End-member Mixing Analysis Research Articles

Land cover influence on catchment scale subsurface water storage investigated by multiple methods: Implications for UK Natural Flood Management

Study regionUnited Kingdom (UK). Study Focus‘Natural flood management’ (NFM) schemes manipulating land use and other catchment features to control runoff are increasingly promoted across the UK. Catchment water storage and mixing processes influence runoff, but our understanding of the effects of land cover change on these processes is still limited. This study combined hydrometric, isotopic and geochemical measurements to investigate land cover versus potential topographic, soil and geological controls. It compared storage-discharge dynamics in nine nested catchments within a 67 km2 managed upland catchment in southern Scotland. Storage and mixing dynamics were characterised from hydrometric data using recession analysis and from isotopic data using mean transit time and young water fraction estimates. To give information on water sources, groundwater fraction was estimated from end member mixing analysis based on acid neutralising capacity. New hydrological insightsThe analysis showed low but variable sub-catchment scale dynamic storage (16–200 mm), mean transit times (134–370 days) and groundwater fractions (0.20–0.52 of annual stream runoff). Soil hydraulic conductivity was most significantly positively correlated with storage and mixing measures, whilst percentage forest cover was inversely correlated. Any effects of forest cover on increasing catchment infiltration and storage are masked by soil hydraulic properties even in the most responsive catchments. This highlights the importance of understanding dominant controls on catchment storage when using tree planting as a flood management strategy.

Contribution of the cryosphere to runoff in “Chinese water tower” based on environmental isotopes

Cryospheric meltwater is an important runoff component and it profoundly influences changes in water resources in the Tibetan Plateau. Significant changes in runoff components occur in the three-river headwater region (TRHR), which is an important part of “Chinese Water Tower” due to climate warming. However, these effects remain unclear owing to the sparse and uneven distribution of monitoring sites and limited field investigations. Quantifying the contribution of cryospheric meltwater to outlet runoff is a key scientific question that needs to be addressed. In this study, we analyzed 907 precipitation, river water, ground ice, supra-permafrost water, and glacier snow meltwater samples collected from October 2019 to September 2020 in the TRHR. The following results were obtained: (1) There was significant spatio-temporal variation in stable isotopes in different waters; (2) The seasonal trends of stable isotopes for different waters, the relationship between each water body and the local meteoric water line (LWML) confirmed that river water was mainly recharged by precipitation, supra-permafrost water, and glacier snow meltwater; (3) Precipitation, supra-permafrost water, and glacier snow meltwater accounted for 52%, 39%, and 9% of river water, respectively, during the ablation period according to the end-member mixing analysis (EMMA); (4) In terms of future runoff components, there will be many challenges due to increasing precipitation and evaporation, decreasing snow cover, glacier retreat, and permafrost degradation. Therefore, it is crucial to establish the “star-machine-ground” observation networks, forecast extreme precipitation and hydrological events, build the “TRHE on the Cloud” platform, and implement systematic hydraulic engineering projects to support the management and utilization of water resources in the TRHR. The findings of environmental isotope analysis provide insights into water resources as well as scientific basis for rational use of water resources in the TRHR.

Quantitative sediment provenance of the northwestern East China Sea: Evidence for tidal current-driven offshore transport and paleogeographic implications

In the northwestern East China Sea, sediment transport and mixing in both along-shelf and cross-shelf dimensions are distinguished using quantitative provenance analysis, with an aim to demonstrate a net transport pattern and thereby infer potential transport and dispersal processes over geological timescales. The dataset comprises 328 bottom sediment samples, which were characterized by detrital-mineral and grain-size analyses. Results show that only in the south of the study area the primary source of sediment is the Yangtze River. In the north, instead, three end-member sources, i.e., the Yangtze, Yellow and Huaihe Rivers, are quantified separately using an end-member mixing analysis. Along-coast mixing between the updrift Huaihe–Old Yellow and downdrift Yangtze River systems is minimized. In exchange, offshore sediment transport is enhanced instead. This conversion from along-shelf to cross-shelf transport is attributed to the presence of a large-scale radial tidal current system off the Jiangsu coast as well as the headland effect produced by the protruding north flank of the subaerial Yangtze delta and the Yangtze riverine plume. This radial tidal current system acts both as a trap for Huaihe–Old Yellow River sediments transported by the southward-direct longshore current, and as a transfer center for sediment dispersal offshore. Radiating transport pathways virtually indicate an extensive mixing of Yangtze sediments and Old/modern Yellow and Huaihe sediments in the southwestern Yellow and northernmost East China Seas. As an independent dynamic system, it acts as a critical link between the Yangtze and modern/Huaihe–Old Yellow River dispersal systems. Thus, we conclude that these three large-scale dispersal systems and their complex interplay dominate sediment transport, redistribution and mixing on the eastern China continental shelf.

Separately tracking the sources of hydrophobic and hydrophilic dissolved organic matter during a storm event in an agricultural watershed

The hydrophobicity of dissolved organic matter (DOM) affects various aspects of its environmental impacts in terms of water quality, sorption behaviors, interactions with other pollutants, and water treatment efficiency. In this study, source tracking of river DOM was conducted separately for hydrophobic acid (HoA-DOM) and hydrophilic (Hi-DOM) fractions using end-member mixing analysis (EMMA) in an agricultural watershed during a storm event. EMMA with optical indices of bulk DOM revealed larger contributions of soil (24 %), compost (28 %), and wastewater effluent (23 %) to riverine DOM under high versus low flow conditions. Molecular level analysis of bulk DOM revealed more dynamic features, showing an abundance of CHO and CHOS formulae in riverine DOM under high- and low flow conditions. CHO formulae originated from soil (78 %) and leaves (75 %) and contributed to the increasing CHO abundance during the storm event, whereas CHOS formulae likely originated from compost (48 %) and wastewater effluent (41 %). The characterization of bulk DOM at the molecular level demonstrated that soil and leaves are the dominant contributors for the high-flow samples. However, in contrast to the results of bulk DOM analysis, EMMA with HoA-DOM and Hi-DOM revealed major contributions from manure (37 %) and leaf DOM (48 %) during storm events, respectively. The results of this study highlight the importance of individual source tracking of HoA-DOM and Hi-DOM for the proper evaluation of the ultimate roles of DOM in affecting river water quality and for a better understanding of DOM dynamics and transformation in natural and engineered systems.

Comparing the Runoff Decompositions of Small Experimental Catchments: End-Member Mixing Analysis (EMMA) vs. Hydrological Modelling

This study is focused on the comparison of streamflow composition simulated with three well-known rainfall–runoff (RR) models (ECOMAG, HBV, SWAT) against hydrograph decomposition evaluated with End-Member Mixing Analysis (EMMA). In situ observations at two small mountain testbed catchments located in the south of Pacific Russia are used. All applied RR models and EMMA analysis demonstrate that two neighboring catchments disagree significantly on the mutual dynamics of the runoff sources. The RR models' benchmark test is based on proximity to EMMA hydrograph composition. Different aggregation intervals (season, month, and pentad) were applied to find a reasonable generalization period ensuring the clarity of results. ECOMAG is most conformable to EMMA outcome; HBV reflects flood events well enough; SWAT exhibits distinctive behavior compared to the other models. It is shown that, along with standard efficiency criteria of simulated and observed runoff proximity, EMMA analysis might provide useful auxiliary information for the validation of modelling results.

Identifying river water sources using end‐member mixing analysis in a subtropical monsoon basin China

AbstractPressure on river water resources may increase continuously under global climate change and the increasing intensity of human activity, and the identification of river water sources is needed to maintain water resource sustainability. In this study, river water sources were studied using hydrochemical tracers (i.e. the major ions) and end‐member mixing analysis (EMMA) during two hydrological years, in the subtropical monsoon basin of the Xiangjiang River in the south‐central China. Various water types including precipitation, river water, and mountain creek water, were collected in the basin at a high frequency. The results of EMMA showed that the average contributions from the direct input of precipitation, near‐surface runoff (represented by mountain creek water), and groundwater (represented by river water sampled during the base flow period) were 28 ± 24%, 49 ± 24% and 23 ± 16%, respectively. The contributions from these water sources to the river water varied greatly within the year, which may indicate a shift in the major flow pathways from direct precipitation input and near‐surface flow pathways in the spring rainy months (e.g. from March to May), to a deeper flow pathway in the dry or rainless months (e.g. January, February, July and December). The shift of the major flow pathways may be due to the factors such as the seasonality of precipitation, evapotranspiration and soil wetness conditions. Groundwater and near‐subsurface runoff dominated the river water and the direct input of precipitation was negligible during the dry or rainless months, and consequently, the river water chemistry was less diluted and more influenced by water‐soil/rock interactions and anthropogenic pollution during these months. The creek water contribution to the river water was relatively high in summer, especially in June and July 2021, which may indicate the substantial inter‐seasonal carryover of precipitation that contributed to the river water. With the projected increased frequency of extreme weather events such as seasonal drought, streamflow in the subtropical monsoon regions may experience greater recharge by deeper flow pathways, with the enhanced role of base flow in regulating streamflow, and there may be an increased risk to the water resource security under the condition of the decreased river dilution capacity and increased anthropogenic pollution.

Towards the development of an isotope‐enabled rainfall‐runoff model: Improving the ability to capture hydrological and anthropogenic change

AbstractGlobal hydrological alterations are being driven by climate change. However, while modelling tools have been instrumental in identifying these changes, their calibration is often dependent solely on streamflow data, which limits the ability to simulate important hydrological processes with the required level of certainty. Constraining hydrological process simulations is required to identify robust model parameters, reducing model uncertainty and providing a baseline model for climate‐related risk assessments. In this study, stable isotope measurements of rainwater, groundwater and stream water (δ2H and δ18O), together with an end member mixing analysis (EMMA) (as a post‐processing step) were integrated with the Jena adaptative modelling system (JAMS)/J2000 rainfall‐runoff model, named J2000iso. The J2000iso models of δ2H and δ18O were able to achieve a streamflow Nash–Sutcliffe efficiency (NSE) of 0.75 and 0.72 and an isotope mixing Kling–Gupta efficiency (KGE) of 0.51 and 0.60, respectively. Compared with the base version, the J2000iso had a much smaller variability with 56% less ensemble variance in the NSE, 13% more simulated interflow which resulted in a better soil‐moisture simulation at an observation point, and lower simulated flow component uncertainty. The J2000iso δ2H model was more robust than the base version during a subsequent validation in terms of KGE and Bias with 0.60 and 0.002 compared with 0.51 and −0.14 for the base version. The EMMA provided a means to improve the hydrograph separation ability of the JAMS/J2000. As many catchments around the world are still ungauged and are affected by anthropogenic activities, the development and enhancement of isotope‐enabled modelling provides a means to improve the simulation of key hydrological processes.

Source apportionment of suspended sediment using grain-size end-member analysis

End-members mixing analysis (EMMA) was performed on in situ suspended sediment grain-size distribution (GSD) data from Haizhou Bay to estimate suspended sediment provenance and the relative contributions of different sediment sources to total seawater suspended sediment. The results show that the suspended sediment in Haizhou Bay can be expressed as a mixture of three EMs. End-member 1 represents fine-grained suspended sediment that was transported over long distances by advection; this shows a genetic connection with the old Huanghe River delta. End-member 2 represents resuspension of local sediment, while EM3 represents riverine suspended sediment. On average, advection, resuspension, and riverine input contributed 41.92%, 37.83%, and 20.25% of the total suspended sediment, respectively. Temporal changes in advection and resuspension caused considerable variability in these relative contributions. The application of EMMA herein demonstrates that it is a feasible approach to explore suspended sediment sources and their mixing processes using suspended sediment GSD data.

Estimation of Lacustrine Groundwater Discharge (LGD) to an urban Himalayan lake using environmental tracers (222Rn, δ18O, EC)

Lacustrine Groundwater Discharge (LGD) is a complex process that controls lake characteristics and plays a dominant role in modifying the hydrological and chemical budget of a lake. The current study was carried out with the aim to assess the groundwater discharge component of the hydrological budget of an urban Himalayan lake. We used natural tracers including radioisotope of radon (222Rn), stable water isotopes (δ2H and δ18O), electrical conductivity and water temperature to identify the potential groundwater discharge zones in a lake. The obtained LGD results, based on radon mass balance model (RMB) and end member mixing analysis (EMMA) of stable water isotopes in combination with physical parameters, show temporal as well as spatial variation. The total LGD to the Dal Lake, estimated from RMB, was 62.25 ± 9 × 104 m3/d (24 ± 3 %) and 33 ± 6 × 104 m3/d (36 ± 4 %) during high and low flow periods, respectively. The results suggested that the stream water is the dominant contributor accounting for 75 % (±7) and 55 % (±8), followed by groundwater as 22 % (±5) and 40 % (±4), during high and low flow periods, respectively. However, the contribution from direct precipitation is very little (3–4 %). High groundwater flux towards northeastern side of the lake is substantiated by more aquifer thickness and high hydraulic gradient. The current study offers first in-depth understanding about LGD of an urban Himalayan lake and could be applicable for lake ecosystem protection policies and water resource management plans in the region and elsewhere.

Contribution of End Member Mixing Analysis Model to Characterize the Sources Responsible for Urban River Water Quality: Case of Houet River in Burkina Faso

The study focused on the assessment of sources responsible for an urban river’s water quality. To do the analysis, water samples were collected from three sources. The first source was rainfall, the second source was a Wastewater Treatment Plant (WWTP) which releases pre-treated wastewater in the river, and the third source was the river itself at upstream and downstream parts from the WWTP discharge point in the river. The results of the chemical analysis performed on those water samples showed that the water discharged from the WWTP into the river has a poor physico-chemical quality and high microbiological pollution. However as expected, water samples of rainfall were of good quality. Water samples from the river revealed the presence of microbiological flora (total coliforms, fecal coliforms, Escherichia coli and fecal Streptococci) and chemical elements such as ammonium (NH4+), manganese (Mn), nickel (Ni) with high concentrations values than those recommended for irrigation waters as defined by World Health Organization (WHO) and the Food and Agriculture Organization (FAO) of the United Nations. However, parameters like temperature (T°), hydrogen potential (pH), electrical conductivity (EC), total dissolved solids (TDS), suspended solids (SS), chemical oxygen demand (COD), biological oxygen demand (BOD5) ortho-phosphate (PO43-), nitrate (NO3-), nitrite (NO2-), sodium (Na+), bicarbonate (HCO3-), calcium (Ca2+), magnesium (Mg2+), chloride (Cl-), zinc (Zn2+) and iron (Fe2+) are in line with the reference values for irrigation. Furthermore, water mixing analysis model "End Members Mixing Analysis (EMMA)" based on principal component analysis (PCA) of physico-chemical parameters of the pre-treated wastewater from the WWTP discharged into the river, the rainfall, and the river collected at upward of WWTP junction discharge point in the river has been developed. The results show that the wastewater pre-treated by the WWTP and discharged into the river contributes to 13.72% of the river water chemistry compared to 33.64% for rainfall and 52.64% for river water before its junction with WWTP. This study revealed that during rainy season, Houet river has high concentrations of NH4+, metallic trace elements (Mn, Ni) and significant microbiological pollution due to (i) the discharge into the river of incomplete treated wastewater coming from the WWTP (ii) but also to the river itself, which minor bed is the depository of urban and domestic wastes. It is true that the river water quality is globally good for market gardening, but to ensure its long-term quality, authorities in charge of water resources and agriculture should (i) monitor and optimize WWTP wastewater treatment efficiency, (ii) and control/limit agricultural and domestic activities with potential pollution risks alongside the river.

Dominant source areas shift seasonally from longitudinal to lateral contributions in a montane headwater stream

Montane ecoregions are important vehicles for downstream hydrologic function, but their dynamics are relatively understudied compared to alpine and subalpine catchments in the western United States. Montane catchments experience shifts in precipitation inputs seasonally, which results in spatiotemporal differences in source area contributions to the stream. We collected hydrometric and geochemical data between 2018 and 2021 from a 2.65 km2 semi-arid headwater catchment in the Front Range of Colorado, USA. Using a combined approach of hydrometric monitoring, geochemical characterization, and end-member mixing analysis (EMMA), we assess hydrologic connectivity between areas with high upslope accumulation and the stream. Within our study area, high upslope accumulation area corresponded to alluvial/ colluvial fans wherein we focused instrumentation and water sample collection. Using observed rainfall, and multiyear measurements of groundwater levels, soil moisture, and streamflow, we observed distinct hydrologic seasons within our catchment characterized by snowmelt during the spring, rainstorms during the summer, and a return to baseflow during the fall. Within this framework, we found that source areas to streamflow shift with longitudinal distance downstream, and among hydrologic seasons. Notably, our EMMA results indicate that contributions from upstream source areas become less important than lateral inputs from spring snowmelt into the fall return to baseflow. This was most pronounced at the upper catchment where upstream contributions to streamflow decreased up to 33.3% between spring and fall. These results suggest that streamflow is maintained by local source areas contributing laterally and vertically. Our results reflect dynamic shifts in hydrologic connectivity in space and in time, which are increasingly important to land and water resource management given rapid climate changes within the western United States.

Novel insights into source apportionment of dissolved organic matter in aquifer affected by anthropogenic groundwater recharge: Applicability of end-member mixing analysis based optical indices

The composition and main sources of dissolved organic matter (DOM) in groundwater may change significantly under long-term anthropogenic groundwater recharge (AGR); however, the impact of AGR on quantitative sources of groundwater DOM has seldom been reported. This study evaluated the applicability of optical indices combined with mixing stable isotope analysis in R (MixSIAR) in end-member mixing analysis (EMMA) of groundwater DOM. Fluorescent indices, including C1%, C2%, and C3%, were more sensitive to AGR than other absorbance indices, as indicated by the significant difference between the dominant area of artificial groundwater recharged by surface water and the dominant area of natural groundwater recharged by atmospheric precipitation (NGRP). BIX-C1% was selected as the optimal dual index after the screening protocol of groundwater DOM for EMMA. Our results showed that DOM in the aquifer was mainly subject to autochthonous DOM and the contribution of background groundwater to AGRSW and NGRP groundwater accounted for 36.15% ± 32.41% and 55.46% ± 37.17% (p < 0.05), respectively. Therefore, AGR significantly changed the native DOM in the groundwater. In allochthonous sources of DOM, sewage and surface water contributed 29.54% ± 24.87% and 21.32% ± 28.08%, and 24.79% ± 15.56% and 15.21% ± 14.20% to AGRSW and NGRP groundwater, respectively. The contribution of surface water to AGRSW groundwater was significantly higher than that to NGRP groundwater (p < 0.05), indicating that AGR introduced significantly more DOM from surface water to groundwater. This study provides novel insights into the quantitative source apportionment of DOM in groundwater under long-term AGR, which will facilitate the environmental risk assessment of present AGR measures and the sustainable management of clean water.

Innovative approach to reveal source contribution of dissolved organic matter in a complex river watershed using end-member mixing analysis based on spectroscopic proxies and multi-isotopes

Dissolved organic matter (DOM) in river watersheds dynamically changes based on its source during a monsoon period with storm event. However, the variations in DOM in urban and rural river watersheds that are dominated by point and non-point sources have not been adequately explored to date. We developed an innovative approach to reveal DOM sources in complex river watershed systems during pre-monsoon, monsoon, and post-monsoon periods using end-member mixing analysis (EMMA) by combining multi-isotope values (δ13C-DOC, δ15N-NO3 and δ18O-NO3) and spectroscopic indices (fluorescence index [FI], biological index [BIX], humification index [HIX], and specific UV absorbance [SUVA]). Several potential end-members of DOM sources were collected from watersheds, including top-soils, groundwater, plant group (fallen leaves, riparian plants, suspended algae), and different effluents (cattle and pig livestock, agricultural land, urban, industry facility, swine treatment facility and wastewater treatment facility). Concentrations of dissolved organic carbon, dissolved organic nitrogen, NO3-N, and NH4-N increased during the monsoon period with an increase in the input of anthropogenic DOM, which have higher HIX values owing to the flushing effect. The results of EMMA indicate that soil and agricultural effluents accounted for a substantial contribution of anthropogenic DOM at varying rates based on seasons. We also found that results of EMMA based on combining spectroscopic indices and δ13C-DOC isotope values were more accurate in tracing DOM sources with respect to land-use characteristics compared to applying only spectroscopic indices. The positive relationship between FI, BIX and δ15N-NO3 were revealed that nitrate would be decomposed from DOM affected by intensive agricultural activities. In addition, consistent with the EMMA results, the molecular composition of the DOM was clearly evidenced by a large number of CHON formulas, accounting for over 50% of the total characterized compounds, including pesticides and pharmaceuticals used in agriculture farmland and livestock. Our results clearly demonstrated that EMMA based on combing multi-stable isotopes and spectroscopic indices could be trace the DOM source, which is important for understanding changes in the DOM quality, and application of nitrate isotopes and molecular analysis supports in-depth interpretation. This study provides easy and intuitive techniques for the estimation of the relative impacts of DOM sources in complex river watersheds, which can be verified in various ways rather than relying on a single technique approach.

The origin and transfer of water and solutes in peatlands: A multi tracer assessment in the carbonated Jura Mountains

AbstractPeatlands provide a large panel of socio‐ecosystemic services such as biodiversity, water and carbon storage and amenities. Hydrological and geochemical interactions between peats and their surroundings are expected to be favoured in mountainous areas, which are nowadays increasingly sensitive to climate changes. In order to provide an integrated scheme of potential interactions, this study evaluates spatio‐temporal patterns of environmental tracers (87Sr/86Sr, δ18O/δ2H, elemental ratios) during high‐ and low‐flow periods in the largest peatland complex of the Jura Mountains (France). Systematically depleted δ18O/δ2H values in the deepest peat pore waters suggest contrasted dynamics and origins, both compatible with either preferential winter recharge or supply from adjacent high‐elevation areas. Combined with strontium isotopes (87Sr/86Sr), we show that these water fluxes are purveyors of solutes derived from water‐rock interactions, modified by mixing, evapotranspiration and dilution with local meteoric inputs. An end member mixing analysis of the peat pore water solute composition is consistent with a major contribution of carbonates from the regional Cretaceous limestone formations, located beneath fluvio‐glacial Quaternary deposits underlying the peat. This contribution implies a significant upward water flux from the underlying syncline that could reach a sufficient hydraulic head thanks to recharge from an adjacent regional anticline. These multiscale (anticline‐syncline, syncline‐peatland, peatland‐surface) constraints allow us to propose a relevant scheme for the hydrogeochemical functioning of the peatland, enabling an improved understanding of the current high socio‐ecosystemic value of the area, and the potential future evolution of the related services.

End‐Member Mixing Analysis as a Tool for the Detection of Major Storms in Lake Sediment Records

AbstractMajor Tropical Cyclone (TC) events cause extensive damage in coastal regions of the western North Atlantic Basin. The short instrumental record leaves significant gaps in understanding long‐term trends in TC recurrence and intensity, creating uncertainty about future storm trends. Analysis of an ∼520‐year core record from Harvey Lake, located &gt;80 km from the Atlantic coast in southwestern New Brunswick, Canada was carried out using: (a) end‐member mixing analysis (EMMA) of lake sediment grain size data to identify storm‐linked sedimentological processes; and (2) ITRAX X‐ray fluorescence (XRF) derived element/ratios (Fe, Ti, Ca/Sr, Zr/Rb, K/Rb, and Br + Cl/Al) associated with precipitation, weathering, catchment runoff, and air masses. Three derived end members were correlated to heavy rainfall events (EM01), spring freshet (EM02), and TCs (EM03). CONISS analysis of the EMMA and XRF core data resulted in recognition of four unique climatic zones distinguished by distinct distributions of TC and rainfall/weathering/runoff/and air masses. Numerous, major (EM01) rainfall events and (EM03) TC events characterized the basal core record during the early Little Ice Age (LIAa; Zone 1) phase, terminating at ∼1645. A near cessation of heavy rainfall and TC events differentiated the subsequent colder LIAb (∼1645–1825; Zone 2) and subsequent Little Ice Age Transition (∼1825–1895; Zone 3). A resurgence of major rainfall and TC events occurred during recovery from the LIA starting in ∼1895 (Zone 4). EMMA provides a robust tool for recognition of TC and major rainfall events, and greatly expands the potential for paleo‐storm activity research well inland from coastal regions.

Water sources and recharge mechanisms of the Yarlung Zangbo River in the Tibetan Plateau: Constraints from hydrogen and oxygen stable isotopes

Investigations of the hydrological processes of the Yarlung Zangbo River (YZR), a sizeable highland river on the southern margin of the Tibetan Plateau (TP), face challenging constraints owing to the complexities in the water sources and cycle pathway. A total of 156 stream water samples from the YZR Basin were collected and analyzed to elucidate our understanding of regional hydroclimate. The isotopic values were more negative in the uppermost reaches of the YZR and progressively increased along the river, with mean δ18O and δD values at − 15.16 ‰ and − 111.58 ‰, respectively. A clear negative gradient of − 0.19 ‰/100 m was obtained from the datasets, which is consistent with that of the southeastern TP. The linear regression for all samples was δD = 8.64 × δ18O + 19.80 (R2 = 0.93, n = 192), and the slope and intercept were highly similar to those of the meteoric water line in the TP, suggesting that precipitation plays a dominant role in stream recharge sources. Combining the results from the air mass trajectory model and the d-excess values, we found that moisture in the YZR originates mainly from the Bay of Bengal, with westerly mixing in the upper reaches. In addition to precipitation, glacial meltwater and geothermal waters were considered significant water sources for the YZR based on geographic and geological conditions. The proportion of glacial meltwater in the uppermost reaches was calculated to range from 68.2 % to 70.4 % using the end-member mixing analysis method. The contribution ratios of precipitation, glacial meltwater, and geothermal water were almost equal in the middle of the basin, while glacial meltwater contribution dominated in the downstream regions. These findings will significantly impact understanding of the hydrological cycle in the study area and provide vital baseline knowledge about the contribution proportion of different recharge sources in the YZR basin.

Characterizing Groundwater Chemistry and Recharge in the Critical Zone of an Agricultural Claypan Watershed

AbstractSoils with low permeability horizons (e.g., claypans) are vulnerable to loss of nutrients through surface runoff along with preferential flow paths through the restrictive horizon to deeper aquifers. Partitioning between these hydrologic pathways is important to determine transport processes and develop strategies that mitigate stream contamination. Our objective was to investigate controls on groundwater chemistry and recharge pathways using natural geochemical tracers in the Goodwater Creek Experimental Watershed in Missouri, U.S. Groundwater samples were collected during 2011–2017 from 32 piezometers ranging from 0.13 to 16 m deep along with stream water and precipitation. Diagnostic tools of mixing models indicated that chemistry of perched water directly above the claypan and shallow groundwater immediately below was controlled primarily by chemical equilibrium. Five solutes behaved conservatively in most deep piezometers (&gt;5 m), reflecting mixing of two end members and the lack of significant denitrification processes. End member mixing analysis showed that the deeper groundwater originated primarily from groundwater at similar depths, often upslope or from strata directly above, with small contributions from perched water, highlighting the importance of both horizontal and vertical preferential recharge pathways. Vertical pathways are likely dictated by soil heterogeneity throughout the critical zone and do not occur synchronously with precipitation events or simultaneously over all piezometer locations. The complex recharge pathways provide stochastic conduits for nitrate transport to deeper aquifers where legacy stores accumulate, presenting a significant challenge for water quality management in watersheds with restrictive soil horizons and spatially and temporally heterogeneous preferential flow pathways, including the Mississippi River Basin.

Identification and quantification of chemical reactions in a coastal aquifer to assess submarine groundwater discharge composition.

In coastal aquifers, two opposite but complementary processes occur: Seawater intrusion (SWI), which may salinize heavily exploited aquifers, and Submarine groundwater discharge (SGD) which transports oligo-elements to the sea. Aquifers are expected to be chemically reactive, both because they provide abundant surfaces to catalyze reactions and the mixing of very different Fresh Water (FW) and Sea Water (SW) promote numerous reactions. Characterizing and quantifying these reactions is essential to assess the quality and composition of both aquifer water, and SGD. Indeed, sampling SGD is difficult, so its composition is usually uncertain. We propose a reactive end-member mixing analysis (rEMMA) methodology based on principal component analysis (PCA) to (i) identify the sources of water and possible reactions occurring in the aquifer and (ii) quantify mixing ratios and the extent of chemical reactions. We applied rEMMA to the Argentona coastal aquifer located North of Barcelona that contains fluvial sediments of granitic origin and overlies weathered granite. The identification of end members (FW and SW) and the spatial distribution of their mixing ratios illustrate the application procedure. The extent of reactions and their spatial distribution allow us to distinguish reactions that occur as a result of mixing from those caused by sediment disequilibrium, which are relevant to recirculated saltwater SGD. The most important reaction is cation exchange, especially between Ca and Na, which promotes other reactions such as Gypsum and Fluorite precipitation. Iron and Manganese are mobilized in the SW portion but oxidized and precipitated in the mixing zone, so that Fe (up to 15 μEq/L) and Mn (up to 10 μEq/L) discharge is restricted to SW SGD. Nitrate is reduced in the mixing zone. The actual reaction amounts are site-specific, but the processes are not, which leads us to conjecture the importance of these reactions to understand the SGD discharge elsewhere.

Effects of coastal aquaculture on sediment organic matter: Assessed with multiple spectral and isotopic indices

Sediment organic matter (SOM) is important in the biogeochemical cycling of carbon, nutrients, and pollutants in the coastal environment, which is increasingly disturbed by aquaculture that is particularly intense in China. However, the identification of aquaculture signals in SOM is rather challenging in the complex coastal environment that receives materials from a variety of sources. This was studied in a typical culture area of shellfish and algae in SE China from July 2019 to October 2020, using a combination of elemental (OC, TN, N/C), isotopic (δ13C and δ15N), spectral (absorption spectroscopy and fluorescence EEMs-PARAFAC), and statistical analysis (principal component analysis, PCA). All indices of SOM quantity and several spectral indices for the SOM composition correlated significantly with grain size, with lower SOM quantity and higher autochthonous contribution in coarse sediments. The strong correlations between elemental and spectral indices suggested that optical analysis could provide valuable indices for assessing the quantity of bulk organic matter. The comparison of SOM indices between different zones and between different months showed an overall limited influence of shellfish and laver culture. This indicated the sustainability of these types of aquaculture that require no manual addition of feeds and thus are generally clean. The further applications of end-member mixing analysis using the IsoSource program and PCA were more sensitive, which identified the removal of SOM by shellfish in the growing season and the contribution from shellfish residuals after the harvest and the cultured laver at some locations. Overall, our results have implications for a better understanding of the biogeochemical processes and ecosystem sustainability in the coastal environment under intense aquaculture activities.

Unravelling groundwater and surface water sources in the Esteros del Iberá Wetland Area: An isotopic approach

In the Esteros del Iberá Wetland Area (EIWA, NE Argentina), the southern sector of the transboundary Guarani Aquifer System (SAG) is overlain by the Ramsar listed Iberá Wetlands and several rivers, that combined extend across 37,930 km2 and represent one of the largest freshwater systems on the South American continent. Previous hydrogeological studies encompassing the entire SAG proposed preferential discharge of groundwater of various origins and ages to the EIWA. In this study, a multi-tracer study using major ionic species, δ18O, δ2H and 222Rn was conducted in lagoons, rivers, wells, and boreholes in the EIWA to confirm if discharge from the transboundary SAG is contributing to the surface water system. End-member Mixing Analysis (EMMA) determined the existence of four main end-members: groundwater from the SAG, more saline groundwater from the deeper Pre-SAG, and two poorly mineralised end-members from shallow, Post-SAG. EMMA calculations clearly illustrated complex binary and ternary mixing patterns involving the four end-members and highlighted the role of geological structures, specifically regional steep faults, in controlling the mixing patterns. 222Rn activities allowed in-situ identification of preferential deep groundwater discharge into both surface waters and shallow groundwaters. These findings provide strong evidence for the widespread existence of upward flows along major faults in this sector of the SAG, inducing complex mixing flow patterns and explaining the presence of old groundwater in shallow aquifers. Mapping the sources of water and the hydrological interactions are relevant for improving water balance estimates and develop management policies towards the preservation of these wetlands.