Origin of polyhalite deposits in the Zechstein (Upper Permian) Zdrada platform (northern Poland)

Polyhalite deposits in the Zechstein (Upper Permian) of northern Poland occur in the Lower Werra Anhydrite. In the Zdrada Sulphate Platform, the polyhalite appears to be a very early replacement of anhydrite. The replacement was caused by the halite-precipitating brines which contained potassium and magnesium ions. The formation of polyhalite was preceded by the syndepositional anhydritization of the original gypsum deposit which has often preserved its primary textures. This anhydritization on the platform and its slopes was a reaction of the precipitated gypsum in a hydrologically open evaporite basin, with brines of salt basins adjacent to the sulphate platform. These brines, when nearly saturated with respect to halite, and potassium and magnesium rich, reacted with anhydrite to precipitate polyhalite along the slopes of the Zdrada Platform. The oxygen and sulphur isotopic compositions of sulphate evaporites indicate that marine solutions were the only source of sulphate ions supplied to the Zechstein basin, and that anhydrite was transformed to polyhalite by reaction with marine brines more concentrated than those that precipitated precursor calcium sulphate minerals.     

The geochemistry of Ca,Sr, Ba and Ra sulfates in some deep brines from the Palo Duro Basin,Texas

The geochemistry of Ca, Sr, Ba and Ra sulfates in some deep brines from the Palo Duro Basin of north Texas, was studied to define geochemical controls on radionuclides such as ⁹⁰Sr and ²²⁶Ra. Published solubility data for gypsum, anhydrite, celestite, barite and RaSO₄ were first reevaluated, in most cases using the ion interaction approach of Pitzer, to determine solubility products of the sulfates as a function of temperature and pressure. Ionic strengths of the brines were from 2.9 to 4.8 m, their temperatures and pressures up to 40°C and 130 bars. Saturation indices of the sulfates were computed with the ion-interaction approach in one brine from the arkosic granite wash fades and four from the carbonate Wolfcamp Formation. All five brines are saturated with respect to gypsum, anhydrite and celestite, and three of the five with respect to barite. All are undersaturated by from 5 to 6 orders of magnitude with respect to pure RaSO₄. ²²⁶Ra concentrations in the brines, which ranged from 10^?11.3 to 10^?12.7 m, are not controlled by RaSO₄ solubility or adsorption, but possibly by the solubility of trace Ra solid solutions in sulfates including celestite and barite.     

The anatomy of a sulphate platform and adjacent basin system in the Leba sub-basin of the Lower Werra Anhydrite (Zechstein, Upper Permian), northern Poland

The Lower Werra Anhydrite (Zechstein, Upper Permian) deposits of the teba area originated in a deep basin setting, in shallow to deep water conditions. Facies changes occur within small distances and suggest fluctuating boundaries between well defined basins and platforms. This pattern of local platforms and adjacent basins developed during deposition. In basinal areas, the sequence is clearly transgressive, whereas on platforms accumulation kept pace with subsidence after an initial transgression. Nodular anhydrite represents a polygenetic deposit which formed at different times with respect to deposition. Massive anhydrite with pseudomorphs after upright-growth gypsum crystals suggest rapid precipitation in a subaqueous environment and/or fluctuating, but generally high, salinity conditions. Massive clastic sulphate originated due to periodic high energy events and resedimentation, or due to brecciation possibly connected with salinity fluctuations and the dissolution of halite. Massive, textureless anhydrite is locally porous and passes upward into breccia, indicating a strongly saline environment. Bedded anhydrite is considered to form in shallow water environments and laminated anhydrite in deep water. Bedded anhydrites contain portions which are graded. Intercalations of sulphate turbidites and upright-growth gypsum suggest fluctuating water depths, with comparatively deep water during turbidite deposition, but shallower conditions during upright-growth gypsum deposition. The sequence observed in slope zones at platform-basin margins, detrital (parautochthonous) sulphate sand to graded beds to basinal laminites, indicates that redistribution processes were important. At the onset of the Lower Werra Anhydrite deposition bathymetric relief existed between the central part of the basin and its margins, where carbonate platforms remained subaerially exposed. Formation of local platforms and adjacent basins required a relatively high subsidence rate, as pre-existing relief cannot account for the total accumulated thickness of the Lower Werra Anhydrite deposits. One implication of this is that the main argument against ‘the shallow water - shallow basin’ evaporite basin model, i.e.,a very fast rate of subsidence, may not be valid for the Łeba Lower Werra Anhydrite basin.     

Sealing of fluid pathways in overpressure cells: a case study from the Buntsandstein in the Lower Saxony Basin (NW Germany)

We studied veins in the Triassic Buntsandstein of the Lower Saxony Basin (NW Germany) with the aim of quantifying the evolution of in-situ stress, fluids and material transport. Different generations of veins are observed. The first generation formed in weakly consolidated rocks without a significant increase in fracture permeability and was filled syntectonically with fibrous calcite and blocky to elongate-blocky quartz. The stable isotopic signature (δ¹⁸O and δ¹³C) indicates that the calcite veins precipitated from connate water at temperatures of 55–122°C. The second vein generation was syntectonically filled with blocky anhydrite, which grew in open fractures. Fluid inclusions indicate that the anhydrite veins precipitated at a minimum temperature of 150°C from hypersaline brines. Based on δ³⁴S measurements, the source of the sulphate was found in the underlying Zechstein evaporites. The macro- and microstructures indicate that all veins were formed during subsidence and that the anhydrite veins were formed under conditions of overpressure, generated by inflation rather than non-equilibrium compaction. The large amount of fluids which are formed by the dehydrating gypsum in the underlying Zechstein and are released into the Buntsandstein during progressive burial form a likely source of overpressures and the anhydrite forming fluids.     

Sequence stratigraphy of a carbonate-evaporite succession (Zechstein 1, Hessian Basin, Germany)

The evaporitic Hessian Zechstein Basin is a sub‐basin of the Southern Zechstein Basin, situated at its southern margin. Twelve facies groups were identified in the Zechstein Limestone and Lower Werra Anhydrite in order to better understand the sequence‐stratigraphic evolution of this sub‐basin, which contains economically important potassium salts. Four different paleogeographic depositional areas were recognized based on the regional distribution of facies. Siliciclastic‐carbonate, carbonate, carbonate‐evaporite and evaporite shallowing‐upward successions are developed. These allow the establishment of parasequences and sequences, as well as correlation throughout the Hessian Basin and into the Southern Zechstein Basin. Two depositional sequences are distinguished, Zechstein sequence 1 and Zechstein sequence 2. The former comprises the succession from the Variscan basement up to the lowermost part of the Werra Anhydrite, including the Kupferschiefer as part of the transgressive systems tract. The highstand systems tract is defined by the Zechstein Limestone, in which two parasequences are developed. In large parts of the Hessian Basin, Zechstein sequence 1 is capped by a karstic, subaerial exposure surface, interpreted as recording a type‐1 sequence boundary that formed during a distinct brine level fall. Low‐lying central areas (Central Hessian Sub‐basin, Werra Sub‐basin), however, were not exposed and show a correlative conformity. Topography was minimal at the end of sequence 1. Widely developed perilittoral, sabkha and salina shallowing‐upward successions indicate a renewed rise of brine level (interpreted as a transgressive systems tract), because of inflow of preconcentrated brines from the Southern Zechstein Basin to the north. This marks the initiation of Zechstein sequence 2, which comprises most of the Lower Werra Anhydrite. In the Central Hessian Sub‐basin, situated proximal to the brine inflow and on the ridges within the Hessian Basin, physico‐chemical conditions were well suited for sulphate precipitation to form a thick cyclic succession. It consists of four parasequences that completely filled the increased accommodation space. In contrast, only minor sulphate accumulation occurred in the Werra Sub‐basin, situated further southwards and distal to the inflow. As a result of substantially different sulphate precipitation rates during increased accommodation, water depth in the region became more variable. The Werra Sub‐basin, characterized by very low sedimentation rates, became increasingly deeper through time, trapping dense halite brines and precipitating rock salt deposits (Werra Halite). This ‘self‐organization’ model for an evaporitic basin, in which depositional relief evolves with sedimentation and relief is filled by evaporite thereafter, contradicts earlier interpretations, that call upon the existence of a tectonic depression in the Werra area, which controlled sedimentation from the beginning of the Zechstein.     

The partitioning of seawater cations during the transformation of gypsum to anhydrite

The coprecipitation of Sr, Mg, Na and K with anhydrite during the dehydration of gypsum was studied in laboratory experiments. The partition coefficients of Mg and Sr between anhydrite and solution decrease with increasing temperature. The partition coefficients of the alkali-ions do not depend upon temperature, but are affected by the brine composition.The mechanism of the phase transformation gypsum → anhydrite occurs via dissolution and precipitation, when the coprecipitated-ions are repartitioned between the new phase and the solution. The partition coefficients established in this study are applicable also for primary anhydrite.During the dehydration of gypsum at elevated temperatures metastable bassanite may form as an intermediate stage. The amount of cations coprecipitated with bassanite is much larger than the amount coprecipitated with anhydrite or gypsum. This phenomenon may have an influence on the partitioning of cations during the dehydration of gypsum, particularly on Sr.The partition coefficients of seawater cations between anhydrite and the brine are similar to those between gypsum and the brine. For this reason the coprecipitated-ions are not expected to be good indicators to distinguish between primary and secondary calcium sulfate minerals.The temperature effect on the coprecipitation of Mg and Sr with anhydrite makes these ions possible indicators for the temperature at which the phase transformation occurred. This temperature corresponds to the depth of burial of the gypsum at the stage of dehydration.The coprecipitation of seawater cations with anhydrite in the natural environment was studied in two systems: A small Pleistocene evaporite lens from the Sinai Peninsula and the Triassic anhydrite of the Mohilla Formation, Israel. The coprecipitated-ion composition of these samples was used to derive the conditions under which the anhydrite was formed.     

Das geochemische Verhalten des Strontiums bei der Genese und Diagenese von Ca-Karbonat- und Ca-Sulfat-Mineralen

Experimental partioning of Sr between solutions, aragonite, calcite, gypsum and anhydrite show that the isomorphous replacement of Ca²⁺ by Sr²⁺ can be described as a linear function. The constants of the distributions are used to calculate primary Sr-contents of the various Ca-carbonates and Ca-sulfates precipitated from seawater and to estimate the point of precipitation of celestite. Comparism of these data with actual Sr-contents in sediments and sedimentary rocks show that in most cases gypsum has to be considered as the primary precipitate. Anhydrite in general is formed by diagenetic alteration of gypsum. The average Sr-content of gypsum rocks make it very probable that the Sr-concentration of seawater has stayed virtually unchanged since the end of Mesozoic. Sr-contents of carbonate rocks show that most of the limestones have been altered diagenetically. The distribution of Sr within the various sedimentary units of the earth's crust make it very probable that this alteration occurred in a system open to pore solutions.     

Geochemical variations within a laminated evaporite deposit: evidence for brine composition during formation of the Permian Castile Formation, Texas and New Mexico, USA

The Upper Permian Castile Formation of the Delaware Basin in northwest Texas and New Mexico consists of up to 600 m of evaporites and is subdivided into units of anhydrite overlain by halite. The Castile Formation has commonly been interpreted as a deep-water, deep-basin deposit in which sediments were laid down in several hundred metres of water or brine. Recent textural observations within anhydrite units, in which the thick-bedded anhydrite horizons have been interpreted as being of shallow-water origin, have challenged this assumption. This geochemical study of the oldest anhydrite unit in the Castile Formation (the Anhydrite 1 Member) attempts to resolve some of the problems regarding brine depth and evolution in the basin. The Anhydrite 1 Member has been subdivided into five major cycles on the basis of the distribution of stratigraphic units of thick-bedded anhydrite.

Stable isotopic analyses of sulphur from anhydrite, and oxygen and carbon from calcite show that the basin waters were chemically homogeneous during precipitation of anhydrite, and do not indicate any significant input of meteoric, continental-derived waters. Throughout the section studied progressive enrichment of ¹⁸O upwards within cored intervals indicates continuous evaporation of the water body. Carbon isotopes appear to indicate fluctuations in organic activity within the cycles. Trace elemental analyses of Fe, Mg, Sr, Mn, Al, Ba, Zn, Pb and Cu from the sulphate fraction of the samples show a very high variability. There is a distinct increase in trace elemental abundances at the tops of cycles which may indicate variations in precipitation kinetics. Analyses of texturally defined cycles show that up-core trends for many of the trace elements correlate with changes in δ¹⁸O, indicating a progressive increase in the influence of evaporation. In addition, cyclical variations in trace elemental composition indicate changes in basin conditions with around a 350-year cyclicity. These changes are independent of δ¹⁸O values. The geochemical data do not provide conclusive proof of water depth during deposition of the Castile Formation. The data are interpreted as reflecting small-scale changes in conditions of deposition, despite the fact that water input remained essentially constant in terms of chemical composition.     

Anhydrite–gypsum transition in the argillites of flooded salt workings in eastern France

This study aims at understanding the physico-chemical interactions between the saturated brine and the rocks enclosing the underground salt workings in Lorraine (eastern France). These anhydrite-rich and argillaceous rocks were characterized in terms of mineralogy, micro-texture and connected porosity. Then, the two main lithofacies, massive anhydrite and anhydrite-rich argillite, were immersed in brine during more than 1 year. During this batch experiment, the argillites were affected by macroscopic splitting, contrarily to the massive anhydrite. Micro-texture and brine chemical analyses clearly show the swelling due to the hydration of anhydrite into gypsum inside the argillites, whereas hydration occurs superficially on the massive anhydrite, due to its very low permeability. Anhydrite–gypsum transformation is promoted by the presence of dissolved strontium and potassium in saturated brine. The low activity of water in saturated brine does not allow the clay fraction to swell significantly during the experiment. Thus, the expansion resulting from the hydration of anhydrite into gypsum might be responsible of the splitting of argillite in a saturated brine environment. The superficial anhydrite hydration on massive anhydrite can be explained by the low amount of connected porosity (less than 1%).     

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.     

Origin and geochemical reaction paths of sabkha brines: Sabkha Jayb Uwayyid, eastern Saudi Arabia

Sabkhas are ubiquitous geomorphic features in eastern Saudi Arabia. Seven brine samples were taken from Sabkha Jayb Uwayyid in eastern Saudi Arabia. Brine chemistry, saturation state with respect to carbonate and evaporate minerals, and evaporation-driven geochemical reaction paths were investigated to delineate the origin of brines and the evolution of both brine chemistry and sabkha mineralogy. The average total dissolved solids in the sabkha brines is 243 g/l. The order of cation dominance is Na⁺   >>  Mg²⁺ >>  Ca²⁺>K⁺, while anion dominance is Cl⁻ >> SO₄ ²⁻ >> HCO₃ ⁻. Based on the chemical divide principle and observed ion ratios, it was concluded that sabkha brines have evolved from deep groundwater rather than from direct rainfall, runoff from the surroundings, or inflow of shallow groundwater. Aqueous speciation simulations show that: (1) all seven brines are supersaturated with respect to calcite, dolomite, and magnesite and undersaturated with respect to halite; (2) three brines are undersaturated with respect to both gypsum and anhydrite, while three brines are supersaturated with respect to both minerals; (3) anhydrite is a more stable solid phase than gypsum in four brines. Evaporation factors required to bring the brines to the halite phase boundary ranged from 1.016 to 4.53. All reaction paths to the halite phase boundary follow the neutral path as CO₂ is degassed and dolomite precipitates from the brines. On average, a sabkha brine containing 1 kg of H₂O precipitates 7.6 g of minerals along the reaction path to the halite phase boundary, of which 52% is anhydrite, 35.3% is gypsum, and 12.7% is dolomite. Bicarbonate is the limiting factor of dolomite precipitation, and sulfate is the limiting factor of gypsum and anhydrite precipitation from sabkha brines.     

Sulphate–borate relations in an evaporitic lacustrine environment: the Sultançayir Gypsum (Miocene, western Anatolia)

Calcium-borates, mainly pandermite (priceite) and howlite, but also bakerite and colemanite, are intercalated within the Sultançayir Gypsum (Miocene, Sultançayir Basin, western Anatolia). This lacustrine unit, represented by secondary gypsum in outcrop, is characterized by: (1) a clear facies distribution of depocentral laminated lithofacies and debris-flow deposits, a wide marginal zone of sabkha deposits, and at least one selenitic shoal located toward the basin margin; (2) evaporitic cycles displaying a shallowing-upward trend; and (3) a diagenetic evolution of primary gypsum to (burial) anhydrite followed by its final re-hydration. The calcium borates precipitated only in the depocentre of the lake and were partly affected by synsedimentary reworking, indicating that they formed during very early diagenesis. The lithofacies, which are made up of a host gypsum (finely laminated) and borates (nodules, irregular masses and discontinuous bands; also fine laminations), indicate that the borates grew interstitially because of the inflow and mixing of borate-rich solutions with basinal brines. Borate growth displaced and replaced primary gypsum beneath a relatively deep depositional floor. Borate formation as free precipitates was much less common. The anhydritization of primary gypsum took place during early to late diagenesis (burial <250 m deep). This process also resulted in partial replacement of pandermite and accompanying borates (bakerite and howlite) as well as other early diagenetic minerals (celestite) by anhydrite. Final exhumation resulted in the replacement of anhydrite by secondary gypsum, and in the partial transformation of pandermite and howlite into secondary calcite.     

四川盆地东部海相下—中三叠统界线的锶同位素年龄标定

中国西南地区海相下—中三叠统以火山碎屑岩为其直观界线,该年龄的标定可为区域地层年表和国际地层委员会全球标准年表研究提供重要的下—中三叠统界线年龄参考值.基于此,本文测试了四川盆地东部华蓥山下—中三叠统界线火山碎屑岩附近的石膏和硬石膏样品87Sr/86Sr比值,以及相应的Si、Ca、Mg、Mn、Sr以及SO42-的含量,根据锶同位素地层学的原理,尝试对下—中三叠统界线进行了年龄标定;同时评估了样品的成岩蚀变性、对海水信息的代表性以及年龄标定结果的可靠性.火山碎屑岩附近5个样品的87Sr/86Sr比值变化在0.708243~0.708391之间,标定的年龄值在240.5~242.5Ma的范围内,2个紧靠火山碎屑岩样品的年龄值在242Ma左右(分别为241.9Ma和242.5Ma),从而为华南地区以火山碎屑岩作为海相下—中三叠统界线的合理性提供了重要的化学地层学依据,也为全球下—中三叠统界线提供了一个新的年龄值.     

A strontium, oxygen and hydrogen isotopic composition of brines, Michigan and appalachian basins, Ontario and Michigan

⁸⁷Sr/⁸⁶Sr ratios of brine from samples from the Michigan and Appalachian Basins, in Ontario and Michigan, covering the stratigraphic interval from the Cambrian to Mississippian, vary from 0.708 to 0.711. With the exception of the salt units of the Salina Formation (Silurian), most values are greater than seawater for the time in question, indicating water-rock interaction. The sources of the radiogenic Sr has not been identified. All samples plot below the GMWL in δ¹⁸O−δ²H space, with the Cambrian and Ordovician samples closest to the line. Mixing of brines meteoric and glacial (Pleistocene) water is indicated in some cases. The more concentrated brines from each stratigraphic unit show a very narrow spread in values. All the Ordovician brines show a narrow range over a 200 km area for Sr, O and H isotopes, indicating extensive lateral migration of the fluids.Strontium in the brine has not equilibrated isotopically with its host rock. In some cases the late-stage minerals saddle dolomite, calcite and anhydrite have the same ⁸⁷Sr/⁸⁶Sr ratios as the brine, indicating that they precipitated from the brine in isotopic equilibrium.     

Late diagenetic calcitization of anhydrite from the Mississippian of Saskatchewan, western Canada

Mississippian nodular anhydrites beneath an unconformity in the subsurface of southern Saskatchewan are locally replaced by calcite, pyrite and celestite. Triassic clastics above the unconformity are green, rather than red, and a usually developed subunconformity alteration zone (where carbonates are dolomitized, and porosity is filled with anhydrite) is absent. The unconformity lacks karstic features (unlike in the USA), and probably formed in a hyperarid climate. Mississippian anhydrites near the unconformity are not preferentially dissolved, nor were they extensively hydrated. Anhydrite calcitization occurred only after the unconformity was shallowly buried by redbeds, and it probably involved sulphate-reducing bacteria. Hydrogen sulphide, generated by bacteria, reduced redbed pigments. The replacement calcite contains pseudomorphs and relicts of anhydrite, and pseudomorphs of secondary gypsum. These indicate calcitization occurred only after original Mississippian gypsum was altered to anhydrite and this, in turn, was partially converted back to secondary gypsum beneath the unconformity. Replacement occurred concurrently with the formation elsewhere of the dolomitized zone beneath the unconformity. Sulphur isotopic ratios of replacement pyrite are depleted relative to Mississippian sulphate values, consistent with the activities of sulphate-reducing bacteria. Carbon isotopic ratios of replacive calcites, however, do not support this interpretation, and are identical to those of Mississippian limestones. Simple replacement of sulphate by pore-water bicarbonate (in equilibrium with host limestones) is unlikely because protons generated during the reaction should have created acidic conditions in which calcite would have dissolved. A full explanation of the calcitization remains elusive, but may involve replacement occurring in an active groundwater system and/or bacterial sulphate reduction occurring upstream of the site of calcitization.     

四川盆地海相三叠系硬石膏和盐卤水的硫同位素组成及意义

四川盆地下、中三叠统硬石膏和盐卤水广布，通过对采集于不同地段不同层位各具代表性的硬石膏、石膏和盐卤水的２４４件样品的分析，可见其同层位硫同位素组成稳定，δ３４Ｓ自下而上具阶梯状递减轻化的趋势，与已知全球海相三叠系硫同位素组成有明显差异。这种硫同位素分布规律对地层划分和对比、蒸发岩形成环境的判断、研究卤水产层和成因、掌握蒸发岩咸化发展方向及预测找钾工作等的意义不容忽视。     

Hydrogen,oxygen, helium and strontium isotopic constraints on the formation of oilfield waters in the western Qaidam Basin,China

Surveys and exploration for oil and gas have revealed many oil-field brines in the Tertiary strata of the western Qaidam Basin, China. The source and formation of these brines are unclear. Brine samples collected from petroleum wells in the oilfield area were analyzed for their general chemical composition and for hydrogen, oxygen, strontium and helium isotopes in order to trace their origin, formation, and resource distribution. Results show that the concentrations of resources such as K, B, Sr, Br and Li are unusually enriched in oil-field brines and have excellent potential for development and utilization in future. The geology, H, O, Sr and He isotopic composition, the chemical composition, and the geophysical measurements all show that the tertiary oil-field brines predominantly originated from the deep mixture of formation water and magmatic residual fluids in the western Qaidam Basin. The tectonic geology, intense and frequent magmatic-hydrothermal activity as well as high ³He/⁴He ratio indicate that the magmatic fluids possibly originate from the upper mantle-derived magmatic fluids. Thus, according to our interpretation of the formation and evolution of the oilfield brine, this source is adequate for the volume and composition to be explored and utilized latterly.     

Strontium distribution and origins in a natural clayey formation (Callovian-Oxfordian, Paris Basin, France): A new sequential extraction procedure

Strontium is a good monitor of geochemical processes in natural clayey formations. In the Callovian-Oxfordian formation of Bure in France, strontium is sorbed on clay minerals and carried by carbonates, detrital minerals and accessory celestite. In order to determine the strontium distribution among these different phases, four-step sequential extractions (1. cobalt hexamine trichloride, 2. acetic acid, 3. EDTA and 4. tri-acid) were performed on samples from different levels of the clayey formation. The leachates were also analyzed for strontium isotopes, in order to determine the strontium origins. This sequential procedure is well suited to determining strontium distribution in claystones, although it is less efficient in clay-rich limestones and in celestite-rich samples. The carbonates (38-47% of the total strontium) show ⁸⁷Sr/⁸⁶Sr ratios (0.7070-0.7071) that have recorded the isotopic composition of the Callovian-Oxfordian seawater. Diagenetic carbonates (dolomite, ankerite and siderite) have almost not incorporated any strontium, which has been trapped by celestite during the late diagenesis. The major part of the celestite shows ⁸⁷Sr/⁸⁶Sr ratios (0.7069-0.7070) quite close to the primary carbonates. However, a second generation of celestite (0.7074) shows a slight ⁸⁷Sr-enrichment and is isotopically in equilibrium with the exchangeable strontium (27-48% of the total strontium with a mean ⁸⁷Sr/⁸⁶Sr value of 0.70745) and the present-day porewater (0.7074). This very low ⁸⁷Sr-enrichment could be explained by the partial destabilisation of detrital minerals (feldspars, micas, clays) which exhibit ⁸⁷Sr/⁸⁶Sr ratios consistent with their pristine Hercynian origin (0.7229-0.7350). Diffusion of strontium from the subjacent Dogger aquifers (0.7076-0.7082) could also be invoked to explain the slight ⁸⁷Sr-enrichment.     

Fluid-rock interactions in a geothermal Rotliegend/Permo-Carboniferous reservoir (North German Basin)

Comprehensive data on the chemical composition of reservoir rocks and geothermal brines from the geothermal well doublet Groβ Schönebeck (North German Basin) drilled into a Rotliegend sedimentary and Permo-Carboniferous volcanic rock reservoir were sampled over the past years. They were characterized with respect to their major and minor elemental composition including various isotope ratios. The study considered the impact of drilling and reservoir operations on fluid composition and aimed at determining fluid–rock interactions to gain information on fluid origin and hydraulic pathways.The highly saline fluids (up to 265 g/L TDS) show δ ¹⁸O and δD of water (2.7–5.6 and −3.1–15, respectively) as well as δ ³⁴S of sulfate (3.6–5), and ⁸⁷Sr/⁸⁶Sr ratios (0.715–0.716) that resemble Rotliegend brines from an area located around 200 km in the west (the Altmark). Halogen ratios indicated that brines developed predominantly by evaporation of meteoric water (primary brine) together with halite dissolution brine (secondary brine). Indication for mixing with Zechstein brine or with younger meteoric water was not found.No geochemical distinction was possible between fluids deriving from different rock formations (dacites or sedimentary rocks, respectively). This is due to the evolution of the sediments from the effusive rocks resulting in a similar mineralogical and chemical composition and due to a hydraulic connectivity between the two types of rock. This connection existed probably already before reservoir stimulation as indicated by a set of faults identified in the area that could connect the Rotliegend formation with both, the volcanic rocks and the lower units of the Zechstein. Additional geochemical indication for a hydraulic connectivity is given by (1) the very high heavy metal contents (mainly Cu and Pb) in fluids and scaling that derive from the volcanic rocks and were that were also found in increased amounts up at the Zechstein border (Kupferschiefer formation). (2) The ⁸⁷Sr/⁸⁶Sr isotope ratios of fluid samples correspond to the ratios determined for the sedimentary rocks indicating that initially the fluids developed in the sedimentary rocks and circulated later, when faults structures were created by tectonic events into the volcanic rocks.     

天青石中锶同位素组成测定——酸溶和碱熔样品分解方法的对比

利用酸溶法和碱熔法分解天青石样品，经过离子交换分离得到纯净的Sr，测定^87Sr／^86Sr同位素比值，实验结果表明两种样品分解方法得到的^87Sr／^86Sr同位素比值的偏差〈0.0001，证明在天青石锶同位素组成测定中，酸溶法和碱熔法都是可行的；但与碱熔法相比，酸溶法更简易并且利于本底值的控制。