Origin and evolution of major salts in the Darling pans,Western Cape,South Africa

Sediment and water samples from 12 saline pans on the semi-arid west coast of South Africa were analysed to determine the origin of salts and geochemical evolution of water in the pans. Pans in the area can be subdivided into large, gypsiferous coastal pans with 79–150 g/kg total dissolved salt (TDS), small inland brackish to saline (2–64 g/kg TDS) pans and small inland brine (168-531 g/kg TDS) pans that have a layer of black sulphidic mud below a halite crust. The salinity of coastal pan waters varies with the seasonal influx of dilute runoff and dissolution of relict Pleistocene marine evaporite deposits. In contrast, inland pans are local topographic depressions, bordered on the north by downslope lunette dunes, where solutes are concentrated by evaporation of runoff, throughflow and groundwater seepage. The composition of runoff and seepage inflow waters is determined by modification of coastal rainfall by weathering, calcite precipitation and ion exchange reactions in the predominantly granitic catchment soils. Evaporation of pan waters leads to precipitation of calcite, Mg–calcite, dolomite, gypsum and halite in a distinct stratigraphic succession in pan sediments. Bicarbonate limits carbonate precipitation, Ca limits gypsum precipitation and Na limits halite precipitation. Dolomitisation of calcite is enhanced by the high Mg/Ca ratio of brine pan waters. Brine pan waters evolve seasonally from Na–Cl dominated brines in the wet winter months to Mg–Cl dominated brines in the dry summer months, when 5–20 cm thick halite crusts cover pan surfaces. Pan formation was probably initiated during a drier climate period in the early Holocene. More recent replacement of natural vegetation by cultivated land may have accelerated salt accumulation in the pans.     

Hydrogeochemical and isotopic constraints on the origins of dryland salinity,Murray Basin,Victoria, Australia

Combined hydrogeological and hydrogeochemical data allow flow systems and the origins of solutes in the Honeysuckle Creek area of the southeastern Murray Basin, which is an area affected by dryland salinity, to be constrained. Recharge occurs both on the uplands that are composed of fractured Violet Town Volcanic rocks and the Riverine Plain that comprises sediments of the Shepparton and Coonambidgal Formations. Groundwater from the Violet Town Volcanics has low salinity (<20 mmol/L Cl) and major ion geochemistry that is controlled largely by dissolution of silicate minerals. Low Cl/Br ratios (as low as 281 molar) suggest that this groundwater has not dissolved halite. Groundwater that recharged through the Riverine Plain sediments has higher Cl/Br ratios (up to 1146) and Cl concentrations of <20 mmol/L, consistent with it dissolving minor halite. Higher salinity (>20 mmol/L) groundwater has intermediate Cl/Br ratios (600–1000), which indicate that the high salinities do not simply result from halite dissolution. Rather, mixing of groundwater homogenises Cl/Br ratios, and evaporation as a consequence of a shallow water table is the dominant process that increases salinity. Oxygen and H isotopes also indicate that mixing and evaporation have occurred. These results indicate that land use over the whole region, not just the uplands, needs to be considered in any salinity management plans. Additionally future development of salinity is controlled by depth to the water table on the plains and the efficiency of recharge rather than by salt stores (halite or brines) in the unsaturated zone.     

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.     

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     

上扬子区(四川盆地)寒武系的含盐性与地质背景

据记载,分布于上扬子区寒武系的石膏岩仅有零星资料。如今,大量蒸发岩如溶蚀角砾岩、硬石膏、石盐岩及富钾卤水等已被发现。沉积相经历了从盆地相、台地相到蒸发岩相的演化过程。在中、下寒武统中找到海退沉积序列。古构造-古地理背景是蒸发岩沉积的重要控矿条件之一。周边板块运动及塑性基底的褶皱,导致台缘隆起及台内坳陷的形成。岩相古地理图展示从碳酸盐、硫酸盐到氯化物盐类的“泪滴式”沉积相带。蒸发岩沉积于台缘隆起及礁生长进入堰塞潟湖至盐湖阶段。在稳定坳陷区沉积盆地中蒸发岩系发育;石盐岩较厚,其溴氯比值为0.2—0.4;古气候炎热、干燥;在蒸发岩体周围有沉积(封层)水及溶滤水,其含钾(K~+)量为0.10—4.76g/L;水文地球化学比值(如钾氯比值、钾盐比值及钾溴比值等)指示含钾异常;盐湖浓缩卤水达到氯化物盐类沉积阶段及相应的构造封闭程度;含盐地质标志广泛分布等等。鉴于上述,估计该区可能具备钾盐成矿条件。然而目的层埋藏太深,因此笔者建议,应在浅埋部位进行有效的成矿预测,为普查指出远景区。     

An evaporated seawater origin for the ore-forming brines in unconformity-related uranium deposits (Athabasca Basin, Canada): Cl/Br and δCl analysis of fluid inclusions

Analyses of halogen concentration and stable chlorine isotope composition of fluid inclusions from hydrothermal quartz and carbonate veins spatially and temporally associated with giant unconformity-related uranium deposits from the Paleoproterozoic Athabasca Basin (Canada) were performed in order to determine the origin of chloride in the ore-forming brines. Microthermometric analyses show that samples contain variable amounts of a NaCl-rich brine (Cl concentration between 120,000 and 180,000 ppm) and a CaCl₂-rich brine (Cl concentration between 160,000 and 220,000 ppm). Molar Cl/Br ratios of fluid inclusion leachates range from ∼100 to ∼900, with most values between 150 and 350. Cl/Br ratios below 650 (seawater value) indicate that the high salinities were acquired by evaporation of seawater. Most δ³⁷Cl values are between −0.6‰ and 0‰ (seawater value) which is also compatible with a common evaporated seawater origin for both NaCl- and CaCl₂-rich brines.Slight discrepancies between the Cl concentration, Cl/Br, δ³⁷Cl data and seawater evaporation trends, indicate that the evaporated seawater underwent secondary minor modification of its composition by: (i) mixing with a minor amount of halite-dissolution brine or re-equilibration with halite during burial; (ii) dilution in a maximum of 30% of connate and/or formation waters during its migration towards the base of the Athabasca sandstones; (iii) leaching of chloride from biotites within basement rocks and (iv) water loss by hydration reactions in alteration haloes linked to uranium deposition.The chloride in uranium ore-forming brines of the Athabasca Basin has an unambiguous dominantly marine origin and has required large-scale seawater evaporation and evaporite deposition. Although the direct evidence for evaporative environments in the Athabasca Basin are lacking due to the erosion of ∼80% of the sedimentary pile, Cl/Br ratios and δ³⁷Cl values of brines have behaved conservatively at the basin scale and throughout basin history.     

The evolution of marine evaporitic brines in inland basins: The Jordan-Dead Sea Rift valley

Marine-evaporitic brines frequently display Na, Cl and Br concentrations that significantly deviate from seawater evaporation paths, yielding markedly conflicting degrees of evaporation calculated for a specific brine. Here we present 493 new and 33 previously reported analyses of Ca-chloridic waters of Neogene age from the Dead Sea Rift (DSR) valley to explain such offsets. The DSR brines plot along an almost perfect mixing line (R² = 0.990) on a Br/Cl-Na/Cl diagram, extending between two end members A and B. Points A and B are located at Na/Cl = 0.804 and Br/Cl = 0.00193, and at Na/Cl = 0.00773 and Br/Cl = 0.0155, respectively, within the halite and bischofite stability fields.Brines A and B originated in a dual-mode evaporation basin. Brine A formed under the classic lagoon scenario (mode A), with seawater inflow and brine outflow at steady state. Occasional drops in water level, imposed by climatic or tectonic causes, resulted in outflow cutoff and in rapid concentration buildup. The second mode (B) initiated upon equilibration of the activity of water in the brine with the overlying relative humidity, resulting in composition and salinity approaching that of brine B, sustaining it until the next reversal to mode A.Thick evaporite deposits inhibited infiltration of brines A and B into the subsurface terrain, a process that was enabled only when the brine reached the permeable carbonate rock rim and border faults of the basin. Hence, brines that formed during the relatively short shifts from mode A to mode B could not penetrate into the deep subsurface, and bittern minerals that were formed during the frequent mode shifts were dissolved and flushed out into the sea upon the next resumption of outflow.The proposed model accounts for the deviations of brines from the marine evaporitic evolution curve by brine mixing, rather than due to a change in ocean chemistry. It also explains the absence of bittern minerals in the thick halite and gypsum/anhydrite succession, and the compositional gap between the widely different end member hypersaline fluids. This model applies directly to the studied DSR brines and evaporites, but it may be relevant to other inland evaporitic basins.     

Origin of salinity of deep groundwater in crystalline rocks

Deep groundwater in fractured crystalline basement has been reported from deep mines and from scientific deep wells. Highly saline brines have been described from several km depth in the continental basement of the Canadian, Fennoscandian and Ukrainian shields and elsewhere in the world. The origin of salinity is unknown and many different possibilities have been presented. We compare the compositional evolution of deep waters in the Black Forest basement, SW Germany, with those of other deep crystalline waters, and use halogen systematics (e.g. Cl/Br ratios) and other parameters of the waters to deduce the origin of their salinity. In the Black Forest the composition of deep thermal waters results from chemical interaction of surface water with the rock matrix (mainly weathering of plagioclase and mica) and from mixing of the reacted water with stagnant saline deep water. Here we show by Na/TDS-and Cl/TDS-investigations, by molality-ratios of the Na and Cl concentrations, and by Cl/Br systematics that these deep saline waters have a marine origin. The Cl/Br ratios in deep crystalline waters are very close to normal marine ratios (Cl/Br = 288 ppm basis). In contrast, Cl/Br ratios of other possible sources of salinity show distinctly different Cl/Br ratios: water derived from dissolved Tertiary halite deposits of the rift valley is in the order of Cl/Br = 2400 and water from dissolved Muschelkalk halite deposits has values of about Cl/Br = 9900. Leaching experiments on crystalline rocks, on the other hand, show that the average Cl/Br ratio of crystalline rocks is far below Cl/Br = 100.     

Evolution of saline waters and brines in the Benue-Trough,Nigeria

Hydrogeochemical assessment of 40 saline waters and brines from 20 locations within the lower (southern) and middle regions of the Benue-Trough, Nigeria are presented and discussed in terms of genesis of the primary salinity and subsequent hydrochemical evolution. The total dissolved ions range from 5263 to 88,800 mg/L and 5148 to 47,145 mg/L in the lower and middle region, respectively.The saline waters and brines are characteristically Na–Cl type enriched in Ca and Sr on the one hand and depleted in Mg and SO₄ on the other, relative to the seawater evaporation trend. Ionic ratios, Na–Cl–Br systematic and divalent cations suggest two likely sources of primary salinity: a fossil seawater source and dissolution of halite. However, water–rock interaction involving Mg uptake by clay minerals and possibly dolomitization during diagenesis appear to be responsible for further modification of the primary chemistry. A conceptualized hydrogeological/flow model for the brines is presented.     

Integration of geochemical and isotopic tracers for elucidating water sources and salinization of shallow aquifers in the sub-Saharan Drâa Basin,Morocco

In the arid sub-Saharan of southern Morocco, groundwater salinization poses a direct threat for agricultural production in six oases’ basins that are irrigated by water imported from the High Atlas Mountains. Here the geospatial distribution of salinity is evaluated in shallow groundwater, springs and surface waters in the Drâa Basin, integrating major and trace element geochemistry and isotopic tracers (O, H, Sr and B). The data show that water discharge from the High Atlas Mountains to the Upper section of the Drâa Basin is characterized by both low and high salinity, a distinctive low δ¹⁸O and δ²H composition (as low as −9‰ and −66‰, respectively), typical for meteoric water from high elevation, a ⁸⁷Sr/⁸⁶Sr range of 0.7078–0.7094, and δ¹¹B of 12–17‰. The Ca–Mg–HCO₃, Na–Cl–SO₄, and Ca–SO₄ compositions as well as the Br/Cl, ⁸⁷Sr/⁸⁶Sr, and δ¹¹B values of the saline water suggest dissolution of Lower Jurassic carbonates and evaporite rocks in the High Atlas Mountain catchment. Storage and evaporation of the imported water in a man-made open reservoir causes an enrichment of the stable isotope ratios with a δ¹⁸O/δ²H slope of <8 but no change in the Sr and B isotope fingerprints. Downstream from the reservoir, large salinity variations were documented in the shallow groundwater from the six Drâa oases, with systematically higher salinity in the three southern oases, up to 12,000 mg/L. The increase of the salinity is systematically associated with a decrease of the Br/Cl ratio, indicating that the main mechanism of groundwater salinization in the shallow aquifers in the Drâa oases is via salt dissolution (gypsum, halite) in the unsaturated zone. Investigation of shallow groundwater that flows to the northern Drâa oases revealed lower salinity (TDS of 500–4225) water that is characterized by depleted ¹⁸O and ²H (as low as −9‰ and −66‰, respectively) and higher ⁸⁷Sr/⁸⁶Sr ratios (∼0.7107–0.7115) relative to irrigation water and groundwater flow from the Upper Drâa Basin. This newly-discovered low-saline groundwater with a different isotopic imprint flows from the northeastern Anti-Atlas Jabel Saghro Mountains to the northern oases of the Lower Drâa Basin. This adjacent subsurface flow results in a wide range of Sr isotope ratios in the shallow oases groundwater (0.7084–0.7131) and appears to mitigate salinization in the three northern Drâa oases. In contrast, in the southern oases, the higher salinity suggests that this mitigation is not as affective and increasing salinization through cycles of water irrigation and salt dissolution appears inevitable.     

Source of salinity in the groundwater of Lenjanat Plain,Isfahan, Iran

The present study aimed at identifying the salinity source in the groundwater of Lenjanat Plain. To do so, non-isotopic geochemical methods were employed: groundwater samples were collected seasonally from 33 wells widespread in the area, and physicochemical parameters as well as major and minor elements were measured in the 132 samples. The data collected from the field and laboratory measurements were interpreted through statistical and hydrogeochemical graphs, mass ratios and saturation indexes obtained from modeling. The results revealed that hydrogeochemical properties of the study aquifer were controlled by rock/water interactions including ion exchange, dissolution of evaporation deposits (halite and gypsum) and precipitation/dissolution of carbonates. Based on the values of Cl/Br ratio in Lenjanat groundwater (329–4,492), dissolution of evaporation deposits in aquifer was the main cause for groundwater salinity. Considering the Lenjanat groundwater geochemical properties, the data confirm the reported Cl/Br ratios for groundwater affected by the dissolution of evaporation deposits (Cl/Br > 300) and overlaps with the range of Cl/Br ratios for domestic sewage effluent groundwater. Selecting the best chemical components and their ratios in non-isotopic geochemical methods provides an accurate distinction between sources of groundwater salinity.     

Characteristics of deep groundwater flow in a basin marginal setting at Sellafield,Northwest England: Cl and halide evidence

A number of chemical and physical processes inside and outside a sedimentary basin (e.g. evaporite dissolution and topographic drive, respectively) affect groundwater flow near the basin’s margin. Contrasting formations at the margin, typically basinal sedimentary rocks and basement, are host to the interplay between these processes so that groundwater flows and compositions change within a relatively small volume. To interpret how groundwater flow and geochemistry have evolved, interactions between these processes must be understood. Such interactions were investigated near the margin of the East Irish Sea Basin in NW England, by sampling deep groundwaters (to 1500 m below sea level) from Ordovician volcanic basement rocks and Carboniferous to Triassic sedimentary cover rocks. Variable Br/Cl ratios and Cl concentrations in deep saline waters and brines indicate mixing patterns. Variations in ³⁶Cl/Cl constrain the timing of mixing. Relatively low Br/Cl ratios (ca. 1 × 10⁻³ by mass) characterise brine from the western sedimentary cover and reflect halite dissolution further west. Saline water with relatively high Br/Cl ratios (ca. 2 × 10⁻³ by mass) of uncertain origin occupies the eastern basement. These two waters mix across the area. However, mixing alone cannot explain variable ³⁶Cl/Cl ratios, which partly reflect differing in situ³⁶Cl production rates in different rock formations. Most ³⁶Cl/Cl ratios in groundwater sampled from the eastern metavolcanic basement (mean = 25 × 10⁻¹⁵) and western sedimentary cover (mean = 10 × 10⁻¹⁵) are at or close to equilibrium with in situ³⁶Cl production. These variations in ³⁶Cl/Cl across the site possibly took >1.5 Ma to be attained, implying that deep groundwater flow responded only slowly to the Quaternary glaciation of the site. Interplay between varied processes in basin marginal settings does not necessarily imply flow instability.     

Identifying sources of salinization using hydrochemical and isotopic techniques, Konarsiah, Iran

Konarsiah salt diapir is situated in the Simply Folded Zone of the Zagros Mountain, south Iran. Eight small permanent brine springs emerge from the Konarsiah salt body, with average total dissolved solids of 326.7 g/L. There are numerous brackish to saline springs emerging from the alluvial and karst aquifers adjacent to the diapir. Concerning emergence of Konarsiah diapir in the study area, halite dissolution is the most probable source of salinity in the adjacent aquifers. However, other sources including evaporation and deep brines through deep Mangerak Fault are possible. The water samples of the study area were classified based on their water-type, salinity, and the trend of the ions concentration curves. The result of this classification is in agreement with the hydrogeological setting of the study area. The hydrochemical and isotopic evaluations show that the groundwater samples are the result of mixing of four end members; Gachsaran sulfate water, Sarvak and Asmari carbonate fresh waters, and diapir brine. The molar ratios of Na/Cl, Li/Cl, Br/Cl, and SO₄/Cl; and isotopic signature of the mixed samples justify a groundwater mixing model for the aquifers adjacent to the salt diapir. The share of brine in each adjacent aquifer was calculated using Cl mass balance. In addition, concentrations of 34 trace elements were determined to characterize the diapir brine and to identify the possible tracers of salinity sources in the mixed water samples. B, Mn, Rb, Sr, Cs, Tl, and Te were identified as trace elements evidencing contact of groundwater with the salt diapir.     

Evaluation of boron isotopes in halite as an indicator of the salinity of Qarhan paleolake water in the eastern Qaidam Basin,western China

In this study, nineteen brine samples from the Qarhan Salt Lake (QSL) in western China were collected and analyzed for boron (B) and chlorine (Cl) concentrations, total dissolved solids (TDS), pH values and stable B isotopic compositions. The B concentrations and δ¹¹B values of brines in the QSL range from 51.6 mg/L to 138.4 mg/L, and from +9.32‰ to +13.08‰, respectively. By comparison of B concentrations and TDS of brines in QSL with evaporation paths of brackish water, we found that B enrichment of brines primarily results from strong evaporation and concentration of Qarhan lake water. Combining with comparisons of B concentrations, TDS, pH values and δ¹¹B values of brines, previously elemental ratios (K/Cl, Mg/Cl, Ca/Cl, B/Cl) and δ¹¹B values of halite from a sediment core (ISL1A), we observe good correlations between B concentrations and TDS, TDS and pH values, pH and δ¹¹B values of brines, which demonstrate that higher B concentrations and more positive δ¹¹B values of halite indicate higher salinity of the Qarhan paleolake water as well as drier paleoclimatic conditions. Based on this interpretation of the δ¹¹B values of halite in core ISL1A, higher salinity of the Qarhan paleolake occurred during two intervals, around 46–34 ka and 26–9 ka, which are almost coincident with the upper and lower halite-dominated salt layers in core ISL1A, drier climate phases documented from the δ¹⁸O record of carbonate in core ISL1A and the paleomoisture record in monsoonal central Asia, and a higher solar insolation at 30°N. These results demonstrate that the δ¹¹B values of halite in the arid Qaidam Basin could be regarded as a new proxy for reconstructing the salinity record of paleolake water as well as paleoclimate conditions.     

Brines in the Carboniferous Sydney Coalfield,Atlantic Canada

Formation waters within Upper Carboniferous sandstones in the sub-sea Prince and Phalen coal mines, Nova Scotia, originated as residual evaporative fluids, probably during the precipitation of Windsor Group (Lower Carboniferous) salts which underlie the coal measures. Salinity varies from 7800 to 176,000 mg/l, and the waters are Na–Ca–Cl brines enriched in Ca, Sr and Br and depleted in Na, K, Mg and SO₄ relative to the seawater evaporation curve. Br:Cl and Na:Cl ratios suggest that the brine composition corresponds to an evaporation ratio of as much as 30. The brines lie close to the meteoric line on H/O isotopic plots but with a compositional range of δ¹⁸O from −4.18 to −6.99 and of δD from −42.4 to −23.5, distant from modern meteoric or ocean water. Mine water composition contrasts with that of nearby salt-spring brines, which are inferred to have originated through dissolution of Windsor Group evaporites by modern meteoric waters. However, a contribution to the mine waters from halite dissolution and from Br in organic matter cannot be ruled out. Present concentrations of several elements in the brines can be explained by water–rock interaction. The original Windsor brines probably moved up into the overlying coal-measure sandstones along faults, prior to the Late Triassic. The high salinity and irregular salinity distribution in the Phalen sandstones suggests that the brines have undergone only modest dilution and are virtually immobile. In contrast, Prince waters show a progressive increase in salinity with depth and are inferred to have mixed with surface waters. Basinal brines from which these modern formation fluids were derived may have been important agents in base-metal and Ba mineralisation from the mid-Carboniferous onwards, as saline fluid inclusions are common in Zn–Pb sulphide deposits in the region.     

Deep reaching fluid flow in the North East German Basin: origin and processes of groundwater salinisation

Major element chemistry, rare-earth element distribution, and H and O isotopes are conjointly used to study the sources of salinisation and interaquifer flow of saline groundwater in the North East German Basin. Chemical analyses from hydrocarbon exploration campaigns showed evidence of the existence of two different groups of brines: halite and halite Ca–Cl brines. Residual brines and leachates are identified by Br^?/Cl^? ratios. Most of the brines are dissolution brines of Permian evaporites. New analyses show that the pattern of rare-earth elements and yttrium (REY) are closely linked to H and O isotope distribution. Thermal brines from deep wells and artesian wells indicate isotopically evaporated brines, which chemically interacted with their aquifer environment. Isotopes and rare-earth element patterns prove that cross flow exists, especially in the post-Rupelian aquifer. However, even at depths exceeding 2,000 m, interaquifer flow takes place. The rare-earth element pattern and H and O isotopes identify locally ascending brines. A large-scale lateral groundwater flow has to be assumed because all pre-Rupelian aquifer systems to a depth of at least 500 m are isotopically characterised by Recent or Pleistocene recharge conditions.     

Fingerprinting groundwater salinity sources in the Gulf Coast Aquifer System,USA

Understanding groundwater salinity sources in the Gulf Coast Aquifer System (GCAS) is a critical issue due to depletion of fresh groundwater and concerns for potential seawater intrusion. The study objective was to assess sources of groundwater salinity in the GCAS using ～1,400 chemical analyses and ～90 isotopic analyses along nine well transects in the Texas Gulf Coast, USA. Salinity increases from northeast (median total dissolved solids (TDS) 340 mg/L) to southwest (median TDS 1,160 mg/L), which inversely correlates with the precipitation distribution pattern (1,370– 600 mm/yr, respectively). Molar Cl/Br ratios (median 540–600), depleted δ²H and δ¹⁸O (?24.7‰, ?4.5‰) relative to seawater (Cl/Br ～655 and δ²H, δ¹⁸O 0‰, 0‰, respectively), and elevated ³⁶Cl/Cl ratios (～100), suggest precipitation enriched with marine aerosols as the dominant salinity source. Mass balance estimates suggest that marine aerosols could adequately explain salt loading over the large expanse of the GCAS. Evapotranspiration enrichment to the southwest is supported by elevated chloride concentrations in soil profiles and higher δ¹⁸O. Secondary salinity sources include dissolution of salt domes or upwelling brines from geopressured zones along growth faults, mainly near the coast in the northeast. The regional extent and large quantities of brackish water have the potential to support moderate-sized desalination plants in this location. These results have important implications for groundwater management, suggesting a current lack of regional seawater intrusion and a suitable source of relatively low TDS water for desalination.     

Geochemistry and isotope chemistry of CaNaCl brines in Silurian strata,Michigan Basin,U.S.A.

Formation waters from Silurian-aged reefs in the northern and southern trends of lower Michigan were collected and analyzed for major, minor and isotope compositions. The results were combined with an analysis of an exceptionally concentrated (TDS 640 g/l) Silurian brine reported by Case in 1945 to determine the origin and possible evolutionary pathways for the chemical and isotope components of the brines. The waters are extremely concentrated(TDS> 450g/l) CaNaCl brines. Bromide values support that they originated from seawater concentrated into the MgSO₄ and possibly the KCl salt facies. The brines have, however, evolved considerably from an expected seawater composition and now contain a dominant CaCl composition. Dolomitization appears to have been very important in the brine evolution, but this process cannot explain all the Ca present in these brines. Four scenarios may explain the enrichment in Ca: (1) halite dissolution accompanied by the exchange of Na for Ca; (2) reactions involving aluminosilicate minerals, carbonates and halite; (3) an input of CaCl₂ solutions derived from altered MgCl₂ fluids released during the metamorphism of carnallite into sylvite; and (4) a pre-existing enrichment of CaCl in the Early Paleozoic seawater that filled the basin. All four are possible, but the favored explanation involves the diagenesis of the Salina A-1 potash salts. The isotope composition of the waters is consistent with evaporated seawater, perhaps enriched by exchange with carbonates or by the input of hydration water from evaporite minerals. The isotopic evolution, however, is equivocal but the brine composition does not indicate they have been diluted with meteoric water. This implies the waters have remained isolated from surface-controlled hydrological systems.     

Geochemical and isotopic evidence for palaeo-seawater intrusion into the south coast aquifer of Laizhou Bay, China

This research aims to improve the current knowledge of groundwater salinisation processes in coastal aquifers using combined hydrochemical and isotopic parameters and inverse hydrochemical modelling. Field investigations were conducted in Laizhou Bay, which is the area most seriously affected by seawater intrusion in north China. During three sampling campaigns along a vertical transect in the Changyi-Liutuan area, 95 ground- and surface-water samples were collected for major ion and isotope analysis (²H/¹⁸O, ³H, ¹⁴C, ³⁴S). The groundwater changes along the general flowpath towards the coast from fresh (<1 g/L), brackish (1-10 g/L), saline (10-100 g/L) to brine water (>100 g/L). Molar Cl/Br ratios are close to those of seawater in almost all groundwater samples, indicating that brines and deep seawater evolved from different events of palaeo-seawater intrusion. Depleted isotopic signatures of brines and deep saline water point to a former, initially depleted seawater reservoir due to runoff dilution. Tritium and ¹⁴C activities in deep saline water below confining units indicate isolation from modern precipitation and significant residence times. Brine water shows a wide range of ³H and ¹⁴C ages due to the complex conditions of mixing without isolation from modern groundwater. Sulphur-34 isotope ratios support seawater intrusion as a possible salt origin, although this parameter does not exclude gypsum dissolution. The combined use of Cl and ¹⁸O yields four different end-members of groundwater, and three different mixing scenarios were identified explaining the hydrochemical composition of groundwater samples with intermediate salinity in the different areas. To improve understanding of the various water types and their related processes in a spatial context, a conceptual model was developed integrating the results derived from the presented data in a vertical cross-section. Results of three inverse modelling simulations using PHREEQC-2 show that all hypothetical mixing scenarios derived from conservative components are thermodynamically feasible. In all scenarios, mixing, ion exchange, dissolution of dolomite and precipitation of gypsum and calcite account for the hydrochemical changes.     

宁夏清水河上游浅层地下水咸化作用研究

认识干旱区地下咸水的形成机制对水资源管理和规划具有重要意义。在宁夏清水河平原上游采集52组浅层地下水化学样品和8组易溶盐样品,分析了地下水咸化的水文地球化学作用,利用元素质量平衡法计算了各作用对地下水盐分的贡献比率。结果表明：沿径流方向,地下水咸化程度呈增加趋势。咸化作用主要为岩石风化,并具空间分异,在补给区以碳酸盐风化为主,在强径流区硫酸盐风化占优,在弱径流区硫酸盐和岩盐风化共同提供了68%～93%的盐量。随着地下水TDS增加,蒸发岩贡献比率上升,碳酸盐和硅酸盐贡献比率下降。蒸发岩风化是导致浅层地下水咸化的首要因素。