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.     

The geochemical and isotopic composition of aquifer systems in the deltaic region of the Po River plain (northern Italy)

The chemical and hydrodynamic characteristics of groundwater in deltaic regions are strongly influenced by the complex stratigraphy of these areas, caused by the continuously varying depositional environments associated with their recent hydrographic evolution. As a case study, the eastern sector of the Po River plain, northern Italy, has been investigated to understand the quality of the available groundwater resources. Based on the analysis of hydrochemical and isotopic data, the recharge characteristics, the groundwater residence time and the aquifer vulnerability are defined. The results show significant qualitative degradation of the unconfined aquifer due to the shallow depth to water, while in the underlying confined aquifer, a hydrochemical facies of Ca–HCO₃ type prevails. The spatial variation and relationship between oxygen-18 and deuterium determine: firstly, hydraulic separation of the two hydrogeological units; secondly, direct infiltration of local precipitation to the unconfined aquifer; thirdly, the occurrence of waters originating in the Alps and locally from the Apennines, pervading the confined aquifer. The tritium results suggest local mixing between the superficial waters and the confined aquifer, occurring along the palaeo-river channels. This increases the pollution vulnerability of the confined hydrogeological unit within the plain, which is the only natural groundwater resource exploited for water supply.     

Hydrochemical evolution and water quality along the groundwater flow path in the Sandıklı plain, Afyon, Turkey

 An unconfined aquifer system suggests an open system in the study area. Hydrochemical evolution is related to the flow path of groundwater. The groundwaters are divided into two hydrochemical facies in the study area, 1) Ca–Mg–HCO₃ and 2) Ca–Mg–SO₄HCO₃. Facies 1 has shallow (young) waters which dominate in recharge areas during rapid flow conditions, whereas facies 2 may show shallow and mixed waters which dominate intermediate or discharge areas during low flow conditions. Ionic concentrations, TDS, EC and water quality are related to groundwater residence time and groundwater types. The groundwaters in the plain are chemically potable and suitable for both domestic and agricultural purposes. Received: 20 May 1996 · Accepted: 30 July 1996     

Comparison of the Sr isotopic signatures in brines of the Canadian and Fennoscandian shields

A synthesis of Sr isotope data from shallow and deep groundwaters, and brines from the Fennoscandian and Canadian Shields is presented. A salinity gradient is evident in the water with concentrations varying from approximately 1–75 g L⁻¹ below 1500 m depth in the Fennoscandian Shield and from 10 up to 300 g L⁻¹ below 650 m depth in the Canadian Shield. Strontium isotope ratios were measured to assess the origin of the salinity and evaluate the degree of water–rock interaction in the systems. In both shields, the Sr concentrations are enriched relative to Cl, defining a positive trend parallel to the seawater dilution line and indicative of Sr addition through weathering processes. The depth distribution for Sr concentration increases strongly with increasing depth in both shields although the variation in Sr-isotope composition does not mirror that of Sr concentrations. Strontium-isotope compositions are presented for surface waters, and groundwaters in several sites in the Fennoscandian and Canadian Shields. Numerous mixing lines can be drawn reflecting water–rock interaction. A series of calculated lines links the surface end-members (surface water and shallow groundwater) and the deep brines; these mixing lines define a range of ⁸⁷Sr/⁸⁶Sr ratios for the deep brines in different selected sites. All sites show a specific ⁸⁷Sr/⁸⁶Sr signature and the occurrence of large ⁸⁷Sr/⁸⁶Sr variations is site specific in both shields. In Canadian Shield brines, the Sr isotope ratios clearly highlight large water rock interaction that increases the ⁸⁷Sr/⁸⁶Sr ratio from water that could have been of marine origin. In contrast to the Canadian Shield, groundwater does not occur in closed pockets in the Fennoscandian, and the well-constrained ⁸⁷Sr/⁸⁶Sr signatures in deep brines should correspond to a large, well-mixed and homogeneous water reservoir, whose Sr isotope signature results from water–rock interaction.     

Chemical evolution of saline waters in the Jordan-Dead Sea transform and in adjoining areas

The Ca–Mg relationship in groundwaters strongly points to the overall dolomitization and local albitization. The Mg/Ca ratios reveal two trends by which saline waters develop: increase of Mg/Ca ratio by evaporation and decreasing Mg/Ca ratios due to dolomitization and albitization. Br/Cl vs. Na/Cl ratios demonstrate that albitization does not play a major role which leaves dolomitization to be the main source for decreasing Mg/Ca ratios in saline waters. In the eastern and southern Region of Lake Kinneret, salinization occurs by mixing with a Ca/Mg molar ratio <1 brine (Ha’On type). Along the western shoreline of the Lake, a Ca/Mg > 1 dominates, which developed by the albitization of plagioclase in abundant mafic volcanics and the dolomitization of limestones. The most saline groundwater of the Tabgha-, Fuliya-, and Tiberias clusters could be regional derivatives of at least two mother brines: in diluted form one is represented by Ha’On water, the other is a Na-rich brine of the Zemah type. Additionally, a deep-seated Ca-dominant brine may ascend along the fractures on the western side of Lake Kinneret, which is absent on the eastern side. Groundwaters of the Lower Jordan Valley are chemically different on both sides of the Jordan River, indicating that the exchange of water is insignificant. All saline waters from the Dead Sea and its surroundings represent a complex mixture of brines, and precipitation and local dissolution of halite and gypsum. Many wells of the Arava/Araba Valley pump groundwater from the Upper Cretaceous limestone aquifer, the origin of the water is actually from the Lower Cretaceous Kurnub Group sandstones. Groundwater drawn from the Quaternary alluvial fill either originates from Kurnub Group sandstones (Eilat 108, Yaalon 117) or from altered limestones of the Judea Group. The origin of these waters is from floods flowing through wadis incised into calcareous formations of the Judea Group. On the other hand, as a result of step-faulting, hydraulic contact is locally established between the Kurnub- and the Judea Groups aquifers facilitating the inter-aquifer flow of the confined Kurnub paleowater into the karstic formations of the Judea Group. Two periods of Neogene brine formation are considered: the post-Messinan inland lagoon resulting in drying up of the Sdom Sea and the evaporation of the Pleistocene Samra Lake, which went further through the stage of Lake Lisan to the present Dead Sea. For the first period, major element hydrochemistry suggests that the saline waters and brines in the Jordan-Dead Sea–Arava Valley transform evolved from the gradual evaporation of an accumulating mixture of sea-, ground-, and surface water. Due to the precipitation of carbonates, gypsum, and halite, such an evaporating primary water body was strongly enriched in Mg, Br, and B and shows high molar ratios of Br/Cl, B/Cl, and Mg/Ca but low Na/Cl ratios. The development of the Br/Cl ratio is chemically modelled, showing that indeed brine development is explicable that way. Along with the evaporation brine, evaporites formed which are leached by infiltrating fresh water yielding secondary brines with Na/Cl ratios of 1. When primary brines infiltrated the sub-surface, they were subjected to Mg–Ca exchange in limestones (dolomitization) and to chloritization and albitization in basic igneous rocks turning them into Ca-Cl brines. These tertiary brines are omnipresent in the Rift. The brines of the late Lisan and Dead Sea were generated by evaporating drainage waters, which leached halite, gypsum, and carbonates from the soil and from the sub-surface. All these brines are still being flushed out by meteoric water, resulting in saline groundwaters. This flushing is regionally enhanced by intensive groundwater exploitation. In variable proportions, the Neogene and late Lisan Lake and Recent Dead Sea brines have to be considered as the most serious sources of salinization of groundwaters in the Rift. Deep-seated pre-Sdom brines cannot strictly be excluded, but if active they play a negligible role only. An erratum to this article can be found at     

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.     

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.     

Salinization of groundwater in the North German Basin: results from conjoint investigation of major, trace element and multi-isotope distribution

Conjoint consideration of distribution of major, rare earth elements (REE) and Y (combined to REY) and of H, O, C, S, Sr isotopes reveals that four types of groundwater are distinguishable by their chemical composition presented by spider patterns. REY patterns indicate thermo-saline deep water and two types of shallow saline groundwaters. Presence of connate waters is not detectable. Sr isotope ratios distinguish three sources of Sr: fast and slow weathering of biotite and K-feldspar in Pleistocene sediments, respectively, and dissolution of limestones. δ¹³C(DIC) indicate dissolution of limestone under closed and open system conditions. Numerous samples show δ¹³C(DIC) > 13‰ which is probably caused by incongruent dissolution of calcite and dolomite. The brines from below 1,000 m represent mixtures of pre-Pleistocene seawater or its evaporation brines and infiltrated post-Pleistocene precipitation. The shallow waters represent mixtures of Pleistocene and Recent precipitation salinized by dissolution of evaporites or by mixing with ascending brines. The distribution of water types is independent on geologic units and lithologies. Even the Tertiary Rupelian aquiclude does not prevent salinization of the upper aquifer.     

Arsenic in groundwaters of the alluvial aquifer of Bardsir plain, SE Iran

Bardsir plain is located in the central part of Kerman Province of Iran. The relative prevalence of arsenic-related cancers, the high concentration of arsenic in nearby plains, as well as the recharge of this aquifer through the mountains composed of high-sulfide volcanic rocks have been motivations of the authors to study the concentration of this element in Bardsir plain. Arsenic concentration was measured in 63 groundwater samples using inductively coupled plasma mass spectrometry method. The results were evaluated through iso-concentration maps, correlation diagrams, and multivariate statistical methods. Accordingly, the concentration of arsenic ranges from 1.3 to 464.5 μg/l with an average value of 134.2 μg/l. So, the groundwaters are enriched with arsenic to much higher levels than permitted for than drinking water acceptable level (10 μg/l). The high arsenic levels in groundwaters of Bardsir plain are ascribed to joint influence of decomposition of sulfides present in mountainous volcanic rocks and the mixing with hydrothermal waters in some locations. Supposedly, the prevalence of higher than 8 pH values has enhanced the release of arsenic from Fe-hydroxides generated during sulfide weathering process.     

浅层地下水氟的溶解／沉淀作用的定量研究

以河北邢台山前平原浅层高氟地下水为例，根据氟的化学热力学分析，确定了控制浅层地下水中氟迁移和富集的固相沉淀物，以及不同化学类型的浅层地下水中含氟固相沉淀物的溶解／沉淀条件；利用浅层地下水化学平衡反应模型和ＰＨＲＥＥＱＥ软件，确定了氟化的稳定区域，计算了氟化钙的饱和指数．研究结果表明，在浅层高氟地下水的整个形成过程中，都表现为氟由固相转入水相的趋势，有利于氟的迁移和富集     

Features of acid–saline systems of Southern Australia

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

The geochemistry of formation waters in the molasse basin of upper Austria

The geochemistry of formation waters in the Molasse basin of Upper Austria has been investigated to ascertain the extent of meteoric water replacement of the connate interstitial fluids in these sediments. The chemistry, isotopic composition, and dissolved gas contents of the groundwaters and of oil and gas associated brines have been determined. The most superficial sediments of the basin, the Innviertel (Miocene), have been completely flushed by meteoric waters within the last 200 ka. The underlying Hall and Puchkirchen formations (Miocene/Oligocene) form gas reservoirs for biogenic methane, and the associated formation waters are chemically and isotopically modified connate brines of the original marine deposition. In the northeastern part of the basin, the connate brines of the deeper sediments (Cretaceous/Jurassic) have been partially or completely replaced by meteoric waters, whereas in the south of the basin these sediments contain high salinity fluids which are substantially of connate origin. These conclusions are supported by the stable isotope composition of the various brines. Oil-associated brines from the Eocene sediments contain large amounts of dissolved radiogenic⁴⁰Ar, which suggests that the oils have migrated from high-temperature environments. This is in contrast with the Puchkirchen, for which the observed absence of radiogenic⁴⁰Ar suggests that the biogenic methane has been formed in situ. The⁴He contents of these brines and of the Cretaceous/Jurassic groundwaters are, however, less than those in the overlying Puchkirchen formation and suggest that He has been removed from the deeper sediments as a result of flushing by meteoric water. The ratios of dissolved methane and nitrogen to argon increase with increasing ammonium content of the formation waters. All of these parameters may be used as indices for the maturation of the system. The heavy noble gases, Kr and Xe, are abnormally abundant in the dissolved gases, and this is attributed to geochemical concentration of these gases by adsorption onto shales in the sediment sequence. The overall geochemical situation confirms the existence of separate hydraulic systems with little interconnection in the several overlying geological horizons.     

Investigation of groundwater mineralization in the Hammamet–Nabeul unconfined aquifer,north-eastern Tunisia: geochemical and isotopic approach

Detailed hydrogeochemical and isotopic data of groundwaters from the Hammamet–Nabeul unconfined aquifer are used to provide a better understanding of the natural and anthropogenic processes that control the groundwater mineralization as well as the sources of different groundwater bodies. It has been demonstrated that groundwaters, which show Na–Cl and Ca–SO₄–Cl water facies, are mainly influenced by the dissolution of evaporates, the dedolomitization and the cation-exchange process; and supplementary by anthropogenic process in relation with return flow of irrigation waters. The isotopic signatures permit to classify the studied groundwaters into two different groups. Non-evaporated groundwaters that are characterized by depleted δ ¹⁸O and δ ²H contents highlighting the importance of modern recharge at higher altitude. Evaporated groundwaters with enriched contents reflecting the significance infiltration of return flow irrigation waters. Tritium data in the studied groundwaters lend support to the existence of pre-1950 and post-1960 recharge. Carbon-14 activities in shallow wells that provide evidence to the large contamination by organic ¹⁴C corroborate the recent origin of the groundwaters in the study area.     

Origin and mobility of humic colloids in the Gorleben aquifer system

The origin and mobility of humic colloids in the Gorleben aquifer system have been examined. For this purpose, the distribution of humic colloids and relevant hydrological and geochemical parameters were examined. An investigation area was selected where sediments have been disturbed by salt dome uplift and glacial events. It is shown that, on a local scale, considerable groundwater movement and intermixing takes place from the surface down to the salt dome. Consequently no effective separation of groundwater layers occurs. Two different humic colloid sources are identified: influx from the humus horizon with recharge water and continuous in situ generation via mineralization of sedimentary organic carbon (SOC). The in situ generation leads to groundwaters with humic colloid concentrations approaching 0.4 g/L, compared to concentrations of less than 0.005 g/L in recharge waters. Young groundwaters (no ¹⁴C decay detected) between approximately 50 and 200 m depth exhibit these highly elevated humic colloid concentrations. At greater depth, salt brines are found with low humic colloid concentrations. This can be attributed to precipitation of humic acid and/or hampering of the in situ generation process due to the high salt content. There is no indication of retention or decomposition of humic colloids. The fate of in situ generated humic colloids cannot be precisely evaluated due to analytical limitations and insufficient understanding of groundwater movement.     

Saturation of groundwaters with respect to minerals of the host rocks

Calculations of the saturation of groundwaters with respect to minerals of the rocks hosting these waters indicate that most of the analyzed groundwaters were saturates with respect to calcite, dolomite, and quartz. Brines of chloride-calcic composition were determined to be saturated with respect to calcite, whereas brines of chloride-sodic composition are saturated with respect to dolomite and quartz. The solution was simultaneously saturated with respect to six minerals for the association ankerite-calcite-dolomite-pyrite-quartz-strontianite. An increase in the number of minerals with respect to which solution is saturated is correlated with an increase in the diversity of types of groundwaters and an increase in the runoff rate. The paper proposes possible avenues for searches for relations between hydrogeological and geochemical parameters that make it possible to adapt the thermodynamic models to real geological-hydrogeological conditions. The research was centered on the testing of groundwaters for their saturation with respect to minerals of the rocks hosting these waters. This parameter plays a significant part in forming the geochemical type of natural waters because it reflects the crystallization of a mineral from a solution and, consequently, the removal of an element from the aqueous solution.     

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.     

Hydrogeochemistry of Roccamonfina volcano (Southern Italy)

This is the first hydro-geochemical investigation carried out on the Roccamonfina Volcanic Complex groundwaters. The chemistry of Roccamonfina waters is defined by water–rock and water–rock–gas interactions. In fact, interactions between rocks of the first eruptive high-K formations and circulating groundwaters are recognized by high K concentrations. On the other hand, inverse concentration of calcium versus alkali metals is related to two different rock interactions occurring in different areas of the volcano: (a) within the caldera where groundwaters flow within latite and pyroclastic formations releasing calcium, and (b) similarly at the base of the volcano where groundwaters flowing from surrounding carbonates got strongly enriched in Ca. These geochemical processes are also associated with K (SE of caldera) and Mg/Ca (in sites located at the NE base of the volcano) decrease. Completely different dynamics occurs at Riardo groundwaters (SE). Here waters are the result of a mix between the Roccamonfina deep aquifer and the carbonate aquifer of the Riardo plain. Rich-CO₂ emissions make these waters strongly mineralized. Minor elements show a similar geochemical behavior of major ions and are crucial defining interactions processes. The evolution of Roccamonfina groundwaters is also evident along the simultaneous enrichment of Ba, Sr, and Ca. Ba increase is the result of deep local carbonate alteration enhanced by CO₂ emissions and, the lower Sr/Ca ratio, from 10 to 2 (ppb/ppm), is also due to the same process. In the light of our results the Roccamonfina aquifer can be schematically divided into two main reservoirs: (a) a superficial aquifer which basically follows the volcanic structure morphology and tectonics and (b) a deeper reservoir, originating within the oldest Roccamonfina volcano ultra potassic lavas and then flowing into the carbonate aquifers of the neighboring plain. Eventually, the chemistry of the Roccamonfina aquifer does not show any specific and visible pollution, contrary to what happens in the volcano surrounding plains. In fact, only 14% of the samples we collected (206) show a NO₃ content >30 mg/l. These sites are all located at the base of the volcano, near the plain.     

The use of bromide and chloride mass ratios to differentiate salt-dissolution and formation brines in shallow groundwaters of the Western Canadian Sedimentary Basin

In the Western Canadian Sedimentary Basin, the petroleum industry handles two geochemically distinctive brines that are traceable in the environment: formation brines extracted along with hydrocarbons from the basin, and salt-dissolution brines, produced by dissolving deep halite formations to create caverns for petroleum product storage. The concentrations of the conservative ions chloride (Cl) and bromide (Br) in many formation brines plot closely to the seawater evaporation trajectory of previous studies. These brines contain Cl/Br mass ratios of around 300, while salt-dissolution brines are relatively Br depleted, having Cl/Br mass ratios in excess of 20,000. An oilfield site in central Alberta had experienced nearby releases of both salt-dissolution and formation brines. Geochemical mixing trends were defined by theoretically mixing samples of local salt-dissolution and formation brine sources with background shallow groundwater. Most site monitoring wells and local surface water samples plotted directly on a salt-dissolution brine dilution trend, while results from four monitoring wells, all located directly downgradient of formation brine spills, suggested the mixing of formation brines into shallow groundwater. This work indicates that there is a large-scale salt-dissolution brine plume beneath the site and reinforces the use of Cl and Br concentrations and mass ratios as environmental tracers.     

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.