End-member Mixing Analysis Research Articles

Utilizing fluorescence indicators to apportion organic sources in estuarine/coastal sediments: A comparison with a stable isotopic model

Coastal sediments accumulate organic matter (OM) from diverse sources, including local anthropogenic pollution. Effective source tracking of sediment OM is crucial for pollution source management. This study compares fluorescence proxies and stable isotopic ratios as tracers for sediment OM in Gangu Port, Korea. An optimized extraction method using distilled water for 0.5 h yielded distinct fluorescence signatures. The humification index (HIX) and protein-like component (C3%) showed ideal mixing behavior with two end-members (fishery market sediment and algae). A Bayesian end-member mixing analysis model revealed that agricultural soil is the prevalent contributor to sediments, aligning with land use patterns. The fluorescence-based model showed higher sensitivity to anthropogenic influences compared to traditional stable isotope ratios. The results strongly agreed with isotope ratio-based predictions, exhibiting a positive correlation (p < 0.05) at 8 out of 14 sites. This study highlights the potential of fluorescence-based tracking to complement or replace conventional stable isotope methods.

Ion sources and seasonal recharge characteristics of groundwater around Dali Lake in semi-arid region of Inner Mongolia Plateau, China

The interaction between groundwater and surface water around an inland lake in semi-arid regions creates a unique ecological pattern and is a key link in the regional ecohydrological cycle. In this paper, the major ions and hydrogen and oxygen isotope characteristics of groundwater, lake water, river water, and rain water were analyzed, which were sampled in Dali Lake and its surrounding areas in the dry and wet seasons. The ion ratio method and the end-member mixing analysis (EMMA) based on principal component analysis (PCA) were applied. The causes of the major ions in groundwater during the dry and wet seasons were analyzed. The temporal and spatial recharge sources and characteristics of groundwater were identified and quantified. The hydraulic relation between groundwater and surface water was clarified. The main hydrochemical type of groundwater was Ca-HCO3 with changed to Ca-Mg-Cl type in some areas in the wet seasons. Rock weathering was the main genetic mechanism of groundwater hydrochemistry which mainly from the dissolution of silicate. River water and precipitation were the main sources of groundwater recharge. However, there was a large difference in spatio-temporal distribution and recharge contribution. Gongar River water and precipitation were the main recharge sources of groundwater during the dry season with a contribution rate of 49 % and 48 % respectively. Haolai River water and Liangzi River water together became the main recharge sources of groundwater during the wet season with a contribution rate of between 83 % and 92 %. Rain water covered from 7 % to 13 % of groundwater recharge during the wet season. Overall, compared with river water and precipitation, the contribution of lake water to groundwater recharge was almost negligible, ranging from 0 % to 6 %.

Characterization of sediment organic matter in the outer Yangtze River Estuary using stable isotopes, optical techniques, and FT-ICR-MS: Implications for the carbon burial mechanism

The burial of sediment organic matter (SOM) in the estuary and shelf plays an important role in the global carbon cycle. However, it is challenging to determine the source, composition, and burial of SOM in the coastal sea, especially at the molecular level. This was explored in the coastal area outside the largest Yangtze River of China with multiple techniques including elemental and stable isotopic analysis, absorption spectroscopy, fluorescence excitation-emission matrices coupled with parallel factor analysis (EEMs-PARAFAC), and ultra-high resolution Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS). The end-member mixing analysis based on δ13C and δ15N showed a dominance of marine contribution (up to 70%) at most stations while the terrestrial contribution increased to >55% nearshore in summer at a high fluvial sediment flux. This was consistent with the offshore decreasing humic-like C1 and C2, humification index (HIX), %lignin-like compounds, and %CHO but increasing tryptophan-like C3, biological index (BIX), %protein-like compounds, and %CHOS from EEMs-PARAFAC and FT-ICR-MS analysis. The %clay correlated positively with SOM content, HIX, %lignin-like compounds, O/C, and modified aromaticity index (AImod) but correlated negatively with %C3, H/C, and the relative abundance of labile formulas (MLBL), while %silt showed contrasting correlations. These results indicated the fine clay sediments adsorbed more humified, aromatic, oxygenated, and terrestrial compounds that were probably more resistant to biodegradation and thus had a higher burial efficiency than those on the silty sediments. Principal component analysis based on SOM indices further revealed different characteristics of SOM in the nearshore, northern offshore, and southern offshore regions, which were probably dependent on the delivery by local current systems. Overall, these findings contributed to unraveling the source and molecular composition of SOM associated with different grain size sediments and local current delivery, which are fundamental for understanding the factors underlying carbon burial in the complex coastal environment.

Sources and pathways of spring flow and climate change effects in the Dungju Ri & Yude Ri catchments, Bhutan Himalaya

Springs and streams are vital water sources for supporting the livelihood of Himalayan residents. Escalating climate change, population growth, and economic development strain the region's freshwater resources. A national survey reveals declining spring and stream flows in Bhutan, necessitating an improved understanding of their generation. Monthly grab water samples were collected during April 2022–January 2023 from main streams, springs and other source waters at various elevations at Yude Ri and Dungju Ri catchments, Bhutan Himalayas. Samples were analyzed for pH, specific conductance, and major ions and end-member mixing analysis in combination with diagnostic tools of mixing models was used to determine sources, relative contributions, and recharge dynamics of spring flows. The results indicated that direct precipitation dominated spring flows (0.59 ± 0.21), followed by shallow groundwater (0.31 ± 0.18), and soil subsurface water (0.10 ± 0.15). The contributions of spring flow components followed an elevation gradient, with higher and lower fractions, respectively, of direct precipitation and shallow groundwater at higher elevations, e.g., 0.90 ± 0.1 to 0.13 ± 0.08 for direct precipitation and 0.03 ± 0.03 to 0.37 ± 0.19 for shallow groundwater from 3266 m to 1558 m. Spring flows primarily relied on precipitation (∼70 % from both direct precipitation and soil water), making them very sensitive to changes in precipitation. Significant contributions of shallow groundwater also indicated the vulnerability of spring flows to decreased snowfall relative to rainfall and the earlier onset of snowmelt, particularly for those located in the snow-rain transition zone (∼2500 m). Our results suggest high vulnerability of spring flows to the climate change in the Himalayas.

Hydrogeochemical evolution and isotopic characteristics of groundwater-surface water interaction processes within the Kawere catchment and its hydrogeotechnical implication on pit slope stability at the Nsuta mine, Ghana

In geo-hazard prone heterogenous mining terrain with multiple geological structures, surface water may interact with its underlying groundwater system conveying large quantities of water to deeper aquifers, which could undoubtedly lead to pit-inflows and slope stability challenges for any close-by mining operation. A total of forty-three (43) water samples were collected from the atmosphere, surface, subsurface and the pit-water during dry and wet seasons, respectively to identify pit-inflow origin using hydrogeochemical evolution paths and end member mixing analysis of the major ions at the only manganese mine in Nsuta, Ghana. The major ions order was Na2+>Ca2+>Mg2+>K+ for cations and anions' order was HCO3− > SO42− > Cl−. The identified hydrogeochemical facies and proportions are Ca–HCO3- (68.75%), Ca–Cl2 (18.75%) and mixed Ca–Mg–Cl (12.5%) in the dry season and mixed Ca–Na–HCO3 (54%) followed by Ca–HCO3 (46%) in the wet season. Na+ is the preeminent cation whilst HCO3− is the preeminent anion. Saturation Index (SI) of carbonate and evaporate minerals, particularly calcite, identified groundwater-surface water (GW-SW) exchange flux pathways in the study area, and thus establishing geochemical modeling as a robust tool for identifying GW-SW exchange flux pathways in riverine and aquifer systems. The isotopic composition of the various water samples is depleted having strong mixing relationship of R2 = 0.96%, suggesting the waters have same origin with low d-excess indicating rainfall under lower humidity. End member mixing analysis suggested GW-SW interaction with the surface water contributing an average of 87% to groundwater in the mine pit during the dry season. The generally low hydrogeochemical and isotopic evidence of the various water sources indicate homogeneity pointing to the existence of GW-SW interaction. The fast-movement of the exchange flux has widened flow path leading to pit slope stability issues and huge pit-inflows. Therefore, the mine managers, stakeholders, and decision makers are strongly advised to promptly integrate hydrogeotechnical assessments into their operations as a sustainable remedial measure. This will enable them to continuously reduce the potentiometric head of the groundwater system and ensure cost-efficient mining activities. It is essential to take these actions due to the mine's location within two river stream catchments.

Innovative Assessment of Mun River Flow Components through ANN and Isotopic End-Member Mixing Analysis

This study innovatively assesses the Mun River flow components in Thailand, integrating artificial neural networks (ANNs) and isotopic (δ18O) end-member mixing analysis (IEMMA). It quantifies the contributions of the Upper Mun River (UMR) and Chi River (CR) to the overall flow, revealing a discrepancy in their estimated contributions. The ANN method predicts that the UMR and CR contribute approximately 70.5% and 29.5% respectively, while IEMMA indicates a more pronounced disparity with 84% from UMR and 16% from CR. This divergence highlights the distinct perspectives of ANN, focusing on hydrological data patterns, and IEMMA, emphasizing isotopic signatures. Despite discrepancies, both methods validate UMR as a significant contributor to the overall flow, highlighting their utility in hydrological research. The findings emphasize the complexity of river systems and advocate for an integrated approach of river flow analysis for a comprehensive understanding, crucial for effective water resource management and planning.

Stream water sourcing from high-elevation snowpack inferred from stable isotopes of water: a novel application of d-excess values

Abstract. About 80 % of the precipitation at the Colorado River's headwaters is snow, and the resulting snowmelt-driven hydrograph is a crucial water source for about 40 million people. Snowmelt from alpine and subalpine snowpack contributes substantially to groundwater recharge and river flow. However, the dynamics of snowmelt progression are not well understood because observations of the high-elevation snowpack are difficult due to challenging access in complex mountainous terrain as well as the cost and labor intensity of currently available methods. We present a novel approach to infer the processes and dynamics of high-elevation snowmelt contributions predicated upon stable hydrogen and oxygen isotope ratios observed in streamflow. We show that deuterium-excess (d-excess) values of stream water could serve as a comparatively cost-effective proxy for a catchment-integrated signal of high-elevation snowmelt contributions to catchment runoff. We sampled stable hydrogen and oxygen isotope ratios of the precipitation, snowpack, and stream water in the East River, a headwater catchment of the Colorado River, and the stream water of larger catchments at sites on the Gunnison River and Colorado River. The d-excess of snowpack increased with elevation; the upper subalpine and alpine snowpack (&gt; 3200 m) had substantially higher d-excess compared to lower elevations (&lt; 3200 m) in the study area. The d-excess values of stream water reflected this because d-excess values increased as the higher-elevation snowpack contributed more to stream water generation later in the snowmelt/runoff season. End-member mixing analyses based on the d-excess data showed that the share of high-elevation snowmelt contributions within the snowmelt hydrograph was on average 44 % and generally increased during melt period progression, up to 70 %. The observed pattern was consistent during 6 years for the East River, and a similar relation was found for the larger catchments on the Gunnison and Colorado rivers. High-elevation snowpack contributions were found to be higher for years with lower snowpack and warmer spring temperatures. Thus, we conclude that the d-excess of stream water is a viable proxy to observe changes in high-elevation snowmelt contributions in catchments at various scales. Inter-catchment comparisons and temporal trends of the d-excess of stream water could therefore serve as a catchment-integrated measure to monitor if mountain systems rely on high-elevation water inputs more during snow drought compared to years of average snowpack depths.

Characteristics of Runoff Components in the Mingyong Glacier Basin, Meili Snow Mountains

As an important hydrological ecosystem component, the glacier basin has great significance for climate and environment, and it is also linked to regional water sustainability. In this paper, the sampling and isotope analysis of glacial ice, ice-melt water, river water (river midstream and river downstream), groundwater (spring), and precipitation were carried out in a hydrological year of the Mingyong Glacier basin, which is located at the Meili Snow Mountains, Southeastern Tibetan Plateau. At the same time, the hydrograph separation of the recharge sources of the lower mountain pass is studied. The results show that the range of δD, δ18O, and d-excess (deuterium excess) in natural water bodies are significantly different, and the precipitation is the most obvious. The high values of δD and δ18O in the water samples all appeared in spring and summer, and the low values appeared in autumn and winter, while glacial ice showed opposite trends. Meanwhile, the local meteoric water line (LMWL) of the Mingyong Glacier basin is δD = 8.04δ18O + 13.06. The End-Member Mixing Analysis (EMMA) was adopted to determine the sources proportion of river water (river downstream) according to the δD, δ18O, and d-excess ratio relationships. The results showed that the proportion of ice-melt water, groundwater, and precipitation in the ablation period was 80.6%, 17.2%, and 2.2% as well as 19.2%, 73.1%, and 7.7% in the accumulation period, respectively. Ice-melt water has a higher conversion recharge rate to groundwater and indirectly recharges river water, especially in nonmonsoon seasons. In other words, the main recharge source of river water in the lower reaches of the Mingyong Glacier basin during the ablation period is ice-melt water. In the accumulation period, the main recharge source of river water in the lower reaches of the Mingyong Glacier basin is groundwater, while nearly half of the recharge of groundwater comes from ice-melt water. Therefore, regardless of the ablation period or the accumulation period, ice-melt water is sustainable and important to this region.

The effect of freeze-thaw action on the dynamic change of supra-permafrost water sources: A stable isotope perspective

Due to the continuous degradation (gradual thawing) of permafrost, supra-permafrost water has become an important component of runoff that occurs in cold regions. However, current research has only focused on the amount of water provided by permafrost, and little has been reported regarding the source and formation mechanisms of supra-permafrost water. Due to the difficulty of observation and sampling in cold regions and insufficient data accumulation, model simulations face various difficulties in regard to solving problems related to hydrological processes. Considering the advantages of stable isotope tracer methods in hydrology, the source of supra-permafrost water in Qilian Mountain was analyzed based on 1,840 samples, and the source of supra-permafrost water was determined by end-member mixing analysis (EMMA). Negative line-conditioned excess (lc-excess), lower slope, and particularly the negative intercept of the evaporation line (EL) indicates strong evaporation effects on supra-permafrost water. Remarkably, the evolutionary process, influencing factors, and relationship with other water bodies all indicate that supra-permafrost water is replenished by precipitation, ground ice meltwater, and snow meltwater. The results indicated that from May to October, the contributions of precipitation to the supra-permafrost water were 79%, 83%, 90%, 84%, 87%, and 83%, respectively. Snow meltwater contributed 11%, 13%, 10%, 16%, 11%, and 9%, respectively. Permafrost degradation impacts the water cycle and can increase the minimum monthly runoff and increase groundwater storage. To mitigate the effects of this change, monitoring and early warning systems are essential for detecting signs of permafrost degradation in a timely manner so that appropriate measures can be taken. This may involve the use of remote-sensing technologies, sensor networks, and other methods for real-time monitoring. Establishing mechanisms for sharing information with the relevant departments is crucial. The research results provide scientific and technological support and aid in decision-making to mitigate the negative effects of continuous permafrost degradation in a changing environment.

River–Spring Connectivity and Hydrogeochemical Processes in a Karst Water System of Northern China: A Case Study of Jinan Spring Catchment

Frequent surface water–groundwater interactions and prevalent anthropogenic inputs make karst water systems vulnerable to human disturbance. As a typical karst region in North China, the Jinan Spring Catchment has become increasingly threatened due to rapid population growth and urban expansion. In this study, the local river–spring interaction and its interference with the hydrogeochemical evolution of groundwater are evaluated based on water stable isotopes and hydrochemistry. Twenty-two karst groundwater, eleven Quaternary pore water, sixteen spring water, and thirty-two surface water samples were collected during low- and high-flow conditions over the course of a year. The isotopic signatures of four different water types display significant differences, reflecting the recharge–discharge relationship of the karst water system. Mountainous springs feature lighter isotopes, whereas urban springs have significantly heavier isotopes. The result of end-member mixing analysis shows that the surface–groundwater interaction varies spatially and temporally within the spring catchment. Urban springs receive considerable replenishment from the surface water, especially after rainy episodes (up to 50%), while mountainous springs show little hydraulic dependence on surface water leakage (4~6%). Local mineral dissolution (including calcite, dolomite, gypsum, and halite), CO2 dissolution/exsolution, and cation exchange are the main hydrogeochemical processes constraining water chemistry in the spring catchment. The deterioration of water quality can be attributed to anthropogenic influences involving the discharge of domestic effluents, agricultural activities, and irrigation return flow. The findings of this work can improve our understanding of the complex karst water system and serve as a reference for sustainable groundwater management in other karst areas of northern China.

Hydrochemical and Stable Isotope characteristics of surface water and groundwater in Xiliugou and Wulagai River basin, North China

The investigation of the correlation between groundwater and surface water in terms of water origin and transformation is crucial for comprehending hydrological processes . Focuses on the Wulagai river and Xiliugou river basin located in East and West Inner Mongolia. It employs hydrochemical analysis and stable HO isotopes techniques to investigate the hydrochemical properties of the basin and quantitatively assess the interconversion between groundwater and surface water. The results suggest that the Xiliugou and Wulagai river basins were originally nourished by atmospheric precipitation, with lower δD and δ18O values in groundwater compared to surface water, attributed to factors such as evaporation, water vapor source, altitude, and latitude. The surface waters in the Xiliugou and Wulagai River exhibit dominance of Na•Ca-SO4•HCO3 and Ca•Na-HCO3 types, respectively, while the groundwater is characterized by dominance of Na•Ca-HCO3 and Ca•Mg-HCO3 types, respectively. The water chemistry of surface water and groundwater in the two basins is influenced by water-rock interactions and processes of evaporation and concentration, primarily observed in the dissolution of carbonate rocks and evaporites. Hydrograph separation using End-Members Mixing Analysis (EMMA) revealed that during the growing season, groundwater in Xiliugou was primarily recharged by precipitation (76.87 %) and surface water (23.13 %), while in Wulagai, groundwater was mainly recharged by precipitation (65 %) and surface water (35 %). The presence of comparable hydrochemical constituents and shared regulatory mechanisms between groundwater and surface water within a given basin provides further evidence of a discernible hydraulic interconnection, primarily driven by the replenishment of groundwater through surface water recharge.

Spatial characteristics of hydrochemistry and stable isotopes in river and groundwater, and runoff components in the Shule River Basin, Northeastern of Tibet Plateau

Water resources play a crucial role in constraining the high-quality development of the arid, necessitating an in-depth investigation and understanding of hydrological processes, hydrochemical characteristics, and their influencing factors amidst climate change. This study meticulously examined and analyzed the hydrochemistry and stable isotope composition (δ18O and δD) of river and groundwater within the Shule River Basin (SRB). Results showed that both river (mean: 8.01) and groundwater (mean: 7.92) had alkaline pH values, while average total dissolved solids were measured at 709.25 mg/L in river and 861.88 mg/L in groundwater, indicating predominance of fresh water sources. HCO3−, SO42−, Na+ and Ca2+ were the most abundant ions, influenced by evaporation-crystallization processes and rock weathering. The dominated hydrochemical facies in both river and groundwater were Ca–HCO3 type in the upper (UR) and the middle reaches (MR), while Ca–Mg–Cl type in the lower reaches (LR). The local meteoric water line (LMWL) was defined as δD = 8.01δ18O + 18.48 (R2 = 0.98, n = 163; P < 0 0.001). The more negative δ18O and δD values in river and groundwater were plotted nearby and lower right of the LMWL, implying that the important recharge source of those waters is from precipitation. The relationship between river δ18O and elevation showed an increase of 0.14‰/100 m in the UR, but a negative correlation with a rate of −0.47‰/100 m in the MR and LR. Precipitation, groundwater, baseflow and meltwater accounted for 62.5%, 19.8%, 11.9% and 5.8% of the UR river, respectively, during the observed period, according to the end-member mixing analysis. These runoff components displayed distinct seasonal variations, primarily driven by precipitation during the early and groundwater/baseflow during the rapid and end-stage ablation periods. The observed alterations in hydrological elements present both opportunities and challenges for water resource management across the SRB, and adaptive measures have been proposed based on our study. These findings provide valuable insights into efficient utilization of water resources from water chemistry and environmental isotopes.

Optimal tracer identification for dissolved organic matter (DOM) source tracking in watersheds using point source effluent load data

In this study, we characterized the optical and molecular weight (MW) properties of dissolved organic matter (DOM) with various sources in an agriculture-forestry watershed. We proposed a guideline to identify optimum DOM source tracers for downstream rivers during both rain and non-rain events, utilizing the load of dissolved organic carbon (DOC) from point sources. Six descriptors were pre-selected based on established criteria in the literature, and fifteen pairs of these descriptors were evaluated for their applicability in end-member mixing analysis (EMMA). The results from EMMA provided inconsistent estimates of relative contributions from DOM sources across the fifteen pairs, with optical descriptors outperforming MW-based descriptors and their combinations. The optimal source tracers were determined by comparing relative contributions of DOM from upstream effluent wastewater using DOC load ratios calculated from on-site monitoring data and predictions based on EMMA. The pair of optical descriptors, HIX (humification index) and BIX (biological index), closely matched the measured load ratios with minimal discrepancies (0.4 ± 0.4 %). According to the EMMA results using pairs of HIX and BIX, non-rain events were primarily influenced by oil-cake fertilizer and treated effluent wastewater, while rain event samples were dominated by manure and soils. These findings offer insights into managing non-point organic pollution sources in agricultural-forestry watersheds, contributing to our understanding of carbon and nutrient cycling in aquatic systems. Notably, this study proposes a validation guideline that employs load ratios of point sources, such as effluent wastewater, to enhance source tracking accuracy.

Assessment of groundwater recharge and connectivity with surface water in a mountainous watershed using natural tracers in Daejeon, Korea

The water supply from headwater streams in mountainous regions is considered an important source for sustaining both water quality and quantity in lowland areas. The Korean terrain is characterized by mountainous regions, the hydrological environment is significantly impacted by seasonal weather conditions. This study focused on investigating the hydrochemistry and isotopic composition of groundwater and surface water to identify hydrological connectivity within a mountainous watershed area in Daejeon, Korea. The estimated recharge rate using water budget methods suggests that approximately 20% of the total precipitation contributes to groundwater recharge in this site. The δ18O–δ2H values of the water samples indicate a meteoric water source for groundwater recharge, while the isotope composition of surface water reveals altitude effects, implying that groundwater recharges at a higher altitude region. Additionally, water revealed altitude effects suggesting that the groundwater was inferred to recharge at a higher altitude region. The hydrochemical conservative components (87Sr/86Sr ratio and Cl−) indicate that this watershed undergoes temporary similar water–rock interactions along its flow path, but it is also impacted by anthropogenic contaminants from the surrounding public area. The results of the three-component endmember mixing analysis demonstrate that groundwater is predominantly influenced by surface water, indicating a close interrelationship among various water bodies in mountain hydrology. These findings provide a comprehensive approach to water resource management by combining recharge rate estimation and the assessment of water body connectivity using natural tracers.

Source of soil water in cold regions based on stable isotope tracers

Soil water plays a key role in vegetation growth and ecological stability in cold regions. The soil water sources in the Qilian Mountains of the northeastern Tibetan Plateau have been quantified based on stable isotope data (δ2H and δ18O) of 1913 samples. The results indicated that δ18O of soil water ranged from ˗14.13–11.21‰, with an average of ˗6.78‰, and on a spatial scale, it increased gradually from the southeast to the northwest, where it became more positive. The stable isotopes of soil water are affected by evaporation, leading to a lower slope and interception of the evaporation line: δ2H = 3.23 δ18O–32.51 (R2 = 0.71, p < 0.01). The relationship between soil water and other water bodies showed that the soil water was mainly replenished by precipitation and ground ice meltwater. End-member mixing analysis (EMMA) showed that precipitation and ground ice accounted for approximately 91 % and 9 % of soil water, respectively, during heavy ablation. In the 0–20 cm, 20–40 cm, 40–60 cm, 60–80 cm, and 80–100 cm soil layers, the contributions of ground ice meltwater to soil water were 0 %, 3 %, 7 %, 13 %, and 18 %, respectively. Notably, the contribution of ground ice meltwater to soil water gradually increased with elevation, whereas that of precipitation decreased. This study has obtained relevant data for the cold region, where it is typically difficult to conduct observations and sampling. More importantly, it analyzes the source and influencing factors of soil water in cold regions using the stable isotope method, which is of great significance for the study of the water cycle in cold regions.

Stable isotopes reveal the surface water-groundwater interaction and variation in young water fraction in an urbanized river zone

Based on 30 sampling campaigns on precipitation, river water and groundwater in Qingbaijiang urban catchment, southwest China, this study reports the spatio-temporal evolution of water isotopes under the impacts of human activities. The seasonal variation of groundwater-surface water interaction is quantitatively evaluated by isotope-aid hydrograph separation, and the young water fraction (Fyw) in river water at different spatial locations is estimated based on the seasonal periodicity of isotopes. The results show that the stable isotopes in river water and groundwater in Qingbaijiang urban catchment grow enriched from upstream to downstream, reflecting the transformation of the dominant water source from plateau river water to local precipitation and the influence of evaporation. The operation of water conservancy projects and construction of impervious surface in urban areas increase the evaporation intensity of river water. The results of the end-member mixing analysis (EMMA) demonstrates that the average annual contributions of river water to near-bank groundwater are 60.17%, 23.55% and 24.90% in the upper, middle and lower parts, respectively. The periodic storage and release of water led by the water conservancy projects enhances the groundwater recharge in the upstream river, while the water exchanges between river water and groundwater in the middle and lower parts of the catchment are reduced. The Fyw at 8 river sections of Qingbaijiang River estimated by the isotopic amplitude ratio method ranges from 0.067 to 0.194, with an overall increasing trend from upstream to downstream. The young water fraction is negatively correlated with mean elevation, mean slope and vegetation coverage, while positively correlated with the proportion of anthropogenic land use and the proportion of low-permeable soil. The construction of impervious surfaces and drainage systems in urban and rural areas is an important driver for the elevated young water fraction.

Evaluation of Legacy Forest Harvesting Impacts on Dominant Stream Water Sources and Implications for Water Quality Using End Member Mixing Analysis

Forests are critical water supply regions that are increasingly threatened by natural and anthropogenic disturbance. Evaluation of runoff-generating processes within harvested and undisturbed headwater catchments provides insight into disturbance impacts on water quality and drinking water treatability. In this study, an extensive hydrologic dataset collected at the experimental Turkey Lakes Watershed (TLW) located on the Canadian Shield was used to quantify sources of stormflow in legacy clear-cut (24-years post harvesting) and forested (control) headwater catchments using an end member mixing analysis (EMMA) model. Stream water, groundwater, soil water, and throughfall water quality were evaluated during spring snowmelt, stormflow, and fall wet-up. Groundwater chemistry was similar to stream water chemistry in both catchments, suggesting that groundwater is a major contributor to stream flow. The water chemistry in small wetlands within the study catchments was comparable to stream water chemistry, suggesting that wetlands are also important contributors to stream flow. Differences in wetland position between the legacy clear-cut and control catchments appeared to have a greater influence on source contributions than legacy harvesting. Results from this study provide insight into runoff-generation processes that reflect event/seasonal flow dynamics and the impacts on water quality.

Influence of Critical Zone Architecture and Snowpack on Streamflow Generation Processes: A Mountain‐Meadow Headwater System in a Mediterranean Climate

AbstractObservations from a granitic watershed within a Mediterranean climate reveal the hydrologic and critical zone functioning of a perennial stream headwater and its upslope contributing area within a meadow system in the Sierra Nevada, California. Chemical analysis (diagnostic tools of mixing models, end member mixing analysis, tritium, etc.) and physical data (stream stage, piezometers, soil water, snowpack, etc.) indicate there are two primary pathways of water input into a headwater stream sourced from a mountain meadow. One input is a shallower and younger subsurface pathway with water that resembles snowpack chemistry, and the other a deeper and older subsurface pathway with water that reflects the chemistry of the groundwater derived from the contributing hillslopes. Multi‐year observations reveal that regardless of snowpack amount, during the period of peak hillslope infiltration, shallow and deep pathways in the hillslope behave similarly to initiate headwater streams. However, during summer dry periods, similarities in active pathways within the meadow center are not maintained between high and low snowpack years. With less snow, perennial groundwater discharge within the meadow center is eliminated, becoming only a seasonal source at the meadow's outlet. At the meadow's edge, geophysically observed downslope thinning in saprolite thickness creates reduced lateral transmissivity and initiation points for headwater streams via enhanced groundwater discharge of upslope water. Combined, these findings suggest how loss of snowpack and critical zone structure can together mediate hydrologic function in a wet meadow system in a Mediterranean climate. Creating new understanding about the stability of hydraulic functioning in headwater wet‐meadow systems under a changing climate.

Hydrogeochemical characterization and CO2 consumption in the Maqu catchment of the Qinghai-Tibetan Plateau by multiple hydrogeochemical methods

The Qinghai-Tibetan Plateau (TP) is the source of many large Asian rivers and has significant social, ecological and economic importance. However, few hydrogeochemistry and stable isotope studies have been performed in the Maqu catchment of the eastern TP. In this study, the hydrogeochemical composition and stable isotopes (δD and δ18O) of surface water and groundwater samples collected in the Maqu catchment were analysed to characterise the surface water and groundwater, investigate the contributions of different sources, and determine CO2 consumptions. Different techniques were used, including inverse modelling, end member mixing analysis (EMMA), and a forward mass balance model. The results indicated that all water samples are of the HCO3-Ca type. Both the surface water and groundwater are of meteoric origin and there is close contact between them (except wetlands). Water in the wetlands is substantially evaporated (0–45%). Calcite and illite generally precipitate, whereas chlorite and CO2 generally dissolve along groundwater flow paths in the east. The mean contributions of fresh surface waters, mountain-front groundwaters, and anthropogenic inputs to the surface water samples are 56%, 16%, and 28%, respectively. Carbonate and silicate weathering are the dominant sources of major cations. Moreover, high CO2 consumption rates in both the surface runoff and groundwater make the Maqu catchment an important carbon sink in the Yellow River Basin. With many newly-found conclusions on the Maqu catchment, the present study not only provides insight into the catchment but also contributes to a comprehensive understanding of the water cycle and CO2 consumptions on the TP.

Hydrologic connectivity between water in permafrost active layer and river water in a small alpine catchment in the northeastern Tibetan Plateau

A total of 256 water samples were collected from the river, precipitation, and permafrost active layer in a typical small alpine catchment during the ablation periods in 2020 and 2021. The results indicated that every water body was alkaline, and the TDS and EC concentrations were in the following order: precipitation < river water < permafrost water. The cation concentrations in river and permafrost water exhibited the order of Na+ + K+ > Ca2+ ≈ Mg2+ and Na+ + K+ > Mg2+ > Ca2+, respectively; the anion concentration showed the order of SO42− > Cl− > NO3−. The results revealed that permafrost and river water had similar geochemical compositions. Similar δ2H and δ18O values were also observed between river and permafrost water. Additionally, the water chemistry of rivers and permafrost revealed that the chemical weathering of carbonate and silicate rocks is an important source of riverine solutes; however, silicate weathering played a more crucial role. Both hydrochemistry and stable isotopes collectively indicated that there was a close hydraulic connectivity between the water content in river and permafrost active layer in the small alpine catchment. Based on the end-member mixing analysis model, the water in permafrost active layer and precipitation accounted for 62% and 38% of the runoff, respectively, indicating that it was dominated by permafrost during the ablation period. The warming and humidification of climate tend to facilitate permafrost degradation. Thus, studying the transformation of different water bodies in alpine regions is imperative to provide water resource security and sustainable development in alpine regions.