Use of hydrogeochemistry and environmental isotopes for evaluation of groundwater in Qingshuihe Basin,northwestern China

Hydrogeochemistry and environmental isotope data were utilized to understand origin, geochemical evolution, hydraulic interconnection, and renewability of groundwater in Qingshuihe Basin, northwestern China. There are four types of groundwater: (1) shallow groundwater in the mountain front pluvial fans, originating from recent recharge by precipitation, (2) deep paleo-groundwater of the lower alluvial plains, which was formed long ago, (3) shallow groundwater in the lower alluvial plains, which has undergone evaporation during the recharge process, and (4) mixed groundwater (shallow and deep groundwater in the plain). The main water types are Na–HCO₃, which dominates type (1), and Na–SO₄, which dominates types (2) and (3). Geochemical evolution in the upper pluvial fans is mainly the result of CO₂ gas dissolution, silicates weathering and cation exchange; in the lower alluvial plains, it is related to mineral dissolution. The evaporative enrichment only produces significant salinity increases in the shallow groundwater of the lower alluvial plains. Shallow groundwater age in the upper plain is 10 years or so, showing a strong renewability. Deep groundwater ages in the lower plain are more than 200 years, showing poor renewability. In the exploitation areas, the renewability of groundwater evidently increases and the circulation period is 70–100 years.     

用氢氧稳定同位素评价闽江河口区地下水输入

通过分析闽江河口区降水、地表水和地下水的氢氧稳定同位素特征,揭示降水的环境同位素效应和地下水的形成演化规律,定量评价河口区多种水体的混合过程及地下水输入量。夏季的降水氢氧同位素组成相对贫化,呈现出降雨量效应。在δ18O与δD关系图上,闽江北岸基岩裂隙水、平原及丘陵区浅层地下水均落在福州降水线上,而南岸平原及丘陵区浅层地下水大部分落在福州降水线右下方,其拟合线与降水线交点与5~9月农灌期降水氢氧同位素加权值接近,表明北岸地下水主要来自降水补给,而南岸地下水同时接受灌溉水和降水补给,并在入渗过程中经历了不同程度的蒸发作用。闽江河口段除接受两岸地下水补给外,局部河段还接受断裂带裂隙水补给。将线性端元混合模型、数字高程模型和地下水文分析法结合起来定量评价地下水的输入和各水体的混合过程,结果显示,在河口段淡水区,地下水混合比率上限为8.8%,其中包括0.4%的断裂带裂隙水;在河口段淡咸水混合区,淡水(河水、地下水)和海水的混合比为53:47,其中地下水的保守混合比率为1.7%;枯水期闽江河口段地下水保守输入量为87.0 m3/s,是闽江径流量的12.8%。     

钾稳定同位素在水文地球化学领域的研究进展与展望

地表硅酸盐岩矿物风化通常是水体中钙、镁、钠、钾等元素的重要来源,然而相比于水体中的钙、镁和钠,目前对钾的水文地球化学行为的认识仍十分有限。表生地球化学领域最新研究证明风化、吸附等多种水岩反应伴随着较大的钾同位素分馏,表明钾同位素技术可以用于示踪地下水中钾的来源及迁移转化。文章通过系统总结上地壳、水圈和其他地表储库（植物、肥料）的钾同位素组成,发现水圈普遍比大陆上地壳富集41K,为识别地下水的钾来源提供了基础;通过总结钾同位素在常见的水岩作用过程（硅酸盐岩矿物溶解、次生黏土形成、吸附作用、离子交换反应）中的分馏行为,发现硅酸盐岩矿物溶解分馏有限,次生黏土矿物形成引起水体富集41K,表面吸附和离子交换使水体富集39K,不同水岩反应中K同位素行为差异为示踪地下水中钾的迁移转化过程提供了基础;列举了应用钾同位素示踪硅酸盐岩风化和水体污染的最新研究成果。由于钾同位素是硅酸盐岩风化的良好示踪剂,可以利用钾同位素揭示CO2较充足含水层中钾元素释放及迁移转化机理;由于表面吸附和离子交换控制的钾同位素分馏方向与风化控制的钾同位素分馏方向不同,可以利用钾同位素识别出地下水循环过程中多种水岩反应对钾迁移转化的共同控制。在此基础上,对钾同位素在水文地球化学领域的应用进行了展望：（1）开展研究区多端元控制下地下水钾来源贡献的研究;（2）开展地下水漫长循环过程中钾迁移转化的定量研究;（3）联合使用多种同位素示踪碳循环相关的过程。     

Source of groundwater salinity in coastline aquifers based on environmental isotopes (Portugal): Natural vs. human interference. A review and reinterpretation

Environmental stable (δ¹⁸O, δ²H, δ¹³C) and radioactive (³H and ¹⁴C) isotopes, together with geochemical data were used to identify the origin of salinization in different environments. Three case studies from sedimentary basins of continental Portugal are presented: (i) two at the Meso-Cenozoic Portuguese southern border (Algarve basin) and (ii) one at the Lower Tagus–Lower Sado basin (central Portugal), with a new data interpretation. Groundwater salinization occurs in all three cases, and may reach values of several grams of Total Dissolved Solids per liter; above accepted limits for drinking water. The source of this high mineralization could be: (a) seawater intrusion (ancient or modern); (b) dissolution from diapiric structures intruding on the aquifer systems; (c) brine dissolution at depth; and (d) evaporation of irrigation water. The results obtained have provided an effective label for seawater and freshwater, to enable seawater intrusion to be traced, as well as the identification of other processes that might be responsible for groundwater salinization, such as salt minerals dissolution and ion exchange.     

基于氢氧稳定同位素的武汉北部新城地表水-地下水转换关系研究

【研究目的】揭示武汉北部新城地表水、地下水的氢氧稳定同位素特征及其相互作用。【研究方法】2019年，采集、测定了降水样7件、河水样6件、水库样14件、民井样98件、泉水样3件和钻孔样11件，并收集到武汉站1986—1998年的监测数据50件，以空间分析和流域分析为基础，氢氧稳定同位素分析为手段。【研究结果】（1）武汉降水氢氧同位素随季节变化，并表现出“降雨效应”明显、“温度效应”不明显的特点；（2）地表水在枯水期受到强烈的蒸散发，表现出一定的“地貌效应”与“干支流效应”的特征；（3）民井、泉和钻孔等地下水均源于大气降水，表现出“含水层埋深效应”与“山区平原效应”的特点；（4）枯水期，界河流域中界河获得了上游水库和地下水的补给，夏家寺水库流域中夏家寺水库得到了地下水补给。【结论】氢氧同位素能显著提高武汉北部新城地表水-地下水相互转换规律的认识。创新点：利用各类水体氢氧同位素组成及空间分布特征，揭示了武汉北部新城降水、地表水和地下水相互转换的规律     

Origin of major dissolved ions in groundwater within the Lower Pra Basin using groundwater geochemistry,source-rock deduction and stable isotopes of 2H and 18O

Hydrochemical and stable isotopes (¹⁸O and ²H) analyses of groundwater samples were employed to establish the origin of major dissolved ions in groundwater within the Lower Pra Basin. Results showed that, the major processes responsible for chemical evolution of groundwater include: silicate (SiO₄)^4? dissolutions, ion exchange reactions, sea aerosol spray and pyrite (FeS₂) and arsenopyrite (FeAsS) oxidations. The groundwater is strongly acidic to neutral, with pH generally range from 3.5 to 7.0 pH units and mean 5.9 (±0.5). Approximately 89 % of boreholes had pH values outside the World Heath Organization (WHO, Guidelines for drinking water quality, 2004) guideline value for drinking water due principally to natural biogeochemical processes and therefore, not suitable for potable purposes. Electrical conductivity (EC) range from 57.6 to 1,201 μS/cm with mean 279.3 (±198.8) μS/cm. Total dissolved solids (TDS) range from 32 to 661 mg/L with mean 151.7 (±106.8) mg/L, with 98.6 % of groundwater as fresh (TDS < 500 mg/L). The chemical constituents generally have low concentrations and are within the WHO (Guidelines for drinking water quality, 2004) guideline value for drinking water. The relative abundance of cations and anions is in the order: Na⁺ > Ca²⁺> Mg²⁺ > K⁺ and HCO₃ ^? > Cl^? > SO₄ ^2?, respectively. A plot of ?¹⁸O ‰ against ²H ‰ showed that, ground and surface waters clustered on or closely along the Global Meteoric Water Line, suggesting that, the waters emanated principally from meteoric source with evaporation playing an insignificant role on the infiltrating water.     

Constraining groundwater flow,residence times,inter-aquifer mixing,and aquifer properties using environmental isotopes in the southeast Murray Basin,Australia

Environmental isotopes (particularly δ¹⁸O, δ²H, and δ¹³C values, ⁸⁷Sr/⁸⁶Sr ratios, and a¹⁴C) constrain geochemical processes, recharge distribution and rates, and inter-aquifer mixing in the Riverine Province of the southern Murray Basin. Due to methanogenesis and the variable δ¹³C values of matrix calcite, δ¹³C values are highly variable and it is difficult to correct ¹⁴C ages using δ¹³C values alone. In catchments where δ¹³C values, ⁸⁷Sr/⁸⁶Sr ratios, and major ion geochemistry yield similar a¹⁴C corrections, ∼15% of the C is derived from the aquifer matrix in the silicate-dominated aquifers, and this value may be used to correct ages in other catchments. Most groundwater has a¹⁴C above background (∼2 pMC) implying that residence times are <30 ka. Catchments containing saline groundwater generally record older ¹⁴C ages compared to catchments that contain lower salinity groundwater, which is consistent with evapotranspiration being the major hydrogeochemical process. However, some low salinity groundwater in the west of the Riverine Province has residence times of >30 ka probably resulting from episodic recharge during infrequent high rainfall episodes. Mixing between shallower and deeper groundwater results in ¹⁴C ages being poorly correlated with distance from the basin margins in many catchments; however, groundwater flow in palaeovalleys where the deeper Calivil–Renmark Formation is coarser grained and has high hydraulic conductivities is considerably more simple with little inter-aquifer mixing. Despite the range of ages, δ¹⁸O and δ²H values of groundwater in the Riverine Province do not preserve a record of changing climate; this is probably due to the absence of extreme climatic variations, such as glaciations, and the fact that the area is not significantly impacted by monsoonal systems.     

基于环境同位素分析吐鲁番盆地地下水流系统

吐鲁番盆地是中国重要的煤炭基地之一,研究盆地地下水流系统对于区域水资源评价具有重要意义。通过在野外开展取样工作,首先根据取样点井深的不同,将所有样点分为4组,结合当地水文地质条件、同位素值的高程效应以及取样点位置,将同位素值以及位置相近的点归为同一个水流系统。经分析,在火焰山以北存在一个相同型式的地下水流动系统,而在火焰山以南随着山区坎尔其水库的修建,水利工程设施的不断完善和农业灌溉制度的改革,存在多级地下水流动系统,其形成条件主要受自然和人类活动影响。其中同位素和TDS值都较高的T1点曾是艾丁湖湖面的边缘,当时湖水水位浅,同位素蒸发效应明显。同时,火焰山地下基岩存在缺口,存在北盆地向南盆地的地下水补给。     

Study of stable isotopes for highly deformed aquifers in the Hsinchu-Miaoli area, Taiwan

This study was based on the analysis of isotopic compositions of hydrogen and oxygen in samples from precipitation, groundwater and stream water. In addition, parts of groundwater samples were dated by carbon-14 and tritium. These data are integrated to provide other views of the hydrologic cycle in the Hsinchu-Miaoli groundwater district. The groundwater district is principally composed of Pleistocene and Holocene aquifers. The Pleistocene aquifers are highly deformed by folding and faults into small sub-districts with areas of only tens of square kilometers. These aquifers are exclusively recharged by local precipitation. The Holocene aquifers cover narrow creek valleys, only tens of meters in thickness. The local meteoric water line (LMWL), constructed from rainfall samples in the Hsinchu Science Park, is described by the equation δD=8.02δ¹⁸O+10.16, which agrees with the global meteoric water line. In addition, the precipitation isotopic compositions can be categorized into two distinct end members: typhoon type and monsoon type. The groundwater isotopic compositions are perfectly located on an LMWL and can be considered a mixture of precipitations. Based on the mass balance of isotopic compositions of oxygen and hydrogen, infiltration is more active in the rainy season with depleted isotopic compositions. The amount of infiltration during May–September is roughly estimated to comprise at least 55% of the whole year’s recharge. The isotopic compositions of stream water are expressed by a regression equation: δD=7.61δ¹⁸O+9.62, which is similar to the LMWL. Although precipitation isotopic compositions are depleted during summer time, the isotopic compositions contrarily show an enriched trend in the upstream area. This is explained by the opposite altitude effect on isotopic compositions for typhoon-related precipitations.     

Environmental isotopes (18O, 2H, and 87Sr/86Sr) as a tool in groundwater investigations in the Keta Basin, Ghana

Analyses of environmental isotopes (¹⁸O, ²H, and ⁸⁷Sr/⁸⁶Sr) are applied to groundwater studies with emphasis on saline groundwater in aquifers in the Keta Basin, Ghana. The ⁸⁷Sr/⁸⁶Sr ratios of groundwater and surface water of the Keta Basin primarily reflect the geology and the mineralogical composition of the formations in the catchments and recharge areas. The isotopic compositions of ¹⁸O and ²H of deep groundwater have small variations and plot close to the global meteoric water line. Shallow groundwater and surface water have considerably larger variations in isotopic compositions, which reflect evaporation and preservation of seasonal fluctuations. A significant excess of chloride in shallow groundwater in comparison to the calculated evaporation loss is the result of a combination of evaporation and marine sources. Groundwaters from deep wells and dug wells in near-coastal aquifers are characterized by relatively high chloride contents, and the significance of marine influence is evidenced by well-defined mixing lines for strontium isotopes, and hydrogen and oxygen stable isotopes, with isotopic compositions of seawater as one end member. The results derived from environmental isotopes in this study demonstrate that a multi-isotope approach is a useful tool to identify the origin and sources of saline groundwater. Electronic Publication     

Hydrogeology of the Nurra Region, Sardinia (Italy): basement-cover influences on groundwater occurrence and hydrogeochemistry

The Nurra district in the Island of Sardinia (Italy) has a Palaeozoic basement and covers, consisting of Mesozoic carbonates, Cenozoic pyroclastic rocks and Quaternary, mainly clastic, sediments. The faulting and folding affecting the covers predominantly control the geomorphology. The morphology of the southern part is controlled by the Tertiary volcanic activity that generated a stack of pyroclastic flows. Geological structures and lithology exert the main control on recharge and groundwater circulation, as well as its availability and quality. The watershed divides do not fit the groundwater divide; the latter is conditioned by open folds and by faults. The Mesozoic folded carbonate sequences contain appreciable amounts of groundwater, particularly where structural lows are generated by synclines and normal faults. The regional groundwater flow has been defined. The investigated groundwater shows relatively high TDS and chloride concentrations which, along with other hydrogeochemical evidence, rules out sea-water intrusion as the cause of high salinity. The high chloride and sulphate concentrations can be related to deep hydrothermal circuits and to Triassic evaporites, respectively. The source water chemistry has been modified by various geochemical processes due to the groundwater–rock interaction, including ion exchange with hydrothermal minerals and clays, incongruent solution of dolomite, and sulphate reduction.     

A study on groundwater recharge in the Anyanghe River alluvial fan,North China Plain,based on hydrochemistry,stable isotopes and tritium

Studies on groundwater recharge are essential for sustainable exploitation of groundwater resources, especially in areas of extensive groundwater exploitation such as the Anyanghe River alluvial fan (ARAF) in the North China Plain (NCP). However, the recharge sources and processes and the contribution of each recharge flow component remain unclear. This study used hydrochemistry, stable isotopes, and tritium to investigate sources and underlying processes of groundwater recharge, along with the steady flow Mixing Cell Model (MCMsf) to quantify the proportion of each source flow for the shallow confined groundwater system in the medial fan. The results showed that groundwater mainly originates from precipitation occurring on the eastern Taihang Mountain area with average elevation estimated at 700–1,000 m above sea level during the East Asia summer monsoon period since 1952. Recharge mechanisms are: (1) river water seepage for the unconfined aquifers of the proximal and medial fan; (2) lateral flow for the confined aquifers of the medial and distal fan; and (3) precipitation infiltration for the phreatic water system. The MCMsf simulation showed that the shallow confined groundwater system in the central zone of the medial fan mainly recharged by the lateral flow from the proximal fan, a constant and considerable recharge flow from the southwestern and southern hills, and river water seepage in the medial fan; the lateral recharge flow from the Zhanghe alluvial aquifer was insignificant by comparison. The results of this study can act as a valuable reference for sustainable groundwater management in the ARAF.

     

Impact of impoundment on groundwater seepage in the Three Gorges Dam in China based on CFCs and stable isotopes

It is a common concern that the groundwater flow field caused by the Three Gorges Dam changes the regional seismic activity and environment. The changes in the seepage region could be effectively reflected through the analysis of the groundwater age using chlorofluorocarbons (CFC)-based techniques. In this study, the influences of the reservoir water on groundwater and the seepage region boundary of the reservoir were investigated using CFCs, stable isotopes, and water level in groundwater, reservoir water, and spring water during the water storage process of the Three Gorges Reservoir. The results show that the water supplied by the groundwater is older, whereas the water supplied by the reservoir and the springs is younger. With an increase in the water level of the reservoir, the water in well W3, which is located at the vice dam of the head region, becomes older due to the reservoir loading effect, whereas the water in well W4 become younger due to the lateral seepage of reservoir water. This finding indicates that the groundwater seepage regions in wells W3 and W4, which are located at upstream of the reservoir, are all influenced by the Three Gorges Reservoir. In contrast, the sampling points in the northern section of the Xiannvshan fault zone, which is farther from the dam, did not exhibit any direct hydraulic connection between the groundwater and the reservoir water; thus, the reservoir seepage effects may not affect the northern part of the Xiannvshan fault zone. These research results provide important reference data that can be used to analyze the effects of the Three Gorges reservoir storage on the regional environment.     

Hydrogeological and hydrochemical investigation of groundwater using environmental isotopes (18O, 2H, 3H, 14C) and chemical tracers: a case study of the intermediate aquifer,Sfax, southeastern Tunisia

Major element concentrations and stable (δ¹⁸O and δ²H) and radiogenic (³H and ¹⁴C) isotopes in groundwater have proved useful tracers for understanding the geochemical processes that control groundwater mineralization and for identifying recharge sources in the semi-arid region of Sfax (southeastern Tunisia). Major-ion chemical data indicate that the origins of the salinity in the groundwater are the water–rock interactions, mainly the dissolution of evaporitic minerals, as well as the cation exchange with clay minerals. The δ¹⁸O and δ²H relationships suggest variations in groundwater recharge mechanisms. Strong evaporation during recharge with limited rapid water infiltration is evident in the groundwater of the intermediate aquifer. The mixing with old groundwater in some areas explains the low stable isotope values of some groundwater samples. Groundwaters from the intermediate aquifer are classified into two main water types: Ca-Na-SO₄ and Ca-Na-Cl-SO₄. The high nitrate concentrations suggest an anthropogenic source of nitrogen contamination caused by intensive agricultural activities in the area. The stable isotopic signatures reveal three water groups: non-evaporated waters that indicate recharge by recent infiltrated water; evaporated waters that are characterized by relatively enriched δ¹⁸O and δ²H contents; and mixed groundwater (old/recent) or ancient groundwater, characterized by their depleted isotopic composition. Tritium data support the existence of recent limited recharge; however, other low tritium values are indicative of pre-nuclear recharge and/or mixing between pre-nuclear and contemporaneous recharge. The carbon-14 activities indicate that the groundwaters were mostly recharged under different climatic conditions during the cooler periods of the late Pleistocene and Holocene.

     

Small-scaled environmental changes: indications from stable isotopes of gastropods (Early Miocene, Korneuburg Basin, Austria)

The Korneuburg Basin, with mainly upper Lower Miocene (Karpatian) sediment filling, is divided by the Mollmannsdorf–Obergänserndorf Swell into two sub-basins characterised by different environmental settings. Paleoecological data indicate a marine northern part and a mainly estuarine southern part. Nevertheless, short-termed marine ingressions from the north allowed marine faunas (ostracods, molluscs, and echinoids) to temporarily settle the southern part of the basin. The carbon and oxygen isotopic composition of gastropod shells from these different environmental settings were investigated. Highest δ¹⁸O and δ¹³C values are found in Turritella shells from the northern part of the basin, and in Turritella shells from layers interpreted as a marine ingression in the south. Generally, components of the mudflat fauna (Tympanotonos cinctus, Granulolabium bicinctum, Terebralia bidendata, and Ocenebra crassilabiata) have slightly lower isotope values. Considerable freshwater influx in the southern part is documented by abundant freshwater genera such as Melanopsis, which show low carbon and oxygen isotope values. Data of identical taxa, especially Turritella and Granulolabium, reflect a trend from higher isotope values at the marine northern part to slightly lower values in the mainly estuarine southern part of the basin. Differences in δ¹⁸O between the marine and the estuarine assemblages are interpreted to be caused by changes in salinity and isotopic composition of ambient water rather than by temperature. Paleotemperature estimates derived from oxygen isotope data are in good agreement with existing paleoclimatic proxies for the Korneuburg Basin. Hence, an annual range of the sea-surface temperature from 13 to 26°C can be predicted within that protected basin.     

The hydrochemical identification of groundwater flowing to the Bet She’an-Harod multiaquifer system (Lower Jordan Valley) by rare earth elements,yttrium, stable isotopes (H,O) and Tritium

The Bet She’an and Harod Valleys in Israel are regional recipients and mixing zones for groundwater draining from a multiple aquifer system, which includes carbonate and basalt aquifers and deep-seated pressurized brines. The aquifers drain through two types of outlets, distinct and mixed. The latter type is mainly conditioned by the occurrence of fault-blocks related to the Jordan Rift system, which act as connecting media between the aquifers and facilitate interaquifer flow. Conjoint application of rare earth element distribution and water isotopes enables detection of the local areas replenishment by rainfall infiltration and, in connection with the position of wells or springs, the identification of groundwater flow paths. Once stationary equilibria are established changes of REY composition between REY in groundwater and their surface adsorption, are negligible. In areas with little soil coverage and vegetation even recharge over young Tertiary and diagenetic Cretaceous limestones is distinguishable by their REY distribution patterns. Groundwater recharged over Tertiary limestones show higher REY abundance and more significant Ce anomalies than those derived from the Cretaceous limestones. Weathering of alkali olivine basalts leads to REY patterns in groundwater depleted in the middle REE. The improved knowledge of the hydrological systems is thought to be useful for regional hydrogeological modeling and for designing rational water management schemes.     

洞庭湖湖区降水-地表水-地下水同位素特征

为探明洞庭湖湖区水体稳定同位素时间和空间上的变化规律,弄清各水体间的相互关系,分别在2012年4月和8月对区域内具有代表性的采样点进行了地表水和地下水的采样。通过对样品进行D、18O同位素分析,结合全球大气降水同位素监测网（GNIP）公布的1988—1992年间长沙降水同位素数据,发现湖区年内受不同盛行风影响,降水及地表水的同位素存在较大的季节性差异,4月份同位素富集,8月份贫化。此外,河水、湖水同位素也呈现明显的空间差异。两个时期地表水的水线斜率均小于当地降水线,地表水在两个时期均存在蒸发作用。虽然地表水和地下水的来源均为大气降水,但与地表水相比,地下水同位素季节变化较小,地下水接受地表水补给是一个较为长期的过程。     

Identifying the recharge sources and age of groundwater in the Songnen Plain (Northeast China) using environmental isotopes

The recharge sources and groundwater age in the Songnen Plain, Northeast China, were confirmed using environmental isotopes. The isotopic signatures of the unconfined aquifers in the southeast elevated plain and the north and west piedmont, cluster along local meteoric water lines (LMWLs) with a slope of about 5. The signature of source water was obtained by the intersection of these LMWLs with the regional meteoric water line (RMWL). This finding provides evidence that the recharge water for these areas originate from the Changbai Mountains and the Low and High Hingan Mountains, respectively. Groundwater in the unconfined aquifer in the low plain yields a LMWL with a slope of 4.4; its nitrate concentration indicates the admixture of irrigation return flow. The δ-values of the unconfined aquifer in the east elevated plain plot along the RMWL, reflecting recharge by local precipitation. The mean residence time of groundwater in these aquifers is less than 50?years. However, the ¹⁴C age of the groundwater in the confined Quaternary aquifer ranges from modern to 19,500?years, and in the Tertiary confined aquifer from 3,100 to 24,900?years. Modern groundwater is mainly recharged to the Quaternary confined aquifer on the piedmont by local precipitation and lateral subsurface flow.