金佛山世界遗产地岩溶地下河系统硝酸盐来源与转化

地下水硝酸盐污染已成为一个普遍的环境问题.为研究重庆金佛山水房泉岩溶地下河系统的硝酸盐来源与转化,于2017年4-10月每24 d左右对地下河系统内的某酒店自来水、化粪池、1^#落水洞、水房泉4个采样点开展监测,进行水化学和δ¹⁵N_nitrate、δ¹⁸O_nitrate同位素分析.某酒店污水经化粪池处理后,由1^#落水洞排入地下河,最后在水房泉排泄.结果表明：①水房泉NO₃^-浓度范围为4.65~10.20 mg/L,相对于我国生活饮用水标准处于较低水平;化粪池、1^#落水洞、水房泉3个采样点电导率和NO₃^-、Cl^-浓度的高值期与游客人数增多对应关系较好.②某酒店自来水δ¹⁵N_nitrate值为3.7‰~5.8‰、δ¹⁸O_nitrate值为1.6‰~2.7‰,说明硝酸盐主要来源为土壤有机氮,处于自然背景值;1^#落水洞δ¹⁵N_nitrate值为14.4‰~21.1‰、δ¹⁸O_nitrate值为3.5‰~11.2‰,显示硝酸盐主要来源为粪肥污水;化粪池和水房泉的δ¹⁵N_nitrate值为3.7‰~17.0‰、δ¹⁸O_nitrate值为-9.0‰~7.3‰,表明硝酸盐主要来源为土壤有机氮与粪肥污水,显示其硝酸盐主要污染源是酒店生活废污水.③某酒店自来水、水房泉地下水的硝酸盐转化过程以同化作用为主;化粪池污水以硝化作用为主,是岩溶地下河系统硝酸盐的重要来源之一;1^#落水洞污水表现为反硝化作用.④基于SIAR模型对水房泉的硝酸盐来源进行定量解析,发现大气降水、土壤有机氮和粪肥污水的贡献率分别为28%、36%和36%左右.     

稳定同位素技术在地表水硝酸盐污染研究中的应用

地表水硝酸盐污染已成为全球面临的主要水环境问题之一,为了有效控制地表水中硝酸盐污染,确定地表水中硝酸盐的来源以及研究其在环境中的迁移转化过程就显得尤为重要.硝酸盐稳定氮(¹⁵N)、氧(¹⁸O)同位素作为一种有效的示踪技术在识别地表水中硝酸盐的来源及迁移转化过程中已得到了广泛的应用,但是硝酸盐在迁移转化过程中,¹⁵N、¹⁸O同位素会因为多种因素而发生分馏,同位素值发生变化使得这种技术的应用存在一定的局限性.本文系统总结了不同来源硝酸盐δ¹⁵N、δ¹⁸O值的组成特征及其影响因素,分析了在不同土地利用类型流域内,利用硝酸盐¹⁵N、¹⁸O同位素技术开展硝酸盐来源识别、负荷估算和反硝化作用评估的方法和研究进展.基于已有研究成果,提出在未来的研究过程中,一方面应以流域为单元,选择适当的研究方法并结合多种辅助指标研究多因素共同作用下NO₃^-污染源的δ¹⁵N-NO₃^-和δ¹⁸O-NO₃^-值的变化规律;另一方面应对比流域污染源详细的调查数据,分析现有负荷估算模型存在的不确定性,并构建合适的负荷计算模型;最后,应深入开展同位素在确定流域和河流中反硝化发生的范围、地点和程度方面的研究,特别是掌握河流系统中沉积物-水体中氮的循环过程.     

太湖流域降雨和湖水酸根阴离子长期变化及其环境意义

为揭示太湖流域降雨和湖水酸根阴离子长期变化特征及环境意义,通过历史数据收集和采样分析,对太湖流域降雨和湖水中的SO₄^2-、NO₃^-变化特征和来源进行了研究.结果表明：自1990s以来太湖流域降雨中SO₄^2-呈显著下降趋势,年平均下降率为0.28 mg/（L·a）;NO₃^-浓度却呈显著上升趋势,年平均增长率为0.05 mg/（L·a）,降雨中氮污染呈现加重的趋势.与之相反,湖水中SO₄^2-呈显著上升趋势,年平均增长率为1.24 mg/（L·a）;NO₃^-浓度却呈显著下降趋势,年平均下降率为0.02 mg/（L·a）.30年以来,太湖水体SO₄^2-/NO₃^-比值不断升高,远高于降水SO₄^2-/NO₃^-比值.研究认为：流域SO₂排放引起的酸沉降是湖水SO₄^2-浓度增长的最重要原因,但氮氧化物排放并未引起湖水NO₃^-浓度升高,说明太湖流域对大气沉降的氮氧化物有滞留作用,而太湖水体是流域大气沉降硫酸盐的重要汇.综合治理太湖流域酸性物质排放对防止太湖水体酸化和治理富营养化都具有重要意义.     

城镇化流域氮、磷污染特征及影响因素——以宁波北仑区小浃江为例

我国快速的城镇化过程造成了河流氮、磷等营养盐的污染和潜在的水体富营养化问题.对城镇流域水体氮、磷污染特征及其演变趋势的识别具有重要意义.本研究选取长三角典型城镇地区宁波市北仑区小浃江流域为研究对象,在流域内根据空间分布、土地利用类型、人类活动强度等情况布设样点,于2017年夏季和冬季采集水样,研究流域水体氮、磷污染的时空分布特征并分析其污染来源和评估其富营养化水平.结果表明：流域内铵态氮（NH₄⁺-N）、;硝态氮（NO₃^--N）、亚硝态氮（NO₂^--N）、总氮（TN）、总磷（TP）和叶绿素a（Chl.a）浓度范围分别为0.63~3.25 mg/L、0.52~3.75 mg/L、0.02~0.22 mg/L、1.61~12.86 mg/L、0.02~0.74 mg/L和0.6~60.57 μg/L.各个采样点氮、磷分布具有较大的空间异质性和季节变化规律.富营养化综合指数EI评估结果显示,整个流域富营养化程度属于贫至中营养级.氮、磷浓度与土地类型面积占比的Spearman相关性统计表明,100 m缓冲区建设用地面积占比与NH₄⁺-N、NO₂^--N、TN、溶解氧（DO）浓度具有显著相关性,湿地面积占比与DO浓度呈显著正相关.汇水区域内林地面积占比与NH₄⁺-N、NO₂^--N、TP、PO₄^3--P、COD、Chl.a浓度呈显著负相关,与DO浓度呈显著正相关.相关性分析和冗余分析表明城镇化的面源污染及可能存在的点源污染是小浃江流域氮、磷污染的主要来源.因此,在小浃江流域100 m范围内,控制建设用地的规模和污染排放是减轻流域氮、磷污染的主要途径.在汇水区域内,增加林地植被的面积对减少氮、磷污染具有重要影响.     

三峡大坝上下游水质时空变化特征

为探索三峡大坝上下游（坝上99.9 km、坝下63.0 km、全长162.9 km）水质时空变化特征,运用主成分分析和方差分析对2016年近坝段水质时空变化特征进行了分析.主成分分析表明,水文因子流量（Q）、气温（T）、水位（Z）和水质因子（水温（WT）、pH、电导率（EC）、溶解氧（DO）、悬浮物（SS）、高锰酸盐指数（COD_Mn）、硫酸盐（SO₄^2-）、氟化物（F^-）、总硬度（T-Hard）、硝态氮（NO₃^--N）、总氮（TN）和硒（Se））的变化主导着研究区域水质变化;各采样点主成分得分和双因素方差分析结果显示研究区域水质因子时间变化主要呈现出季节和不同水库运行时期的差异.消落期（2-5月）,T-Hard、F^-、SO₄^2-和EC是影响河流水质变化的主导因子;汛期（7-8月）,Q、SS、COD_Mn、NO₃^--N、TN和Se是影响河流水质变化的主导因子;T和WT主导着汛末（9月）河流水质变化,并引起了DO等理化特性的变化;高水位运行期（12月）,Cl^-是影响河流水质变化的主导因子.现阶段,DO、有机污染物（COD_Mn）、无机盐（SO₄^2-和F^-）、营养盐类（NO₃^--N和TN）、类金属元素（Se）和水体的矿化程度（T-Hard）的变化主导着区域水质的变化,是三峡大坝近坝段水域水质的控制因子.方差分析表明,河流的理化特性（DO、pH和SS）、营养盐组分构成（NH₃-N和NO₃^--N）、无机盐类（EC和Cl^-）、石油类有机污染物及粪大肠菌群（FC）等指标在坝上与坝下断面存在显著性差异.气温、水温、降雨、含沙量的季节性影响因素和水库调度运行模式是影响近坝段水质时间差异的主要因子;空间差异主要受城区污染排放和三峡水库调度引起的坝上和坝下水文和水动力学条件差异影响.因此控制研究区域因人类活动等造成的外源性污染,并针对不同类污染物质的季节变化特征实施合理的水库运行方式是近坝段水质提升的关键.     

基于15N稳定同位素示踪技术的太湖梅梁湾浮游植物群落氮吸收动力学研究

浮游植物对氮的吸收与其生长繁殖密切相关,太湖梅梁湾湖区蓝藻水华频频暴发,对该水域浮游植物氮吸收进行研究具有重要意义.本文分别在冬、春、夏、秋4个季节于梅梁湾采样,对水体常规理化指标和浮游植物群落结构进行分析,并利用¹⁵N稳定同位素示踪技术研究了浮游植物对铵态氮（NH₄⁺-N）、硝态氮（NO₃^--N）和尿素态氮（Urea-N）吸收的动力学特征.结果表明,太湖梅梁湾浮游植物群落除了秋季对NH₄⁺-N的吸收不符合米氏方程外,其余均符合.冬季和春季3种形态氮最大吸收速率（V_max）的大小依次为：NH₄⁺-N > NO₃^--N > Urea-N,而夏季为：NH₄⁺-N > Urea-N > NO₃^--N.3种形态氮V_max的季节变化规律为夏季 > 秋季 > 春季 > 冬季.V_max在不同季节以及不同形态氮之间的差异性可能与浮游植物群落组成以及水体中NH₄⁺-N浓度不同有关.浮游植物对NH₄⁺-N吸收的K_S值在冬、春季高于夏季,对Urea-N吸收的K_s值则在夏、秋季高于冬、春季,而对NO₃^--N吸收的K_s值则在夏季显著高于其他3个季节.冬季和春季梅梁湾浮游植物群落最容易受到NO₃^--N限制,而最不容易受到Urea-N的限制;而夏季,则最容易受到NO₃^--N限制,而最不容易受到NH₄⁺-N的限制,且浮游植物群落对NH₄⁺-N的亲和力最高.与NO₃^--N相比,秋季浮游植物更容易受到Urea-N的限制.不同季节,容易对浮游植物产生限制作用的氮的形态不同.     

生态补水对白洋淀流域地表水和地下水水化学特征的影响

生态补水是维持和改善白洋淀生态环境的重要途径.为研究生态补水对白洋淀水环境的影响,分别在补水前与补水后采集淀水、河水及地下水样品,分析区域地表水和地下水水化学特征.结果表明：（1）白洋淀补水前、后地表水与地下水的水化学组成中Na⁺为主要阳离子,补水后阴离子以HCO₃^-为主,淀区南部地表水电导率高;补水后地表水与地下水Ca²⁺、Mg²⁺和HCO₃^-浓度显著增加,水体电导率降低.（2）补水前地下水为Na-HCO₃型水,地表水主要为Na-Cl·SO₄及Na-Cl·HCO₃类型;补水后地表水与浅层地下水向Ca·Mg-HCO₃型演化,深层地下水水化学类型基本保持不变.（3）生态补水使白洋淀水位升高,淀区水面积增大,缓解了水资源短缺的问题;同时也使浅层地下水水化学组成发生改变,而深层地下水暂未受到影响.生态补水后,受稀释和混合作用的影响,水体Na⁺、Cl^-和SO₄^2-浓度显著下降,Ca²⁺、Mg²⁺及HCO₃^-浓度增加.在白洋淀生态补水中应"先治污,后补水",以减少补水过程中污染物向淀区的运移,还应注意区域地下水位上升过程中的阳离子交换及水岩相互作用,为合理调配生态补水及改善白洋淀生态环境提供科学依据.     

不同水生植物对富营养化水体无机氮吸收动力学特征

采用浓度梯度法,研究了鸢尾(Iris louisiana)、狐尾藻(Myriophyllum verticillatum)、茭白(Zizania latifolia)和水芹(Oenanthe clecumbens)对硝态氮(NO₃^--N)和铵态氮(NH₄⁺-N)吸收动力学特征.结果表明:4种水生植物对水体NO₃^--N和NH₄⁺-N吸收可用Michaelis-Menten酶动力学方程描述,随溶液NO₃^--N和NH₄⁺-N浓度增加,植物吸收NO₃^--N和NH₄⁺-N速率增加,当溶液NO₃^--N和NH₄⁺-N浓度接近于2.0 mmol/L时,吸收速率增加趋缓;4种水生植物对NO₃^--N和NH₄⁺-N的V_max值大小为水芹 >茭白 >鸢尾 >狐尾藻,对NO₃^--N的K_m值大小为水芹 >鸢尾=茭白=狐尾藻,对NH₄⁺-N的K_m值大小为水芹 >狐尾藻 >茭白=鸢尾.根据吸收动力学参数(V_max,K_m)判断水芹适宜于净化NO₃^--N和NH₄⁺-N浓度较高的水体,茭白、鸢尾和狐尾藻适合净化NO₃^--N和NH₄⁺-N浓度较低水体;4种水生植物对NO₃^--N、NH₄⁺-N表现出不同的吸收偏好性,鸢尾吸收NO₃^--N的潜力大于吸收NH₄⁺-N的,但对NH₄⁺-N的亲和力大于NO₃^--N,表明能在NO₃^--N浓度较高环境中优先吸收NH₄⁺-N.狐尾藻和水芹对NO₃^--N和NH₄⁺-N能均衡吸收.茭白对NH₄⁺-N具有较高的吸收潜力与亲和力.     

富营养化湖泊中硫酸盐对蓝藻衰亡产甲烷过程的影响

随着外源性硫酸盐（SO₄^2-）的持续性输入,富营养化湖泊水体的SO₄^2-浓度持续升高.野外长期监测结果表明,近几十年太湖水体的SO₄^2-浓度逐渐升高,达到了96 mg/L的水平.此外,富营养化湖泊中蓝藻水华衰亡会产生并释放大量的甲烷（CH₄）,湖泊水体的SO₄^2-浓度升高是否会对沉积物产CH₄过程造成影响仍缺乏相关研究.本实验构建了蓝藻水体沉积物微宇宙系统,通过添加30、60、90、120和150 mg/L五组浓度的硫酸盐,探究不同SO₄^2-浓度下蓝藻衰亡过程中水体的SO₄^2-、还原性硫化物（∑S^2-）和CH₄的变化规律.结果表明,蓝藻聚积衰亡的第6~9天硫酸盐还原作用最为强烈,此时水体中的SO₄^2-浓度快速下降到最低值,依次为7.65、8.87、21.21、41.14和56.54 mg/L.伴随着硫酸盐还原过程的进行,水柱中∑S^2-的浓度不断上升,并达到最高值,依次为4.77、6.98、7.49、7.49和7.43 mg/L.蓝藻聚积衰亡的第10~21天水体中的SO₄^2-浓度维持在较低水平,∑S^2-浓度逐渐下降,并趋近于0.培养开始时,CH₄增长缓慢,SO₄^2-浓度下降之后,CH₄浓度逐渐上升,并在第6~9天迅速上升,培养结束时,CH₄的最终浓度随着水体初始SO₄^2-浓度的增加而降低,依次为546.39、207.24、79.61、37.25和5.56 μmol/L,CH₄的浓度与初始水体SO₄^2-浓度呈指数型负相关关系.因此,对于精准评估富营养化湖泊的产甲烷过程,需要考虑不断上升的SO₄^2-浓度所带来的影响.     

湖光岩玛珥湖水体中营养盐的时空分布特征及其影响因素

湖光岩玛珥湖是世界上最大的玛珥湖,它几乎是封闭的,受外界的干扰小.目前有关玛珥湖的研究主要集中在古气候及生态环境研究方面,而有关玛珥湖营养盐在一年中的生物地球化学循环的研究较少,因此研究湖光岩玛珥湖营养盐的生物地球化学过程具有重要意义.于2015年10月-2016年9月对湖光岩玛珥湖全水柱的营养盐及其他相关参数进行逐月调查,分析营养盐的结构特征、垂直分布特征和时间变化情况,并讨论营养盐时空变化的影响因素.结果表明,湖光岩玛珥湖水中的无机氮（DIN）以铵态氮（NH₄⁺-N）为主（>60%）,其次是硝态氧（NO₃^--N）,亚硝态氮（NO₂^--N）所占比利最低.湖光岩玛珥湖水中的硅酸盐（SiO₃^2--Si）浓度较高,水体浮游植物生长受磷限制.冬季风期间,水体垂直混合较均匀,导致营养盐的垂直分布比较均匀;夏季风期间,水体层化,营养盐浓度在浅层水体较低,在深层水体较高.湖光岩玛珥湖表层水中的NO₃^--N、NH₄⁺-N和SiO₃^2--Si具有明显的时间变化规律：NO₃^--N浓度从10月-次年3月升高,从3-9月降低;NH₄⁺-N浓度从10月-次年5月降低;SiO₃^2--Si浓度从11月-次年5月降低,从5-9月持续升高.营养盐浓度的时间变化受有机质的矿化分解、水体的季节性混合、浮游植物的吸收、降雨的输入等多种因素的综合影响.     

Hydrogeochemical characteristics of surface water and groundwater in the karst basin,southwest China

Groundwater is a very significant water source used for irrigation and drinking purposes in the karst region, and therefore understanding the hydrogeochemistry of karst water is extremely important. Surface water and groundwater were collected, and major chemical compositions and environmental isotopes in the water were measured in order to reveal the geochemical processes affecting water quality in the Gaoping karst basin, southwest China. Dominated by Ca²⁺, Mg²⁺, HCO₃^? and SO₄^2?, the groundwater is typically characterized by Ca? Mg? HCO₃ type in a shallow aquifer, and Ca? Mg? SO₄ type in a deeper aquifer. Dissolution of dolomite aquifer with gypsiferous rocks and dedolomitization in karst aquifers are important processes for chemical compositions of water in the study basin, and produce water with increased Mg²⁺, Ca²⁺ and SO₄^2? concentrations, and also increased TDS in surface water and groundwater. Mg²⁺/Ca²⁺ molar ratios in groundwater decrease slightly due to dedolomitization, while the mixing of discharge of groundwater with high Mg²⁺/Ca²⁺ ratios may be responsible for Mg²⁺/Ca²⁺ ratios obviously increasing in surface water, and Mg²⁺/Ca²⁺ ratios in both surface water and groundwater finally tending to a constant. In combination with environmental isotopic analyses, the major mechanism responsible for the water chemistry and its geochemical evolution in the study basin can be revealed as being mainly from the water–rock interaction in karst aquifers, the agricultural irrigation and its infiltration, the mixing of surface water and groundwater and the water movement along faults and joints in the karst basin. Copyright © 2009 John Wiley & Sons, Ltd.     

Source and Quality of Groundwater Surrounding the Qinghai Lake,NE Qinghai-Tibet Plateau

Comprehensive studies on the spatial distribution, water quality, recharge source, and hydrochemical evolution of regional groundwater form the foundation of rational utilization of groundwater resources. In this study, we investigated the water levels, hydrochemistry, and stable isotope composition of groundwater in the vicinity of the Qinghai Lake in China to reveal its recharge sources, hydrochemical evolution, and water quality. The level of groundwater relative to the level of water in the Qinghai Lake ranged from −1.27 to 122.91 m, indicating most of the groundwater to be flowing into the lake. The local evaporation line (LEL) of groundwater was simulated as δ²H = 6.08 δ¹⁸O-3.01. The groundwater surrounding the Qinghai Lake was primarily recharged through local precipitation at different altitudes. The hydrochemical type of most of the groundwater samples was Ca-Mg-HCO₃; the hydrochemistry was primarily controlled by carbonate dissolution during runoff. At several locations, the ionic concentrations in groundwater exceeded the current drinking water standards making it unsuitable for drinking. The main source of nitrate in groundwater surrounding the Qinghai Lake was animal feces and sewage, suggesting that groundwater pollution should be mitigated in areas practicing animal husbandry in the Qinghai-Tibet Plateau, regardless of industrial and urbanization rates being relatively low in the region. The scientific planning, engineering, and management of livestock manure and wastewater discharge from animal husbandry practices is a crucial and is urgently required in the Tibetan Plateau.     

Chemistry of the Karst Sarabkalan Spring,Iran, and Controls of PDO and ENSO Climate Indices on It

The Sarabkalan Spring serves as a primary water supply to irrigation and domestic use in the Sirvan Region, Iran. As it has a highly variable discharge, understanding its teleconnections with large-scale climate variability is crucial. In this study, we first characterize the springshed and its corresponding karst aquifer system using genetic algorithm analysis on the spring discharge, water balance calculations, temporal variations of physicochemical parameters, and stable isotopes along with considering its geological settings. Then, the large-scale climate indices teleconnections with precipitation and spring discharge are studied using wavelet analysis. Results reveal that the springshed contains two karst subaquifers resulting from geological and morphological settings. Unlike most developed karst systems in Zagros, which show one peak, the spring has two principal flow peaks over most hydrological years where the second peak occurs over the dry season. It takes ∼99 d (from lag correlation over 2008-2019) and ∼145 d (from δ¹⁸O measurements over 2018-2019) for rain water to reach the Sarabkalan Spring. Moreover, intense precipitations would result in an increase in discharge and a decrease in electrical conductivity, Ca + Mg, HCO₃, SO₄, Cl, ionic strength, and δ¹⁸O of the spring because of the developed karst conduit(s). It is further found that a positive Pacific Decadal Oscillation phase coupled with El Niño causes an increase in both the precipitation and spring discharge, signifying the influence of the atmospheric circulations of the Pacific Ocean on the spring behavior.     

Hydrochemical variations during flood pulses in the south‐west China peak cluster karst: impacts of CaCO3–H2O–CO2 interactions

High‐resolution measurements of rainfall, water level, pH, conductivity, temperature and carbonate chemistry parameters of groundwater at two adjacent locations within the peak cluster karst of the Guilin Karst Experimental Site in Guangxi Province, China, were made with different types of multiparameter sonde. The data were stored using data loggers recording with 2 min or 15 min resolution. Waters from a large, perennial spring represent the exit for the aquifer's conduit flow, and a nearby well measures water in the conduit‐adjacent, fractured media. During flood pulses, the pH of the conduit flow water rises as the conductivity falls. In contrast, and at the same time, the pH of groundwater in the fractures drops, as conductivity rises. As Ca²⁺ and HCO₃^? were the dominant (>90%) ions, we developed linear relationships (both r² > 0·91) between conductivity and those ions, respectively, and in turn calculated variations in the calcite saturation index (SI_C) and CO₂ partial pressure (P) of water during flood pulses. Results indicate that the P of fracture water during flood periods is higher than that at lower flows, and its SI_C is lower. Simultaneously, P of conduit water during the flood period is lower than that at lower flows, and its SI_C also is lower. From these results we conclude that at least two key processes are controlling hydrochemical variations during flood periods: (i) dilution by precipitation and (ii) water–rock–gas interactions. To explain hydrochemical variations in the fracture water, the water–rock–gas interactions may be more important. For example, during flood periods, soil gas with high CO₂ concentrations dissolves in water and enters the fracture system, the water, which in turn has become more highly undersaturated, dissolves more limestone, and the conductivity increases. Dilution of rainfall is more important in controlling hydrochemical variations of conduit water, because rainfall with higher pH (in this area apparently owing to interaction with limestone dust in the lower atmosphere) and low conductivity travels through the conduit system rapidly. These results illustrate that to understand the hydrochemical variations in karst systems, considering only water–rock interactions is not sufficient, and the variable effects of CO₂ on the system should be evaluated. Consideration of water–rock–gas interactions is thus a must in understanding variations in karst hydrochemistry. Copyright © 2004 John Wiley & Sons, Ltd.     

Isotopic and hydrochemical insights into the groundwater characteristics along an arid to semi-humid climate gradient in China

In arid to semi-arid regions, groundwater is a critical water resource heavily relied upon, with the recharge sources and patterns being predominantly shaped by climate change and regional disparities. To compare the characteristics of groundwater in the endorheic and exorheic river basins with the climate transition zone of Gansu Province, this study uses isotopic hydrochemical analyses. This study summarizes the differences in regional groundwater recharge and evolutionary patterns. The results shows that the distribution patterns of precipitation isotopes in endorheic and exorheic river basins are opposite to those of groundwater isotopes. Specifically, the precipitation in the endorheic areas is more depleted in heavy isotopes, whereas the groundwater is more enriched. Both endorheic areas and exorheic areas exhibit similar characteristics of groundwater hydrochemical evolution, evolving from low-mineralization Mg²⁺ HC ${\mathrm{O}}_3^{-}$ recharge water to Na⁺ Cl⁻ type water with saline characteristics. The former is primarily replenished by surface water, whereas the latter is primarily replenished by precipitation. Variations in recharge patterns along with the differences in climatic conditions lead to distinct groundwater conditions in the two regions.     

Origin of sulphate in the unsaturated zone and groundwater of a loess aquifer

The use of the sulphate mass balance (SMB) between precipitation and soil water as a supplementary method to estimate the diffuse recharge rate assumes that the sulphate in soil water originated entirely from atmospheric deposition; however, the origin of sulphate in soil and groundwater is often unclear, especially in loess aquifers. This study analysed the sulphur (δ³⁴S-SO₄) and oxygen (δ¹⁸O-SO₄) isotopes of sulphate in precipitation, water-extractable soil water, and shallow groundwater samples and used these data along with hydrochemical data to determine the sources of sulphate in the thick unsaturated zone and groundwater of a loess aquifer. The results suggest that sulphate in groundwater mainly originated from old precipitation. When precipitation percolates through the unsaturated zone to recharge groundwater, sulphates were rarely dissolved due to the formation of CaCO₃ film on the surface of sulphate minerals. The water-extractable sulphate in the deep unsaturated zone (>10 m) was mainly derived from the dissolution of evaporite minerals and there was no oxidation of sulphide minerals during the extraction of soil water by elutriating soil samples with deionized water. The water-extractable concentration of SO₄ was not representative of the actual SO₄ concentration in mobile soil water. Therefore, the recharge rate cannot be estimated by the SMB method using the water-extractable concentration of SO₄ in the loess areas. This study is important for identifying sulphate sources and clarifying the proper method for estimating the recharge rate in loess aquifers.     

Effects of ultrafiltration on salt migration and isotopic composition of pore water in groundwater depression area in Hengshui,NCP

Clay aquitards are semipermeable membranes that allow groundwater flow while retarding solute migration has been researched extensively but also subjected to much debate. At present, there is no evidence of whether the physical and chemical properties of clay soil and the isotopic composition of pore water affect the semipermeable membrane effect. In this study, we collected clay samples from drilling cores (30–90 m) in the Hengshui area located in the North China Plain (NCP), then extracted pore water using a high-pressure squeezing device. Vertical hydrochemical and isotopic profile variation trends for the pore water were revealed using hydrochemical (Cl⁻, Na⁺, Ca²⁺, K⁺, Mg²⁺, and SO₄²⁻) and stable isotopic measurements of H, O and Cl. The results showed that the hydrochemical clay interlayer pore water of the saline aquifer is Cl/SO₄-Na/Mg type and the average total dissolved solids (TDS) are 10.17 g/L. However, the hydrochemical clay aquitard pore water is of the Cl/SO₄-Na/Ca type with an average TDS of 1.90 g/L. The hydrochemical clay interlayer pore water of aquifer II is of Cl-Na/Ca type with an average TDS of 1.10 g/L. Our results showed that the water quality of the aquifer II is not affected by the upper part of the saline aquifer, thus the clay aquitard acts as a significant barrier to salt movement. A polarization layer concentrated in ions was formed between the upper part of the saline aquifer and the clay aquitard. The concentration polarization layer increases the salt-inhibition effect. H, O and Cl isotopic composition results showed significant fractionation. The pore water of aquifer II lacked heavy isotopes (²H, ¹⁸O, ³⁷Cl), but had significant heavy isotope enrichment in the concentrated polarized layer (the δ²H value was −76‰, the δ¹⁸O value was −8.4‰, and the δ³⁷Cl value was 1.59‰). Hyperfiltration thus played a significant role in isotope fractionation.     

Hydrochemical characteristics and salinization processes of groundwater in the shallow aquifer of Eastern Laizhou Bay,China

Groundwater salinization has become a crucial environmental problem worldwide and is considered the most widespread form of groundwater contamination in the coastal zone. In this study, a hydrochemical investigation was conducted in the eastern coastal shallow aquifer of Laizhou Bay to identify the hydrochemical characteristics and the salinity of groundwater using ionic ratios, deficit or excess of each ions, saturation indices and factor analysis. The results indicate that groundwater in the study area showed wide ranges and high standard deviations for most of hydrochemical parameters and can be classified into two hydrochemical facies, Ca²⁺‐Mg²⁺‐Cl^‐ facies and Na⁺‐Cl^‐ facies. The ionic ratio, deficit or excess of each ions and SI were applied to evaluate hydrochemical processes. The results obtained indicate that the salinization processes in the coastal zones were inverse cation exchange, dissolution of calcite and dolomite, and intensive agricultural practices. Factor analysis shows that three factors were determined (Factor 1: TDS, EC, Cl^‐, Mg²⁺, Na⁺, K⁺, Ca²⁺ and SO₄^2‐; Factor 2: HCO₃^‐ and pH; Factor 3: NO₃^‐ and pH), representing the signature of seawater intrusion in the coastal zone, weathering of water–soil/rock interaction, and nitrate contamination, respectively. Copyright © 2011 John Wiley & Sons, Ltd.     

Using hydrochemical,stable isotope,and river water recharge data to identify groundwater flow paths in a deeply buried karst system

The deeply buried river‐connected Xishan karst aquifer (XKA) in western Beijing, China, has been suffering from diminishing recharge for several decades, which in turn leads to the disappearing of spring water outflows and continuously lowering of groundwater level in the area. Thus, it is important to correctly recognize the groundwater recharge and flow paths for the sustainable development of the XKA. To investigate these issues, the hydrochemical and isotopic compositions are analysed for both surface water and groundwater samples collected over an area of about 280 km². Results show that (a) the river water is characterized by high Na contents; (b) the δ²H and δ¹⁸O values in the river water are distinctively higher than those of groundwater samples, after experiencing the long‐time evaporative enrichment in the upstream reservoir; (c) the Sr concentrations and ⁸⁷Sr/⁸⁶Sr ratios of groundwater clearly indicated the interaction between water and carbonate minerals but excluded the water–silicate interaction; and (d) the groundwater samples in the direct recharge area of the XKA have the lowest Na concentrations and the δ²H and δ¹⁸O values. Based on the large differences in the Na contents and ¹⁸O values of groundwater and surface water, a simple two‐component mixing model is developed for the study area and the fractions of the river water are estimated for groundwater samples. We find that the distribution pattern of the river water fractions in the XKA clearly shows a change of directions in the preferential flow path of the groundwater from its source zone to the discharge area. Overall, our results suggest that the recharged surface water can be a useful evidence for delineating the groundwater flow path in river‐connected karst aquifer. This study improves our understanding of the heterogeneity in karst groundwater systems.