in saline mudflats. Red‐bed mudstone and siltstone with little or no displacive halite, but with abundant cracking, root and plant features, suggest deposition in a dry mudflat. Red‐bed sandstone, composed of well‐sorted, well‐rounded quartz grains cemented with halite, indicate aeolian and rare shallow‐water deposition. Most deposition took place in halite‐dominated ephemeral saline lakes surrounded by saline and dry mudflats, sandflats and sand dunes. Evaporation, desiccation, flooding and wind played significant roles in this environment. The Nippewalla Group siliciclastics and evaporites represent an evolution from a perennial lacustrine system to a non‐marine, acidic saline pan system in the mid‐continent of North America. The problem of distinguishing between ancient marine and non‐marine evaporites, as well as recognizing those evaporites deposited in acid settings, with detailed field, core and petrographical study of both evaporite deposits and associated sedimentary rocks has successfully been addressed. In addition, interpretations of mid‐Permian palaeoclimate data in the form of short‐term air temperature proxies within longer‐term wet–dry trends have been made. These data provide a new palaeogeographic and palaeoclimatic model for the mid‐Permian of western Pangaea.     

Thermochemical sulphate reduction in the Upper Devonian Cairn Formation of the Fairholme carbonate complex (South-West Alberta, Canadian Rockies): evidence from fluid inclusions and isotopic data

The Fairholme carbonate complex is part of the extensively dolomitized Upper Devonian carbonate reefs in west-central Alberta. The studied formations contain moulds (up to 10 cm in diameter), which are filled partially with (saddle) dolomite, quartz and calcite cements. These cements precipitated from a mixture of brines that acquired high salinity by dissolution of halite and brines derived from evaporated sea water. The fluids were warm (homogenization temperature of primary fluid inclusions of 76 to 200 °C) and saline (20 to 25 wt% NaCl equivalent) and testify to thermochemical sulphate reduction processes. The latter is deduced from S in solid inclusions, CO₂ and H₂S in volatile-rich aqueous inclusions and depleted δ¹³C values down to −26‰ Vienna Pee Dee Belemnite. High ⁸⁷Sr/⁸⁶Sr values (0·7094 to 0·7110) of the cements also indicate interaction of the fluids with siliciclastic sequences. The thermochemical sulphate reduction-related cements probably formed during early Laramide burial. Another (younger) calcite phase, characterized by depleted δ¹⁸O values (−23·9‰ to −13·9‰ Vienna Pee Dee Belemnite), low Na (27 to 37 p.p.m.) and Sr (39 to 150 p.p.m.) concentrations and non-saline (∼0 wt% NaCl equivalent) fluid inclusions, is attributed to post-Laramide meteoric water.     

新疆巴里坤盐湖物质成分及湖体演化

新疆巴里坤盐湖是一个常年性固、液并存的硫酸盐型盐湖。盐湖卤水中含Ｎａ＋、Ｋ＋、Ｃａ２＋、Ｃｌ－、ＳＯ２－４、ＨＣＯ－３、ＣＯ２－３等主要成分，沉积物中有芒硝、无水芒硝、石膏、水钙芒硝、半水石膏、石盐等盐类矿物及碳酸盐和泥质矿物。盐湖中有大量卤虫及卤虫卵自湖中心向湖岸呈环带状分布，在成盐过程中起着重要作用。盐湖形成于第三纪，第四纪以来，曾经历２次成岩期，约自１７ｋａＢ．Ｐ．湖水多次蒸发浓缩，成岩作用加强，形成芒硝等矿产     

含油气盆地蒸发盐矿物成因类型及其地质意义*

中国是一个多盐湖国家,然而盐湖研究主要集中于分析湖水化学性质、盐类物质来源和盐矿资源开发等,对盐类矿物沉积特征和埋藏成岩改造研究较少,造成从蒸发岩角度去理解古代盐湖盆地的油气富集规律较为困难。在广泛阅读国内外大型盐湖文献的基础上,笔者介绍了盐湖分类方案和蒸发岩中盐类矿物的主要成因类型,并总结了中国陆相含油气盆地中常见的硫酸盐、氯化物、含钠碳酸盐和硼酸盐的沉积—成岩过程及其古环境和古气候意义。同时,尝试利用盐湖沉积最新研究成果去探讨中国含油气盆地蒸发岩研究中存在争议或值得关注的问题,得出: (1)深部热液可为湖泊输送大量元素离子,但要在湖泊环境下富集大量蒸发岩,则(半)干旱气候和蒸发浓缩作用是前提条件;(2)易溶蒸发岩(如石盐)在沉积中心单层厚度大,而在斜坡—边缘区缺失,这是季节性气温变化和温跃层浮动引发“中心聚集效应”的结果;(3)温度可影响蒸发岩中盐类矿物溶解度、晶体结构形态和发育深度,而部分无水盐类矿物在常温常压下却无法结晶,这一现象可用来指示古地温和地层埋藏史;(4)碳酸盐型盐湖中的Na-碳酸盐种类可指示大气CO₂浓度和古温度。     

含油气盆地蒸发盐矿物成因类型及其地质意义*

中国是一个多盐湖国家,然而盐湖研究主要集中于分析湖水化学性质、盐类物质来源和盐矿资源开发等,对盐类矿物沉积特征和埋藏成岩改造研究较少,造成从蒸发岩角度去理解古代盐湖盆地的油气富集规律较为困难。在广泛阅读国内外大型盐湖文献的基础上,笔者介绍了盐湖分类方案和蒸发岩中盐类矿物的主要成因类型,并总结了中国陆相含油气盆地中常见的硫酸盐、氯化物、含钠碳酸盐和硼酸盐的沉积—成岩过程及其古环境和古气候意义。同时,尝试利用盐湖沉积最新研究成果去探讨中国含油气盆地蒸发岩研究中存在争议或值得关注的问题,得出: (1)深部热液可为湖泊输送大量元素离子,但要在湖泊环境下富集大量蒸发岩,则(半)干旱气候和蒸发浓缩作用是前提条件;(2)易溶蒸发岩(如石盐)在沉积中心单层厚度大,而在斜坡—边缘区缺失,这是季节性气温变化和温跃层浮动引发“中心聚集效应”的结果;(3)温度可影响蒸发岩中盐类矿物溶解度、晶体结构形态和发育深度,而部分无水盐类矿物在常温常压下却无法结晶,这一现象可用来指示古地温和地层埋藏史;(4)碳酸盐型盐湖中的Na-碳酸盐种类可指示大气CO₂浓度和古温度。     

Hydrochemical evolution of Na-SO4-Cl groundwaters in a cold, semi-arid region of southern Siberia

The Shira region of Khakassia in southern Siberia exhibits many features governing the evolution of groundwater and surface-water chemistry that are common to other cold, semi-arid areas of the world: (1) a continental climate, (2) location in a rain shadow, (3) low density of surface-water drainage, (4) occurrence of saline lakes, and (5) occurrence of palaeo- and modern evaporite mineralisation. In lowland areas of Shira, the more saline groundwaters and lake waters have a sodium-sulphate (-chloride) composition. Results of thermodynamic modelling suggest that these evolve by a combination of silicate weathering and gypsum and halite dissolution, coupled with carbonate precipitation to remove calcium and bicarbonate ions. An approximately 1:1 sodium:sulphate ratio occurs even in groundwaters from non-evaporite-bearing aquifers. This may indicate the formation of secondary sodium sulphate evaporites (in or near saline lakes or in soil profiles where the water table is shallow), which are subsequently distributed throughout the study area by atmospheric transport. Several urban groundwaters are characterised by very high nitrate concentrations, conceivably derived from sewage/latrine leakage. Received, June 1998 /Revised, May 1999, August 1999 /Accepted, August 1999     

Choosing the best ancient analogue for projected future temperatures: A case using data from fluid inclusions of middle-late Eocene halites

After the Paleocene–Eocene Thermal Maximum (PETM), global temperature and CO₂ levels decreased concurrently in the middle-late Eocene. Using different approaches, estimated CO₂ levels of the middle-late Eocene are very similar to the 1000 ppm CO₂ level projected for the next 100 years. As a result of increasing greenhouse gas concentrations, the average global temperature is projected to increase from 1.4 to 5.8 °C by 2100 relative to 2001 levels. Thus, the middle-late Eocene may be the best ancient analogue for a future with increased temperatures due to burning of fossil fuels.In order to explore the sensitivity range of global annual temperature with respect to CO₂ concentration, exact atmospheric CO₂ concentrations and air temperatures of ancient analogs must be known. Previous palynological studies provide only indirect estimates of temperature; however, the homogenization temperature of fluid inclusions in halites, obtained by the ‘cooling nucleation’ method, can provide the exact temperature of saline lake water, which is similar to overlying air temperature in shallow lakes. In this paper, we measured the range of homogenization temperatures (from 5.8 to 43.3 °C) of fluid inclusions in middle-late Eocene halites of the Yunying depression, central China. The maximum homogenization temperature of fluid inclusions (Th_max) in these middle-late Eocene halites is 4.6 °C higher than the modern extreme highest temperature (38.7 °C) recorded for this area.     

Degree of Brine Evaporation and Origin of the Mengyejing Potash Deposit: Evidence from Fluid Inclusions in Halite

The Mengyejing potash deposit is located in the southern port of the Simao Basin, Yunnan Province, and is hosted in mid-Cretaceous strata. The chemical compositions of fluid inclusions in halite crystals, collected from the level-610 adit in the deposit, were analysed by laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). The results show that the brine is of the Na-K-Mg-Ca-Cl type and has K concentrations that are distinctly higher than those of Mg and Ca, unlike normal brines associated with Cretaceous halite. The high K concentrations indicate that the degree of evaporation of the ancient Mengyejing saline lake was very high, reaching the sylvite deposition stage but rarely reaching the carnallite deposition stage. The trajectory of the H and O isotopic compositions of the brines in the halite-hosted fluid inclusions corresponds to intense evaporation, indicating that the net evaporation exceeded the net inflow of brines. These brine compositions in halite-hosted fluid inclusions were likely formed by the dissolution of previously deposited K-bearing minerals by fresh continental and/or seawater, forming a type of modified seawater, with deep hydrothermal fluids potentially supplying additional potassium. The basin likely experienced multiple seawater incursion, dissolution and redeposition events in a high-temperature environment with high evaporation rates.     

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。     

The evolution of alkaline, saline ground- and surface waters in the southern Siberian steppes

Groundwaters, river and lake waters have been sampled from the semi-arid Siberian Republic of Khakassia. Despite the relatively sparse data set, from a diversity of hydrological environments, clear salinity-related trends emerge that indicate the main hydrochemical evolutionary processes active in the region. Furthermore, the major ion chemistry of the evolution of groundwater baseflow, via rivers, to terminal saline lake water, can be adequately and simply modelled (using PHREEQCI) by invoking: (i) degassing of CO₂ from groundwater as it emerges as baseflow in rivers (rise in pH); (ii) progressive evapoconcentration of waters (parallel accumulation of Cl⁻, Na⁺, SO₄²⁻, and increase in pH due to common ion effect); and (iii) precipitation of calcite (depletion of Ca from waters, reduced rate of accumulation of alkalinity). Dolomite precipitation is ineffective at constraining Mg accumulation, due to kinetic factors. Silica saturation appears to control dissolved Si in low salinity waters and groundwaters, while sepiolite saturation and precipitation depletes Si from the more saline surface waters. Gypsum and sodium sulphate saturation are only approached in the most saline environments. Halite remains unsaturated in all waters. Sulphate reduction processes are important in the lower part of lakes.     

Glauberite–halite association of the Zaragoza Gypsum Formation (Lower Miocene, Ebro Basin, NE Spain)

Glauberite is the most common mineral in the ancient sodium sulphate deposits in the Mediterranean region, although its origin, primary or diagenetic, continues to be a matter of debate. A number of glauberite deposits of Oligocene–Miocene age in Spain display facies characteristics of sedimentologic significance, in particular those in which a glauberite–halite association is predominant. In this context, a log study of four boreholes in the Zaragoza Gypsum Formation (Lower Miocene, Ebro Basin, NE Spain) was carried out. Two glauberite–halite lithofacies associations, A and B, are distinguished: association (A) is composed of bedded cloudy halite and minor amounts of massive and clastic glauberite; association (B) is made up of laminated to thin‐bedded, clear macrocrystalline, massive, clastic and contorted lithofacies of glauberite, and small amounts of bedded cloudy halite. Transparent glauberite cemented by clear halite as well as normal‐graded and reverse‐graded glauberite textures are common. This type of transparent glauberite is interpreted as a primary, subaqueous precipitate. Gypsum, thenardite or mirabilite are absent in the two associations. The depositional environment is interpreted as a shallow perennial saline lake system, in which chloride brines (association A) and sulphate–(chloride) brines (association B) are developed. The geochemical study of halite crystals (bromine contents and fluid inclusion compositions) demonstrates that conditions for co‐precipitation of halite and glauberite, or for precipitation of Na‐sulphates (mirabilite, thenardite) were never fulfilled in the saline lake system.     

内蒙古伊克昭盟现代碱湖区矿层的矿物组成及分布特征

内蒙伊克昭盟是我国现代碱湖分布最集中的地区,各碱湖矿层的主要盐类矿物是泡碱,其次是芒硝,天然碱和石盐及少量单斜钠钙石,氯碳钠镁石,钙水碱和水碱。泡碱普遍存在于各个碱湖的矿层中,芒硝主要存在于西部碱湖的矿层中,天然碱集中分嘏于碱湖区西南部的几个碱湖中,且只分布于矿层的某些部位,碱湖矿层剖面上,天然碱与芒硝呈互为消长关系,天然碱和石盐则呈正相关。