Groundwater origins and mixing pattern in the multilayer aquifer system of the Gafsa-south mining district: a chemical and isotopic approach

Major ion geochemistry and environmental isotopes were used to identify the origins and the mineralisation processes of groundwater flowing within the three aquifer levels of the multilayer system of the Gafsa-south mining district (Southwestern Tunisia). It has been demonstrated that groundwaters are characterised by a Ca–Mg–SO₄ water type. Geochemical pattern is mainly controlled by the dissolution of halite, gypsum and/or anhydrite as well as by the incongruent dissolution of dolomite. δ¹⁸O and δ²H values are much lower than the isotopic signature of regional precipitation and fall close to the meteoric water lines, indicating that groundwaters have not been significantly affected by evaporation or mineral–water reactions. The distribution of stable and radiogenic isotopes (δ¹⁸O, δ²H, δ¹³C and ¹⁴C) within the aquifer levels suggests that the deep confined aquifer receives a significant modern recharge at higher altitudes, while, the shallow unconfined aquifer has been mainly recharged under cooler paleoclimatic condition, likely during Late Pleistocene and Early Holocene humid periods. However, waters from the intermediate confined/unconfined aquifer have composite isotopic signatures, highlighting that they are derived from a mixture of the two first end-members.     

Salt Waters of the Northern Apennine Foredeep Basin (Italy): Origin and Evolution

The salt waters from the Emilia-Romagna sector of the Northern Apennine Foredeep have been investigated using major and trace element and stable isotope (δ²H, δ¹⁸O, δ³⁷Cl, δ⁸¹Br and ⁸⁷Sr/⁸⁶Sr ratio). Ca, Mg, Na, K, Sr, Li, B, I, Br and SO₄ vs. Cl diagrams suggest the subaerial evaporation of seawater beyond gypsum and before halite precipitation as primary process to explain the brine’s salinity, whereas saline to brackish waters were formed by mixing of evaporated seawater and water of meteoric origin. A diagenetic end-member may be a third component for mud volcanoes and some brackish waters. Salinization by dissolution of (Triassic) evaporites has been detected only in samples from the Tuscan side of the Apennines and/or interacting with the Tuscan Nappe. In comparison with the seawater evaporation path, Ca–Sr enrichment and Na–K–Mg depletion of the foredeep waters reveal the presence of secondary processes such as dolomitization–chloritization, zeolitization–albitization and illitization. Sulfate concentration, formerly buffered by gypsum-anhydrite deposition, is heavily lowered by bacterial and locally by thermochemical reduction during burial diagenesis. From an isotopic point of view, data of the water molecule confirm mixing between seawater and meteoric end-members. Local ¹⁸O-shift up to +11‰ at Salsomaggiore is related to water–rock interaction at high temperature (≈150°C) as confirmed by chemical (Mg, Li, Ca distribution) and isotopic (SO₄–H₂O) geothermometers. ³⁷Cl/³⁵Cl and ⁸¹Br/⁷⁹Br ratios corroborate the marine origin of the brines and evidence the diffusion of halogens from the deepest and most saline aquifers toward the surface. The ⁸⁷Sr/⁸⁶Sr ratio suggests a Miocene origin of Sr and rule out the hypothesis of a Triassic provenance of the dissolved components for the analyzed waters issuing from the Emilia-Romagna sector of the foredeep. Waters issuing from the Tuscan side of the Apennines and from the Marche sector of the foredeep show higher ⁸⁷Sr/⁸⁶Sr ratios because of the interaction with siliciclastic rocks.     

Stable Carbon Isotope Biogeochemistry and Anthropogenic Impacts on Karst Ground Water, Zunyi, Southwest China

Natural and anthropogenic impacts on karst ground water, Zunyi, Southwest China, are discussed using the stable isotope composition of dissolved inorganic carbon and particulate organic carbon, together with carbon species contents and water chemistry. The waters can be mainly characterized as HCO₃–Ca type, HCO₃ · SO₄–Ca type, or HCO₃ · SO₄–Ca · Mg type, according to mass balance considerations. It is found that the average δ¹³C_DIC values of ground waters are higher in winter (low-flow season) than in summer (high-flow season). Lower contents of dissolved inorganic carbon (DIC) and lower values of δ¹³C_DIC in summer than in winter, indicate that local rain events in summer and a longer residence time of water in winter play an important role in the evolution of ground water carbon in karst flow systems; therefore, soil CO₂ makes a larger contribution to the DIC in summer than in winter. The range of δ¹³C_DIC values indicate that dissolved inorganic carbon is mainly controlled by the rate of carbonate dissolution. The concentrations of dissolved organic carbon and particulate organic carbon in most ground water samples are lower than 2.0 mg C L⁻¹ and 0.5 mg C L⁻¹, respectively, but some waters have slightly higher contents of organic carbon. The waters with high organic carbon contents are generally located in the urban area where lower δ¹³C_DIC values suggest that urbanization has had an effect on the ground water biogeochemistry and might threaten the water quality.     

Paleowaters in Silurian-Devonian carbonate aquifers: Geochemical evolution of groundwater in the Great Lakes region since the Late Pleistocene

Changes in the climatic conditions during the Late Quaternary and Holocene greatly impacted the hydrology and geochemical evolution of groundwaters in the Great Lakes region. Increased hydraulic gradients from melting of kilometer-thick Pleistocene ice sheets reorganized regional-scale groundwater flow in Paleozoic aquifers in underlying intracratonic basins. Here, we present new elemental and isotopic analyses of 134 groundwaters from Silurian-Devonian carbonate and overlying glacial drift aquifers, along the margins of the Illinois and Michigan basins, to evaluate the paleohydrology, age distribution, and geochemical evolution of confined aquifer systems. This study significantly extends the spatial coverage of previously published groundwaters in carbonate and drift aquifers across the Midcontinent region, and extends into deeper portions of the Illinois and Michigan basins, focused on the freshwater-saline water mixing zones. In addition, the hydrogeochemical data from Silurian-Devonian aquifers were integrated with deeper basinal fluids, and brines in Upper Devonian black shales and underlying Cambrian-Ordovician aquifers to reveal a regionally extensive recharge system of Pleistocene-age waters in glaciated sedimentary basins. Elemental and isotope geochemistry of confined groundwaters in Silurian-Devonian carbonate and glacial drift aquifers show that they have been extensively altered by incongruent dissolution of carbonate minerals, dissolution of halite and anhydrite, cation exchange, microbial processes, and mixing with basinal brines. Carbon isotope values of dissolved inorganic carbon (DIC) range from −10 to −2‰, ⁸⁷Sr/⁸⁶Sr ratios range from 0.7080 to 0.7090, and δ³⁴S-SO₄ values range from +10 to 30‰. A few waters have elevated δ¹³C_DIC values (>15‰) from microbial methanogenesis in adjacent organic-rich Upper Devonian shales. Radiocarbon ages and δ¹⁸O and δD values of confined groundwaters indicate they originated as subglacial recharge beneath the Laurentide Ice Sheet (14-50 ka BP, −15 to −13‰ δ¹⁸O). These paleowaters are isolated from shallow flow systems in overlying glacial drift aquifers by lake-bed clays and/or shales. The presence of isotopically depleted waters in Paleozoic aquifers at relatively shallow depths illustrates the importance of continental glaciation on regional-scale groundwater flow. Modern groundwater flow in the Great Lakes region is primarily restricted to shallow unconfined glacial drift aquifers. Recharge waters in Silurian-Devonian and unconfined drift aquifers have δ¹⁸O values within the range of Holocene precipitation: −11 to −8‰ and −7 to −4.5‰ for northern Michigan and northern Indiana/Ohio, respectively. Carbon and Sr isotope systematics indicate shallow groundwaters evolved through congruent dissolution of carbonate minerals under open and closed system conditions (δ¹³C_DIC = −14.7 to−11.1‰ and ⁸⁷Sr/⁸⁶Sr = 0.7080-0.7103). The distinct elemental and isotope geochemistry of Pleistocene- versus Holocene-age waters further confirms that surficial flow systems are out of contact with the deeper basinal-scale flow systems. These results provide improved understanding of the effects of past climate change on groundwater flow and geochemical processes, which are important for determining the sustainability of present-day water resources and stability of saline fluids in sedimentary basins.     

Geochemical and stable isotopic evolution of the Guarani Aquifer System in the state of São Paulo, Brazil

The purpose of this report is to explain geochemical and stable isotopes trends in the Brazilian unit of the Guarani Aquifer System (Botucatu and Piramboia aquifers) in S?o Paulo State, Brazil. Trends of dissolved species concentrations and geochemical modeling indicated a significant role of cation exchange and dissolution of carbonates in downgradient evolution of groundwater chemistry. Loss of calcium by the exchange for sodium drives dissolution of carbonates and results in Na–HCO₃ type of groundwater. The cation-exchange front moves downgradient at probably much slower rate compared to the velocity of groundwater flow and at present is located near to the cities of Sert?ozinho and águas de Santa Barbara (wells PZ-34 and PZ-148, respectively) in a shallow confined area, 50–70 km from the recharge zone. Part of the sodium probably enters the Guarani Aquifer System. together with chloride and sulfate from the underlying Piramboia Formation by diffusion related to the dissolution of evaporates like halite and gypsum. High concentrations of fluorine (up to 13.3 mg/L) can be explained by dissolution of mineral fluoride also driven by cation exchange. However, it is unclear if the dissolution takes place directly in the Guarani Aquifer System or in the overlying basaltic Serra Geral Formation. There is depletion in δ ²H and δ ¹⁸O values in groundwater downgradient. Values of δ ¹³C(DIC) are enriched downgradient, indicating dissolution of calcite under closed system conditions. Values of δ ¹³C(DIC) in deep geothermal wells are very high (>–6.0‰) and probably indicate isotopic exchange with carbonates with δ ¹³C about –3.0‰. Future work should be based on evaluation of vertical fluxes and potential for penetration of contamination to the Guarani Aquifer System. Electronic Publication     

Stable isotope characterisation of co-existing carbonates from the Holocene Gallocanta lake (NE Spain): palaeolimnological implications

The sedimentary succession of Gallocanta lake, a closed saline lake located in the Iberian Range (NE Spain), documents two successive lacustrine stages: (1) brackish lake stage and (2) shallow saline lake stage. The saline stage corresponds to the present-day situation in which the lake water properties are mainly controlled by a strongly negative annual water balance. The carbonates of the brackish lake stage have relatively constant δ¹⁸O values, however, they are rather high (δ¹⁸O_Do = 2.4‰ and δ¹⁸O_Cc = 4.5‰ mean values) suggesting a hydrologically closed lake with a long residence time of the waters. δ¹⁸O values of carbonates from the saline stage vary greatly, and are lighter than in the previous stage (δ¹⁸O_Do = 0.5‰, δ¹⁸O_Cc = −0.7‰, δ¹⁸O_Mgs = −2.3‰ mean values). These carbonates also precipitated in a hydrologically closed lake, but in equilibrium with a lake water of more variable isotopic composition. The δ¹³C values for carbonates of both stages reflect a mixing of different pools of carbon, but during saline stage δ¹³C values have been more controlled by the equilibrium of the lake waters with atmospheric CO₂. During the current stage, calcite and dolomite precipitate in Gallocanta lake mainly during spring and summer, although dolomite precipitation is more favoured towards the summer. Magnesite precipitates at the beginning of autumn, when the first rainfall re-dissolves the saline surface crust, producing saline waters with a high Mg²⁺ content. The isotopic composition of lake waters sampled in 2005 are far higher than those calculated from the carbonates. It is considered that this could be due to two factors: either because there have not been many extremely dry years (like the year 2005) during the development of the lake, or because the physical and chemical characteristics of the lake waters in such conditions are not appropriate for the development of these minerals.     

Hydrogeochemical and isotopic study of groundwater in the Habor Lake Basin of the Ordos Plateau,NW China

Hydrogeochemistry and isotopes were used to understand the origin and geochemical evolution in the Habor Lake Basin, northwestern China. Groundwater samples were taken, and the isotopic compositions δD, δ¹⁸O and major ions were analyzed. The groundwater can be divided into three types: the Quaternary groundwater, the shallow Cretaceous groundwater and the deep Cretaceous groundwater. The groundwater chemistry is mainly controlled by the feldspar weathering and dolomite weathering, the dissolution of Glauber’s salt, and cation exchange. Chemistry of lake water is mainly controlled by evaporation and precipitation. The stable isotopes of oxygen and hydrogen in groundwater cluster along the local meteoric water line, indicating that groundwater is of meteoric origin. Comparing with shallow groundwater, deep groundwater is depleted in heavy isotopes indicating that deep groundwater was recharged during late Pleistocene and Holocene, during which the climate was more wetter and colder than today.     

Plankton and dissolved inorganic carbon isotopic composition in a river-dominated estuary: Apalachicola Bay, Florida

To characterize the isotopic composition of organisms at the base of the food web and the controls on their variability, the concentration and δ¹³C isotopic composition of dissolved inorganic carbon (DIC) and plankton δ¹³C, δ¹⁵N, and δ³⁴S were measured. The measurements were made during periods of high and low river flow in Apalachicola Bay, Florida, United States, over 3 yr. DIC concentration and δ¹³C values were related to salinity, indicating that conservative mixing of riverine and marine waters was responsible for the overall distributions. The usefulness of DIC δ^13C data for characterizing the trophic processes within the estuary was dependent upon the residence time of water within the season. Plankton δ¹³C values varied from −22‰ to −30‰ and were directly related to estuarine DIC δ¹³C, offset by a factor of roughly −20‰. This offset factor varied with salinity. Values of δ³⁴S in estuarine plankton (station means ranged from 11.4‰ to 13.1‰) were depleted relative to marine plankton (17.7±0.4‰) possibly due to the admixture of³⁴S-depleted sedimentary sulfide with estuarine samples. Values of δ³⁴S in plankton were not related to δ¹³C values of plankton and were only weakly correlated to the salinity of the water from which the plankton were collected, indicating that marine sulfate was the primary source of planktonic sulfur. Values of δ¹⁵N in plankton varied from 5.5‰ to 10.7‰ and appeared related to dominance of the sample by phytoplankton or zooplankton. Estuarine plankton was¹⁵N enriched relative to offshore plankton and estuarine sediment.     

Origin and evolution of oilfield brines from Tertiary strata in western Qaidam Basin: Constraints from <Superscript>87</Superscript>Sr/<Superscript>86</Superscript>Sr, δD, δ<Superscript>18</Superscript>O, δ<Superscript>34</Superscript>S and water chemistry

Chemistry of major and minor elements, ⁸⁷Sr/⁸⁶Sr, δD, δ¹⁸O and δ³⁴S of brines were measured from Tertiary strata and Quaternary salt lakes in the western Qaidam Basin. The water chemistry data show that all oilfield brines are CaCl₂ type. They were enriched in Ca²⁺, B³⁺, Li⁺, Sr²⁺, Br⁻, and were depleted in Mg²⁺, SO₄ ²⁻, which indicated that these brines had the characteristics of deeply circulated water. The relationship between δD and δ¹⁸O shows that all data of these brines decline towards the Global Meteoric Water Line (GWL) and Qaidam Meteoric Water Line (QWL), and that the intersection between oilfield brines and Meteoric Water Lines was close to the local spring and fresh water in the piedmont in the western Qaidam Basin. The results suggest that oilfield brines has initially originated from meteoric water, and then might be affected by water-rock metamorphose, because most oilfield brines distribute in the range of metamorphosing water. The ⁸⁷Sr/⁸⁶Sr values of most oilfield brines range from 0.71121 to 0.71194, and was less than that in salt lake water (>0.712), but close to that of halite in the study area. These imply that salt dissolution occurred in the process of migration. In addition, all oilfield brines have obviously much positive δ³⁴S values (ranging from 26.46‰ to 54.57‰) than that of salt lake brines, which was caused by bacterial sulfate reduction resulting in positive shift of δ³⁴S value and depleteed SO₄ ²⁻ in oilfield brines. Combined with water chemical data and δD, δ¹⁸O, ⁸⁷Sr/⁸⁶Sr, δ³⁴S values, we concluded that oilfield brines mainly originate from the deeply circulated meteoric waters, and then are affected by salt dissolution, water-rock metamorphose, sulfate reduction and dolomitization during the process of migration. These processes alter the chemical compositions of oilfield brines and accumulate rich elements (such as B, Li, Sr, Br, K and so on) for sustainable utilization of salt lake resources in the Qaidam Basin.     

Origin of the Rubian carbonate-hosted magnesite deposit, Galicia, NW Spain: mineralogical, REE, fluid inclusion and isotope evidence

The Rubian magnesite deposit (West Asturian—Leonese Zone, Iberian Variscan belt) is hosted by a 100-m-thick folded and metamorphosed Lower Cambrian carbonate/siliciclastic metasedimentary sequence—the Cándana Limestone Formation. It comprises upper (20-m thickness) and lower (17-m thickness) lens-shaped ore bodies separated by 55 m of slates and micaceous schists. The main (lower) magnesite ore body comprises a package of magnesite beds with dolomite-rich intercalations, sandwiched between slates and micaceous schists. In the upper ore body, the magnesite beds are thinner (centimetre scale mainly) and occur between slate beds. Mafic dolerite dykes intrude the mineralisation. The mineralisation passes eastwards into sequence of bedded dolostone (Buxan) and laminated to banded calcitic marble (Mao). These show significant Variscan extensional shearing or fold-related deformation, whereas neither Rubian dolomite nor magnesite show evidence of tectonic disturbance. This suggests that the dolomitisation and magnesite formation postdate the main Variscan deformation. In addition, the morphology of magnesite crystals and primary fluid inclusions indicate that magnesite is a neoformed hydrothermal mineral. Magnesite contains irregularly distributed dolomite inclusions (<50 μm) and these are interpreted as relics of a metasomatically replaced dolostone precursor. The total rare earth element (REE) contents of magnesite are very similar to those of Buxan dolostone but are depleted in light rare earth elements (LREE); heavy rare earth element concentrations are comparable. However, magnesite REE chondrite normalised profiles lack any characteristic anomaly indicative of marine environment. Compared with Mao calcite, magnesite is distinct in terms of both REE concentrations and patterns. Fluid inclusion studies show that the mineralising fluids were MgCl₂–NaCl–CaCl₂–H₂O aqueous brines exhibiting highly variable salinities (3.3 to 29.5 wt.% salts). This may be the result of a combination of fluid mixing, migration of pulses of variable-salinity brines and/or local dissolution and replacement processes of the host dolostone. Fluid inclusion data and comparison with other N Iberian dolostone-hosted metasomatic deposits suggest that Rubian magnesite probably formed at temperatures between 160 and 200°C. This corresponds, at hydrostatic pressure (500 bar), to a depth of formation of ~~5 km. Mineralisation-related Rubian dolomite yields δ ¹⁸O values (δ ¹⁸O: 12.0–15.4‰, mean: 14.4±1.1‰) depleted by around 5‰ compared with barren Buxan dolomite (δ ¹⁸O: 17.1–20.2‰, mean: 19.4±1.0‰). This was interpreted to reflect an influx of ¹⁸O-depleted waters accompanied by a temperature increase in a fluid-dominated system. Overlapping calculated δ ¹⁸O_fluid values (~+5‰ at 200°C) for fluids in equilibrium with Rubian dolomite and magnesite show that they were formed by the same hydrothermal system at different temperatures. In terms of δ ¹³C values, Rubian dolomite (δ ¹³C: −1.4 to 1.9‰, mean: 0.4±1.3‰) and magnesite (δ ¹³C: −2.3 to 2.4‰, mean: 0.60±1.0‰) generally exhibit more negative δ ¹³C values compared with Buxan dolomite (δ ¹³C: −0.2 to 1.9‰, mean: 0.8±0.6‰) and Mao calcite (δ ¹³C: −0.3 to 1.5‰, mean: 0.6±0.6‰), indicating progressive modification to lower δ ¹³C values through interaction with hydrothermal fluids. ⁸⁷Sr/⁸⁶Sr ratios, calculated at 290 Ma, vary from 0.70849 to 0.70976 for the Mao calcite and from 0.70538 to 0.70880 for the Buxan dolostone. The ⁸⁷Sr/⁸⁶Sr ratios in Rubian magnesite are more radiogenic and range from 0.71123 to 0.71494. The combined δ ¹⁸O–δ ¹³C and ⁸⁷Sr/⁸⁶Sr data indicate that the magnesite-related fluids were modified basinal brines that have reacted and equilibrated with intercalated siliciclastic rocks. Magnesite formation is genetically linked to regional hydrothermal dolomitisation associated with lithospheric delamination, late-Variscan high heat flow and extensional tectonics in the NW Iberian Belt. A comparison with genetic models for the Puebla de Lillo talc deposits suggests that the formation of hydrothermal replacive magnesite at Rubian resulted from a metasomatic column with magnesite forming at higher fluid/rock ratios than dolomite. In this study, magnesite generation took place via the local reaction of hydrothermal dolostone with the same hydrothermal fluids in very high permeability zones at high fluid/rock ratios (e.g. faults). It was also possibly aided by additional heat from intrusive dykes or sub-cropping igneous bodies. This would locally raise isotherms enabling a transition from the dolomite stability field to that of magnesite.Editorial handling: F. Tornos     

Hydrogeochemical properties of CO2-rich thermal–mineral waters in Kayseri (Central Anatolia), Turkey

The present study highlights the hydrogeological and hydrogeochemical characteristics of the CO₂-rich thermal–mineral waters in Kayseri, Turkey. These waters of Dokuzpınar cold spring (DPS) (12–13°C), Yeşilhisar mineral spring (YMS) (13–16°C), Acısu mineral spring (ACMS) (20–22.5°C), Tekgöz thermal spring (TGS) (40–41°C), and Bayramhacı thermal-mineral spring (BTMS) (45–46.5°C) have different physical and chemical compositions. The waters are located within the Erciyes basin in the Central Anatolian Crystalline complex consisting of three main rock units. Metamorphic/crystalline rocks occur as the basement, sedimentary rocks of Upper Cretaceous-Quaternary age form the cover, and volcanosedimentary rocks Miocene-Quaternary in age represent the extrusive products of magmatism acting in that period. All these units are covered unconformably by terrace and alluvial deposits, and travertine occurrences have variable permeability. Dokuzpinar cold spring, YMS and ACMS localized mainly along the faults within the region have higher Na⁺ and Cl⁻ contents whereas TGS and BTMS have higher amounts of Ca²⁺ and HCO ₃ ⁻ . The high concentrations of Ca²⁺ and HCO ₃ ⁻ are mainly related to the high CO₂ contents resulting from interactions with carbonate rocks. Whereas the high Na⁺ content is derived from the alkaline rocks, such as syenite, tuff and basalts, the Cl⁻ is generally connected to the dissolution of the evaporitic sequences. These waters are of meteoric-type. BTMS deviates from meteoric water line. The content is related to the increases in the δ¹⁸O compositions due to mineral–water interaction (re-equilibrium) process. CO₂-dominated YMS and ACMS with low temperatures have higher mineralizations. Yeşilhisar mineral spring, ACMS, TGS and BTMS are oversaturated in terms of calcite, aragonite, dolomite, goethite and hematite, and undersaturated with respect to gypsum, halite and anhydrite. Yeşilhisar mineral spring, ACMS and BTMS are also characterized by recent travertine precipitation. Dokuzpınar cold spring is undersaturated in terms of the above minerals. The higher ratios of Ca/Mg and Cl/HCO₃, and lower ratios of SO₄/Cl in BTMS than TGS suggest that TGS has shallow circulation compared to BTMS, and/or has much more heat-loss enroute the surface. The sequence of hydrogeochemical and isotopic compositions of the waters is in an order of DPS>YMS>ACMS>TGS>BTMS and this suggests a transition period from a shallow circulation to a deep circulation path.     

Hydrogeochemical and isotopic investigation of the Bursa-Oylat thermal waters, Turkey

The Oylat spa is located 80 km southeast of Bursa and 30 km south of Ineg?l in the Marmara region. With temperature of 40°C and discharge of 45 l/s, the Oylat main spring is the most important hot water spring of the area. Southeast of the spa the Forest Management spring has a temperature of 39.4°C and discharge of 2 l/s. The G?z spring 2 km north of the spa, which is used for therapy of eye disease, and cold waters of the Saadet village springs with an acidic character are the further important water sources of the area. EC values of Main spring and Forest Management hot spring (750–780 μS/cm) are lower than those of Saadet and G?z spring waters (2,070–1,280 μS/cm) and ionic abundances are Ca > Na + K > Mg and SO₄ > HCO₃ > Cl. The Oylat and Sızı springs have low Na and K contents but high Ca and HCO₃ concentrations. According to AIH classification, these are Ca–SO₄–HCO₃ waters. Based on the results of δ¹⁸O, ²H and ³H isotope analyses, the thermal waters have a meteoric origin. The meteoric water infiltrates along fractures and faults, gets heated, and then returns to surface through hydrothermal conduits. Oylat waters do not have high reservoir temperatures. They are deep, circulating recharge waters from higher enhanced elevations. δ¹³C_DIC values of the Main spring and Forest Management hot spring are −6.31 and −4.45‰, respectively, indicating that δ¹³C is derived from dissolution of limestones. The neutral pH thermal waters are about +18.7‰ in δ³⁴S while the sulfate in the cold waters is about +17‰ (practically identical to the value for the neutral pH thermal waters). However, the G?z and Saadet springs (acid sulfate waters) have much lower δ³⁴S values (~+4‰).     

贵州七星洞系统中水文地球化学特征对滴水δ~(13)C_(DIC)的影响及其意义

2003年4月至2004年5月,笔者对贵州七星洞(QXD)进行了较为详细的监测,逐月采集了土壤水和洞穴滴水等样品,分别测定了样品的稳定碳同位素组成和水文地球化学参数。结果显示,9个滴水点同期的溶解无机碳同位素值(δ13CDIC)之间存在着大的差异,最大达6.9‰;δ13CDIC值偏重的Ⅰ组滴水,其Ca、Sr、HCO3、电导率(EC)和方解石饱和指数(SIC)等水文地球化学指标偏小,而Mg/Ca比值偏大,Ⅱ组则相反;不同滴水点的δ13CDIC值分别与相应滴水的Ca、Sr、HCO3、EC、Mg/Ca和SIC等水文地球化学指标之间存在较好的相关关系。进一步分析表明,与土壤水δ13CDIC平均值-9.9‰相比,Ⅰ组1#、2#、6#、7#和8#滴水点δ13CDIC值偏重4.5‰～5.7‰,主要是由大量的基岩溶解以及前期方解石沉积(prior calcite precipitation,PCP)共同作用的结果;Ⅱ组3#、4#、5#和9#滴水点δ13CDIC值偏重0.6‰～1.6‰,受基岩溶解和PCP过程影响较小,尤其是9#滴水点受影响最小。因此,若不考虑基岩溶解和PCP过程影响作用,将会极大地影响洞穴化学沉积物碳同位素记录的准确解释。     

Fluid flow through the sedimentary cover in northern Switzerland recorded by calcite–celestite veins (Oftringen borehole,Olten)

Abundant veins filled by calcite, celestite and pyrite were found in the core of a 719 m deep borehole drilled in Oftringen near Olten, located in the north-western Molasse basin, close to the thrust of the Folded Jura. Host rocks are calcareous marl, argillaceous limestone and limestone of the Dogger and Malm. The δ¹⁸O values of vein calcite are lower than in host rock carbonate and, together with microthermometric data from fluid inclusions in vein calcite, indicate precipitation from a seawater-dominated fluid at average temperatures of 56–68°C. Such temperatures were reached at the time of maximum burial of the sedimentary pile in the late Miocene. The depth profile of δ¹³C and ⁸⁷Sr/⁸⁶Sr values and Sr content of both whole-rock carbonate and vein calcite show marked trends towards negative δ¹³C, high ⁸⁷Sr/⁸⁶Sr, and low Sr content in the uppermost 50–150 m of the Jurassic profile (upper Oxfordian). The ⁸⁷Sr/⁸⁶Sr of vein minerals is generally higher than that of host rock carbonate, up to very high values corresponding to Burdigalian seawater (Upper Marine Molasse, Miocene), which represents the last marine incursion in the region. No evidence for internally derived radiogenic Sr (clay minerals) has been found and so an external source is required. S and O isotope composition of vein celestite and pyrite can be explained by bacterial reduction of Miocene seawater sulphate. The available data set suggests the vein mineralization precipitated from descending Burdigalian seawater and not from a fluid originating in the underlying Triassic evaporites.     

Temporal and spatial differences in salinity and water chemistry in SW Florida estuaries: Effects of human-impacted watersheds

Three estuaries near Naples, Florida with variably modified watersheds have been investigated to understand the chemical consequences of altering drainage patterns. Blackwater River (near natural drainage, control site), Henderson Creek (moderately modified watershed), and Faka-Union Canal (severe channelization) were sampled for temperature, salinity, δ¹⁸O, δ¹³C of dissolved inorganic carbon (DIC), molality of CO₂ (ΣCO₂), and Mg:Ca and Sr:Ca ratios between freshwater and marine water end members over a 17-mo period. Carbon isotope composition followed similar seasonal patterns as salinity. Freshwater and seawater end members are more negative than the global average, likely reflecting equilibration with local carbon sources derived from mangrove leaf litter and groundwater. δ¹³C responds to differences in primary productivity between estuaries. Henderson Creek has higher primary productivity than Blackwater River (probable due to higher sewage input and agricultural runoff) and has more positive δ¹³C and lower ΣCO₂. δ¹⁸O is affected by seasonal input of freshwater from atmospheric precipitation, evaporation, and groundwater. Late summer and fall rains lower the δ¹⁸O of estuarine water, whereas evaporative conditions in the dry season elevate δ¹⁸O to values that can be more positive upstream than those from the Gulf of Mexico (estuarine inversion). Evaporation produces water in the Gulf of Mexico that is >1‰ more positive than the global sea surface average most of the year. The very negative δ¹⁸O values in Blackwater River and Henderson Creek likely reflect atmospheric and groundwater contribution. Mg:Ca and Sr:Ca ratios of Gulf water from all three estuaries are similar to global averages at low latitudes. Freshwater end members among estuaries are different in that Blackwater River has higher ratios, suggesting a groundwater contribution. Dolomitic rocks in the subsurface likely provide a source of Mg ions.     

Hydrogeochemistry,environmental isotopes and the origin of the Hamamayagi-Ladik thermal spring (Samsun,Turkey)

Hamamayagi thermal spring (HTS) is located along the North Anatolian Fault Zone. The thermal spring has a temperature of 36°C, with total dissolved solids ranging from 485.6 to 508.5 mg/L. Hard, brittle, and gray limestones Permian aged are the reservoir rocks of the HTS. δ¹⁸O–δ²H isotope ratios clearly indicate a meteoric origin for the waters. The δ³⁴S value of sulfate in the thermal water is nearly 4.1‰ and implies a diagenetic environment characterized by reduced sulfur compounds. The δ¹³C ratio for dissolved inorganic carbonate in the HTS lies between −1.78 and −1.62‰, showing that it originates from the dissolution of fresh-water carbonates. Quartz geothermometry suggests a reservoir temperature of 52–85°C for the Hamamayagi geothermal field, but chalcedony geothermometers suggest reservoir temperatures between 30 and 53°C.     

Study on Modern Plant C－13 in Western China and Its Significance

Organic carbon isotopic composition(δ^13C) is one of the important proxies in paleoenvironment studies.In this paper modern plant δ^13C in the arid areas of China and Tibetan Plateau is studied.It is found that most terrestrial plant species in western China are C3 plants with δ^13C values ranging from -32.6‰ to -23.2‰ and only few species are C4 plants with δ^13C values from -16.8‰ to -13.3‰.The δ^13C is closely related to precipitation (or humidity),i.e., light δ^13C is related to high precipitation(or humid climate),while heavy δ^13C to low precipitation (or dry climate),but there is almost no relation between plant δ^13C and temperature.Submerged plants have δ^13C values ranging from -22.0‰ to -12.7‰,like C4 plants,while merged plants have δ^13C values ranging from -28.1‰ to -24.5‰，like C3 C4 plants,while marged plants have δ^13C values ranging from -28.1‰ to -24.5‰,like C3 plants.It can then be concluded that organic δ^13C variations in terrestrial sediments such as loeas and soil in western China can indicate precipitation changes,but those in lake sediments can reflect organic sources and the productivity of different types of aquatic plants.     

Transmission of <Emphasis Type="Italic">δ</Emphasis><Superscript>13</Superscript>C signals and its paleoclimatic implications in Liangfeng Cave system of Guizhou Province,SW China

A series of samples, including vegetation, soil organic matter, soil waters, spring, bedrock, pool water, drip waters (upper-drip waters and ground-drip waters) and their corresponding speleothems were collected at Liangfeng Cave (LFC) system of Guizhou Province, southwest of China, respectively, from 2003 to 2004 year, then their stable carbon isotopes were measured and analyzed. Results reveal that vegetation is C₃ type in LFC system; cave overlying δ ¹³C signals, including values and variations, could be transmitted to drip water (speleothem); speleothem δ ¹³C mainly shows a biogenic δ ¹³C value character (soil CO₂ from plant respiration and decay); and there are remarkable seasonal variations of δ ¹³C values for drip water TDIC (speleothem), which are lighter at least 2.0‰ in the rainy seasons than in the dry ones. So, it could be feasible to reconstruct high-resolution changes of paleoecology and paleoclimate by using speleothem δ ¹³C values.     

Fluid inclusion and carbon, oxygen, and strontium isotope study of the Polaris Mississippi Valley-type Zn–Pb deposit, Canadian Arctic Archipelago: implications for ore genesis

The Polaris deposit is one of the largest Mississippi Valley-type deposits in the world, with 22 million tonnes of ore at 14% Zn and 4% Pb contained in a single, compact orebody surrounded by dolomitized host rocks. Using detailed sampling of carbonates in the orebody and the dolostone halo, this paper aims to characterize the temporal and spatial evolution of the mineralizing system, and to understand the mechanisms that controlled the accumulation of this large, compact Zn–Pb deposit. Five types of dolomite have been distinguished, including three replacement (RD) and two pore-filling dolomites (PD). The paragenetic order is RD1, RD2, RD3, PD1, and PD2. Pore-filling calcite (PC) postdates all other minerals. In most cases, sulfides and dolomite did not co-precipitate, but sphalerite and galena largely overlap with RD3 and PD1. Various dolomites are dissolved or replaced by sulfide-precipitating fluids; sulfides in turn can be overgrown by dolomites. Colloform texture in sphalerite is widespread. Fluid inclusions were studied in RD3, PD1, PD2, sphalerite, and PC. The overall ranges of homogenization temperatures (T _h) and last ice-melting temperatures (T _m-ice) for fluid inclusions in dolomites and sphalerite are from 67 to 141 °C and from −46.7 to −27.0 °C, respectively, consistent with warm basinal brines with high salinities and Ca/Na ratios. Gas chromatographic analysis of these fluid inclusions indicates low concentrations of hydrocarbons (<0.06 mol%). C, O, and Sr isotopes were analyzed for all dolomites and PC, as well as for the fine-grained host limestone and early diagenetic calcite (SC–RC). The isotopic values of RD2, RD3, PD1, and PD2 cluster tightly and form largely overlapping domains. With respect to the host limestone, they are depleted in ¹⁸O, similar in δ¹³C, and slightly enriched in ⁸⁷Sr. There are no regular spatial variations for fluid inclusion and isotope data, indicating an overall geochemical homogeneity in the hydrothermal system. However, certain samples close to the fracture zones in the orebody with slightly elevated T _h and ⁸⁷Sr/⁸⁶Sr values and depleted δ¹⁸O values suggest that the fracture zone was the conduit for the hot brines. Based on the geological and geochemical characteristics of the deposit, we propose that sulfide precipitation at Polaris was caused by mixing of a reduced, metal-rich, sulfur-poor fluid with a reduced, metal-poor, sulfur-rich fluid at the site of mineralization. The metal-carrying fluid ascended along fractures from below the deposit and was hotter than the host rocks, whereas the reduced sulfur-carrying fluid was delivered to the site of mineralization laterally and was in thermal equilibrium with the host rocks. This model can readily explain the dissolution of dolomite during sulfide precipitation and the abundance of colloform sphalerite, as well as the low concentrations of hydrocarbons in fluid inclusions. Accepted: 20 December 1999     

Genesis of the Assif El Mal Zn–Pb (Cu,Ag) vein deposit. An extension-related Mesozoic vein system in the High Atlas of Morocco. Structural,mineralogical, and geochemical evidence

The Assif El Mal Zn–Pb (Cu–Ag) vein system, located in the northern flank of the High Atlas of Marrakech (Morocco), is hosted in a Cambro-Ordovician volcaniclastic and metasedimentary sequence composed of graywacke, siltstone, pelite, and shale interlayered with minor tuff and mudstone. Intrusion of synorogenic to postorogenic Late Hercynian peraluminous granitoids has contact metamorphosed the host rocks giving rise to a metamorphic assemblage of quartz, plagioclase, biotite, muscovite, chlorite, amphibole, chloritoid, and garnet. The Assif El Mal Zn–Pb (Cu–Ag) mineralization forms subvertical veins with ribbon, fault breccia, cockade, comb, and crack and seal textures. Two-phase liquid–vapor fluid inclusions that were trapped during several stages occur in quartz and sphalerite. Primary inclusion fluids exhibit T _h mean values ranging from 104°C to 198°C. Final ice-melting temperatures range from −8.1°C to −12.8°C, corresponding to salinities of ∼15 wt.% NaCl equiv. Halogen data suggest that the salinity of the ore fluids was largely due to evaporation of seawater. Late secondary fluid inclusions have either Ca-rich, saline (26 wt.% NaCl equiv.), or very dilute (3.5 wt.% NaCl equiv.) compositions and homogenization temperatures ranging from 75°C to 150°C. The δ¹⁸O and δD fluid values suggest an isotopically heterogeneous fluid source involving mixing between connate seawater and black-shale-derived organic waters. Low δ¹³C_VPDB values ranging from −7.5‰ to −7.7‰ indicate a homogeneous carbon source, possibly organic matter disseminated in black shale hosting the Zn–Pb (Cu–Ag) veins. The calculated δ³⁴S_H2S values for reduced sulfur (22.5‰ to 24.3‰) are most likely from reduction of SO₄ ²⁻ in trapped seawater sulfate or evaporite in the host rocks. Reduction of sulfate probably occurred through thermochemical sulfate reduction in which organic matter was oxidized to produce CO₂ which ultimately led to precipitation of saddle dolomite with isotopically light carbon. Lead isotope compositions are consistent with fluid–rock interaction that leached metals from the immediate Cambro-Ordovician volcaniclastic and metasedimentary sequence or from the underlying Paleo-Neoproterozoic crustal basement. Geological constraints suggest that the vein system of Assif El Mal formed during the Jurassic opening of the central Atlantic Ocean.