Stable isotope evidence for multiple fluid regimes during carbonate cementation of the Upper Tertiary Hazeva Formation, Dead Sea Graben, southern Israel

Stable carbon- and oxygen-isotope compositions of calcite and dolomite cements have been used to understand porewater evolution in the Upper Tertiary Hazeva Formation within the Dead Sea Graben, southern Israel. Sandstone samples were obtained from four boreholes in three tectonic blocks of the graben over depths of 253–6448 m, a variation that largely reflects differential subsidence of individual fault-bounded blocks. Early carbonate cements dominate diagenesis. Calcite occurs at <1600 m, but was replaced by dolomite at greater depths. Dolomite at 1600–2700 m is Fe-poor (<0.8 mol% FeCO₃), and at 4700–6200 m, Fe-rich (0.5–7.2 mol% FeCO₃). Magnesite, anhydrite and halite are the final diagenetic phases. Calcite has positively correlated δ¹⁸O (+21‰ to +25‰) and δ¹³C (−6‰ to −2‰) values that generally decrease with depth. Dolomite has a wider variation in δ¹⁸O (+18‰ to +30‰) and δ¹³C (−8‰ to −1‰) values, which also generally are lower with increasing depth. However, the δ¹³C and δ¹⁸O values of dolomite from the uppermost 400 m of the Hazeva Formation in the Sedom Deep-1 borehole are anomalous in spanning the entire range of stable carbon and oxygen isotopic compositions over this relatively small interval.The decreasing dolomite δ¹³C values likely indicate an increased contribution of carbon from organic sources with increasing depth. Except for the uppermost 400 m, Hazeva Formation dolomite in the Sedom Deep-1 borehole has stable carbon-isotope compositions that imply initial dolomitization at much shallower levels, prior to the preferential subsidence of this tectonic block. The oxygen isotopic compositions of the calcite cement are best explained by equilibration at present burial temperatures (≤55 °C) with porewater of meteoric origin. Its δ¹⁸O values increased from −5‰ at the shallowest depths to 0‰ at 1600 m. The dolomite oxygen isotopic compositions also reflect equilibration at present burial temperatures with porewaters ranging from 0‰ at 1600 m to +7‰ at 3600 m (100 °C). In the deepest fault block (Sedom Deep-1 borehole), however, increasingly Fe-rich dolomite has (re)equilibrated with porewater whose δ¹⁸O values decreased from +9‰ at 4750 m (120 °C) to +1‰ to +2‰ by 6200 m (150 °C).Much of the dolomite likely formed at relatively shallow depths from saline brines derived from precursors to the Dead Sea. These infiltrated the Hazeva Formation, mixing with and largely displacing meteoric water, and dolomitizing calcite. Rock–water ratios tended to be high during these processes. However, the upper 400 m of the Hazeva Formation in the deepest fault block were likely deposited during its rapid tectonic subsidence, and largely escaped the initial style of dolomitization pervasive elsewhere in the study area. These sediments were also capped by evaporites. This relatively thin interval likely became a preferential conduit for brines that escaped underlying and overlying strata, including the Fe-rich, lower ¹⁸O fluids (evolved seawater?) present in the deepest part of the graben. These rocks present the most promising target for the passage and accumulation of hydrocarbons in the study area.     

Preliminary mineralogical and petrological study of the Ortosa Au–Bi–Te ore deposit: a reduced gold skarn in the northern part of the Rio Narcea Gold Belt, Asturias, Spain

The Ortosa deposit (NW Spain) in the northern part of the Rio Narcea Gold Belt (RNGB) is located in the Cantabrian Zone of the Iberian Massif. This zone corresponds to the westernmost exposure of the European Hercynides. The deposit is hosted by marine shales, siltstones, calcareous siltstones and interbedded sandy limestones of the upper part of the Silurian Furada Formation. These rocks are intruded by a main stock and numerous sills and dikes consisting of a reduced, ilmenite-bearing quartz-monzodiorite (Ortosa intrusion). Skarn metasomatism and associated gold mineralization overprinted these sedimentary and igneous rocks, forming endo- and exoskarns.The earliest stage of alteration involved potassium metasomatism from which metasomatic biotite developed in the hornfels around the intrusion. In the endoskarn, the first metasomatic mineral to form is actinolite. Subsequently, quartz, pyroxene (Hd_30–45), and sulfides (mainly arsenopyrite and pyrrhotite) formed, followed by a second generation of amphibole (ferroactinolite and ferrohornblende). The exoskarn is a pyroxene-garnet skarn, which is often banded. The prograde minerals are pyroxene (Hd_10–30) and grossular garnet. The retrograde mineralogy consists of hedenbergite-rich pyroxene (Hd_50–87), amphibole (ferroactinolite–ferrohornblende), and the metallic minerals with minor fluorapatite, K-feldspar, albite, epidote–clinozoisite, vesuvianite and calcite. A final stage of retrograde alteration is characterized by calcite, quartz, and chlorite.Pyrrhotite and arsenopyrite are the more abundant metallic minerals, and löllingite, chalcopyrite, pyrite and sphalerite are present in smaller amounts. The gold occurs as native gold and maldonite, and is accompanied by hedleyite, native bismuth, and bismuthinite. These Au–Bi–Te mineral assemblages occupy cavities and fractures in the arsenopyrite or in the pyrrhotite.Estimated physiochemical conditions of formation based on the composition and stability fields of major calc-silicate and sulfide minerals indicate that the hedenbergite-rich pyroxene and the earliest sulfides (löllingite–pyrrhotite–arsenopyrite) crystallized at temperatures between 470 and 535°C at low log fS₂ between −10 and −6.5 and low log fO₂ of −22. The Ortosa skarns can be included in the reduced gold skarn subtype defined by Meinert (Mineralogical Association of Canada, Quebec city, Que., Canada, 1998, 26,359–414 ).     

Conceptual model for early diagenetic chert and dolomite, Amuri Limestone Group, north-eastern South Island, New Zealand

The Late Cretaceous to Early Eocene, dominantly micritic, Amuri Limestone Group (ALG) was deposited in an approximately NW trending trough, in eastern Marlborough, New Zealand. The ALG comprises: the Mead Hill Formation; the Teredo, Lower and Middle Limestone formations; and the Upper and Lower Marl formations. Chert and dolomite are concentrated in the Mead Hill Formation, which contains five of six recognized diagenetic zones: Zone I at the base of the ALG consists almost entirely of chert; Zone II consists solely of chert and dolomite; Zone III comprises chert and limestone; Zone IV is composed of chert plus dolomite; Zone V is a chertified mudstone; and the minor amounts of chert found in the Middle Limestone Formation comprise Zone VI. With the exception of Zones IV and V, chert decreases stratigraphically upwards and away from the basin centre. All the dolomites are composed of <1 mm diameter rhombohedra in discontinuous beds and lenses. Generally Ca-rich, and non- to slightly ferroan, the dolomite contains approximately 500–900 ppm Mn and 200–400 ppm Sr. δ¹³C values average 1–2%_PDB with δ¹⁸O ratios of about -4%_PDB. Mass balance calculations indicate that the Mg²⁺ for dolomitization was derived from sea water. Sr, Fe and Mn concentrations are interpreted as indicating dolomite formation in the marine environment, with no influence from meteoric waters. The intimate association with pyrite implies dolomite formation in association with sulphate reduction, in the upper sediment column. δ¹⁸O data show that the bulk of the dolomite formed at temperatures below 50°C. All chert samples contain in excess of 90 wt% SiO₂, about 1 wt% Al₂O₃ and 1 wt% from losses on ignition. Generally all other major elements total less than 2 wt% oxide. δ¹⁸O values range from 26·8 to 29·0%_SMOW. Chert chemistry is consistent with the replacement of host carbonate and expulsion of carbonate-bound components from the site of chertification, and the effective dilution by SiO₂ of non-carbonate-bound insoluble residues. δ¹⁸O data indicate that chert formed in fluids of similar composition and temperature as the dolomite. The abundance of disseminated pyrite in cherts implies an association with sulphate reduction. Silica for chertification is thought to have initially come from dissolution of siliceous organisms. However, there is insufficient biogenic silica available to form the volumes of chert observed. It is suggested that the bulk of the silica came from SiO₂-rich pore waters generated by clay mineral reactions in the thick underlying mudstones. The ALG compacted down through these pore waters. Chert and dolomite nucleation are considered to have been penecontemporaneous. Dolomitization was initially probably the faster process, continuing as long as sulphate reduction prevailed and there was an adequate supply of Mg²⁺. The nucleation of chert, although initially slower (probably due to a relatively lower initial SiO₂ supply), continued after cessation of dolomitization to the extent of completely chertifying the dolomite intercrystalline matrix. The amount of chertification decreased progressively as SiO₂ supplies diminished, both stratigraphically upwards and away from the basin centre.     

Geochemical characteristics and controlling factors of chemical composition of groundwater in a part of Guntur district,Andhra Pradesh,India

A survey on quality of groundwater was carried out for assessing the geochemical characteristics and controlling factors of chemical composition of groundwater in a part of Guntur district, Andhra Pradesh, India, where the area is underlain by Peninsular Gneissic Complex. The results of the groundwater chemistry show a variation in pH, EC, TDS, Ca²⁺, Mg²⁺, Na⁺, K⁺, HCO₃ ^?, Cl^?, SO₄ ^2?, NO₃ ^? and F^?. The chemical composition of groundwater is mainly characterized by Na⁺?HCO₃ ^? facies. Hydrogeochemical type transits from Na⁺–Cl^?–HCO₃ ^? to Na⁺–HCO₃ ^?–Cl^? along the flow path. Graphical and binary diagrams, correlation coefficients and saturation indices clearly explain that the chemical composition of groundwater is mainly controlled by geogenic processes (rock weathering, mineral dissolution, ion exchange and evaporation) and anthropogenic sources (irrigation return flow, wastewater, agrochemicals and constructional activities). The principal component (PC) analysis transforms the chemical variables into four PCs, which account for 87% of the total variance of the groundwater chemistry. The PC I has high positive loadings of pH, HCO₃ ^?, NO₃ ^?, K⁺, Mg²⁺ and F^?, attributing to mineral weathering and dissolution, and agrochemicals (nitrogen, phosphate and potash fertilizers). The PC II loadings are highly positive for Na⁺, TDS, Cl^? and F^?, representing the rock weathering, mineral dissolution, ion exchange, evaporation, irrigation return flow and phosphate fertilizers. The PC III shows high loading of Ca²⁺, which is caused by mineral weathering and dissolution, and constructional activities. The PC IV has high positive loading of Mg²⁺ and SO₄ ^2?, measuring the mineral weathering and dissolution, and soil amendments. The spatial distribution of PC scores explains that the geogenic processes are the primary contributors and man-made activities are the secondary factors responsible for modifications of groundwater chemistry. Further, geochemical modeling of groundwater also clearly confirms the water–rock interactions with respect to the phases of calcite, dolomite, fluorite, halite, gypsum, K-feldspar, albite and CO₂, which are the prime factors controlling the chemistry of groundwater, while the rate of reaction and intensity are influenced by climate and anthropogenic activities. The study helps as baseline information to assess the sources of factors controlling the chemical composition of groundwater and also in enhancing the groundwater quality management.     

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.     

Evaluation of hydrogeochemical processes in arsenic-contaminated alluvial aquifers in parts of Mid-Ganga Basin,Bihar, Eastern India

The study region covers 1,650 km² of the Mid-Ganga Basin in Bihar, experiencing intensive groundwater draft. The area forms a part of the Gangetic alluvial plain where high incidence of arsenic groundwater contamination (>50 μg/l) has recently been detected. Seventy-seven groundwater samples have been collected and analysed for major ions, iron and arsenic. Arsenic contamination (max 620 μg/l) is confined in hand pump zones (15–35 m) within the newer alluvium deposited during Middle Holocene to Recent age. The older alluvial aquifers are arsenic-safe and recorded maximum concentration as 9 μg/l. Out of 12 hydrochemical facies identified, four have been found arsenic-affected: Ca–HCO₃, Mg–HCO₃, Ca–Mg–HCO₃ and Mg–Ca–HCO₃. The geochemical evolution of groundwater, as investigated by graphical interpretation and statistical techniques (correlation, principal component analysis) revealed that dissolution of detrital calcite, dolomite and infiltration of rainwater are the major processes shaping the groundwater chemistry in the newer alluvium. Arsenic and iron showed strong positive correlation. Rainfall infiltration, carrying organic matter from recently accumulated biomass from this flood-prone belt, plays a critical role in releasing arsenic and iron present in the sediments. Geochemical evolution of groundwater in older alluvium follows a different path, where cation-exchange has been identified as a significant process.     

Stable carbon and oxygen isotope investigation in historical lime mortar and plaster – Results from field and experimental study

Lime mortar and plaster were sampled from Roman, medieval and early modern buildings in Styria. The historical lime mortar and plaster consist of calcite formed in the matrix during setting and various aggregates. The stable C and O isotopic composition of the calcite matrix was analyzed to get knowledge about the environmental conditions during calcite formation. The δ¹³C_matrix and δ¹⁸O_matrix values range from −31 to 0‰ and −26 to −3‰(VPDB), respectively. Obviously, such a range of isotope values does not represent the local natural limestone assumed to be used for producing the mortar and plaster. In an ideal case, the calcite matrix in lime mortar and plaster is isotopically lighter in the exterior vs. the interior mortar layer according to the relationship δ¹⁸O_matrix = 0.61 · δ¹³C_matrix − 3.3 (VPDB). Calcite precipitation by uptake of gaseous CO₂ into alkaline Ca(OH)₂ solutions shows a similar relationship, δ¹⁸O_calcite = 0.67 · δ¹³C_calcite − 6.4 (VPDB). Both relationships indicate that the ¹³C/¹²C and ¹⁸O/¹⁶O values of the calcite reflect the setting behaviour of the lime mortar and plaster. Initially, CO₂ from the atmosphere is fixed as calcite, which is accompanied by kinetic isotope fractionation mostly due to the hydroxylation of CO₂ (δ¹³C_matrix ≈  −25‰ and δ¹⁸O_matrix ≈ −20‰). As calcite formation continued the remaining gaseous CO₂ is subsequently enriched in ¹³C and ¹⁸O causing later formed calcite to be isotopically heavier along the setting path in the matrix. Deviations from such an ideal isotopic behaviour may be due to the evolution of H₂O, e.g. evaporation, the source of CO₂, e.g. from biogenic origin, relicts of the natural limestone, and secondary effects, such as recrystallization of calcite. The results of the field and experimental study suggest that isotope values can be used as overall proxies to decipher the origin of carbonate and the formation conditions of calcite in the matrix of ancient and recent lime mortar and plaster. Moreover, these proxies can be used to select calcite matrix from historical lime mortar and plaster for ¹⁴C dating.     

Geochemical mass balances of major chemical constituents in the watershed of the Changhuajian River in China

Based on the geological background, R-mode factor statistics, and the analysis of the stability diagram for the corresponding system, five weathering reactions controlling the surface-water chemical composition in the watershed of the Changhuajiang River are deduced. In the mass balance model, the precipitation accounts for some solute input, since the rainwater is dilute without pollution. Most of the Ca²⁺ and HCO ₃ ^– ions are from the dissolution of calcite, K⁺, Na⁺, H₄SiO₄ and some of the Mg²⁺ and HCO ₃ ^– come from albite and biotite weathering to kaolinite. The dissolution of dolomite and gypsum controls the mass balances of Mg²⁺ and SO ₄ ^2– . The dissolution of calcite is the dominant chemical weathering reaction in the watershed because of its reactivity and high concentration. In the watershed in 1986, the chemical weathering rate was 0.073 (kg/m² a), and the mechanical denudation rate is 0.093 (kg/m² a). The chemical weathering mass output proportion of carbonate rocks to silicate rocks was about three to one.     

Pollution par les nitrates des nappes phréatiques sous environnement semi-urbain non assaini: example de la nappe de Yeumbeul, Sénégal

High nitrate concentrations, above the WHO guideline of 50 mg l⁻¹, were observed in samples of shallow wells reaching the Yeumbeul suburb (Senegal) area groundwater. This groundwater is exploited by 7000 houses and therefore there are health implications. Correlations between parameters such as nitrate content (NO₃⁻) in the groundwater and soil water, the distance between shallow wells and family latrines, and soil water chloride (Cl⁻) and colon bacillus content led to two possible sources of groundwater pollution: first, contamination by non impervious and shallow latrines; and second, the leaching of soil NO₃⁻ from waste organic matter carried in groundwater.     

Origin of groundwater salinity and hydrogeochemical processes in a confined coastal aquifer: Case of the Rhône delta (Southern France)

The Rhône delta, South of France (Camargue, 750 km²) is a coastal saline wetland located along the Mediterranean Sea. The confined aquifer of this delta shows high values of electrical conductivity rising from the north (4 mS/cm) to the shoreline (58 mS/cm). This work aims to identify the origin of groundwater salinity and the geochemical processes occurring in this coastal confined aquifer according to the degree of salinity. A natural tracing approach is considered using monthly sampling in 8 piezometers for chemical and isotopic analyses (¹⁸O, ²H, ¹³C_TDIC). Ionic and isotopic ratios demonstrate that strong salinities are due to a simple mixing between Mediterranean seawater and freshwater; seawater contribution reaches up to 98% at 8 km from the shoreline. Seawater intrusion induces a particular groundwater chemistry which varies with the degree of seawater contribution: (1) In the less saline part of the aquifer (seawater contribution <20%), the intrusion induces an increase of Na⁺ in groundwater leading to Ca²⁺/Na⁺ exchange processes. The δ¹³C_TDIC analyses show that matrix exchange processes most likely occur for the less saline samples. (2) In the saline part of the aquifer (seawater contribution >20%), the intrusion induces SO₄ reduction which is confirmed by highly depleted δ¹³C_TDIC values (up to −19‰). The δ¹³C_TDIC also reveals that methanogenesis processes may occur in the most reductive part of the aquifer. Due to SO₄ reduction, the intrusion induces a shift in carbonate equilibrium leading to supersaturation with respect to dolomite and/or magnesian calcite. Thus carbonate precipitation may occur in the area strongly influenced by seawater.     

Saltwater intrusion and nitrate pollution in the coastal aquifer of Dar es Salaam, Tanzania

Dar es Salaam Quaternary coastal aquifer is a major source of water supply in Dar es Salaam City used for domestic, agricultural, and industrial uses. However, groundwater overdraft and contamination are the major problems affecting the aquifer system. This study aims to define the principal hydrogeochemical processes controlling groundwater quality in the coastal strip of Dar es Salaam and to investigate whether the threats of seawater intrusion and pollution are influencing groundwater quality. Major cations and anions analysed in 134 groundwater samples reveal that groundwater is mainly affected by four factors: dissolution of calcite and dolomite, weathering of silicate minerals, seawater intrusion due to aquifer overexploitation, and nitrate pollution mainly caused by the use of pit latrines and septic tanks. High enrichment of Na⁺ and Cl^? near the coast gives an indication of seawater intrusion into the aquifer as also supported from the Na–Cl signature on the Piper diagram. The boreholes close to the coast have much higher Na/Cl molar ratios than the boreholes located further inland. The dissolution of calcite and dolomite in recharge areas results in Ca–HCO₃ and Ca–Mg–HCO₃ groundwater types. Further along flow paths, Ca²⁺ and Na⁺ ion exchange causes groundwater evolution to Na–HCO₃ type. From the PHREEQC simulation model, it appears that groundwater is undersaturated to slightly oversaturated with respect to the calcite and dolomite minerals. The results of this study provide important information required for the protection of the aquifer system.     

The mechanism of cation and oxygen isotope exchange in alkali feldspars under hydrothermal conditions

The mechanism of re-equilibration of albite in a hydrothermal fluid has been investigated experimentally using natural albite crystals in an aqueous KCl solution enriched in ¹⁸O at 600°C and 2 kbars pressure. The reaction is pseudomorphic and produces a rim of K-feldspar with a sharp interface on a nanoscale which moves into the parent albite with increasing reaction time. Transmission electron microscopy (TEM) diffraction contrast and X-ray powder diffraction (XRD) show that the K-feldspar has a very high defect concentration and a disordered Al, Si distribution, compared to the parent albite. Raman spectroscopy shows a frequency shift of the Si-O-Si bending vibration from ~476 cm⁻¹ in K-feldspar formed in normal ¹⁶O aqueous solution to ~457 cm⁻¹ in the K-feldspar formed in ¹⁸O-enriched solution, reflecting a mass-related frequency shift due to a high enrichment of ¹⁸O in the K-feldspar silicate framework. Raman mapping of the spatial distribution of the frequency shift, and hence ¹⁸O content, compared with major element distribution maps, show a 1:1 correspondence between the reaction rim formed by the replacement of albite by K-feldspar, and the oxygen isotope re-equilibration. The textural and chemical characteristics as well as the kinetics of the replacement of albite by K-feldspar are consistent with an interface-coupled dissolution-reprecipitation mechanism.     

Investigation of the hydrogeochemical processes in an alluvial channel aquifer located in a typical Karoo Basin of Southern Africa

An investigation was conducted to assess the hydrogeochemical processes of an alluvial channel aquifer located in a typical Karoo Basin of Southern Africa. The investigation was aimed at identifying and describing the groundwater chemistry evolution and its contribution to the overall groundwater quality. X-ray fluorescent spectrometry (XRF) and X-ray diffractometry (XRD) analyses were performed on geological samples to identify and quantify the major element oxides and minerals. The study utilises the conventional Piper diagram, bivariate plots and PHREEQC hydrogeochemical model to analyse groundwater chemistry data obtained during the wet (February and May) and dry seasons (August and December) of 2011. The XRF and XRD results show that the channel deposits are dominated by SiO₂ element oxides and quartz minerals, thus elevated concentrations of silicon (Si⁴⁺) were found in the groundwater. Dolomite and calcite minerals were also detected in the unconsolidated aquifer sediments. The detailed study of the alluvial aquifer system has shown that dissolution of dolomite and calcite minerals and ion exchange are the dominant hydrogeochemical processes influencing the groundwater quality. The groundwater evolves from Ca²⁺–Mg²⁺–HCO₃ ^? recharge water that goes through ion exchange with Na⁺ in the clay-silt sediment to give a Na⁺–HCO₃ ^? water type. The groundwater is supersaturated with respect to quartz, dolomite and calcite minerals. The study shows the potential usefulness of simple bivariate plots as a complimentary tool to the conventional methods for analyzing groundwater hydrogeochemical processes.     

Fluid–rock reactions in an evaporitic mélange, Permian Haselgebirge, Austrian Alps

Tectonically isolated blocks of carbonate rocks present within the anhydritic Haselgebirge mélange of the Northern Calcareous Alps record a complex history of deformation and associated deep-burial diagenetic to very low-grade metamorphic reactions. Fluids were hot (up to ≈ 250 °C) and reducing brines charged with carbon dioxide. Individual carbonate outcrops within the mélange record different regimes of brine–rock reactions, ranging from pervasive dolomite recrystallization to dedolomitization. Early diagenetic features in these carbonates were almost entirely obliterated. Matrix dolomite alteration was related to thermochemical sulphate reduction (TSR) recognized by the replacement of anhydrite by calcite + pyrite ± native sulphur. Pyrite associated with TSR is coarsely crystalline and characterized by a small sulphur isotope fractionation relative to the precursor Permian anhydrite. Carbonates associated with TSR show low Fe/Mn ratios reflecting rapid reaction of ferrous iron during sulphide precipitation. As a result, TSR-related dolomite and calcite typically show bright Mn(II)-activated cathodoluminescence in contrast to the dull cathodoluminescence of many (ferroan) carbonate cements in other deep-burial settings. In addition to carbonates and sulphides, silicates formed closely related to TSR, including quartz, K-feldspar, albite and K-mica. ⁴⁰Ar/³⁹Ar analysis of authigenic K-feldspar yielded mostly disturbed step-heating spectra which suggest variable cooling through the argon retention interval for microcline during the Late Jurassic. This timing coincides with the recently recognized subduction and closure of the Meliata-Hallstatt ocean to the south of the Northern Calcareous Alps and strongly suggests that the observed deep-burial fluid–rock reactions were related to Jurassic deformation and mélange formation of these Permian evaporites.     

Diagenesis of a mixed siliciclastic/evaporitic sequence of the Middle Muschelkalk (Middle Triassic), the Catalan Coastal Range, NE Spain

The Middle Muschelkalk (Middle Triassic) of the Catalan Coastal Range (north-east Spain) comprises sandstone, mudstone, anhydrite and minor carbonate layers. Interbedded sandstones and mudstones which are dominant in the north-eastern parts of the basin are terminal alluvial fan deposits. South-westward in the basin, the rocks become dominated by interbedded evaporites and mudstones deposited in sabkha/mudflat environments. The diagenetic and pore water evolution patterns of the Middle Muschelkalk suggest a strong facies control. During eodiagenesis, formation of microdolomite, anhydrite, baryte, magnesite, K-feldspar and mixed-layer chlorite/smectite was favoured within and adjacent to the sabkha/mudflat facies, whereas calcite, haematite, mixed-layer illite/smectite and quartz formed mainly in the alluvial facies. Low δ¹⁸O_SMOW values for microdolomite (+23.7 to +28.4%) and K-feldspar overgrowths (+17.3 to +17.7%) suggest either low-temperature, isotopic disequilibrium or precipitation from low-¹⁸O porewaters. Low-¹⁸O waters might have developed, at least in part, during low-temperature alteration of volcanic rock fragments. During mesodiagenesis, precipitation of quartz overgrowths and coarse dolomite occurred in the alluvial sandstones, whereas recrystallization of microdolomite was dominant in the sabkha/mudflat facies. The isotopic compositions of these mesogenetic phases reflect increasing temperature during burial. Upon uplift and erosion, telogenetic calcite and trace haematite precipitated in fractures and replaced dolomite. The isotopic composition of the calcite (δ¹⁸O_SMOW=+21.5 to +25.6%o; δ¹³C= 7.7 to - 5.6%o) and presence of haematite indicate infiltration of meteoric waters.     

Hydrochemical and isotopic characteristics of groundwater in the Souss Upstream Basin, southwestern Morocco

Heterogeneous shallow Plio-Quaternary formations of the Souss Plain represent the most important aquifer in southern High Atlas Mountains in Morocco. The present work was conducted in the Souss Upstream Basin to identify the chemical characteristics and the origin of groundwater in an aquifer under semi-arid climate. Isotopic and hydrochemical compositions combined with geological and hydrogeological data were used for this purpose. The total dissolved solids vary from 239 to 997 mg l⁻¹, and the following groundwater types are recognized: Ca²⁺–Mg²⁺–HCO₃⁻, Ca²⁺–Mg²⁺–SO₄²⁻ and Ca²⁺–Mg²⁺–Cl⁻. The groundwater is saturated and slightly supersaturated with respect to carbonate minerals and undersaturated with respect to evaporite minerals, which means that the groundwater composition is largely controlled by the dissolution of carbonate rocks known in the basin. The isotopic contents of groundwaters ranged from −8‰ to −5.2‰ for δ¹⁸O, from −52‰ to −34‰ for δD, and from 0 to 5.5 TU for tritium. The hydrogen (δD) and oxygen (δ¹⁸O) isotope signatures reveal a significant infiltration before evaporation takes place, indicating a major recharge directly from fractures in the crystalline and limestone formations of Atlas Mountains (above 800 m a.s.l.) and infiltration of surface water in the alluvial cones at the border of the Atlas basins. The very low tritium values suggest that the groundwater recharge follows a long flow path and a mixing between old and modern water is shown. However, a slight evaporation effect is noted in the southern part of the basin close to the Anti-Atlas Mountains.     

Origin of methane in high-arsenic groundwater of Taiwan – Evidence from stable isotope analyses and radiocarbon dating

Groundwaters in the confined aquifers of the Chianan and Ilan coastal plains of Taiwan are rich in dissolved methane (CH₄). Serious endemic “blackfoot disease”, which occurred in the Chianan plain, especially during AD1950-1970, has been demonstrated to have arisen from drinking highly reducing groundwater with abnormal arsenic and humic substance levels. In order to explore the origin of CH₄ and its hydrological implications, stable carbon isotope ratios (δ¹³C) and radiocarbon (¹⁴C) ages of exsolved CH₄, dissolved inorganic carbon (DIC), and sedimentary biogenic sediments from a total of 34 newly completed water wells at 16 sites were determined. The main results obtained are as follows: (1) The δ¹³C_CH4 (−65‰ to −75‰) values indicate that, except for one thermogenic sample (δ¹³C_CH4=38.2‰) from the Ilan plain, all CH₄ samples analyzed were produced via microbially mediated CO₂ reduction. Many δ¹³C_DIC values are considerably greater than −10‰ and even up to 10‰ due to Rayleigh enrichment during CO₂ reduction. (2) Almost all the ¹⁴C ages of CH₄ samples from the shallow aquifer (I) (<60 m depth) are greater than the ¹⁴C ages of coexisting DIC and sediments, suggesting the presence of CH₄ from underlying aquifers. (3) The ¹⁴C ages of coexisting CH₄, DIC and sediments from aquifer (II) of the Chianan plain are essentially equal, reflecting in-situ generation of CH₄ and DIC from decomposition of sedimentary organic matter and sluggishness of the groundwater flow. On the other hand, both CH₄ and DIC from each individual well of the relatively deep aquifers (III) and (IV) in the Chianan plain are remarkably younger than the deposition of their coexisting sediments, indicating that current groundwaters entered these two aquifers much later than the deposition of aquifer sediments. (4) Each CH₄ sample collected from the Ilan plain is older than coexisting DIC, which in turn is distinctly older than the deposition of respective aquifer sediments, demonstrating the presence of much older CO₂ and CH₄ from underlying strata.     

Selected geochemical factors influencing diagenesis of eocene carbonate rocks,peninsular Florida,U.S.A.

The geochemical significance of three selected ions (Mg²⁺, Na⁺, and Sr²⁺) supports a model of dolomitization by brackish groundwater. This groundwater zone contains sufficient quantities of Mg²⁺ to facilitate dolomitization ($\text{Mg}\text{Ca}\text{ratios 1}$). Rising and falling of sea level and fluctuations of the phreatic zone related to climatic variations account for the thickness of the dolomite layers and the chemical distributions within these layers. Sodium concentrations in the calcite are 70–185 ppm, indicating formation in brackish water. Dolomite has sodium concentrations between 50–1400 ppm, suggesting formation in waters of similar salinity.Strontium in calcite ranges from 320–600 ppm, suggesting diagenesis in slightly saline waters in an open system. Dolomite contains 241 ppm Sr²⁺ on the average and calcite has 418 ppm Sr²⁺. The Sr²⁺ concentrations of the dolomite are characteristic of diagenesis in water less saline than sea water. Average strontium concentrations in the dolomite occur in two distinct groups, 260 ppm for dolomite with 39–43 mole-% MgCo₃ and 195 ppm for the dolomite with 44–50 mole-% MgCO₃. The difference in the Sr²⁺ concentrations of the two dolomite groups indicates the higher mole-% MgCO₃ dolomite recrystallized in a less saline environment than the lower mole-% MgCO₃ dolomite. These different environments are attributed to a relatively more saline coastal environment and a less saline inland environment.The more nearly stoichiometric dolomite (44–50 mole-% MgCO₃) has less scatter when mole-% MgCO₃ is plotted against Sr²⁺ and Na⁺. This suggests a greater approach to equilibrium with the dolomitizing fluid than the lower mole-% MgCO₃ (39–43) dolomite. The more saline environment has higher Mg/Ca ratios and promotes more calcium-rich dolomite during diagenesis because of the inhibition from competing foreign ions and because it is thermodynamically a more favorable environment which causes more rapid crystallization. The less saline waters allow recrystallization to proceed more slowly, producing better ordering in the dolomites, textural preservation and development of subhedral to euhedral rhombic crystals.     

The partitioning of Fe and Mg between olivine and carbonate and the stability of carbonate under mantle conditions

We have investigated the effect of Fe on the stabilities of carbonate (carb) in lherzolite assemblages by determining the partitioning of Fe and Mg between silicate (olivine; ol) and carbonates (magnesite, dolomite, magnesian calcite) at high pressures and temperatures. Fe enters olivine preferentially relative to magnesite and ordered dolomite, but Fe and Mg partition almost equally between disordered calcic carbonate and olivine. Measurement of K _d (X _Fe ^carb X _Mg ^ol /X _Fe ^ol X _Mg ^carb ) as a function of Fe/ Mg ratio indicates that Fe–Mg carbonates deviate only slightly from ideality. Using the regular solution parameter for olivine W _FeMg ^ol of 3.7±0.8 kJ/mol (Wiser and Wood 1991) we obtain for (FeMg)CO₃ a W _FeMg ^carb of 3.05±1.50 kJ/mol. The effect of Ca–Mg–Fe disordering is to raise K _d substantially enabling us to calculate W _CaMg ^carb -W _CaFe ^carb of 5.3±2.2 kJ/mol. The activity-composition relationships and partitioning data have been used to calculate the effect of Fe/Mg ratio on mantle decarbonation and exchange reactions. We find that carbonate (dolomite and magnesian calcite) is stable to slightly lower pressures (by 1 kbar) in mantle lherzolitic assemblages than in the CaO–MgO–SiO₂(CMS)–CO₂ system. The high pressure breakdown of dolomite + orthopyroxene to magnesite + clinopyroxene is displaced to higher pressures (by 2 kbar) in natural compositions relative to CMS. CO₂. We also find a stability field of magnesian calcite in lherzolite at 15–25 kbar and 750–1000°C.     

Major ion chemistry of groundwaters in the Bahar area, Hamadan, western Iran

Hydrochemical investigations were carried out in Bahar area, Hamadan, western Iran, to assess the chemical composition of groundwater. The area falls in a semi-arid type of climate. In this area, groundwater has been exploited over the past century mainly for irrigation and water supply. A total of 135 representative groundwater samples were collected from different wells to monitor the water chemistry of various ions. Chemical analysis of the groundwater shows that the mean concentration of the cations is of the order Ca²⁺>Mg ²⁺>Na⁺>K⁺, while that for anions is SO₄^2–>HCO₃^–>Cl^–>NO₃^–. Statistical analyses indicate positive correlation between the following pairs of parameters Cl^– and Mg ²⁺ (r=0.71), Cl^– and Na⁺ (r=0.76), HCO₃^– and Na⁺ (r=0.56), SO₄^2– and Mg²⁺ (r=0.76), SO₄^2– and Na⁺ (r=0.69). Water presents a large spatial variability of the chemical facies (Ca-HCO₃, Ca-SO₄, Mg-HCO₃, Mg-SO₄, Na-HCO₃) which is in relation to their interaction with the geological formations of the basin (carbonates, dolomite and various silicates) and evaporation. The hydrochemical types Ca-HCO₃ and Ca-SO₄ dominate the largest part of the studied area. The dissolution of halite, calcite, dolomite, and gypsum explains part of the contained Na ⁺, Ca²⁺, Mg²⁺, Cl^–, SO₄^2– and HCO₃^–, but other processes, such as cation exchange and weathering of aluminosilicates also contribute to the water composition.