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[1] End member mixing analysis (EMMA) is a commonly applied method to identify and quantify the dominant runoff producing sources of water. It employs tracers to determine the dimensionality of the hydrologic system. Many EMMA studies have been conducted using two to six tracers, with some of the main tracers being Ca, Na, Cl À , water isotopes, and alkalinity. Few studies use larger tracer sets including minor trace elements such as Li, Rb, Sr, and Ba. None of the studies has addressed the question of the tracer set size and composition, despite the fact that these determine which and how many end members (EM) will be identified. We examine how tracer set size and composition affects the conceptual model that results from an EMMA. We developed an automatic procedure that conducts EMMA while iteratively changing tracer set size and composition. We used a set of 14 tracers and 9 EMs. The validity of the resulting conceptual models was investigated under the aspects of dimensionality, EM combinations, and contributions to stream water. From the 16,369 possibilities, 23 delivered plausible results. The resulting conceptual models are highly sensitive to the tracer set size and composition. The moderate reproducibility of EM contributions indicates a still missing EM. It also emphasizes that the major elements are not always the most useful tracers and that larger tracer sets have an enhanced capacity to avoid false conclusions about catchment functioning. The presented approach produces results that may not be apparent from the traditional approach and it is a first step to add the idea of statistical significance to the EMMA approach.

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Organic carbon (OC) sequestration in degraded semi-arid environments by improved soil management is assumed to contribute substantially to climate change mitigation. However, information about the soil organic carbon (SOC) sequestration potential in steppe soils and their current saturation status remains unknown. In this study, we estimated the OC storage capacity of semi-arid grassland soils on the basis of remote, natural steppe fragments in northern China. Based on the maximum OC saturation of silt and clay particles <20 μm, OC sequestration potentials of degraded steppe soils (grazing land, arable land, eroded areas) were estimated. The analysis of natural grassland soils revealed a strong linear regression between the proportion of the fine fraction and its OC content, confirming the importance of silt and clay particles for OC stabilization in steppe soils. This relationship was similar to derived regressions in temperate and tropical soils but on a lower level, probably due to a lower C input and different clay mineralogy. In relation to the estimated OC storage capacity, degraded steppe soils showed a high OC saturation of 78-85% despite massive SOC losses due to unsustainable land use. As a result, the potential of degraded grassland soils to sequester additional OC was generally low. This can be related to a relatively high contribution of labile SOC, which is preferentially lost in the course of soil degradation. Moreover, wind erosion leads to substantial loss of silt and clay particles and consequently results in a direct loss of the ability to stabilize additional OC. Our findings indicate that the SOC loss in semi-arid environments induced by intensive land use is largely irreversible. Observed SOC increases after improved land management mainly result in an accumulation of labile SOC prone to land use/climate changes and therefore cannot be regarded as contribution to long-term OC sequestration.

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Abstract:There exists a growing need to improve our understanding of catchment processes on larger scales. This need is especially enhanced in rapidly developing countries such as China where the turnover of traditionally used land to urbanized and industrialized areas influences water resources. In this study, we chose a multi-tracer approach in a large, ungauged basin in Inner Mongolia to elucidate the processes that generate stream flow. We applied end member mixing analysis (EMMA) to identify and quantify the major runoff generating sources in a three end member system. Stream water and a set of eight possible end members were sampled throughout three consecutive vegetation periods. Samples were analysed with an inductively coupled plasma-mass spectrometry (ICP-MS) and an ion chromatograph (IC) for a suite of 33 solutes including 24 cations and 7 anions. We determined that seven tracers exhibited conservative behaviour, they were Li, Rb, Sr, Na, Mg, Cl and electrical conductivity (EC). Stable water isotopes (υD and υ 18 O) highlight differences between the end members. Our results indicate strong interannual variability of end member composition and contribution between the 3 years. We were able to identify shallow groundwater aquifers as important runoff generating sources in some years and deeper groundwater aquifers in other years which vary in rainfall and discharge. A shallow sand dune aquifer which covers a significant part of the area plays an important role in storing and contributing water to the river. Our results also suggest that the major runoff generating source in the dryer year has not been identified yet. Our results prompt us to focus future work on understanding interannual changes in end member contribution especially in semi-arid regions.

Combinations of runoff characteristics are commonly used to represent distinct conceptual models of stormflow generation. In this study, three runoff characteristics: hydrograph response, time source of runoff water, and flow path are used to classify catchments. Published data from the scientific literature are used to provide evidence from small, forested catchments. Each catchment was assigned to one of the eight conceptual models, depending on the combination of quick/slow response, old/new water, and overland/ subsurface flow. A standard procedure was developed to objectively diagnose the predominant conceptual model of stormflow generation for each catchment and assess its temporal and spatial support. The literature survey yielded 42 catchments, of which 30 catchments provide a complete set of qualitative runoff characteristics resulting in one of the eight conceptual models. The majority of these catchments classify as subsurface flow path dominated. No catchments were found for conceptual models representing combinations of quick response-new water-subsurface flow (SSF), slow-new-SSF, slow-old-overland flow (OF) nor new-slow-OF. Of the 30 qualitatively classified catchments, 24 provide a complete set of quantitative measures. In summary, the field support is strong for 19 subsurface-dominated catchments and is weak for 5 surface flow path dominated catchments (six catchments had insufficient quantitative data). Two alternative explanations exist for the imbalance of field support between the two flow path classes: (1) the selection of research catchments in past field studies was mainly to explain quick hydrograph response in subsurface dominated catchments; (2) catchments with prevailing subsurface flow paths are more common in nature. We conclude that the selection of research catchments needs to cover a wider variety of environmental conditions which should lead to a broader, and more widely applicable, spectrum of resulting conceptual models and process mechanisms. This is a prerequisite in studies where catchment organization and similarity approaches are used to develop catchment classification systems in order to regionalize stormflow.

Stormflow generation in headwater catchments dominated by subsurface flow has been studied extensively, yet catchments dominated by surface flow have received less attention. We addressed this by testing whether stormflow chemistry is controlled by either (a) the event‐water signature of overland flow, or (b) the pre‐event water signature of return flow. We used a high‐resolution hydrochemical data set of stormflow and end‐members of multiple storms in an end‐member mixing analysis to determine the number of end‐members needed to explain stormflow, characterize and identify potential end‐members, calculate their contributions to stormflow, and develop a conceptual model of stormflow. The arrangement and relative positioning of end‐members in stormflow mixing space suggest that saturation excess overland flow (26–48%) and return flow from two different subsurface storage pools (17–53%) are both similarly important for stormflow. These results suggest that pipes and fractures are important flow paths to rapidly release stored water and highlight the value of within‐event resolution hydrochemical data to assess the full range and dynamics of flow paths.