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.     

Origin of components in Chilean thermal waters

Thermal waters of northern (18°–27°S) and southern (37°–45°S) Chile occur in two very different climatic, geologic and hydrologic environments: arid closed basins with abundant evaporites in the north; humid climate and well drained valleys in the south. The origin and behavior of the main components of the two groups of waters are examined and compared to each other. The modeling of the alteration of volcanic rocks leads to water compositions very different from those observed both in the north and south. In addition to hydrothermal alteration and deep emanations, the Cl/Br ratio reveals a major contribution of saline waters to the two groups: infiltrating brines from salt lakes in the north; seawater in the south.In the north, concentrations of Cl, Br, Na, K, Ca, SO₄, Li, B, Si result from the mixing of alteration waters with recycled brines. Hydrothermal alteration is obscured by this massive saline input, except for Mg. δ³⁴S values are consistent with an origin of sulfate from salar brines, which are themselves derived from deep Tertiary gypsum. In the south, two processes account for the composition of thermal waters: mixing of alteration waters with seawater and deep magmatic contribution. The mixing process controls the concentration of Cl, Br, Na, Alk, Si, K, Ca, Mg. Magmatic inputs are detectable for SO₄, Li and B. δ³⁴S suggests that sulfate stems from the mixing of alteration waters with either marine SO₄ in coastal waters or with deep SO₂ in inland waters. In both the north and south, the Mg concentration is drastically lowered (<1 μmol/L) by the probable formation of a chlorite-type mineral. In the south, very small amounts of seawater (<1% in volume) are sufficient to imprint a clear signature on thermal waters. Not only coastal springs are affected by seawater mixing, but also remote inland springs, as far as 150 km from the sea. Subduction of marine sediments in the accretive margin could be the source of the marine imprint in thermal waters of southern Chile. Seawater may be expelled from the subducted lithosphere and incorporated into the mantle source.     

Origin and distribution of saline groundwaters in the upper Miocene aquifer system, coastal Rhodope area, northeastern Greece

 This paper describes the origins and distribution of saline groundwaters in the coastal area of Rhodope, Greece. The aquifer system includes two aquifers within coarse-grained alluvial sediments in the coastal part of the study area. Two major water-quality groups occur in the study area, namely Ca²⁺-rich saline groundwater and Ca²⁺-poor, almost fresh groundwater. The main process controlling the groundwater chemistry is the exchange of calcium and sodium between the aquifer matrix and intruding seawater. The natural salt water in the study area is probably residual water that infiltrated the aquifer system during repeated marine transgressions in late Pleistocene time. Seawater intrusion into the coastal aquifer system occurs as a result of overpumping in two seawater wedges separated vertically by a low-permeability layer. The rate of intrusion averages 0.8 m/d and is less than expected due to a decline of the aquifer's permeability at the interface with the seawater. The application of several hydrochemical techniques (Piper and Durov diagrams; Na⁺/Cl^–, Ca²⁺/Cl^–, Mg²⁺/Cl^–, and Br^–/Cl^– molar ratios; Ca²⁺/Mg²⁺ weight ratio; and chloride concentrations), combined with field observations, may lead to a better explanation of the origin of the saline groundwater. Received, May 1997 / Revised, May 1998, December 1998 / Accepted, February 1999     

National scale evaluation of groundwater chemistry in Korea coastal aquifers: evidences of seawater intrusion

Pollution of groundwater by seawater intrusion poses a threat to sustainable agriculture in the coastal areas of Korea. Therefore, seawater intrusion monitoring stations were installed in eastern, western, and southern coastal areas and have been operated since 1998. In this study, groundwater chemistry data obtained from the seawater intrusion monitoring stations during the period from 2007 to 2009 were analyzed and evaluated. Groundwater was classified into fresh (<1,500 μS/cm), brackish (1,500–3,000 μS/cm), and saline (>3,000 μS/cm) according to EC levels. Among groundwater samples (n = 233), 56, 7, and 37% were classified as the fresh, brackish, and saline, respectively. The major dissolved components of the brackish and saline groundwaters were enriched compared with those of the fresh groundwater. The enrichment of Na⁺ and Cl⁻ was especially noticeable due to seawater intrusion. Thus, the brackish and saline groundwaters were classified as Ca–Cl and Na–Cl types, while the fresh groundwater was classified as Na–HCO₃ and Ca–HCO₃ types. The groundwater included in the Na–Cl types indicated the effects of seawater mixing. Ca²⁺, Mg²⁺, Na⁺, K⁺, SO₄ ²⁻, and Br⁻ showed good correlations with Cl⁻ of over r = 0.624. Of these components, the strong correlations of Mg²⁺, SO₄ ²⁻, and Br⁻ with Cl⁻ (r ≥ 0.823) indicated a distinct mixing between fresh groundwater and seawater. The Ca/Cl and HCO₃/Cl ratios of the groundwaters gradually decreased and approached those of seawater. The Mg/Cl, Na/Cl, K/Cl, SO₄/Cl, and Br/Cl ratios of the groundwaters gradually decreased, and were similar to or lower than those of seawater, indicating that Mg²⁺, Na⁺, K⁺, SO₄ ²⁻, and Br⁻, as well as Cl⁻ in the saline groundwater can be enriched by seawater mixing, while Ca²⁺ and HCO₃ ⁻ are mainly released by weathering processes. The influence of seawater intrusion was evaluated using threshold values of Cl⁻ and Br⁻, which were estimated as 80.5 and 0.54 mg/L, respectively. According to these criteria, 41–50% of the groundwaters were affected by seawater mixing.     

Comparison of stable isotopes,ratios of Cl/Cl and I/I in brine and deep groundwater from the Pacific coastal region and the eastern margin of the Japan Sea

Fifty-three samples, including brines associated with oil and natural gas reservoirs and groundwater samples from deep boreholes, were collected from the Pacific and Japan Sea coastal regions in Japan. The ¹²⁹I/¹²⁷I and ³⁶Cl/Cl ratios, and stable isotopes (δD and δ¹⁸O) are compared to investigate differences related to the geotectonic settings of the two regions. The δD and δ¹⁸O data indicate that brine and groundwater from the Pacific coastal region reflect mixing of meteoric water with connate seawater in the pores of sedimentary rocks. On the other hand, brine and groundwater from the Japan Sea coastal region have been hydrothermally altered. In particular, brines associated with petroleum accumulations at Niigata and Akita showed the same isotopic characteristics as fluids found in the Kuroko deposits of the Green Tuff region in northeastern Japan. There is little difference in the ³⁶Cl/Cl ratios in brine and groundwater from the Pacific and Japan Sea coasts. Most brine and some deep groundwater, except those from the Pleistocene Kazusa Group, have already reached the average secular equilibrium ratio of 9.9 ± 2.7 × 10⁻¹⁵ for their mudstone and sandstone reservoirs. There was no correlation between the ³⁶Cl/Cl ratios and differences in geotectonic setting between the Pacific and the Japan Sea coast. The molar I/Br ratio suggests that the I in all of water samples was of biogenic origin. The average ¹²⁹I/¹²⁷I ratio was 290 ± 130 × 10⁻¹⁵ to 294 ± 105 × 10⁻¹⁵ in both regions, showing no relationship to the different geotectonic settings. The uncontaminated brine and groundwater samples are likely to have retained the original ¹²⁹I/¹²⁷I ratios of marine I released from the old organic matter stored in sedimentary rock.     

Groundwater resource degradation in coastal plains: The example of the Cecina area (Tuscany – Central Italy)

The paper describes the degradation of the groundwater resources in the Cecina area, where seawater intrusion, B contamination and NO₃ pollution are all affecting the heavily exploited Pleistocene aquifer. Over-pumping has brought water levels to about 0 m.a.s.l. as far as about 7 km from the shore line, thereby promoting the seawater intrusion. The intrusion, which is characterized by cation exchange phenomena and Ca–Cl type waters, enters the plain mostly through the shallower horizons. The saline front, which advanced from 0.5 to 1 km in 4 a, has by now reached the foot of the hills to the east of the town, where it is also affecting wells of the local aqueduct. Boron contamination, linked to past discharge of industrial waste transported downstream by the river, reached concentrations as high as 3.5 mg/L in the mid-1980s. Although a decreasing trend is now under way, B content is still close to 1 mg/L. The presence of high NO₃, which, together with the seawater intrusion, represents a major issue for groundwater management in the area, is linked to the widespread utilization of fertilizers. Nitrate concentration, which reaches a maximum of about 300 mg/L in the shallow aquifer horizons and then decreases rather regularly with depth, is strongly influenced by precipitation. However, irrigation also contributes significantly to transporting the NO₃ contamination to depth, as clearly shown by δ¹⁸O data. The severe decline in the quality of the groundwater resource in the Cecina area is further compounded by an overall decrease in water availability in the region of Tuscany, as evidenced by long-term monitoring of precipitation and fluvial discharge.     

Determining groundwater protection zones for the Quaternary aquifer of northeastern Nile Delta using GIS-based vulnerability mapping

The area of study lies at the northeastern part of Nile Delta. Global shoreline regression and sea-level rise have their own-bearing on the groundwater salinization due to seawater intrusion. A new adopted approach for vulnerability mapping using the hydrochemical investigations, geographic information system and a weighted multi-criteria decision support system (WMCDSS) was developed to determine the trend of groundwater contamination by seawater intrusion. Six thematic layers were digitally integrated and assigned different weights and rates. These have been created to comprise the most decisive criteria used for the delineation of groundwater degradation due to seawater intrusion. These criteria are represented by the total dissolved solids, well discharge, sodium adsorption ratio, hydrochemical parameter (Cl/HCO₃), hydraulic conductivity and water types. The WMCDSS modeling was tried, where a groundwater vulnerability map with four classes ranging from very low to high vulnerability was gained. The map pinpointed the promising localities for groundwater protection, which are almost represented by the very low or low vulnerability areas (53.69 % of the total study area). The regions having high and moderate groundwater vulnerability occupy 46.31 % of total study area, which designate to a deteriorated territory of groundwater quality, and needs special treatment and cropping pattern before use. However, the moderate groundwater vulnerability class occupies an area of about 28.77 % of the total mapped area, which highlighted the need for certain management practices to prevent the saltwater intrusion from expanding further to the south. There was a good correlation of the constructed vulnerability map with the recently gathered water quality data and hydrochemical facies evolution. The plotting of water quality data on Piper trilinear diagram revealed the evolution of freshwater into the mixing and the saline zones as an impact of seawater intrusion, which validates the model results.     

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.     

Delineation of groundwater salinization in a coastal aquifer, Bousheher, South of Iran

The geochemical processes controlling chemical composition of groundwater are studied using hydrochemical and isotopic data in Abdan-Dayer coastal plain, south of Iran. The salinity of groundwater in the coastal plain ranges from 1,000, a fresh end-member, to more than 50,000 μS cm^?1, a saline end-member. Groundwater salinity increases from the recharge area toward areas with a shallow water table close to the Persian Gulf coast due to direct evaporation and sea water intrusion as confirmed by mixing binary diagrams, stable isotope content, and Br^?/Cl^? ratio. Groundwater flow pattern in the study area has been modified due to over-pumping of groundwater in recent years which resulted in further saline water migration toward fresh water and their mixing. The maximum mixing ratio is estimated about 15% in different parts of the study area according to chloride concentration.     

Limiting hydrochemical factors for sustainability of water resources: The Cisjordanian experience

In Cisjordan, surface- and groundwater flow are either towards the Jordan Valley-Dead Sea-Arava Valley (the Rift) or the Mediterranean Sea. Due to upstream exploitation by riparians to the Jordan River, the historical annual flow, which fluctuated between 250 and 1100 Mm³, has declined to a mere 100-200 Mm³. The remaining flow south of Lake Kinneret is highly polluted and heavily loaded with salts. Lake Kinneret (Sea of Galilee) is one of the major water resources in the area. Annually, between 200 and 700 Mm³ reach the Lake as surface and groundwater flow. The relatively high salinity of the Lake is caused by thermomineral water discharging from springs and seepages located onshore and on the bottom of the Lake. The main factors causing deterioration of the groundwater quality in the Rift are of geogenic character. These are different types of brines, whose outflow and penetration into freshwater aquifers was triggered by overpumpage. Contemporary encroachment of seawater caused by intensive water exploitation in the Coastal Plain is manageable and reversible. However, due to lack of hydrogeological evidence, no such statement can be made about the circulation of seawater beneath the Coastal Plain and into the deep-seated Yarkon-Taninim aquifer or the upflow of brines in the Rift.The flow regimes of the different brine bodies could not be elucidated. Whether each such brine-body flows by its particular hydrological regime or whether the movement of the different bodies is intradependent or interdependent with the regional movement of fresh groundwater, remain open questions. Therefore, sustainable development of groundwater resources is clearly dependent on the elucidation of the relationship between changes in the pressure of the brine with depth and its relationship to the overlying freshwater.The average total annual recharge of all water sources in Cisjordan is 1820 Mm³, which means that the total production of water must be managed within the limits of this annual volume. During drought years, total groundwater extraction exceeds the safe yield, causing drastic lowering of water levels and upflow of saline waters from greater depths.Because of the structural complexity of aquifers and hydrochemical variability of the numerous groundwater bodies, new hydrochemical methods have been developed for the identification of groundwater bodies and for the elucidation of their origins. These methods combine macrochemical, microchemical, and isotopic evidences. By combining distribution patterns of rare earths, yttrium and stable isotopes, a complete picture of catchment lithology and the altitude and latitude of precipitation could be obtained.The area west of the Jordan River is characterized by the occurrence of transboundary surface- and groundwater basins in which fresh and saline water and brines flow across political borders between Israel and the Palestinian Authority. It is very difficult to assess separately the annual safe yield of water resources for each of the two national entities. Neither country may dispose independently of its waters and is usually at the mercy of the other riparian. There is as yet no general multilateral international treaty in force allocating the water resources of international watercourses. At present there are two rules for the management of the waters of an international drainage basin—the rule of Equitable Distribution, and the obligation Not to Cause Significant Harm. The rules of equitable distribution have tended to focus on the issue of quantities of water rather than on quality of water, which is really relevant to the issue of equitable distribution. Future negotiations on the uses of the basin will need to deal with issues of characteristic salinities and geochemical features and on their impact on equitable sharing of water resources.     

环境同位素特征对滨海岩溶地区海水入侵过程的指示意义

大连大魏家水源地位于中国北方典型滨海岩溶地区。近30年来,地下淡水的不合理开采造成的地下水位降落漏斗引发了严重的海水入侵。以大魏家水源地为研究对象,通过大量的水文地质调查和水化学及同位素采样测试分析,探讨海水入侵形成的水动力条件,通过分析滨海岩溶含水层中地下水主要水化学和多种同位素(δ2H-δ18O,δ34S,δ13C)组成特征,识别了海水入侵过程中发生的主要水文地球化学作用,并对其进行了定量模拟,从而阐明了岩溶含水层中的海水入侵机理。研究结果表明:大连大魏家海水入侵主要通道为大魏家地区存在的导水断裂、岩溶裂隙以及第四系松散地层。对δ2H-δ18O同位素的组成分析表明,研究区地下水主要来自大气降水补给,结合Cl-浓度分布,认为除海水入侵淡水含水层后增加了地下水中的盐分外,浅层地下水的蒸发也对地下水中盐分的累积起到了重要作用。根据不同水体中δ34SSO4,δ13CHCO3等同位素特征,结合水化学成分(如SO2-4,Cl-)分析认为,研究区微咸水和咸水并不是地下水淡水和海水简单混合而成。利用反向水文地球化学模拟揭示了控制滨海岩溶含水层中水化学演化的主要水文地球化学反应有方解石、蒙脱石和石膏的溶解作用,伊利石的沉淀作用以及Ca-Na离子交换作用,伴随着CO2的释放。     

Origin of groundwater salinity (current seawater vs. saline deep water) in a coastal karst aquifer based on Sr and Cl isotopes. Case study of the La Clape massif (southern France)

In this study a typical coastal karst aquifer, developed in lower Cretaceous limestones, on the western Mediterranean seashore (La Clape massif, southern France) was investigated. A combination of geochemical and isotopic approaches was used to investigate the origin of salinity in the aquifer. Water samples were collected between 2009 and 2011. Three groundwater groups (A, B and C) were identified based on the hydrogeological setting and on the Cl⁻ concentrations. Average and maximum Cl⁻ concentrations in the recharge waters were calculated (Cl_Ref. and Cl_Ref.Max) to be 0.51 and 2.85 mmol/L, respectively). Group A includes spring waters with Cl⁻ concentrations that are within the same order of magnitude as the Cl_Ref concentration. Group B includes groundwater with Cl⁻ concentrations that range between the Cl_Ref and Cl_Ref.Max concentrations. Group C includes brackish groundwater with Cl⁻ concentrations that are significantly greater than the Cl_Ref.Max concentration. Overall, the chemistry of the La Clape groundwater evolves from dominantly Ca–HCO₃ to NaCl type. On binary diagrams of the major ions vs. Cl, most of the La Clape waters plot along mixing lines. The mixing end-members include spring waters and a saline component (current seawater or fossil saline water). Based on the Br/Cl_molar ratio, the hypothesis of halite dissolution from Triassic evaporites is rejected to explain the origin of salinity in the brackish groundwater.Groundwaters display ⁸⁷Sr/⁸⁶Sr ratios intermediate between those of the limestone aquifer matrix and current Mediterranean seawater. On a Sr mixing diagram, most of the La Clape waters plot on a mixing line. The end-members include the La Clape spring waters and saline waters, which are similar to the deep geothermal waters that were identified at the nearby Balaruc site. The ³⁶Cl/Cl ratios of a few groundwater samples from group C are in agreement with the mixing hypothesis of local recharge water with deep saline water at secular equilibrium within a carbonate matrix. Finally, PHREEQC modelling was run based on calcite dissolution in an open system prior to mixing with the Balaruc type saline waters. Modelled data are consistent with the observed data that were obtained from the group C groundwater. Based on several tracers (i.e. concentrations and isotopic compositions of Cl and Sr), calculated ratios of deep saline water in the mixture are coherent and range from 3% to 16% and 0% to 3% for groundwater of groups C and B, respectively.With regard to the La Clape karst aquifer, the extension of a lithospheric fault in the study area may favour the rise of deep saline water. Such rises occur at the nearby geothermal Balaruc site along another lithospheric fault. At the regional scale, several coastal karst aquifers are located along the Gulf of Lion and occur in Mezosoic limestones of similar ages. The ⁸⁷Sr/⁸⁶Sr ratios of these aquifers tend toward values of 0.708557, which suggests a general mixing process of shallow karst waters with deep saline fossil waters. The occurrence of these fossil saline waters may be related to the introduction of seawater during and after the Flandrian transgression, when the highly karstified massifs invaded by seawater, formed islands and peninsulas along the Mediterranean coast.     

Hydrochemical changes in a small tropical island’s aquifer: Manukan Island, Sabah, Malaysia

Small islands groundwater are often exposed to heavy pumpings as a result of high demand for freshwater consumption. Intensive exploitation of groundwater from Manukan Island’s aquifer has disturbed the natural equilibrium between fresh and saline water, and has resulted increase the groundwater salinity and leap to the hydrochemical complexities of freshwater–seawater contact. An attempt was made to identify the hydrochemical processes that accompany current intrusion of seawater using ionic changes and saturation indices. It was observed that the mixing between freshwater–seawater created diversity in geochemical processes of the Manukan Island’s aquifer and altered the freshwater and seawater mixture away from the theoretical composition line. This explained the most visible processes taking place during the displacement.     

Groundwater resource sustainability in the Wadi Watir delta, Gulf of Aqaba, Sinai, Egypt

The Wadi Watir delta, in the arid Sinai Peninsula, Egypt, contains an alluvial aquifer underlain by impermeable Precambrian basement rock. The scarcity of rainfall during the last decade, combined with high pumping rates, resulted in degradation of water quality in the main supply wells along the mountain front, which has resulted in reduced groundwater pumping. Additionally, seawater intrusion along the coast has increased salinity in some wells. A three-dimensional (3D) groundwater flow model (MODFLOW) was calibrated using groundwater-level changes and pumping rates from 1982 to 2009; the groundwater recharge rate was estimated to be 1.58?×?10⁶ m³/year. A variable-density flow model (SEAWAT) was used to evaluate seawater intrusion for different pumping rates and well-field locations. Water chemistry and stable isotope data were used to calculate seawater mixing with groundwater along the coast. Geochemical modeling (NETPATH) determined the sources and mixing of different groundwaters from the mountainous recharge areas and within the delta aquifers; results showed that the groundwater salinity is controlled by dissolution of minerals and salts in the aquifers along flow paths and mixing of chemically different waters, including upwelling of saline groundwater and seawater intrusion. Future groundwater pumping must be closely monitored to limit these effects.     

广东硇洲岛地下水化学演化及成因机理

地下水一直是广东硇洲岛唯一的水资源,但近年来许多地区地下水咸化趋势加剧,严峻威胁着岛上居民的用水安全,研究地下水化学演化及成因机理,对预防和减缓水质变咸意义重大。本文结合区域水文地质条件、地形地貌条件及水化学资料分析了整个岛屿地下水水质状况,在此基础上采用Piper三线图研究了水化学特征,并利用PHREEQC软件对水文地球化学演化规律进行模拟研究,结果表明:(1)海水入侵是造成地下水咸化的主要原因,咸化对水质的影响主要表现为Cl-的增加,Ca2+在区分该地区不同水体时反应灵敏,是良好的识别指标之一;(2)海水入侵的过程中,过渡带前缘不存在经受长期古海水演化而成的卤水与地下淡水的混合作用,地下水中Mg2+、Ca2+与Na+之间存在着强烈的离子交换,石膏、白云石及方解石处于不饱和状态;(3)浅层地下水与深层地下水之间无明显的水力联系,属于相对独立的地下水流系统。在全球变暖,海平面上升的总趋势下,海岛地下水开发必须合理规划、严格管理,以防引发大规模海水入侵灾害的发生。     

Study of shallow groundwater quality evolution under saline intrusion with environmental isotopes and geochemistry

Evolution of the shallow groundwater quality under saline intrusion in porous aquifer system has been studied with environmental isotopes and geochemistry in the Laizhou Bay area, China. Two campaigns of water sampling from various sources were carried out in spring and winter for environmental isotopic and chemical analyses. The origin of groundwater salinity from intrusion of both modern seawater and deep brine water was identified by analysing the correlations between ¹⁸O, D, T, Cl⁻, SO₄²⁻ and electrical conductivity. The results indicate that the brine is originated from evaporating and concentrating of intruded seawater and its δD and δ¹⁸O are different from modern seawater but similar to those of mixture of seawater with fresh groundwater. It is hard to distinguish the salinity origin in this area by the δD–δ¹⁸O relationship alone. The relations between δ¹⁸O and conductivity, Cl⁻ and SO₄²⁻ have been used to identify the salinity origin due to the distinct difference in salinity between the brine and seawater, conjunctively with use of T. A threshold of T = 12 TU was adopted to identify the origin of saline groundwater.     

Evaluation of groundwater quality in coastal areas: implications for sustainable agriculture

Seawater intrusion is a problem in the coastal areas of Korea. Most productive agricultural fields are in the western and southern coastal areas of the country where irrigation predominantly relies on groundwater. Seawater intrusion has affected agricultural productivity. To evaluate progressive encroachment of saline water, the Korean government established a seawater intrusion monitoring well network, especially in the western and southern part of the peninsula. Automatic water levels and EC monitoring and periodic chemical analysis of groundwater help track salinization. Salinization of fresh groundwater is highly associated with groundwater withdrawal. A large proportion of the groundwaters are classified as Na–Cl and Ca–Cl types. The Na–Cl types represent effects of seawater intrusion. The highest EC level was over 1.6 km inland and high Cl values were observed up to 1.2 km inland. Lower ratios of Na/Cl and SO₄/Cl than seawater values indicate the seawater encroachment. A linear relation between Na and Cl represents simple mixing of the fresh groundwater with the seawater. The saline Na–Cl typed groundwaters showed Br/Cl ratios similar to or less than seawater values. The Ca–HCO₃ type groundwaters had the highest Br/Cl ratios. Substantial proportions of the groundwaters showed potential for salinity and should be better managed for sustainable agriculture.     

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.     

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.     

The use of O,H, B,Sr and S isotopes for tracing the origin of dissolved boron in groundwater in Central Macedonia,Greece

The groundwater B concentration in Mesozoic karst, Neogene and alluvial aquifers in the West part of Chalkidiki province in Central Macedonia, Greece reaches 6.45 mg L⁻¹, which exceeds the limit of 1 mg L⁻¹, set by the European Union for drinking water. The high B contents have been detected in this area, not only near the shoreline, where seawater intrusion occurs, but also in the inland part of the basin. Multi isotope (²H, ¹⁸O, ³⁴S, ¹⁸O_(SO4), ¹¹B, ⁸⁷Sr/⁸⁶Sr) data from borehole and thermal water springs allow identification of the possible B sources. The B dissolved in groundwater in the Chalkidiki area is mainly geogenic. The low δ¹¹B values, 0–1‰, similar to those of thermal fluids from continental geothermal fields, and the low Cl/B ratio compared to seawater both indicate a geothermal origin for B and reflect deep circulation and interaction with igneous rocks. The ⁸⁷Sr/⁸⁶Sr ratio also indicates that the deep-aquifer granodiorite is the predominant rock source of Sr, while the shallow limestone unit has negligible effects on the dissolved Sr budget in these thermal karst waters which O and H isotopes show to be of meteoric origin. The main source of high B in borehole water is mainly mixing with B-rich geothermal water. The mixing between geothermal water and water from the Neogene aquifer is also reflected by isotopic contents of SO₄.