Studying catchment storm response using event- and pre-event-water volumes as fractions of precipitation rather than discharge

Catchment response to precipitation is often investigated using two-component isotope-based hydrograph separation, which quantifies the contribution of precipitation (i.e., event water Qe) or water from storage (i.e., pre-event water Qpe) to total discharge (Q) during storm events. In order to better understand streamflow-generating mechanisms, two-component hydrograph separation studies often seek to relate the event-water fraction Qe∕Q to storm characteristics or antecedent wetness conditions. However, these relationships may be obscured because the same factors that influence Qe also necessarily influence total discharge Q as well. Here we propose that the fractions of event water and pre-event water relative to total precipitation (Qe∕P and Qpe∕P), instead of total discharge, provide useful alternative tools for studying catchment storm responses. These two quantities separate the well-known runoff coefficient (Q∕P, i.e., the ratio between total discharge and precipitation volumes over the event timescale) into its contributions from event water and pre-event water. Whereas the runoff coefficient Q∕P quantifies how strongly precipitation inputs affect streamflow, the fractions Qe∕P and Qpe∕P track the sources of this streamflow response.We use high-frequency measurements of stable water isotopes for 24 storm events at a steep headwater catchment (Erlenbach, central Switzerland) to compare the storm-to-storm variations in Qe∕Q, Qe∕P and Qpe∕P. Our analysis explores how storm characteristics and antecedent wetness conditions affect the mobilization of event water and pre-event water at the catchment scale. Isotopic hydrograph separation shows that catchment outflow was typically dominated by pre-event water, although event water exceeded 50&thinsp;% of discharge for several storms. No clear relationships were found linking either storm characteristics or antecedent wetness conditions with the volumes of event water or pre-event water (Qe, Qpe), or with event water as a fraction of discharge (Qe∕Q), beyond the unsurprising correlation of larger storms with greater Qe and greater total Q. By contrast, event water as a fraction of precipitation (Qe∕P) was strongly correlated with storm volume and intensity but not with antecedent wetness, implying that the volume of event water that is transmitted to streamflow increases more than proportionally with storm size under both wet and dry conditions. Conversely, pre-event water as a fraction of precipitation (Qpe∕P) was strongly correlated with all measures of antecedent wetness but not with storm characteristics, implying that wet conditions primarily facilitate the mobilization of old (pre-event) water, rather than the fast transmission of new (event) water to streamflow, even at a catchment where runoff coefficients can be large.Thus, expressing event- and pre-event-water volumes as fractions of precipitation rather than discharge was more insightful for investigating the Erlenbach catchment's hydrological behaviour. If Qe∕P and Qpe∕P exhibit similar relationships with storm characteristics and antecedent wetness conditions in other catchments, we suggest that these patterns may potentially be useful as diagnostic fingerprints of catchment storm response.</p

Sensitivity of young water fractions to hydro-climatic forcing and landscape properties across 22 Swiss catchments

The young water fraction Fyw, defined as the proportion of catchment outflow younger than approximately 2–3 months, can be estimated directly from the amplitudes of seasonal cycles of stable water isotopes in precipitation and streamflow. Thus, Fyw may be a useful metric in catchment inter-comparison studies that investigate landscape and hydro-climatic controls on streamflow generation. Here, we explore how Fyw varies with catchment characteristics and climatic forcing, using an extensive isotope data set from 22 small- to medium-sized (0.7–351&thinsp;km2) Swiss catchments. We find that flow-weighting the tracer concentrations in streamwater resulted in roughly 26&thinsp;% larger young water fractions compared to the corresponding unweighted values, reflecting the fact that young water fractions tend to be larger when catchments are wet and discharge is correspondingly higher. However, flow-weighted and unweighted young water fractions are strongly correlated with each other among the catchments. They also correlate with terrain, soil, and land-use indices, as well as with mean precipitation and measures of hydrologic response. Within individual catchments, young water fractions increase with discharge, indicating an increase in the proportional contribution of faster flow paths at higher flows. We present a new method to quantify the discharge sensitivity of Fyw, which we estimate as the linear slope of the relationship between the young water fraction and flow. Among the 22 catchments, discharge sensitivities of Fyw are highly variable and only weakly correlated with Fyw itself, implying that these two measures reflect catchment behaviour differently. Based on strong correlations between the discharge sensitivity of Fyw and several catchment characteristics, we suggest that low discharge sensitivities imply greater persistence in the proportions of fast and slow runoff flow paths as catchment wetness changes. In contrast, high discharge sensitivities imply the activation of different dominant flow paths during precipitation events, such as when subsurface water tables rise into more permeable layers and/or the river network expands further into the landscape.</p

Technical note: Two-component electrical-conductivity-based hydrograph separation employing an exponential mixing model (EXPECT) provides reliable high-temporal-resolution young water fraction estimates in three small Swiss catchments

The young water fraction represents the portion of water molecules in a stream that have entered the catchment relatively recently, typically within 2–3 months. It can be reliably estimated in spatially heterogeneous and nonstationary catchments from the amplitude ratio of seasonal isotope (δ18O or δ2H) cycles of stream water and precipitation, respectively. Past studies have found that young water fractions increase with discharge (Q), thus reflecting the higher direct runoff under wetter catchment conditions. The rate of increase in the young water fraction with increasing Q, defined as the discharge sensitivity of the young water fraction (Sd*), can be useful for describing and comparing catchments' hydrological behaviour. However, the existing method for estimating Sd*, which only uses biweekly isotope data, can return highly uncertain and unreliable Sd* when stream water isotope data are sparse and do not capture the entire flow regime. Indeed, the information provided by isotope data depends on when the respective sample was taken. Accordingly, the low sampling frequency results in information gaps that could potentially be filled by using additional tracers sampled at a higher temporal resolution. By utilizing high-temporal-resolution and cost-effective electrical conductivity (EC) measurements, along with information obtainable from seasonal isotope cycles in stream water and precipitation, we develop a new method that can estimate the young water fraction at the same resolution as EC and Q measurements. These high-resolution estimates allow for improvements in the estimates of the Sd*. Our so-called EXPECT (Electrical-Conductivity-based hydrograph separaTion employing an EXPonential mixing model) method is built upon the following three key assumptions: We construct a mixing relationship consisting of an exponential decay of stream water EC with increasing young water fraction. This has been obtained based on the relationship between flow-specific young water fractions and EC. We assume that the two-component EC-based hydrograph separation technique, using the above-mentioned exponential mixing model, can be used for a time-source partitioning of stream water into young (transit times &lt; 2–3 months) and old (transit times &gt; 2–3 months) water. We assume that the EC value of the young water endmember (ECyw) is lower than that of the old water endmember (ECow). Selecting reliable values from measurements of ECyw and ECow to perform this unconventional EC-based hydrograph separation is challenging, but the combination of information derived from the two tracers allows for the estimation of endmembers' values. The two endmembers have been calibrated by constraining the unweighted and flow-weighted average young water fractions obtained with the EC-based hydrograph separation to be equal to the corresponding quantities derived from the seasonal isotope cycles. We test the EXPECT method in three small experimental catchments in the Swiss Alptal Valley using two different temporal resolutions of Q and EC data: sampling resolution (i.e. we only consider Q and EC measurements during dates of isotope sampling) and daily resolution. The EXPECT method has provided reliable young water fraction estimates at both temporal resolutions, from which a more accurate discharge sensitivity of the young water fraction (SdEXP) could be determined compared with the existing approach. Also, the method provided new information on ECyw and ECow, yielding calibrated values that fall outside the range of measured EC values. This suggests that stream water is always a mixture of young and old water, even under very high or very low wetness conditions. The calibrated endmembers revealed a good agreement with both endmembers obtained from an independent method and EC measurements from groundwater wells. For proper use of the EXPECT method, we have highlighted the limitations of EC as a tracer, identified certain catchment characteristics that may constrain the reliability of the current method and provided recommendations about its adaptation for future applications in catchments other than those investigated in this study.</p

Ideas and perspectives : Tracing terrestrial ecosystem water fluxes using hydrogen and oxygen stable isotopes – challenges and opportunities from an interdisciplinary perspective

The authors thank Marialaura Bancheri, Michele Bottazzi, Roman Cibulka, Massimo Esposito, Alba Gallo, Cesar D. Jimenez-Rodriguez, Angelika Kuebert, Ruth Magh, Stefania Mambelli, Alessia Nannoni, Paolo Nasta, Vladimir Rosko, Andrea Rücker, Noelia Saavedra Berlanga, Martin Šanda, and Anna Scaini for their contributions during the discussion at the workshop “Isotope-based studies of water partitioning and plant–soil interactions in forested and agricultural environments”. The authors also thank “Villa Montepaldi” and the University of Florence for the access to the workshop location, and the municipality of San Casciano in Val di Pesa for logistical support. The authors thank the Department of Innovation, Research and University of the Autonomous Province of Bozen/Bolzano for covering the Open Access publication costs. Last, but not least, the authors wish to thank Matthias Sprenger, Stephen Good, and J. Renée Brooks, as well as the Editor David R. Bowling, whose constructive reviews greatly improved this manuscript.Peer reviewedPublisher PD

Metropolis simulations of Met-Enkephalin with solvent-accessible area parameterizations

We investigate the solvent-accessible area method by means of Metropolis simulations of the brain peptide Met-Enkephalin at 300$K$. For the energy function ECEPP/2 nine atomic solvation parameter (ASP) sets are studied. The simulations are compared with one another, with simulations with a distance dependent electrostatic permittivity $\epsilon (r)$, and with vacuum simulations ($\epsilon =2$). Parallel tempering and the biased Metropolis techniques RM$_1$ are employed and their performance is evaluated. The measured observables include energy and dihedral probability densities (pds), integrated autocorrelation times, and acceptance rates. Two of the ASP sets turn out to be unsuitable for these simulations. For all other systems selected configurations are minimized in search of the global energy minima, which are found for the vacuum and the $\epsilon(r)$ system, but for none of the ASP models. Other observables show a remarkable dependence on the ASPs. In particular, we find three ASP sets for which the autocorrelations at 300$$K are considerably smaller than for vacuum simulations.Comment: 10 pages and 8 figure

Citizen science’s transformative impact on science, citizen empowerment and socio-political processes

Citizen science (CS) can foster transformative impact for science, citizen empowerment and socio-political processes. To unleash this impact, a clearer understanding of its current status and challenges for its development is needed. Using quantitative indicators developed in a collaborative stakeholder process, our study provides a comprehensive overview of the current status of CS in Germany, Austria and Switzerland. Our online survey with 340 responses focused on CS impact through (1) scientific practices, (2) participant learning and empowerment, and (3) socio-political processes. With regard to scientific impact, we found that data quality control is an established component of CS practice, while publication of CS data and results has not yet been achieved by all project coordinators (55%). Key benefits for citizen scientists were the experience of collective impact (“making a difference together with others”) as well as gaining new knowledge. For the citizen scientists’ learning outcomes, different forms of social learning, such as systematic feedback or personal mentoring, were essential. While the majority of respondents attributed an important value to CS for decision-making, only few were confident that CS data were indeed utilized as evidence by decision-makers. Based on these results, we recommend (1) that project coordinators and researchers strengthen scientific impact by fostering data management and publications, (2) that project coordinators and citizen scientists enhance participant impact by promoting social learning opportunities and (3) that project initiators and CS networks foster socio-political impact through early engagement with decision-makers and alignment with ongoing policy processes. In this way, CS can evolve its transformative impact

Twenty-three unsolved problems in hydrology (UPH) – a community perspective

This paper is the outcome of a community initiative to identify major unsolved scientific problems in hydrology motivated by a need for stronger harmonisation of research efforts. The procedure involved a public consultation through on-line media, followed by two workshops through which a large number of potential science questions were collated, prioritised, and synthesised. In spite of the diversity of the participants (230 scientists in total), the process revealed much about community priorities and the state of our science: a preference for continuity in research questions rather than radical departures or redirections from past and current work. Questions remain focussed on process-based understanding of hydrological variability and causality at all space and time scales. Increased attention to environmental change drives a new emphasis on understanding how change propagates across interfaces within the hydrological system and across disciplinary boundaries. In particular, the expansion of the human footprint raises a new set of questions related to human interactions with nature and water cycle feedbacks in the context of complex water management problems. We hope that this reflection and synthesis of the 23 unsolved problems in hydrology will help guide research efforts for some years to come

A lab in the field: high-frequency analysis of water quality and stable isotopes in stream water and precipitation

High-frequency measurements of solutes and isotopes (18O and 2H) in rainfall and streamflow can shed important light on catchment flow pathways and travel times, but the workload and sample storage artifacts involved in collecting, transporting, and analyzing thousands of bottled samples severely constrain catchment studies in which conventional sampling methods are employed. However, recent developments towards more compact and robust analyzers have now made it possible to measure chemistry and water isotopes in the field at sub-hourly frequencies over extended periods. Here, we present laboratory and field tests of a membrane-vaporization continuous water sampler coupled to a cavity ring-down spectrometer for real-time measurements of δ18O and δ2H combined with a dual-channel ion chromatograph (IC) for the synchronous analysis of major cations and anions. The precision of the isotope analyzer was typically better than 0.03 ‰ for δ18O and 0.17 ‰ for δ2H in 10 min average readings taken at intervals of 30 min. Carryover effects were less than 1.2 % between isotopically contrasting water samples for 30 min sampling intervals, and instrument drift could be corrected through periodic analysis of secondary reference standards. The precision of the ion chromatograph was typically  ∼  0.1–1 ppm or better, with relative standard deviations of  ∼  1 % or better for most major ions in stream water, which is sufficient to detect subtle biogeochemical signals in catchment runoff. We installed the coupled isotope analyzer/IC system in an uninsulated hut next to a stream of a small catchment and analyzed stream water and precipitation samples every 30 min over 28 days. These high-frequency measurements facilitated a detailed comparison of event-water fractions via endmember mixing analysis with both chemical and isotope tracers. For two events with relatively dry antecedent moisture conditions, the event-water fractions were &lt; 21 % based on isotope tracers but were significantly overestimated (40 to 82 %) by the chemical tracers. These observations, coupled with the storm-to-storm patterns in precipitation isotope inputs and the associated stream water isotope response, led to a conceptual hypothesis for runoff generation in the catchment. Under this hypothesis, the pre-event water that is mobilized by precipitation events may, depending on antecedent moisture conditions, be significantly shallower, younger, and less mineralized than the deeper, older water that feeds baseflow and thus defines the pre-event endmember used in hydrograph separation. This proof-of-concept study illustrates the potential advantages of capturing isotopic and hydrochemical behavior at a high frequency over extended periods that span multiple hydrologic events

Technical note: An improved discharge sensitivity metric for young water fractions

Recent virtual and experimental investigations have shown that the young water fraction Fyw (i.e. the proportion of catchment outflow younger than circa 2–3 months) increases with discharge in most catchments. The discharge sensitivity of Fyw has been defined as the rate of increase in Fyw with increasing discharge (Q) and has been estimated by the linear regression slope between Fyw and Q, hereafter called DS(Q). The combined use of both metrics, Fyw and DS(Q), provides a promising method for catchment inter-comparison studies that seek to understand streamflow generation processes. Here we explore the discharge sensitivity of Fyw in the intensively sampled small Mediterranean research catchment Can Vila. Intensive sampling of high flows at Can Vila allows young water fractions to be estimated for the far upper tail of the flow frequency distribution. These young water fractions converge toward 1 at the highest flows, illustrating a conceptual limitation in the linear regression method for estimating DS(Q) as a metric of discharge sensitivity: Fyw cannot grow with discharge indefinitely, since the fraction of young water in discharge can never be larger than 1. Here we propose to quantify discharge sensitivity by the parameter of an exponential-type equation that expresses how Fyw varies with discharge. The exponential parameter (Sd) approximates DS(Q) at moderate discharges where Fyw is well below 1; however, the exponential equation and its discharge sensitivity metric better capture the non-linear relationship between Fyw and Q and are robust with respect to changes in the range of sampled discharges, allowing comparisons between catchments with strongly contrasting flow regimes.This research was supported by the projects TransHyMed (CGL2016-75957-R AEI/FEDER, UE) and Drought-CH (National Research Programme NRP 61 by the Swiss National Science Foundation). We are grateful to Carles Cayuela, Gisela Bertràn, Maria Roig-Planasdemunt and Elisenda Sánchez for their support during field work at the Can Vila catchment and to Michael Eaude for his English style improvements. Financial support. This research has been supported by the Ministerio de Ciencia, Innovación y Universidades (Spain) (grant no. CGL2016‐75957‐R AEI/FEDER, UE) and the Swiss National Science Foundation (Switzerland) (National Research Programme NRP 61).Peer reviewe

Contact potential and heterogenous catalysis

It is shown that in the case of metals connected by a first order conductor the decomposition of formic acid is less at the element of lower work function while it is more at the element of higher work function. The metals used were Ni, Cd, Zn. The results correspond to the investigations of other authors 1 who showed that the activation energy on alloys depends on how far the concentration of electrons is from full saturation of the lattice type. This effect is explicable in terms of the development of a contact potential, the conditions in the case of metals being similar to those in the case of alloy