典型岩溶水系统碳汇通量估算

现代岩溶学研究成果表明,碳酸盐岩在全球碳循环中响应极其迅速,水循环过程中的碳汇效应显著。本研究选取广西桂林寨底地下河系统、广西环江大安地下河系统、重庆北碚青木关地下河系统三个典型岩溶地下水系统,利用各系统地下河的流量和HCO3-浓度的监测资料,采用简单化学平衡模式法估算碳汇通量(CO2)。结果显示,寨底地下河系统的单位面积年碳汇通量为68.82 t/(km2.a),大安地下河系统的单位面积年碳汇通量为81.18 t/(km2.a),青木关地下河系统的单位面积年碳汇通量为100.07 t/(km2.a)。分析认为同一个岩溶水系统的结构特征和环境条件基本上是稳定的;地下河的流量和HCO3-浓度是影响岩溶碳汇强度的关键因素,尤其是地下河流量的变化对碳汇强度的影响显著;不同岩溶水系统的碳汇通量不但受水化学条件和地下水动力条件的控制,同时受土地利用变化的影响。该研究对于改进碳循环模型和评价岩溶地质碳汇有重要意义。     

亚热带典型岩溶水系统的碳汇效应对比研究

选择中国南方亚热带地区具有不同地质背景和生态状况的广西柳州市官村地下河(灌木林生态环境、人类活动影响显著)、云南省广南县木美地下河(石漠化严重)和贵州茂兰板寨地下河(原始森林生态)3个岩溶水系统为例,对比研究岩溶水中溶解无机碳浓度和碳汇效应的差异。结果表现,(1)流域管道水的溶解无机碳平均浓度排列顺序为:官村>木美>板寨,表层岩溶带泉水的排列顺序为:木美>官村>板寨。(2)水的PCO2分压计算结果显示:3个流域岩溶水的方解石溶解度基本达到饱和,PCO2的大小顺序为:官村地下河>木美地下河>板寨地下河。(3)根据一个水文年的流量监测计算官村地下河流域的岩溶碳汇强度为12.34tC/(km2?a),板寨地下河流域的为11.8tC/(km2?a),木美地下河流域为34.11tC/(km2?a)。木美地下河流域的石漠化现状相当严重,石漠化面积高达90%,而板寨地下河为原始森林区,但木美地下河流域的岩溶碳汇强度却最大,这与其流域面积大、调蓄功能强,且有外源水补给有关。这也同时表明,单从生态环境的角度去研究岩溶作用碳汇潜力是不够的。      

Global significance of the carbon cycle in the karst dynamic system: evidence from geological and ecological processes

On the basis of proposing the existence of a karst carbon cycle and carbon sink at a watershed scale, this paper provides four pieces of evidence for the integration of geology and ecology during the carbon cycle processes in the karst dynamic system, and estimated the karst carbon sink effect using the methods of comparative monitoring of paired watersheds and the carbon stable isotope tracer technique. The results of the soil carbon cycle in Maocun, Guilin, showed that the soil carbon cycle in the karst area, the weathering and dissolution of carbonate rocks under the soil, resulted in a lower soil respiration of 25% in the karst area than in a non-karst area (sandstone and shale), and the carbon isotope results indicated that 13.46% of the heavy carbon of the limestone is involved in the soil carbon cycle. The comparative monitoring results in paired watersheds, suggesting that the HCO₃^- concentration in a karst spring is 10 times that of a rivulet in a non-karst area, while the concentration of inorganic carbon flux is 23.8 times. With both chemical stoichiometry and carbon stable isotopes, the proportion of carbon in karst springs derived from carbonate rocks was found to be 58.52% and 37.65% respectively. The comparison on carbon exchange and isotopes at the water-gas interface between the granite and carbonate rock basins in the Li River showed that the CO₂ emission of the karst water is 10.92 times that of the allogenic water from the non-karst area, while the carbon isotope of HCO₃^- in karst water is lighter by 8.62‰. However, this does not mean that the karst water body has a larger carbon source effect. On the contrary, it means the karst water body has a greater karst carbon sink effect. When the karst subterranean stream in Zhaidi, Guilin, is exposed at the surface, carbon-rich karst water stimulated the growth of aquatic plants. The values of carbon stable isotopes in the same species of submerged plants gradually becomes heavier and heavier, and the 512 m flow process has a maximum range of 15.46‰. The calculation results showed that 12.52% of inorganic carbon is converted into organic carbon. According to the data that has been published, the global karst carbon sink flux was estimated to be 0.53-0.58 PgC/a, equivalent to 31.18%-34.41% of the global forest carbon sink flux. In the meanwhile, the karst carbon sink flux in China was calculated to be 0.051 PgC/a, accounting for 68% of its forest carbon sink flux.     

西南典型地下河系统无机-有机指标特征及健康风险评价

岩溶地下水为全球约25%的人口提供饮用水源,地下河作为主要岩溶地下水类型,是中国西南岩溶区重要供水水源,掌握其水质污染状况及人体健康风险,对岩溶区水资源保护与安全用水具有重要意义。本文以广西桂林会仙狮子岩地下河系统为例,采集地下河水样品22组(无机和有机样品各11组),采用电感耦合等离子体质谱、离子色谱、气相色谱-质谱等方法测定11项无机离子、10项金属元素及41项有机指标的质量浓度,运用单指标污染标准指数法、健康风险评价模型揭示了研究区无机与有机指标分布、污染及健康风险。结果表明：(1)狮子岩地下河水中无机超标指标有NH~+₄(1.33倍)、Fe(1.2倍)、Al(1.5倍)和Mn(1.01倍),超标点多位于地下河排泄区;检出18项有机物,其中挥发性有机物(VOCs)、半挥发性有机物(SVOCs)和有机氯农药(OCPs)检出率分别为18.75%、30.77%和91.67%,研究区存在普遍的农药残留(49.14～109.83ng/L)。(2)与地下水对照值相比,研究区受到10项无机指标的轻度～中度污染、14项有机指标的轻度污染,个别采样点受到NO~-_3<...     

Hydrogeological characterization and environmental effects of the deteriorating urban karst groundwater in a karst trough valley: Nanshan,SW China

The unique hydrogeology of karst makes the associated groundwater respond quickly to rainfall events and vulnerable to anthropogenic pollutions. In this study, high-frequency monitoring of spring discharge, temperature, electrical conductivity (EC) and pH, along with monthly hydrochemical and microbial analyses, was undertaken at the outlet of Laolondong karst underground river in Nanshan, southwestern China. The aim was to explore the environmental effects of the catchment’s urban area on the karst groundwater resources. The monitoring data of a tracer test and the response of discharge to rainfall events demonstrate that conduits and narrow fissures coexist in the Laolongdong karst aquifer. The EC, Na⁺, Cl^? and SO₄^2? values (840 μS/cm, 33.7, 38.6 and 137.2 μg/L, respectively), along with high concentrations of fecal coliform bacteria, at the outlet indicate considerable urban pollution in this area. The contaminants sulfate and nitrate showed different relationships with discharge and EC in different stages of a rainfall event. This behavior provided information about aquifer structure and the influence of transport properties. Meanwhile, the hydrological processes of groundwater flow could be modified by urbanization and result in increasing magnitude of urban floods in the underground river. In addition, sulfuric and nitric acids introduced by urbanization not only impact the karst groundwater quality, but also result in a significant perturbation to the carbon cycling system in the karst area.     

Effects of carbon anhydrase on utilization of bicarbonate in microalgae: a case study in Lake Hongfeng

A bidirectional labeling method was established to distinguish the proportions of HCO₃^? and CO₂ utilization pathways of microalgae in Lake Hongfeng. The method was based on microalgae cultured in a medium by adding equal concentrations of NaH¹³CO₃ with different δ¹³C values simultaneously. The inorganic carbon sources were quantified according to the stable carbon isotope composition in the treated microalgae. The effects of extracellular carbonic anhydrase (CAex) on the HCO₃^? and CO₂ utilization pathways were distinguished using acetazolamide, a potent membrane-impermeable carbonic anhydrase inhibitor. The results show utilization of the added HCO₃^? was only 8% of the total carbon sources in karst lake. The proportion of the HCO₃^? utilization pathway was 52% of total inorganic carbon assimilation. Therefore, in the natural water of the karst area, the microalgae used less bicarbonate that preexisted in the aqueous medium than CO₂ derived from the atmosphere. CAex increased the utilization of inorganic carbon from the atmosphere. The microalgae with CAex had greater carbon sequestration capacity in this karst area.     

Carbonate and carbon isotopic evolution of groundwater contaminated by produced water brine with hydrocarbons

The major ionic and dissolved inorganic carbon (DIC) concentrations and the stable carbon isotope composition of DIC (δ¹³C_DIC) were measured in a freshwater aquifer contaminated by produced water brine with petroleum hydrocarbons. Our aim was to determine the effects of produced water brine contamination on the carbonate evolution of groundwater. The groundwater was characterized by three distinct anion facies: HCO₃⁻-rich, SO₄²⁻-rich and Cl⁻-rich. The HCO₃⁻-rich groundwater is undergoing closed system carbonate evolution from soil CO_2(g) and weathering of aquifer carbonates. The SO₄²⁻-rich groundwater evolves from gypsum induced dedolomitization and pyrite oxidation. The Cl⁻-rich groundwater is contaminated by produced water brine and undergoes common ion induced carbonate precipitation. The δ¹³C_DIC of the HCO₃⁻-rich groundwater was controlled by nearly equal contribution of carbon from soil CO_2(g) and the aquifer carbonates, such that the δ¹³C of carbon added to the groundwater was −11.6‰. In the SO₄²⁻-rich groundwater, gypsum induced dedolomitization increased the ¹³C such that the δ¹³C of carbon added to the groundwater was −9.4‰. In the produced water brine contaminated Cl⁻-rich groundwater, common ion induced precipitation of calcite depleted the ¹³C such that the δ¹³C of carbon added to the groundwater was −12.7‰. The results of this study demonstrate that produced water brine contamination of fresh groundwater in carbonate aquifers alters the carbonate and carbon isotopic evolution.     

Isotopic and Chemical Constraints on the Biogeochemistry of Dissolved Inorganic Carbon and Chemical Weathering in the Karst Watershed of Krka River (Slovenia)

The hydrogeochemical and carbon isotope characteristics of the Krka River, Slovenia, were investigated to estimate the carbon transfer from the land ecosystem in the watershed. During the 3-year sampling period (2008–2010), temperature, pH, electrical conductivity, major ion content, dissolved inorganic carbon (DIC) and dissolved organic carbon content, and the isotopic composition of DIC (δ¹³C_DIC) were monitored in the main stream of the Krka River and its tributaries. The major solute composition of analysed waters is dominated by an input of HCO₃ ^?, Ca²⁺ and Mg²⁺ originating from carbonate dissolution. The Mg²⁺/Ca²⁺ and Mg²⁺/HCO₃ ^? molar ratio values ranging from 0.24 to 0.71 and 0.05 to 0.30, respectively, indicate a high degree of dolomite dissolution relative to calcite. Dissolved CO₂ concentrations in the river were up to tenfold supersaturated relative to the atmosphere, resulting in supersaturation with respect to calcite and degassing of CO₂ downstream. The δ¹³C values in river water range from ?15.6 to ?9.4 ‰ and are controlled by the input of tributaries, exchange with atmospheric CO₂, degradation of organic matter, and dissolution of carbonates. The mass balance calculations for riverine DIC suggest that the contribution from carbonate dissolution and degradation of organic matter have major influence, whereas the exchange with atmospheric CO₂ has minor influence on the inorganic carbon pool in the Krka River.     

Carbonate weathering and connate seawater influencing karst groundwaters in the Gevas–Gurpinar–Güzelsu basins,Turkey

There are 59 springs at the Gevas–Gurp?nar–Güzelsu basins, 38 of these springs emerge from the fractured karst aquifers (recrystallized limestone and travertine) and 21 emerge from the Yuksekova ophiolites, K?rkgeçit formation and alluvium. The groundwater samples collected from 38 out of the total of 59 springs, two streams, one lake and 12 wells were analyzed physico-chemically in the year 2002. EC and TDS values of groundwater increased from the marble (high altitude) to the ophiolites and alluvium (toward Lake Van) as a result of carbonate dissolution and connate seawater. Five chemical types of groundwater are identified: Ca–Mg–HCO₃, Mg–Ca–HCO₃, Mg–Na–HCO₃, Na–Ca–HCO₃ and Mg–Ca–Na–HCO₃. The calculations and hydrochemical interpretations show that the high concentrations of Ca²⁺, Mg²⁺ and HCO₃ ^? as predominant ions in the waters are mainly attributed to carbonate rocks and high pCO₂ in soil. Most of the karst springs are oversaturated in calcite, aragonite and dolomite and undersaturated in gypsum, halite and anhydrite. The water–rock interaction processes that singly or in combination influence the chemical composition of each water type include dissolution of carbonate (calcite and dolomite), calcite precipitation, cation exchange and freshening of connate seawater. These processes contribute considerably to the concentration of major ions in the groundwater. Stable isotope contents of the groundwater suggest mainly direct integrative recharge.     

Hydrochemical evolution of groundwater in a riparian zone affected by acid mine drainage (AMD), South China: the role of river–groundwater interactions and groundwater residence time

Investigations were undertaken in the riparian zone near Shangba village, an AMD area, in southern China to determine the effects that river–groundwater interactions and groundwater residence time have had on environmental quality and geochemical evolution of groundwater. Based on the Darcy’s law and ionic mass balances as well as the method of isotopic tracer, the results showed that there were active interactions between AMD-contaminated river water and groundwater in the riparian zone in the study area. River water was found to be the main source of groundwater recharge in the northwestern part of the study area, whereas groundwater was found to be discharging into the river in the southeastern part of the study area throughout the year. End-member mixing analysis quantified that the contributions of river water to groundwater decreased gradually from 35.9% to negligible levels along the flow path. The calculated mixing concentrations of major ions indicated that water–rock reactions were the most important influence on groundwater quality. The wide range of Ca²⁺?+?Mg²⁺ and HCO₃^? ratios and the change of groundwater type from Ca²⁺–SO₄^2? type to a chemical composition dominated by Ca²⁺–HCO₃^? type indicated a change of the major water–rock reaction process from the influence of H₂SO₄ (AMD) to that of CO₂ (soil respiration) along a groundwater flow path. Furthermore, the kinetics interpretation of SO₄^2? and HCO₃^? concentrations suggested that the overlapping time of their kinetics triggered the hydrochemical evolution and the change of major weathering agent. This process might take approximately 8 years and this kinetic time will be continued when a steady source of contamination enter the aquifer.     

Hydrogeochemistry and dissolved inorganic carbon isotopic composition on karst groundwater in Maolan, southwest China

The forest ecosystem in the Maolan karst forest, southwest China is the only concentrated, intact, and relatively stable karst forest ecosystem which has survived in the area at the same latitude in the world, and is a valuable karst forest plant resource as well. Groundwater samples from Maolan karst forest were collected from wells and springs during summer; and concentrations of major ions and dissolved inorganic carbon (DIC) isotopic compositions were measured. The pH values range from 7.2 to 8.3 results from the dissolution of carbonate, HCO₃ ⁻ is the dominant species of DIC in groundwater. Calcium and HCO₃ ⁻, followed by Mg²⁺ and SO₄ ²⁻ dominate the chemical composition of major ions in the groundwaters. Groundwater samples have δ¹³C values in the range from −8.1‰ to −16.6‰, which are lower than that of the other karst city groundwaters in the southwest China. Combining δ¹³C_DIC ratios with measurements of HCO₃ ⁻ and pH clearly distinguishes the principal processes underlying the geochemical evolution of groundwater in Carboniferous carbonate aquifers, where processes can be both degradation of organic matters in the soil and the carbonate dissolution.     

Identifying the Sources of Solutes in Karst Groundwater in Chongqing,China: a Combined Sulfate and Strontium Isotope Approach

Groundwater from karst subterranean streams is among the world’s most important sources of drinking water supplies, and the hydrochemical characteristics of karst water are impacted by both natural environment and people. Therefore, the study of hydrochemistry and its solutes’ sources is very important to ensure the normal function of life support systems. In this paper, thirty?five representative karst groundwater samples were collected from different aquifers (limestone and dolomite) and various land use types in Chongqing to trace the sources of solutes and relative hydrochemical processes. Hydrogeochemical types of karst groundwater in Chongqing were mainly of the Ca?HCO3 type or Ca (Mg)?HCO3 type. However, some hydrochemical types of karst groundwater were the K+Na+Ca?SO4 type (G25 site) or Ca?HCO3+SO4 type (G26 and G14 site), indicating that the hydrochemistry of these sites might be strongly influenced by anthropogenic activities or unique geological characteristics. The dissolved Sr concentrations of the studied groundwater ranged from 0.57 to 15.06 μmmol/L, and the 87Sr/86Sr varied from 0.70751 to 0.71627. The δ34S?SO42? fell into a range of ?6.8‰?21.5‰, with a mean value of 5.6‰. The variations of both 87Sr/86Sr and Sr values of the groundwater samples indicated that the Sr element was controlled by the weathering of limestone, dolomite and silicate rock. However, the figure of 87Sr/86Sr vs. Sr2+/[K++Na+] showed that the anthropogenic inputs also obviously contributed to the Sr contents. For tracing the detailed anthropogenic effects, we traced the sources of solutes collected karst groundwater samples in Chongqing according to the δ34S value of potential sulfate sources. The variations of both δ34S and 1/SO42? values of the groundwater samples indicated that the atmospheric acid deposition (AAD), dissolution of gypsum (GD), oxidation of sul?de mineral (OS) or anthropogenic inputs (SF: sewage or fertilizer) have contributed to solutes in karst groundwater. The influence of oxidation of sul?de mineral, atmospheric acid deposit and anthropogenic inputs to groundwater in Chongqing karst areas was much widespread.     

Stable Carbon Isotope Biogeochemistry and Anthropogenic Impacts on Karst Ground Water, Zunyi, Southwest China

Natural and anthropogenic impacts on karst ground water, Zunyi, Southwest China, are discussed using the stable isotope composition of dissolved inorganic carbon and particulate organic carbon, together with carbon species contents and water chemistry. The waters can be mainly characterized as HCO₃–Ca type, HCO₃ · SO₄–Ca type, or HCO₃ · SO₄–Ca · Mg type, according to mass balance considerations. It is found that the average δ¹³C_DIC values of ground waters are higher in winter (low-flow season) than in summer (high-flow season). Lower contents of dissolved inorganic carbon (DIC) and lower values of δ¹³C_DIC in summer than in winter, indicate that local rain events in summer and a longer residence time of water in winter play an important role in the evolution of ground water carbon in karst flow systems; therefore, soil CO₂ makes a larger contribution to the DIC in summer than in winter. The range of δ¹³C_DIC values indicate that dissolved inorganic carbon is mainly controlled by the rate of carbonate dissolution. The concentrations of dissolved organic carbon and particulate organic carbon in most ground water samples are lower than 2.0 mg C L⁻¹ and 0.5 mg C L⁻¹, respectively, but some waters have slightly higher contents of organic carbon. The waters with high organic carbon contents are generally located in the urban area where lower δ¹³C_DIC values suggest that urbanization has had an effect on the ground water biogeochemistry and might threaten the water quality.     

Geochemical evolution of groundwater in carbonate aquifers in Taiyuan, northern China

Thirty-nine samples of both cold and thermal karst groundwater from Taiyuan, northern China were collected and analyzed with the aim of developing a better understanding of the geochemical processes that control the groundwater quality evolution in the region’s carbonate aquifers. The region’s karst groundwater system was divided into three geologically distinct sub-systems, namely, the Xishan Mountain karst groundwater subsystem (XMK), the Dongshan Mountain karst groundwater subsystem (DMK) and the Beishan Mountain karst groundwater subsystem (BMK). Hydrochemical properties of the karst groundwaters evolve from the recharge zones towards the cold water discharge zones and further towards the thermal water discharge zones. In the XMK and the DMK, the hydrochemical type of the groundwater evolves from HCO₃-Ca·Mg in the recharge - flow-through zone, to HCO₃·SO₄-Ca·Mg/SO₄·HCO₃-Ca·Mg in the cold water discharge zone, and further to SO₄-Ca·Mg in the thermal water discharge zone. By contrast, the water type changes from HCO₃-Ca·Mg to HCO₃·SO₄-Ca·Mg in the BMK, with almost invariable TDS and temperatures all along from the recharge to the discharge zone. The concentrations of Sr, Si, Fe, F⁻ and of some trace elements (Al, B, Li, Mn, Mo, Co, Ni) increase as groundwater temperature increases. Different hydrogeochemical processes occur in the three karst groundwater sub-systems. In the XMK and the DMK, the geochemical evolution of the groundwater is jointly controlled by carbonate dissolution/precipitation, gypsum dissolution and dedolomitization, while only calcite and dolomite dissolution/precipitation occurs in the BMK without dedolomitization. The hydrogeochemical data of the karst groundwaters were used to construct individual geochemical reaction models for each of the three different karst groundwater sub-systems. The modeling results confirm that dedolomization is the major process controlling hydrochemical changes in the XMK and the DMK. In the thermal groundwaters, the dissolution rates of fluorite, siderite and strontianite were found to exceed those of the cold karst groundwater systems, which can explain the higher concentrations of F⁻, Fe and Sr²⁺ that are found in these waters.     

表层岩溶系统中土-气-水界面碳流通的短尺度效应——以贵州茂兰国家喀斯特森林公园的秋季日动态监测为例

在2001年秋季对贵州省荔波县茂兰国家喀斯特森林公园林地、草地植被下土壤CO₂呼吸释放及岩溶表层泉水HCO₃及其^δ13C值的变化进行了日动态的野外监测,表明岩溶系统中土-气-水界面间存在着碳交换的日动态变化以及所伴随的同位素交换的变化,这种变化与土温的日动态有密切的关系。林地植被显示了平抑这种日动态幅度的效应,而草地植被则显示响应于温度变化的较灵敏的动态变化。这种短尺度的变化构成了表层岩溶系统对外界条件的灵敏响应,进一步揭示了在生物作用下岩溶地质作用在碳循环过程及其同位素交换上的灵敏性和动态性。其不同植被系统下的日动态差异在解释岩溶沉积记录和讨论岩溶作用与碳循环时值得充分注意     

Carbon Fluxes and Sinks: the Consumption of Atmospheric and Soil CO2 by Carbonate Rock Dissolution

Carbonate rock outcrops cover 9%–16% of the continental area and are the principal source of the dissolved inorganic carbon (DIC) transferred by rivers to the oceans, a consequence their dissolution. Current estimations suggest that the flux falls between 0.1–0.6 PgC/a. Taking the intermediate value (0.3 PgC/a), it is equal to 18% of current estimates of the terrestrial vegetation net carbon sink and 38% of the soil carbon sink. In China, the carbon flux from carbonate rock dissolution is estimated to be 0.016 PgC/a, which accounts for 21%, 87.5%–150% and 2.3 times of the forest, shrub and grassland net carbon sinks respectively, as well as 23%–40% of the soil carbon sink flux. Carbonate dissolution is sensitive to environmental and climatic changes, the rate being closely correlated with precipitation, temperature, also with soil and vegetation cover. HCO3- in the water is affected by hydrophyte photosynthesis, resulting in part of the HCO3? being converted into DOC and POC, which may enhance the potential of carbon sequestration by carbonate rock dissolution. The possible turnover time of this carbon is roughly equal to that of the sea water cycle (2000a). The uptake of atmospheric/soil CO2 by carbonate rock dissolution thus plays an important role in the global carbon cycle, being one of the most important sinks. A major research need is to better evaluate the net effect of this sink in comparison to an oceanic source from carbonate mineral precipitation.     

Spatial distribution of groundwater quality parameters in the Velika Morava River Basin,central Serbia

The reported study includes analysis of 14 physico-chemical parameters of alluvial groundwater based on data collected from 26 piezometers in the Velika Morava River Basin from 2004 to 2014. Eleven of the parameters were assessed applying hierarchical cluster analysis and principal component analysis to examine the spatial distribution, identify the main processes in groundwater variations and segregate the dominant sampling sites based on the characteristic parameters. A Piper diagram shows that the studied alluvial groundwaters are predominantly of the Ca²⁺–HCO₃^? type (67.3%) and to a lesser extent of the mixed Ca²⁺–Mg²⁺–HCO₃^? type (21.6%). Hierarchical clustering results in four clusters depending on the similarities of the hydrochemical parameters. Principal component analysis explains 65.4% of total variance with PC1 (32.5% variance), PC2 (19.8% variance) and PC3 (13.1% variance). A comparative analysis reveals that the main processes responsible for the hydrochemical composition of groundwater in the Velika Morava alluvion are carbonate dissolution-anthropogenic pressure, feldspar weathering and migration caused by river–aquifer interaction. Considerable loading of the alluvial groundwater caused by a complex geologic framework, natural factors and human activities in the river basin contributed to the segregation of six dominant sampling sites. The obtained results can be very useful in the development of an optimal spatial plan for groundwater monitoring, focusing on increasing the density of the national monitoring network and frequency of assessing alluvial groundwater on the dominant sampling sites (from annual to seasonal).     

Carbon isotopes and geochemical processes in CO2-rich cold mineral water,N-Portugal

This paper summarizes a new outlook on the conceptual model of Melgaço–Messegães CO₂-rich cold (≈18 °C) mineral water systems, issuing in N of Portugal, based on their isotopic (²H, ³H, ¹³C, ¹⁴C and ¹⁸O) and geochemical features. Stable isotopes indicate the meteoric origin of these CO₂-rich mineral waters. Based on the isotopic fractionation with the altitude, a recharge altitude between 513 up to 740 m a.s.l. was estimated, corroborating the tritium results. The lowest ³H content (0 TU) is found in the groundwater samples with the highest mineralization. The mineral waters circulation are mainly related to a granitic and granodioritic environment inducing two different groundwater types (Ca/Na–HCO₃ and Na/Ca–HCO₃), indicating different underground flow paths. Calcium dissolution is controlled by hydrolysis of rock-matrix silicate minerals (e.g. Ca-plagioclases) and not associated to anthropogenic sources. The shallow dilute groundwaters exhibit signatures of anthropogenic origins (e.g. NO₃) and higher Na/Ca ratios. The stable isotopes together with the geochemistry provided no indication of mixing between the regional shallow cold dilute groundwater and mineral water systems. The heavy isotopic signatures identified in the δ¹³C data (δ¹³C = 4.7 ‰, performed on the total dissolved inorganic carbon (TDIC) of CO₂-rich mineral waters) could be derived from a deep-seated (upper mantle) source or associated to methanogenesis (CH₄ source). The negligible ¹⁴C content (≈2 pmC) determined in the TDIC of the mineral waters, corroborates the hypothesis of a mantle-derived carbon source to the mineral groundwater systems or dissolution of carbonate layers at depth.     

Hydrogeochemistry of karst groundwater for the environmental and health risk assessment: The case of the suburban area of Chongqing (Southwest China)

Karst groundwater is a vital resource for drinking, living and irrigation purposes in karst agricultural areas of the world. Due to the vulnerability of karst aquifers, surface pollutants are easily transferred to the subsurface and make karst groundwater be deteriorated, thereby restricting the rational exploitation of karst groundwater resource. In view of this, 49 karst groundwater samples were collected from spring (SW) and underground river (URW) sites in the suburban area of Chongqing City and analyzed for various hydrochemical components. Particularly, the karst groundwater quality was comprehensively uncovered by combining characteristics of hydrogeochemical evolution and health risks caused by nitrate and fluoride. The results revealed that the karst groundwater was slightly alkaline in nature and the water types were mainly characterized by Ca-HCO₃ accounting for 93.88% of the total samples due to the heavy dissolution of carbonate rock. The relatively high concentrations of Na⁺, SO₄^2? and NO₃^? up to 271.88 mg/L, 277.94 mg/L and 56.94 mg/L were over the corresponding maximum acceptable limits for drinking water, which can be predominately attributed to the emissions of industrial park, dissolution of gypsum and pyrite and excessive application of chemical fertilizers. Although agricultural activities were stopped and chemical fertilizers were no longer applied during the sampling period, long-term application of fertilizers have a persistent adverse effect on the karst groundwater NO₃^?. The pollution index of the karst groundwater (PIG) revealed that the low pollution and potential pollution zones were noticed in the northwestern parts of the study area. With respect of the SW, all the total hazard index (HI) values were below 1 suggesting no significant health risk. On the contrary, HI values of 0.11–1.16 for adults, 0.15–1.61 for children and 0.17–1.83 for infants in the URW indicated significant noncarcinogenic health risks. Particularly, infants and children were more vulnerable to karst groundwater NO₃^? than adults. Furthermore, the noncarcinogenic health risks of karst groundwater can be mainly attributed to NO₃^?, confirmed by the higher contribution ratio (66.55%) to the HI values. Therefore, special and targeted measures need to be taken to decrease the NO₃^? concentration in agricultural area.     

Dolomite Versus Calcite Weathering in Hydrogeochemically Diverse Watersheds Established on Bedded Carbonates (Sava and So?a Rivers, Slovenia)

The relative contributions of dolomite to calcite weathering related to riverine fluxes are investigated on a highly resolved spatial scale in the diverse watersheds of Slovenia, which previous work has shown have some of the highest carbonate-weathering intensities in the world and suggests that dolomite weathering is favored over limestone weathering in mixed carbonate watersheds. The forested Sava and So?a River watersheds of Slovenia with their headwaters in the Julian Alps drain alpine regions with thin soils (<30 cm) and dinaric karst regions with thicker soils (0 to greater than 70 cm) all developed over bedded Mesozoic carbonates (limestone and dolomite), and siliclastic sediments is the ideal location for examining temperate zone carbonate weathering. This study extends previous work, presenting geochemical data on source springs and documenting downstream geochemical fluctuations within tributaries of the Sava and So?a Rivers. More refined sampling strategies of springs and discrete drainages permit directly linking the stream Mg²⁺/Ca²⁺ ratios to the local bedrock lithology and the HCO₃ ^? concentrations to the relative soil depths of the tributary drainages. Due to differences in carbonate source lithologies of springs and tributary streams, calcite and dolomite weathering end members can be identified. The Mg²⁺/Ca²⁺ ratio of the main channel of the Sava River indicates that the HCO₃ ^? concentration can be attributed to nearly equal proportions by mass of dolomite relative to calcite mineral weathering (e.g., Mg²⁺/Ca²⁺ mole ratio of 0.33). The HCO₃ ^? concentration and pCO₂ values increase as soil thickness and alluvium increase for discrete spring samples, which are near equilibrium with respect to calcite. Typically, this results in approximately 1.5 meq/l increase in HCO₃ ^? from the alpine to the dinaric karst regions. Streams in general do not change in HCO₃ ^?, Mg²⁺/Ca²⁺, or Mg²⁺/HCO₃ ^? concentrations down course, but warming and degassing of CO₂ produce high degrees of supersaturation with respect to calcite. Carbonate-weathering intensity (mmol/km²-s) is highest within the alpine regions where stream discharge values range widely to extreme values during spring snowmelt. Overall, the elemental fluxes of HCO₃ ^?, Ca²⁺, and Mg²⁺ from the tributary watersheds are proportional to the total water flux because carbonates dissolve rapidly to near equilibrium. Importantly, dolomite weathers preferentially over calcite except for pure limestone catchments.