Karst Water Resources Research Articles

Carbonate rocks and karst water resources in the Mediterranean region

Carbonate rocks in the Mediterranean region form karst landscapes with a variety of morphological and hydrological features, and are of particular interest from a water management perspective as they represent major karst aquifers. The Mediterranean Karst Aquifer Map and Database (MEDKAM) provides a 1:5,000,000 scale map showing the distribution of carbonate and evaporite rocks that can host karst groundwater resources, with additional information on other hydrogeological settings, selected terrestrial and submarine karst springs, caves and karst groundwater-dependent ecosystems. A statistical evaluation shows that carbonate rocks cover ~39.5% of the Mediterranean region within a 250-km focus area from the coastline. North Africa has the largest continuous area of carbonate rocks, while smaller countries in the Middle East and the Dinarides have the largest proportion of carbonate rocks in relation to their total area. Carbonate rocks are also widespread in coastal areas, occurring along ~33.6% (14,000 km) of the total Mediterranean coastline, including large islands such as Crete and Mallorca, and ~25.9% (6,400 km) of the continental coastline. Two additional maps display (1) groundwater recharge, showing a climatic gradient from north to south, and (2) groundwater storage trends, indicating a mean annual karst groundwater loss from 2003 to 2020 of 436 million m3 in the 250-km area. This study quantifies the carbonate rocks in the Mediterranean region and shows their importance for groundwater resources. MEDKAM will serve as a basis for further research and improved international cooperation in karst groundwater management.

Multiple contamination sources, pathways and conceptual model of complex buried karst water system:constrained by hydrogeochemistry and δ2H, δ18O, δ34S, δ13C and 87Sr/86Sr isotopes

Karst groundwater contamination has emerged as a worldwide environmental and health hazard. Karst aquifers, even for the buried karst systems, have strong contamination sensitivity and great pollution risk due to the good pipe fracture connectivity. The large burial depth and invisible hydrologic connectivity pose a challenge for the diagnosis of the contamination sources and identification of the contamination pathways of buried karst aquifers. To address it, a comprehensive application of hydrogeological and hydrogeochemical investigation combined with multiple isotopes (δ2H, δ18O, δ34S, δ13C and 87Sr/86Sr) were performed to elucidate the multiple contamination sources and migration pathways of contaminants in Jinci Spring, a complex buried karst water system. The results obtained highlight that the hydrological connectivity and source availability determine the specific contamination process in buried karst aquifer. Karst aquifer under the river channel is observed to be influenced by the vertical infiltration of polluted river water as indicated by elevated chloride levels (mean 79.4 mg/L) and higher δ2H (mean −8.8 ‰) and δ18O (mean −64.5 ‰) values. Evidenced by the excess of sulfate (mean: 1454 mg/L) and depleted δ34S (mean: −1.6 ‰), the lower karst aquifer may receive the leaking recharge of the mining waste water in the overlying coal seams. The occurrence of nitrate in karst water may be induced by reverse recharge from neighboring confined quaternary aquifers, indicated by the elevated nitrate concentration (15.0–50.8 mg/L) with high 87Sr/86Sr ratios (mean 0.7124). Our findings suggest that over-pumping of deep karst waters may produce additional pollution sources by altering the natural recharge relationship between montanic karst waters and the neighboring pore waters within the basin. Research in this paper improves our understanding of groundwater pollution and hydrological connectivity in buried carbonate aquifers and the protection of karst water resources.

Hydrochemical characterization of a Dinaric karst catchment in relation to emerging organic contaminants

The main findings of a hydrochemical investigation conducted within a typical Dinaric karst catchment located in Southern Croatia are outlined. The studied aquifer is drained by the Jadro and Žrnovnica springs, which are important for the regional and local water supplies, respectively. Presumably, there is intercatchment groundwater flow coming from the neighbouring Cetina River catchment. Various factors governing aquifer hydrochemistry and their interplay with emerging organic contaminants (EOCs) that were detected at different water resources in ng/L concentrations was assessed. A total of 26 sampling campaigns (October 2019 – October 2022) were conducted at two springs, in a river and at a deep borehole, all representative of this complex hydrogeological system. Assessment of major ion constituents and saturation indices calculated with PHREEQC revealed the sampled water resources are of a Ca-HCO3 type due to the predominant weathering of the carbonate mineral calcite. Sharp spikes observed in chemographs indicated a highly karstified system with an effective conduit network allowing rapid spring responses to precipitation events. Water resources are of good chemical status, as affirmed by anthropogenic contamination indicators, with nitrates, chlorides and sulphates all below maximum threshold values. Strong positive correlations were found between EOCs concentration, number of detected compounds, and nitrates in the Cetina River, indicating a common origin, most likely wastewater. Identification of persistent EOCs including widely used repellent N,N-diethyl- metatoluamide (DEET) during base flow conditions and its strong positive correlation with the Ca2+ content in both the Cetina and Jadro samples, suggests potential storage in the epikarst and aquifer matrix. This coupling of conventional hydrochemical indicators and novel markers of anthropogenic impacts, including EOCs, in vulnerable karst water resources is a crucial advancement in the assessment and management of emerging environmental and potential human health risks. Such an approach is pivotal for the sustainable protection of hydrogeologically intricate sites.

Application of Principal Component Analysis in Determining the Hydrogeochemistry Characteristics of Karst Water in Bac Kan and Cao Bang

Research on the origin and processes affecting the hydrogeochemical characteristics of karst water provides useful information for the management and exploitation of karst water resources. Principal Component Analysis (PCA) was applied to the karst water physicochemical data, including temperature, pH, Electronic Conductivity (EC), Ca2+, Mg2+, Na+, K+, Cl-, HCO3-, SO42-, and NO3- in Ba Be lake (Bac Kan province) and Ha Quang, Trung Khanh (Cao Bang province). The Piper diagram described the main type of hydrochemical facies in karst water at 24/25 survey points as Ca2+-HCO3-. The combination of eleven physicochemical properties was reduced into four main components (PC1, PC2, PC3, PC4) based on eigenvalues of 4,0; 2,5; 1,3 and 1,2, respectively. A total of 81,53% of the variance was represented by four main components, in which PC1 (36,36%) represented the rock-water interaction, PC2 (22,88%) represented pollution sources related to human activities, PC3 and PC4 (22,29%) represented the dissolution of magnesium minerals. The moderate-strong correlation between parameters of the Mia Le Formation’s sample in Ba Be Lake area and PC1 indicated that the major chemical composition of karst water is strongly influenced by the interaction between carbonate rocks and water. This process also occurs intensely at some survey points in the Bac Son, Song Hien, and Cao Bang formations. Meanwhile, some samples NK.19, NK.23, NK.25 of the Bac Son and Song Hien formations had a moderate positive correlation with PC2 and are affected by human activities. Research results have shown that the combination of principal component analysis PCA and correlation analysis is an effective tool in determining karst water characteristics in the area.

Laboratory and numerical simulations of infiltration process and solute transport in karst vadose zone

Groundwater in karst systems is a vital resource, which is often highly vulnerable to contaminants that infiltrate through the vadose zone. Understanding the processes of water and contaminant infiltration in the vadose zone is extremely important for protecting and managing karst water resources. A laboratory-scale physical model based on a typical conceptual model of the karst vadose zone was constructed to characterize the influence of the rainfall intensity and internal structure on the infiltration process and solute transport in the karst vadose zone under controlled conditions. Five factors, including the rainfall intensity, the surface slope, the degree of karstification, the thickness of the transfer zone, and the existence of epikarst, were considered in laboratory experiments. A corresponding lumped-parameter model was subsequently developed to further analyze and investigate the water and solute infiltration processes in the laboratory scale physical model. Recession- and breakthrough curves generated from the lab experiments and the water and solute loss from each reservoir generated from the simulation results were analyzed. The downward trend of breakthrough curves' peak value and the variation of solute loss's proportion in three rainfall events demonstrate that both the increase in thickness and karstification degree will intensify the buffer effect of the karst vadose zone, and this buffer effect is mainly affected by the slow flow system which can be inferred from the increasing percentage of cumulative discharge of slow reservoir (qS). With increasing karstification degree, the recession coefficient (α) exhibits opposite trends depending on the existence of epikarst or not, indicating the karstification degree has a more significant effect on hydraulic conductivity (K) when an epikarst is present while affecting effective porosity (φ) more noticeably in the absence of epikarst. The rainfall intensity affects the results of both experimental and numerical simulation most significantly. The percentage of discharge and solutes flowing from the slow reservoir (qS and msoil_S) have negative correlations with rainfall intensity, suggesting a greater influence on fast flow with increasing rainfall intensity.

Characterizing occurrence of emerging organic contaminants in Dinaric karst catchment of Jadro and Žrnovnica springs, Croatia

The occurrence of emerging organic contaminants (EOCs) was investigated in vulnerable Dinaric karst catchment of Jadro and Žrnovnica springs in Croatia, under varying flow conditions and across three different water resource types (groundwater, springs, and surface water). The maximal EOCs concentration in both springs were observed following autumn recharge events, while during peak discharge no detection above the limits of detection (LOD) was recorded due to dilution process. Contrarily to springs, groundwater from deep borehole exhibited highest total EOCs concentration under low flow conditions, underscoring the considerable karst aquifer vulnerability and its oligotrophic nature. The peak EOCs concentration in karstic Cetina River coincided with the river's lowest discharge. The highest mass flux of 1013 g/day was determined for very mobile pharmaceutical metformin detected in Cetina. The presence of potentially persistent to very persistent compounds, like DEET and 1H-benzotriazole, which exhibited highest detection frequencies across all sampling sites, was observed in association with varying hydrological conditions. Hypotheses regarding the occurrence of identified EOCs include surface contamination infiltrating directly through ponors and highly karstified areas, potential persistence in the epikarst and aquifer matrix, and site-specific contamination sources for compounds such as 1H-benzotriazole, gabapentin, and ketoprofen found in groundwater. To evaluate the risk of inadvertent human exposure to EOCs across various age groups, we utilized measured spring concentrations and calculated drinking water equivalent levels (DWEL), which ranged from 1.4 μg/L for cotinine to 503 mg/L for sucralose, both detected in Jadro spring. Although EOCs concentrations in ng/L are unlikely to pose a significant risk to healthy population, long-term exposure to EOCs mixture remains unknown. Given scarcity of research on EOCs in karst environments on both global and national levels, our study enhances comprehension of their occurrence and behaviour across different karst water resources that hold crucial importance for drinking water supply in regions like Dinarides.

Hydrogeological Characteristics of the Makaresh Carbonate Karst Massif (Central Albania)

Carbonate rocks cover about 23% of Albania, with exploitable karst water resources estimated at 2.84 × 109 m3/year (about 65% of the total exploitable groundwater resources in the country). The Kruja tectonic zone is characterized by the presence of SE–NW-oriented carbonate structures, rich in fresh and thermal groundwaters. More than 80% of the thermal springs in Albania are present in this tectonic zone. One of its most interesting carbonate structures, with the presence of both cold and thermal waters, is the small karst structure of Makaresh, with a surface of 22 km2. The purpose of this article is to describe the hydrogeological characteristics of this massif; based on the physico-chemical characteristics, groundwaters of the study area are classified as cold waters (belonging to the local flow system) and thermal waters (originating in intermediate/deep flow systems). The former are mainly of HCO3-Ca or HCO3-Ca-Mg type (electrical conductivity 580–650 μS/cm, Temperature 13.9–16.6 °C). Thermal waters are mainly of the Cl-Na-Ca type (EC 7200–7800 μS/cm, T 18.5–22.5 °C); they are further characterized by high hydrogen sulfide concentration, up to about 350 mg/L. The presence of two groundwater types in the Makaresh massif is connected to the presence of two groundwater circulation systems. The main factors of the groundwater physico-chemical quality are the dissolution of rocks and minerals contained therein, the presence of hypogenic speleogenesis, and the mixing of the groundwater of the two systems. The hydrogeological studies proved that karst rocks contain considerable freshwater resources, partly used for water supply. Thermal waters are not currently exploited due to their temperature, but they are potentially suitable for thermal uses by drilling boreholes to a depth of about 1000 m.

A New Index to Assess the Effect of Climate Change on Karst Spring Flow Rate

Karstic aquifers, because of their conduit system, are susceptible to climate change. Ten karst springs in the Zagros region were selected to investigate the impact of climate change under three CMIP6 scenarios: SSP1-1.9, SSP2-4.5, and SSP5-8.5. This study was conducted in three steps: downscaling climate projection, analyzing spring discharge time series, and introducing a new index to assess the impact of climate change on spring flow rate. Applying LARS-WG6, precipitation was downscaled at 14 stations in the study area. Moreover, time series and trend analysis showed that the selected springs have experienced a decrease in their flow rate. Assuming the covariance function between precipitation and spring discharge is constant, new indices (i.e., IQd, IdQd, and Icc) were introduced to highlight the effect of climate change according to the three scenarios. dQd is the variability of spring discharge from past to future, IdQd is spring discharge variability over the historical data, and Icc is the effect of precipitation and spring discharge change together. Icc has a range from −0.25 to 0.25 below and above, which is indicative that two extreme conditions including the spring dryness and overflow are in effect, respectively. The main results revealed that the degree of impact at each spring is a function of climate change scenarios and hydrogeological characteristics of the karstic systems. A more noticeable negative trend in spring flow rate is observed for the karst springs characterized by a dominant conduit flow regime and low matrix storage, located in the areas with low cumulative rainfall, and has a stronger relationship with precipitation. Based on the results, decisions on the management of karst water resources should be made considering where the springs bear free surface and pressurized flow conditions.

Hydrogeochemical Characteristics and Genetic Analysis of Karst Groundwater in the Fengfeng Mining Area

The karst water resources in the Fengfeng mining area are an important water supply source in the region. In recent years, due to the influence of external environment changes, the hydrochemical environment of karst groundwater has changed. In order to scientifically understand karst groundwater and rationally develop groundwater resources, it is necessary to study the hydrochemical characteristics and evolution laws of groundwater in this area. In this study, major elements in karst groundwater of different years and hydrogen and oxygen isotopes in 2022 were analyzed. The hydrochemical types of the study area were analyzed by using the Piper trilinear diagram drawn with Aquachem10.0 software. D and 18O were used to analyze the source and elevation of groundwater recharge. Origin software was used to draw Gibbs diagrams, three-terminal diagrams, ion ratio diagrams, etc., to analyze the influencing factors of groundwater chemical components. The research results show that: (1) The groundwater in the study area is mainly HCO3-Ca(Mg) type water; (2) The main supply source of karst water in the study area is atmospheric precipitation, and the supply elevation ranges from 1166.7 to 1533.3 m; (3) Most of the karst groundwater in the study area is affected by the dissolution of carbonate and silicate rocks; (4) With the influence of human activities, mainly agricultural activities, with the passage of time, the impact of industrial activities on groundwater has been weakening.

Impact of land-use change on karst spring response by integration of surface processes in karst hydrology: The ISPEEKH model

Karst groundwater represents a source of freshwater for a quarter of the world's population. Modeling the hydrological behavior of karst aquifers while accounting for the spatial variability of the recharge processes and the land-use change impacts on water availability remains a challenge for karst water resources management. Therefore, this study proposes a new semi-distributed hydrological model named Integration of Surface ProcEssEs in Karst Hydrology (ISPEEKH) for simulating the surface-underground water flows in karst-dominated catchments. ISPEEKH couples the restructured version of the Soil and Water Assessment Tool (SWAT+) with a non-linear three-reservoir groundwater model that represents the epikarst and matrix-conduit flow components in a karst aquifer. ISPEEKH was applied to the Baget karst catchment (13.25 km2) in the Pyrénées mountains of southwest France, characterized by a conduit-dominated spring flow and low surface runoff. The model simulated the catchment daily discharge satisfactorily, with NSE = 0.67 and R2 = 0.68 for the 2008–2013 calibration period, and NSE = 0.65 and R2 = 0.69 for the 2014–2018 validation period. The catchment evapotranspiration and discharge amounted to 33 % and 67 % of the average annual precipitation, respectively, and nearly 80 % of the discharge was attributed to spring flow. The matrix-to-conduit flow accounted for 4–7 % of the monthly spring flow during the high-flow period (December to June), and up to 22 % during the low-flow period (July to October). ISPEEKH was then used to assess the hydrological response of the Baget catchment to land-use change scenarios of afforestation and deforestation for wood production and pasture development. Afforestation of the full catchment area did not alter the catchment hydrology significantly. Deforestation for wood production reduced annual evapotranspiration by 12–18 % and increased annual recharge by 7–8 %, resulting in annual discharge rising by 6–9 %. These changes in the water balance components were most noticeable during the low-flow season and would augment freshwater availability. Conversely, deforestation for pasture development raised annual evapotranspiration by 13–17 % while reducing annual recharge by around 7 % and discharge by 5–7 %. These changes in the hydrological components were most remarkable during the high-flow season and affected discharge below 2.5 m3.s−1.

From cave to spring: Understanding transport of suspended sediment particles in a fully phreatic karst conduit using particle analysis and geochemical methods

AbstractKarst aquifers are vulnerable to contamination, especially in the context of heavy rainfall events. Contamination is often associated with turbidity that can originate from the soil zone, infiltrating surface waters or resuspension of previously deposited sediments within the aquifer. While turbidity events can be well monitored at karst springs, related information about the sediment origin and the spatiotemporal input function usually remain unknown. Thus, the mobility and attenuation of the particulate matter and associated pollutants can hardly be determined quantitatively. A tracer test with suspended cave sediments and solute tracers for comparison has hence been performed in a karst aquifer at the Blue Spring (Blautopf) in Southern Germany. The tracers were injected in the cave system, at the beginning of a fully phreatic karst conduit, and monitored at the spring after a travel distance of 1250 m. The particle‐size distribution was monitored using a particle counter and sediment samples were filtered with 0.45‐μm cellulose acetate filters. Particles on the filter were analysed for major and trace elements as well as rare earth elements (REE) by ICP‐MS after acid digestion. Results show that (1) sediment particles were transported faster than solutes, which was interpreted as a transport in the main flow path of the conduit, whereas conservative tracers tend to diffuse into smaller fissures as well. (2) All measured particles sizes were transported at similar flow velocities. (3) A transport associated to sediment particles could be shown for all measured elements. This study presents a methodological improvement of comparative sediment tracer tests as well as deeper insights into particle and element transport processes in karst aquifers, originating from previously deposited cave sediment. Results provide deeper knowledge into transport processes of sediment‐associated contaminants, such as heavy metals which may strongly be affected by the particle size. This knowledge contributes to a better management of karst water resources in the context of turbidity events.

Delay-aware karst spring discharge prediction

As an essential component of the hydrological cycle at both regional and global scales, karst aquifers store large amounts of water, serving as the main source of fresh water supply in many areas. Karst springs provide a natural drainage pathway for karst groundwater systems to participate in the hydrological cycle. Accurate prediction of karst spring discharge is of great value to the long-term planning and management of karst water resources. The mainstream methods proposed have achieved high prediction accuracy by introducing deep learning technology. However, these methods ignore the delay time of spring water discharge to water supply or drainage, so there is still room for improvement in prediction accuracy. To address this issue, this paper proposes a delay-aware spring discharge prediction (DSDP) framework that introduces the delay time to predict spring discharge. Specifically, the framework consists of three modules, including a time calibration module, a variation estimation module and a discharge prediction module. The time calibration module identifies the delay time of spring discharge to each element to calibrate the observations. And the variation estimation module utilizes a neural network to infer spring discharge variations. Finally, the discharge prediction module predicts spring discharge with derived discharge variations. This study validates the performance of the proposed method by using spring discharge data from Jinci Spring, a typical karst spring in China. The experimental results show that the proposed method outperforms baselines, with significant decreases in both MAE and RSM. The study will provide evidence for the precise management of Jinci Spring, and provide a methodological reference for the discharge prediction of other springs.

Influence of the karst matrix hydraulic conductivity and specific yield on the estimation accuracy of karstic water storage variation

Karst water plays a crucial role as a freshwater source, which provides drinking water for millions of people worldwide. Accurate assessment of karst water resources and prediction of the impact of rainfall events on karst systems require a comprehensive understanding of medium parameters, such as the karst matrix hydraulic conductivity and specific yield. Therefore, in this paper, we investigated the effects of karst matrix hydrogeological parameters on the estimation accuracy of karstic water storage variation using a numerical modelling approach. Specifically, we considered matrix–conduit coupled karst systems and analysed the spring flow recession hydrograph following rainfall events. The objective of this study was to explore the vertical and horizontal variations in karst matrix parameters and their effects on the estimation accuracy of karstic water storage variation and to provide insights into the role of the hydraulic conductivity and specific yield in controlling groundwater dynamics. The results of this study have important implications for karst water resource management, highlighting the necessity for improved characterization of karst aquifer medium properties.

Insight into heterogeneous karst catchment by the dynamical system approach

The hydrological process heterogeneity in karst catchments makes collecting sufficient information about the karst system properties extremely difficult. Consequently, the parameterization and application of currently available modeling approaches is highly uncertain in karst. We implemented a modified dynamical system approach and explored the possibilities to analyze, simulate and characterize karst springs and sinking streams in the heterogeneous Ljubljanica river catchment in Slovenia. The discharge sensitivity functions were used to simulate the hydrographs and identify the differences in the temporal dynamics of the discharge recession. Most of the derived karst springs and sinking streams discharge sensitivity functions express dual discharge recession behavior most likely controlled by the hydraulic conveyance characteristics of karst underground conduits. The implemented approach offers a high potential for advancement in karst hydrology by using basic discharge data for analyses of karst catchment characteristics and future planning of karst water resource management.

Isotopic insights on quantitative assessments of interaction of eco-hydrological processes in multi-scale karst watersheds

The dynamics of hydrological processes and the storage mechanisms of karst water resources are the most important issues in karst hydrology. The impact of environmental changes on water quantity, and the evaluation and quantification of eco-hydrological processes remain poorly addressed. In this study, high-frequency continuous monitoring in multi-scale karst watersheds in Southwest China combined the approaches of water isotopes and the hybrid single-particle lagrangian integrated trajectory (HYSPLIT) model to identify the recharge mechanisms between atmospheric vapor, rainfall, surface water, and groundwater, and to reveal the interaction of eco-hydrological processes. The dominant moisture sources in Puding (PD) County were the Indian Ocean (43–69%) and local moisture (24–33%). The δ18O and deuterium excess (d-excess) values showed a positive correlation indicating that secondary or sub-cloud evaporation was prominent in the wet seasons. Karst water line-conditioned excess (lc-excess) indicated that karst water interacted with recent precipitation, groundwater, and evaporation across seasons. Owing to its specific hydrogeological structure, surface water and rainwater have a higher contribution rate to groundwater replenishment. The Chenqi stream replenished the Houzhai River mainly in the form of groundwater, with percentages ranging from 38.1 to 93.5% in the wet season, and 47.8–80.1% in the dry season. In the Houzhai outlet, surface water and groundwater interconverted frequently with a percentage of 45.6–49.1%. We believe this is the first systematic study to quantify the supply relationship between water vapor transport, rainfall, surface water and groundwater in the Chinese karst zone, making a significant move forward in the field of karst hydrological processes and improving the efficiency of water resource evaluation and management.

Revealing the positive influence of young water fractions derived from stable isotopes on the robustness of karst water resources predictions

Introducing additional information sources, such as hydrochemical signatures and water isotopes, into the model calibration has shown to be useful to enhance model robustness by increasing parameter identifiability and maintaining simulation reliability. Our study explores the added value of discharge young water fractions (Fyw, derived from the volume-weighted δ18O concentrations) on the model reliability as a calibration constraint. For this, we coupled a karst hydrological model (VarKarst) with a catchment-scale transport model (StorAge Selection (SAS) function approach) to simulate discharge δ18O concentration (δ18OQ) and corresponding Fyw. We performed a multi-variable calibration scheme by simultaneously constraining a large model ensemble (1x106 realizations) with respect to the model performance on discharge and Fyw. By searching a model output space in which the model performance on discharge and model performance on Fyw provides an optimal trade-off, we extracted hydrologically more informative model realizations. We tested our calibration approach at the Wasseralm spring, which supplies drinking water to the city of Vienna, Austria. The contribution of the information content of Fyw to the model robustness was assessed by the degree of reduction in the parameter and simulation uncertainties. Our results indicate that the inclusion of Fyw notably reduced the uncertainty in model parameters (6 parameters out of 8), simulations (14 % vs. 10 % by δ18OQ), and water balance components for the model internal states (around 40 %). Our findings reveal that Fyw confirms the model reliability (KGE: 0.71 ± 0.01 in validation) in that it mainly reduces the parameter equifinality by providing physically more plausible and identifiable parameter sets. Therefore, Fyw is a potentially useful metric to better constrain the model outputs, thereby limiting the model uncertainty.

Influences of anthropogenic acids on carbonate weathering and CO2 sink in an agricultural karst wetland (South China)

Carbonate minerals are the largest carbon (C) reservoir on earth. Quantitative assessment of carbonate weathering and CO2 sink flux caused by anthropogenic acids in karst wetland regions is imperative to improve understanding of the hydrogeochemical evolution and global C cycle in karst ecosystem. In this study, a typical field observation was conducted in the Huixian karst wetland (HKW) in South China. The hydrogeochemical and isotopic (δ15N-NO3–, δ18O-NO3–, and δ13CDIC) analyses combined with the MixSIAR model and stoichiometric coefficients were used to quantitatively estimate the influence of H2CO3, HNO3 and H2SO4 on carbonate weathering and CO2 sink flux. The results obtained showed that anthropogenic HNO3 and H2SO4 affect carbonate weathering in the HKW, evidenced by the significant correlations between hydrogeochemical parameters and δ13CDIC value. The quantitative results showed high contributions of HNO3 and H2SO4 to carbonate weathering in karst groundwater, with contribution ratio values of 20.91 ± 19.29 and 21.69 ± 26.88%, respectively. Besides karst water over-exploitation, this finding suggested that these anthropogenic acids were also an important cause of a decrease in ecological water levels, resulting in the shortage of karst water resource and degradation of wetland ecosystem. Moreover, the involvement of anthropogenic acids in the natural chemical weathering has significantly decreased the CO2 sink flux by 11.23 ± 7.94 and 41.60 ± 30.24% for surface water and groundwater, respectively, thereby potentially affecting the karst C cycle and global climate change. This present study provided an integrated quantitative approach for estimating the influence of H2CO3, HNO3, and H2SO4 on carbonate weathering and CO2 sink in karst wetland regions. Our study highlighted that the effects of anthropogenic acids on carbonate weathering need to be considered in future studies on the restoration of wetland ecosystems, particularly in intensive agricultural study areas.

Accumulation, conversion and storage of solute from sinkholes to karst spring under concentrated recharge conditions

Concentrated recharge processes can define water quantity and quality in karst aquifer systems. Hydrological and hydrochemical dynamics at Qinglongkou (QLK) spring and two sinkholes were synchronously monitored to elucidate solute migration processes under concentrated recharge conditions. The results show that the hydrological and hydrochemical processes of the sinkholes and karst spring have corresponding impulse responses after rainfall events. The components of the leachate including Ca2+, Mg2+, Sr2+ and HCO3− in QLK spring decrease due to dilution during the periods of concentrated recharge, but their fluxes increase by 4% to 271% compared to the sinkholes input owing to the continuous water–rock interactions. Most chemical indicators are diluted along the hydrograph peaks, but the pollutants including nitrogen and phosphorus are aggregated to higher values after rainstorms, both at sinkholes and spring outlet, with total inorganic nitrogen and PO43− concentrations up to 11.34 mg/L and 1.16 mg/L. During heavy rainfall events, the nutrients from agricultural activities are easily dissolved into overland flow, and nitrification mainly controls the nitrogen conversion in karst aquifer system. Pollutant fluxes of karst spring are lower than that of sinkholes due to solute storage, and pollutant concentrations are 2∼3 times higher than their natural background values in spring outlet after rainstorms. Accumulation and storage of pollutants are problems that cannot be underestimated for the clean utilization of karst water resources and the prevention, control, and repair of karst groundwater pollution, which pose severe threats to the karst water quality.

A Review of the Application of the Soil and Water Assessment Tool (SWAT) in Karst Watersheds

Karst water resources represent a primary source of freshwater supply, accounting for nearly 25% of the global population water needs. Karst aquifers have complex recharge characteristics, storage patterns, and flow dynamics. They also face a looming stress of depletion and quality degradation due to natural and anthropogenic pressures. This prompted hydrogeologists to apply innovative numerical approaches to better understand the functioning of karst watersheds and support karst water resources management. The Soil and Water Assessment Tool (SWAT) is a semi-distributed hydrological model that has been used to simulate flow and water pollutant transport, among other applications, in basins including karst watersheds. Its source code has also been modified by adding distinctive karst features and subsurface hydrology models to more accurately represent the karst aquifer discharge components. This review summarizes and discusses the findings of 75 SWAT-based studies in watersheds that are at least partially characterized by karst geology, with a primary focus on the hydrological assessment in modified SWAT models. Different karst processes were successfully implemented in SWAT, including the recharge in the epikarst, flows of the conduit and matrix systems, interbasin groundwater flow, and allogenic recharge from sinkholes and sinking streams. Nonetheless, additional improvements to the existing SWAT codes are still needed to better reproduce the heterogeneity and non-linearity of karst flow and storage mechanisms in future research.

The Ratio Distribution of Evapotranspiration to Precipitation well Related With Soil Thickness in Karst Watershed of Southwest China

AbstractEvapotranspiration (ET) is predominant variable for water management in various types of ecosystems, and it has been intensively studied through in situ measuring and modeling methods. However, it is challenging to measure actual ET and upscale it to regional level for karst landscapes, where aquifers typically show remarkable and rapid responses to precipitation events. There is an urgent need to quantify water fluxes to provide reliable evidence for the protection and sustainable management of karst water resources. Therefore, in this study, five plots were built to observe actual ET based on Thermal Dissipation Probes, redesigned ventilated chamber and in‐site microlysimeters in a karst watershed in southwest China. Then, three models (Penman‐Monteith‐Leurning, PML; Remote Sensing‐Priestley and Taylor; and Hargreaves) were constructed to upscale ET estimation to the regional level based on Landsat‐8 images and MODIS data. The results showed that: (a) The PML model performed better than other models (p < 0.01) with higher R2 values (0.72 for MODIS images and 0.87 for Landsat‐8 images); (b) Daily ET exhibited significant seasonal variability and different spatial distribution, and yearly ET exhibited well related with soil thickness (R2 = 0.58); (c) Daily ET had a slightly positive correlation with DEM, however, had a negative correlation with ground temperature. This study is helpful to improve accuracy of measured and estimated ET by combining remote sensing data, and it has important implications for upscaling it to regional level. It suggests that ET is strongly regulated by constant supply of water, vegetation coverage, and available energy in karst catchments.