Genesis and evolution of high-pCO2 groundwaters of the Mukhen spa (Russian Far East)

We present the chemical and isotope compositions of the water and gas phases of the unique Mukhen cold high-pCO₂ spa. Estimated 5¹⁸O, 5D, and 5¹³C_tic values and data on geology and hydrogeology of the studied area indicate that the source of the groundwaters is meteoric waters, whereas carbon dioxide is of deep genesis and numerous regional faults are gas-feeding channels. Calculations of equilibrium reactions in the water-rock system show that the upper-aquifer waters (HCO₃-Ca-Mg) with low TDS are undersaturated with carbonate minerals, montmorillonites, and aluminosilicates but are oversaturated with kaolinite, whereas the lower-aquifer waters (HCO3-Na) with high TDS are oversaturated with calcite, dolomite, and clay minerals but are undersaturated with main aluminosilicates. We propose a new concept of the formation of these groundwaters, demonstrating that long interaction between rocks and groundwaters in the presence of CO₂ and considerable precipitation of secondary minerals are responsible for the high TDS of the lower-aquifer waters (up to 14 g/L) and their geochemical type (HCO₃-Na) and unusual isotope composition (5¹⁸O = -25.2%c, 5D = -69.0%c).     

Geochemistry of carbonated mineral waters from the Fadeevskoe deposit of the Primorye region

The geochemical study of bed rocks, underground and surface waters, and associated gases in the Fadeevskoe deposit of carbonated waters (Sikhote Alin, Primorye region) revealed that the chemical composition of these waters is formed in the zone of active water exchange in the limited area of the discharge zone, where hydro carbonate calcic waters with mineralization of up to 1 g/1 are formed in largely potassic-sodic rocks. Calculations of the saturation indices show that the mineral waters are characterized by the early stage of Ca saturation, being undersaturated with carbonates and aluminosilicates. The main factors that influence the water mineralization are the excess carbon dioxide in water and the circulation time. The oxygen and carbon isotope ratios indicate the atmospheric genesis of the aqueous component (δ²H = —117; δ¹⁸O = —15.4%o) and the carbon isotope content in the CO₂ implies the mantle nature of the carbon dioxide (δ¹³C = -9.9%o).     

Analysis of accumulation conditions of minor elements in mineral waters: An example of hydrocarbonate sodic waters of the Nagutskoe mineralized groundwater field

Computer simulations of carbon dioxide leaching of Aptian–Albian sandstone at the Nagutskoe groundwater field, Caucasian Mineral Waters, are compared with laboratory experimental data obtained using a high-pressure autoclave under parameters close to conditions under which mineral waters are formed at the Nagutskoe and Essentuki fields (temperatures 20–25 and 65–70°C, carbon dioxide pressure up to 4.04 MPa). The solvents were distilled water and naturally occurring groundwaters from the Caucasian Mineral Waters (CMW) area, individual experimental runs lasted for 2 h, the starting material (rock) was crushed to 0.25 mm, and the gas phase was carbon dioxide. In most of the experiments, the solid: liquid phase (R/W) ratio was 1: 5 and was varied from 1: 10 to 1: 100 in other experiments. Our simulation results indicate that multiple-cycle (10 cycles) leaching leads to an increase in mineralization from 1.3 g/L to 4 g/L and transformation of the geochemical type of the waters from the hydrocarbonate calcic–sodic one (leaching cycle 1) to chloride–hydrocarbonate sodic (cycles 5 and later). The mineralization increased mostly because the and Na⁺ ions are transferred into solution at an insignificant increase in the Cl concentration and a practically unchanging concentrations of the sulfate, calcium, and magnesium ions. With regard for the averaged mineralogical composition of the sandstone (quartz, feldspars, mica, glauconite, magnetite, ilmenite, garnet, rutile, zircon, and tourmaline) used in our thermodynamic simulations, we arrived at the conclusion that the chemical compositions of the waters, including their minor-element compositions, are controlled by (i) the composition of the cement (clay, calcareous, siliceous, limonitic, chloritic, zeolitic, phosphate, sulfate, or mixed) of the rocks, (ii) weight percentages of minerals containing certain elements, and (iii) temperature, at a given composition of the gas phase of the simulated system (silty sandstone–rainwater–CO₂ gas phase).     

Groundwater in-situ generation of aquatic humic and fulvic acids and the mineralization of sedimentary organic carbon

In this paper the groundwater in-situ generation of dissolved organic carbon (DOC) is discussed based on the origin of groundwaters, their physico-chemical and isotopic properties, chemical composition and the dissolved inorganic carbon (DIC) concentration and its ¹³C content. Three aquifer systems are investigated. Two of these have relatively well defined hydrological and geochemical conditions (Fuhrberg and Munich) and are used as reference systems. The third aquifer (Gorleben) is a complex system containing DOC concentrations up to 200 mg C/L in deep groundwaters. From this aquifer system 19 groundwaters from different hydrogeochemical conditions are analyzed. The in-situ generation of DOC is found to occur in conjunction with the microbiologically mediated mineralization of sedimentary organic carbon (SOC). Thereby, SO₄ is reduced and phosphate is released into the groundwater. Where SO₄ is depleted, the mineralization of SOC occurs via fermentation, resulting in CH₄ generation.     

Arsenic mobility in groundwater/surface water systems in carbonate-rich Pleistocene glacial drift aquifers (Michigan)

Within the Lower Peninsula of Michigan, groundwaters from the Marshall Formation (Mississippian) contain As derived from As-rich pyrites, often exceeding the World Heath Organization drinking water limit of 10 μg/L. Many Michigan watersheds, established on top of Pleistocene glacial drift derived from erosion of the underlying Marshall Formation, also have waters with elevated As. The Huron River watershed in southeastern Lower Michigan is a well characterized hydrogeochemical system of glacial drift deposits, proximate to the Marshall Fm. subcrop, which hosts carbonate-rich groundwaters, streams, and wetlands (fens), and well-developed soil profiles. Aqueous and solid phase geochemistry was determined for soils, soil waters, surface waters (streams and fens) and groundwaters from glacial drift aquifers to better understand the hydrogeologic and chemical controls on As mobility. Soil profiles established on the glacial drift exhibit enrichment in both Fe and As in the oxyhydroxide-rich zone of accumulation. The amounts of Fe and As present as oxyhydroxides are comparable to those reported from bulk Marshall Fm. core samples by previous workers. However, the As host in core samples is largely unaltered pyrite and arsenopyrite. This suggests that the transformation of Fe sulfides to Fe oxyhydroxides largely retains As and Fe at the oxidative weathering site. Groundwaters have the highest As values of all the waters sampled, and many were at or above the World Health limit. Most groundwaters are anaerobic, within the zones of Fe³⁺ and As(V) reduction. Although reduction of Fe(III) oxyhydroxides is the probable source of As, there is no correlation between As and Fe concentrations. The As/Fe mole ratios in drift groundwaters are about an order of magnitude greater than those in soil profiles, suggesting that As is more mobile than Fe. This is consistent with the dominance of As(III) in these groundwaters and with the partitioning of Fe²⁺ into carbonate cements. Soil waters have very low As and Fe contents, consistent with the stability of oxyhydroxides under oxidizing vadose conditions. When CO₂ charged groundwaters discharge in streams and fens, dissolved As is effectively removed by adsorption onto Fe-oxides or carbonate marls. Although Fe does not display conservative behavior with As in groundwaters, a strong positive correlation exists between As and Sr concentrations. As water–rock interactions proceed, the As/Fe and Sr/Ca ratios would be expected to increase because both As and Sr behave as incompatible elements. Comparisons with groundwater chemistries from other drift-hosted aquifers proximate to the Marshall sandstone are consistent with these relations. Thus, the Sr content of carbonate-rich groundwaters may provide useful constraints on the occurrence, origin and evolution of dissolved As in such systems.     

Magma-derived gas influx and water-rock interactions in the volcanic aquifer of Mt. Vesuvius, Italy

We report in this paper a systematic investigation of the chemical and isotopic composition of groundwaters flowing in the volcanic aquifer of Mt. Vesuvius during its current phase of dormancy, including the first data on dissolved helium isotope composition and tritium content. The relevant results on dissolved He and C presented in this paper reveal that an extensive interaction between rising magmatic volatiles and groundwaters currently takes place at Vesuvius.Vesuvius groundwaters are dilute (mean TDS ∼ 2800 mg/L) hypothermal fluids ( mean T = 17.7°C) with a prevalent alkaline-bicarbonate composition. Calcium-bicarbonate groundwaters normally occur on the surrounding Campanian Plain, likely recharged from the Apennines. δD and δ¹⁸O data evidence an essentially meteoric origin of Vesuvius groundwaters, the contribution from either Tyrrhenian seawater or ¹⁸O-enriched thermal water appearing to be small or negligible. However, the dissolution of CO₂-rich gases at depth promotes acid alteration and isochemical leaching of the permeable volcanic rocks, which explains the generally low pH and high total carbon content of waters. Attainment of chemical equilibrium between the rock and the weathering solutions is prevented by commonly low temperature (10 to 28°C) and acid-reducing conditions.The chemical and isotope (C and He) composition of dissolved gases highlights the magmatic origin of the gas phase feeding the aquifer. We show that although the pristine magmatic composition may vary upon gas ascent because of either dilution by a soil-atmospheric component or fractionation processes during interaction with the aquifer, both ¹³C/¹²C and ³He/⁴He measurements indicate the contribution of a magmatic component with a δ¹³C ∼ 0‰ and R/R_a of ∼2.7, which is consistent with data from Vesuvius fumaroles and phenocryst melt inclusions in olivine phenocrysts.A main control of tectonics on gas ascent is revealed by data presented in this paper. For example, two areas of high CO₂ release and enhanced rock leaching are recognized on the western (Torre del Greco) and southwestern (Torre Annunziata-Pompeii) flanks of Vesuvius, where important NE-SW and NW-SE tectonic structures are recognized. In contrast, waters flowing through the northern sector of the volcano are generally colder, less saline, and CO₂ depleted, despite in some cases containing significant concentrations of magma-derived helium. The remarkable differences among the various sectors of the volcano are reconciled in a geochemical interpretative model, which is consistent with recent structural and geophysical evidences on the structure of Somma-Vesuvius volcanic complex.     

Geochemistry of the mineral waters and gases of the Mukhen deposit,Far East

This work reports new hydrochemical data on the two types of cold high p CO₂ groundwaters from the Mukhen deposit (Khabarovsk district). The first type is classed with HCO₃-Ca-Mg waters with a relatively low TDS (up to 1.7 g/l) and high concentrations of Fe²⁺, Mn²⁺, Ba²⁺, and SiO₂. The second type is of HCO₃-Na composition with high TDS (up to 14 g/l) and elevated Li⁺, B, Sr²⁺, Br^?, and I^?. New oxygen (δ¹⁸O) and hydrogen (δD) isotopic data on the waters and carbon (δ¹³C) isotopic data on the gas phase, together with a detailed geological and hydrogeological analysis of the study area, allowed us to decipher the origin of both the mineral waters. Based on the tritium content (³H) in the ground and surface waters of the area, the duration of the mineral water circulation was estimated. It was established that the both types of groundwaters were formed during interaction of meteoric water with bedrock under active influence of CO₂, however HCO₃-Na groundwaters have longer residence time than HCO₃-Ca-Mg groundwaters.     

Br/Cl ratios and O, H, C, and B isotopic constraints on the origin of saline waters from eastern Canada

Saline groundwaters were recovered from undisturbed (Restigouche deposit) and active (Brunswick #12 mine) Zn-Pb volcanogenic massive sulfide deposits in the Bathurst Mining Camp (BMC), northern New Brunswick, Canada. These groundwaters, along with fresh to brackish meteoric ground and surface waters from the BMC, have been analyzed to determine their major, trace element and stable isotopic (O, H, C, and B) compositions. Saline groundwaters (total dissolved solids = 22-45 g/L) are characterized by relatively high Na/Ca ratios compared to brines from the Canadian Shield and low Na/Cl_molar and δ¹¹B isotopic compositions (−2.5‰ to 11.1‰) compared to seawater. Although saline waters from the Canadian Shield commonly have oxygen and hydrogen isotopic compositions that plot to the left of the global meteoric water line, those from the BMC fall close to the water line. Fracture and vein carbonate minerals at the Restigouche deposit have restricted carbon isotopic compositions of around −5‰ to −6‰. The carbon isotopic compositions of the saline waters at the Restigouche deposit (+12‰ δ¹³C_DIC) are the result of fractionation of dissolved inorganic carbon by methanogenesis. We suggest that, unlike previous models for shield brines, the composition of saline waters in the BMC is best explained by prolonged water-rock reaction, with no requirement of precursor seawater. We suggest that elevated Br/Cl ratios of saline waters compared to seawater may be explained by differential uptake of Br and Cl during groundwater evolution through water-rock reaction.     

Volcanic degassing at Somma–Vesuvio (Italy) inferred by chemical and isotopic signatures of groundwater

A geochemical model is proposed for water evolution at Somma–Vesuvio, based on the chemical and isotopic composition of groundwaters, submarine gas emission and chemical composition of the dissolved gases. The active degassing processes, present in the highest part of the volcano edifice, strongly influence the groundwater evolution. The geological–volcanological setting of the volcano forces the waters infiltrating at Somma–Vesuvio caldera, enriched in volcanic gases, to flow towards the southern sector to an area of high pCO₂ groundwaters. Reaction path modelling applied to this conceptual model, involving gas–water–rock interaction, highlights an intense degassing process in the aquifer controlling the chemical and isotopic composition of dissolved gases, total dissolved inorganic C (TDIC) and submarine gas emission. Mapping of TDIC shows a unique area of high values situated SSE of Vesuvio volcano with an average TDIC value of 0.039 mol/L, i.e., one order of magnitude higher than groundwaters from other sectors of the volcano. On the basis of TDIC values, the amount of CO₂ transported by Vesuvio groundwaters was estimated at about 150 t/d. This estimate does not take into account the fraction of gas loss by degassing, however, it represents a relevant part of the CO₂ emitted in this quiescent period by the Vesuvio volcanic system, being of the same order of magnitude as the CO₂ diffusely degassed from the crater area.     

Hydrogeochemistry,groundwater ages and sources of salts in a granitic batholith on the Canadian Shield,southeastern Manitoba

The hydrogeochemistry of the Lac du Bonnet granitic batholith has been determined for the region of the Whiteshell Research Area (WRA) in southeastern Manitoba, Canada. This work forms part of the geosciences studies performed for the Canadian Nuclear Fuel Waste Management Program over the period 1980–1995 by Atomic Energy of Canada Limited (AECL). Knowledge of the variation of groundwater chemistry and its causes is useful in assessing the performance and safety of a nuclear fuel waste vault located at depths of up to 1000 m in a crystalline rock formation of the Canadian Shield. Groundwaters and matrix pore fluids have been obtained by standard sampling methods from shallow piezometers in clay-rich overburden, from packer-isolated borehole zones intersecting fractures or fault zones in the bedrock, and from boreholes in unfractured rock in AECL's Underground Research Laboratory (URL). Eighty-six individual fracture groundwaters have been sampled and analysed from permeable zones in 53 boreholes drilled to depths of up to 1000 m in the Lac du Bonnet batholith. In addition, 28 groundwaters from piezometers in a large wetland area near the URL have been sampled and analysed to determine the influence of clay-rich overburden on the bedrock hydrogeochemistry. Analyses have been made for major and minor ions, pH, Eh, trace metals, and stable and radioactive isotopes, to characterise these groundwaters and relate them to their hydrogeologic regimes. Shallow groundwaters in the fractured bedrock are generally dilute (TDS <0.3 g/l), Ca–Na–HCO₃ waters and show little indication of mixing with Ca–Mg–HCO₃–SO₄ groundwater from overburden sediments. The near-modern levels of ³H and ¹⁴C, and a warm-climate ²H/¹⁸O signature in these groundwaters, indicates that the upper ∼200 m of fractured bedrock contains an active groundwater circulation system with a residence time of tens to hundreds of years. Deeper fracture groundwaters (200–400 m depth) in recharge areas, are more alkaline, Na–Ca–HCO₃ waters and evolve to Na–Ca–HCO₃–Cl–SO₄ waters with increasing distance along the flow path. Isotopic data indicate the presence of a glacial melt-water component suggesting that the residence times of these waters are 10³–10⁵ a. These waters form a transition zone between the upper, advective flow regime and a deeper regime in sparsely fractured rock where groundwater in fractures and fracture zones is largely stagnant. At these depths (> 500 m), Na–Ca–Cl–SO₄ waters of increasing salinity (up to 50 g/l) with depth are found and in some fractures the waters have evolved to a Ca–Na–Cl composition. Isotopic data indicate that these waters are warm-climate and pre-glacial in origin, with residence times of over 1 Ma. Pore fluids observed to drain from the unfractured rock matrix in the URL facility are almost pure Ca–Cl in composition, ∼90 g/l salinity, and have a ²H/¹⁸O composition displaced well to the left of the global meteoric water line, about which all other WRA groundwaters lie. This information indicates that these pore fluids have undergone prolonged water-rock interaction and have residence times of 10¹–10³ Ma. Most of the deeper fracture groundwaters and pore fluids have low Br/Cl ratios and moderate to high δ³⁴S values of dissolved SO₄ which indicates that their salinity could be derived from a marine source such as the basinal sedimentary brines and evaporites to the west of the batholith. These fluids may have entered the batholith during early Paleozoic times when sedimentary rocks were deposited over the granite and were driven by a hydraulic gradient resulting from higher ground in western Canada. The hydrogeochemical data and interpretations show that below ∼500 m in the WRA, fracture-hosted groundwaters are very saline, reducing and old, and are, therefore, indicative of stagnant conditions over the period of concern for nuclear waste disposal (1 Ma). The intact rock matrix at these depths is extremely impermeable as indicated by the presence of pore fluids with unusual geochemical and isotopic characteristics. The pore fluids may represent basinal brines that have evolved geochemically and isotopically to their current composition over periods as long as 10³ Ma.     

Stable isotope geochemistry of ground and surface waters associated with undisturbed massive sulfide deposits; constraints on origin of waters and water-rock reactions

Stable isotopes (H, O, C) were determined for ground and surface waters collected from two relatively undisturbed massive sulfide deposits (Halfmile Lake and Restigouche) in the Bathurst Mining Camp (BMC), New Brunswick, Canada. Additional waters from active and inactive mines in the BMC were also collected. Oxygen and hydrogen isotopes of surface and shallow groundwaters from both the Halfmile Lake and Restigouche deposits are remarkably uniform (− 13 to − 14‰ and − 85 to − 95‰ for δ¹⁸O_VSMOW and δ²H_VSMOW, respectively). These values are lighter than predicted for northern New Brunswick and, combined with elevated deuterium excess values, suggest that recharge waters are dominated by winter precipitation, recharged during spring melting. Deeper groundwaters from the Restigouche deposit, and from active and inactive mines have heavier δ¹⁸O_VSMOW ratios (up to − 10.8‰) than shallow groundwaters suggesting recharge under warmer climate or mixing with Shield-type brines. Some of the co-variation in Cl concentrations and δ¹⁸O_VSMOW ratios can be explained by mixing between saline and shallow recharge water end-members. Carbon isotopic compositions of dissolved inorganic carbon (DIC) are variable, ranging from − 15 to − 5‰ δ¹³C_VPDB for most ground and surface waters. Much of the variation in the carbon isotopes is consistent with closed system groundwater evolution involving soil zone CO₂ and fracture zone carbonate minerals (calcite, dolomite and siderite; average = − 6.5‰ δ¹³C_VPDB). The DIC of saline Restigouche deposit groundwater is isotopically heavy (∼+ 12‰ δ¹³C_VPDB), indicating carbon isotopic fractionation from methanogenesis via CO₂ reduction, consistent with the lack of dissolved sulfate in these waters and the observation of CH₄-degassing during sampling.     

Controls on the geochemistry of rare earth elements along a groundwater flow path in the Carrizo Sand aquifer,Texas, USA

Groundwater samples were collected along a groundwater flow path in the Carrizo Sand aquifer in south Texas, USA. Field measurements that included pH, specific conductivity, temperature, dissolved oxygen (DO), oxidation–reduction potentials (Eh in mV), alkalinity, iron speciation, and H₂S concentrations were also conducted on site. The geochemistry (i.e., concentrations, shale-normalized patterns, and speciation) of dissolved rare element elements (REEs) in the Carrizo groundwaters are described as a function of distance along a flow path. Eh and other redox indicators (i.e., DO, Fe speciation, H₂S, U, and Re) indicate that redox conditions change along the flow path in the Carrizo Sand aquifer. Within the region of the aquifer proximal to the recharge zone, groundwaters exhibit both highly oxidizing and localized mildly reducing conditions. However, from roughly 10 km to the discharge zone, groundwaters are reducing and exhibit a progressive decrease in redox conditions. Dissolved REE geochemical behavior exhibits regular variations along the groundwater flow path in the Carrizo Sand aquifer. The changes in REE concentrations, shale-normalized patterns, and speciation indicate that REEs are not conservative tracers. With flow down-gradient, redox conditions, pH and solution composite, and adsorption modify groundwater REE concentrations, fractionation patterns, and speciation.     

Radon-222 in medicinal groundwaters of Szczawno Zdrój (Sudety Mountains, SW Poland)

 Radon is a significant component of the groundwaters that discharge in the springs of Szczawno Zdrój and are recognized as medicinal. However, among the five exploited springs adjoining each other, it is only in Marta Spring that radon occurs in large concentrations (up to 325.6 Bq/dm³). Therefore, the authors have made an attempt to describe and clarify this fact. They found out from their own research and archival data that ²²²Rn dissolves in the waters of Marta Spring after acidulous waters of deep circulation have mixed with poorly mineralized shallow waters in their outflow zone. The genesis of the gas is determined by the content of its parent nuclide, ²²⁶Ra, in the sandstones in the vicinity of the intake. The volume of the rocks providing radon to the waters of this intake has been estimated at several hundred cubic metres. No seasonal fluctuations in radon concentration have been observed and ²²²Rn concentration changes do not seem to be influenced by changes in the concentration of other chemical components of the waters or by the discharge of the intake. The process of dissolving ²²²Rn in the medicinal groundwaters of Marta Spring is the last, the shortest, and the most local of the processes that form the chemical composition and the physical properties of these waters. Received: 7 January 2000 · Accepted: 12 August 2000     

Obruks, as giant collapse dolines caused by hypogenic karstification in central Anatolia, Turkey: Analysis of likely formation processes

Understanding the development of collapse dolines is crucially important because sudden formation of these landforms threatens property and life. Obruks are mega collapse dolines developed in the lacustrine Neogene carbonates of the Konya Closed Basin in central Turkey. These landforms with diameters and depths reaching several hundreds of meters are characterized by their cylindrical or inverted truncated cone shaped surface morphology and contain lakes if they intersect the local water table. Evaluations based on geological, geophysical, hydrogeological data and the groundwater’s chemical and isotopic compositions suggest a hypogenic mechanism for the development of obruks. This process seems to be driven by the upward migration of a deep-seated carbon dioxide flux from an intrusive magmatic body. Presence of volcanogenic elements (i.e. Li and F) and remarkably high dissolved carbon dioxide (logPCO₂?=?10^?1 atm) in fresh groundwater, hydrothermal springs with elevated He contents (R/Ra?=?4.77), highly enriched carbon-13 isotopic composition of total dissolved inorganic carbon (¹³C_TDIC?=??1.12 ‰ V-PDB) in the regional groundwater and presence of widespread carbon dioxide discharges, constitute apparent evidence for the hypogenic fluid migration into the Neogene aquifer where enhanced dissolution due to mixing between the shallow-fresh and deep-saline groundwaters gives rise to obruk formation.     

Geochemistry and14C dating of groundwaters from Jurassic aquifers of North Aquitaine Basin (France)

Twenty-seven samples from a confined Lower-Middle Jurassic aquifer and an unconfined Oxfordian aquifer of the North Aquitaine Basin (France) have been analysed for their major elements, Br⁻,¹⁸O,²H,¹³C and¹⁴C contents. Hydrochemistry indicates (1) a dissolution of carbonate and anhydrite near the recharge zone and (2) a dilution of a saline water derived from a seawater/halite mixing in the deeper part of the aquifer. The mixing is also visible in a δ¹⁸O vs Cl⁻ diagram in which two different groups appear: recent waters and old waters indicating a mixing process between fresh and saline groundwaters. The composition of the saline water is likely to be 34,100±11,200 ppm in Cl, 70±20 ppm in Br and more than −3.5±07‰ vs SMOW in¹⁸O.¹³C contents indicate (1) a C exchange with CaCO₃ matrix for groundwaters near the recharge zone and (2) a participation of organic matter in the deep part of the aquifer.Residence times for waters near the area of the aquifer outcrop correspond to Holocene and Late Pleistocene periods. The depletion in stable isotopes of 10 to 15,000 y B.P. waters show a late glacial period infiltration to the aquifer. After a distance of about 10 km in the aquifer, the¹⁴C activities are 0 pmc showing the presence of ‘old’ groundwaters.     

Hydrochemical and isotopic characterisation of groundwaters to define aquifer type and connectivity in a subtropical coastal setting,Fraser Coast,Queensland

Physico-chemical parameters, major ion chemistry and isotope composition of surface and groundwaters were determined in forested coastal catchments and adjacent coastal plains. Results showed obvious characterisation related to physical and hydrological setting, and highly variable spatial differences reflecting the complexities of these areas. All these coastal waters are dominated by Na–Cl and fall on a common dilution line; hydrochemical grouping is largely due to anionic differences (Cl, SO₄ and HCO₃), although Na and Mg ratios also vary. Six major hydrochemical facies were determined. For groundwaters, compositional differences are largely related to aquifer material and level of confinement; for coastal groundwaters important are tidal effects and proximity to the shoreline. Differentiation for surface waters is mainly by drainage morphology, flow regime plus proximity to the coast. Connectivity between water bodies is reflected by minor base flow to catchment streams, including with flood plain wetlands, but mostly occurs in low-lying zones where there is mixing of fresh and saline water within surface water and subterranean estuaries, or by seawater intrusion enhanced by overuse. Oxygen and hydrogen isotopic data for confined and semi-confined groundwaters along the coast indicates local recharge; fresh surface waters in the elevated catchments are shown to be sourced further inland plus have experienced evaporation.     

Concentrations and speciation of arsenic along a groundwater flow-path in the Upper Floridan aquifer, Florida, USA

Arsenic (As) concentrations and speciation were determined in groundwaters along a flow-path in the Upper Floridan aquifer (UFA) to investigate the biogeochemical “evolution“ of As in this relatively pristine aquifer. Dissolved inorganic As species were separated in the field using anion-exchange chromatography and subsequently analyzed by inductively coupled plasma mass spectrometry. Total As concentrations are higher in the recharge area groundwaters compared to down-gradient portions of UFA. Redox conditions vary from relatively oxic to anoxic along the flow-path. Mobilization of As species in UFA groundwaters is influenced by ferric iron reduction and subsequent dissolution, sulfate reduction, and probable pyrite precipitation that are inferred from the data to occur along distinct regions of the flow-path. In general, the distribution of As species are consistent with equilibrium thermodynamics, such that arsenate dominates in more oxidizing waters near the recharge area, and arsenite predominates in the progressively reducing groundwaters beyond the recharge area.     

Major ion geochemistry of groundwaters from southern Nevada and eastern California, USA

The dissolved ionic constitutents of groundwaters are,in part,a recored of the minerals and rocks in aquifers through which the water has flowed.The chemical composition and association of these major ions in groundwaters have been used to trace groundwater flow paths and sources,In general,the chemical compostion of water in carbonate-rock aquifers in dominated by calcium,magnesium,and bicarbonate,whereas sodium,chloride,and sulfate can be dominant ions in the water that comes from volcanic aquifers or clay minerals.Since the 1990‘s,we have dealt with the geochemistry of groundwaters from more than 100 springs and wells in southern Nevada and eastrn california ,USA for major solutes and trace elements.This paper compiles the hydrochemical data of major ions of these groundwaters.Based on major ion geochemistry,groundwaters from southern Nevada and eastern California can be classified as carbonate aquifer water,volcanic aquifer water,and mixing water (either mixing of cabonate and volcanic aquifer waters or mixing with local recharges),Piper and stiff diagrams of major ions have graphically shown the general chemical characteristics,classification,and mixing relationships of groundwaters from southern Nevada and eastern California.     

Water-rock interaction and chemistry of groundwaters from the Canadian Shield

The chemical and isotopic compositions of groundwaters in the crystalline rocks of the Canadian Shield reflect different degrees of rock-water interactions. The chemistry of the shallow, geochemically immature groundwaters and especially of the major cations is controlled by local rock compositions, whereby dissolution reactions dominate. Conservative constituents, such as chloride and bromide, however, are not entirely a result of such reactions but appear to be readily added from leachable salts during the initial stages of the geochemical evolution of these waters. Their concentration changes little as major cations increase, until concentrations of Total Dissolved Solids (TDS) reach 3000 to 5000 mg 1^?1. The isotopic composition of these shallow waters reflects local, present day precipitations.In contrast to the shallow groundwaters, the isotopic and chemical compositions of the deep, saline waters and brines are determined by extensive, low-temperature rock-water interactions. This is documented in major ion chemistries, ¹⁸O contents and strontium isotopic compositions. These data indicate that the deep brines have been contained in hydrologically isolated “pockets”. The almost total loss of primary compositions make discussions on the origin of these brines very speculative. However, all brines from across the Canadian Shield have a very similar chemical composition, which probably reflects a common geochemical history. The concentrations of some major and most minor elements in these fluids appear to be governed by reactions with secondary mineral assemblages.     

Chemical and isotopic (<Superscript>18</Superscript>O/<Superscript>16</Superscript>O and D/<Superscript>1</Superscript>H) composition of groundwaters of central and southern Primorye

Groundwaters of Primorye, including its coastal areas, were studied during the past ten years. The macro-and microelement composition of more than 130 samples showed that shallow groundwaters of southern Primorye with pH ranging between 5.4 and 8.4 contain oxygen (up to 10 mg/l) and typically have a mixed ionic composition. The microelement variations reflect both the natural features of the host rocks and possible anthropogenic pollution in the most populated areas. No seawater intrusions were recognized in the study areas, which is confirmed by the chemical composition of the waters, the oxygen and hydrogen isotopic composition of the groundwaters, the atmospheric precipitation, and the coastal seawaters of Primorye. In spite of the variations of individual components, the quality of the groundwaters used for potable purposes is rather satisfactory as compared to the Russian and the World Health Organization standards. At the same time, taking into account the increase of various microelements and biogenic components in the waters, the monitoring and control of the water composition is strongly recommended to preserve their potable quality.