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Abstract Environmental DNA (eDNA) has revolutionized ecological research, particularly for biodiversity assessment in various environments, most notably aquatic media. Environmental DNA analysis allows for non‐invasive and rapid species detection across multiple taxonomic groups within a single sample, making it especially useful for identifying rare or invasive species. Due to dynamic hydrological processes, eDNA samples from running waters may represent biodiversity from broad contributing areas, which is convenient from a biomonitoring perspective but also challenging, as hydrological knowledge is required for meaningful biological interpretation. Hydrologists could also benefit from eDNA to address unsolved questions, particularly concerning water movement through catchments. While naturally occurring abiotic tracers have advanced our understanding of water age distribution in catchments, for example, current geochemical tracers cannot fully elucidate the timing and flow paths of water through landscapes. Conversely, biological tracers, owing to their immense diversity and interactions with the environment, could offer more detailed information on the sources and flow paths of water to the stream. The informational capacity of eDNA as a tracer, however, is determined by the ability to interpret the complex biological heterogeneity at a study site, which arguably requires both biological and hydrological expertise. As eDNA data has become increasingly available as part of biomonitoring campaigns, we argue that accompanying eDNA surveys with hydrological observations could enhance our understanding of both biological and hydrological processes; we identify opportunities, challenges, and needs for further interdisciplinary collaboration; and we highlight eDNA's potential as a bridge between hydrology and biology, which could foster both domains. This article is categorized under:Science of Water > Hydrological ProcessesScience of Water > MethodsWater and Life > Nature of Freshwater Ecosystems 

Abstract Stable isotope ratios of H (δ²H), O (δ¹⁸O), and C (δ¹³C) are linked to key biogeochemical processes of the water and carbon cycles; however, the degree to which isotope-associated processes are reflected in macroscale ecosystem flux observations remains unquantified. Here through formal information assessment, new measurements ofδ¹³C of net ecosystem exchange (NEE) as well asδ²H andδ¹⁸O of latent heat (LH) fluxes across the United States National Ecological Observation Network (NEON) are used to determine conditions under which isotope measurements are informative of environmental exchanges. We find all three isotopic datasets individually contain comparable amounts of information aboutNEEandLHfluxes as wind speed observations. Such information from isotope measurements, however, is largely unique. Generally,δ¹³C provides more information aboutLHas aridity increases or mean annual precipitation decreases.δ²H provides more information aboutLHas temperatures or mean annual precipitation decreases, and also provides more information aboutNEEas temperatures decrease. Overall, we show that the stable isotope datasets collected by NEON contribute non-trivial amounts of new information about bulk environmental fluxes useful for interpreting biogeochemical and ecohydrological processes at landscape scales. However, the utility of this new information varies with environmental conditions at continental scales. This study provides an approach for quantifying the value adding non-traditional sensing approaches to environmental monitoring sites and the patterns identified here are expected to aid in modeling and data interpretation efforts focused on constraining carbon and water cycles’ mechanisms. 

Abstract Field measurements of hydrologic tracers indicate varying magnitudes of geochemical separation between subsurface pore waters. The potential for conventional soil physics alone to explain isotopic differences between preferential flow and tightly-bound water remains unclear. Here, we explore physical drivers of isotopic separations using 650 different model configurations of soil, climate, and mobile/immobile soil-water domain characteristics, without confounding fractionation or plant uptake effects. We find simulations with coarser soils and less precipitation led to reduced separation between pore spaces and drainage. Amplified separations are found with larger immobile domains and, to a lesser extent, higher mobile-immobile transfer rates. Nonetheless, isotopic separations remained small (<4‰ for δ²H) across simulations, indicating that contrasting transport dynamics generate limited geochemical differences. Therefore, conventional soil physics alone are unlikely to explain large ecohydrological separations observed elsewhere, and further efforts aimed at reducing methodological artifacts, refining understanding of fractionation processes, and investigating new physiochemical mechanisms are needed. 

A frequent goal of chemical forensic analyses is to select a panel of diagnostic chemical featurescolloquially termed a chemical fingerprintthat can predict the presence of a source in a novel sample. However, most of the developed chemical fingerprinting workflows are qualitative in nature. Herein, we report on a quantitative machine learning workflow. Grab samples (n = 51) were collected from five chemical sources, including agricultural runoff, headwaters, livestock manure, (sub)urban runoff, and municipal wastewater. Support vector classification was used to select the top 10, 25, 50, and 100 chemical features that best discriminate each source from all others. The cross-validation balanced accuracy was 92− 100% for all sources (n = 1,000 iterations). When screening for diagnostic features from each source in samples collected from four local creeks, presence probabilities were low for all sources, except for wastewater at two downstream locations in a single creek. Upon closer investigation, a wastewater treatment facility was located ∼3 km upstream of the nearest sample location. In addition, using simulated in silico mixtures, the workflow can distinguish presence and absence of some sources at 10,000-fold dilutions. These results strongly suggest that this workflow can select diagnostic subsets of chemical features that can be used to quantitatively predict the presence/absence of various sources at trace levels in the environment. 

Abstract While yearly budgets of CO₂flux (F_c) and evapotranspiration (ET) above vegetation can be readily obtained from eddy‐covariance measurements, the separate quantification of their soil (respiration and evaporation) and canopy (photosynthesis and transpiration) components remains an elusive yet critical research objective. In this work, we investigate four methods to partition observed total fluxes into soil and plant sources: two new and two existing approaches that are based solely on analysis of conventional high frequency eddy‐covariance (EC) data. The physical validity of the assumptions of all four methods, as well as their performance under different scenarios, are tested with the aid of large‐eddy simulations, which are used to replicate eddy‐covariance field experiments. Our results indicate that canopies with large, exposed soil patches increase the mixing and correlation of scalars; this negatively impacts the performance of the partitioning methods, all of which require some degree of uncorrelatedness between CO₂and water vapor. In addition, best performances for all partitioning methods were found when all four flux components are non‐negligible, and measurements are collected close to the canopy top. Methods relying on the water‐use efficiency (W) perform better whenWis known a priori, but are shown to be very sensitive to uncertainties in this input variable especially when canopy fluxes dominate. We conclude by showing how the correlation coefficient between CO₂and water vapor can be used to infer the reliability of differentWparameterizations. 

Abstract The timescales associated with precipitation moving through watersheds reveal processes that are critical to understanding many hydrologic systems. Measurements of environmental stable water isotope ratios (δ²H and δ¹⁸O) have been used as tracers to study hydrologic timescales by examining how long it takes for incoming precipitation tracers become stream discharge, yet limited measurements both spatially and temporally have bounded macroscale evaluations so far. In this observation driven study across North American biomes within the National Ecological Observation Network (NEON), we examined δ¹⁸O and δ²H stable water isotope in precipitation (δP) and stream water (δQ) at 26 co‐located sites. With an average 54 precipitation samples and 139 stream water samples per site collected over 2014–2022, assessment of local meteoric water lines and local stream water lines showed geographic variation across North America. Taking the ratio of estimated seasonal amplitudes of δP and δQ to calculate young water fractions (F_yw), showed aF_ywrange from 1% to 93% with most sites havingF_ywbelow 20%. Calculated mean transit times (MTT) based on a gamma convolution model showed a MTT range from 0.10 to 13.2 years, with half of the sites having MTT estimates lower than 2 years. Significant correlations were found between theF_ywand watershed area, longest flow length, and the longest flow length/slope. Significant correlations were found between MTT and site latitude, longitude, slope, clay fraction, temperature, precipitation magnitude, and precipitation frequency. The significant correlations between water timescale metrics and the environmental characteristics we report share some similarities with those reported in prior studies, demonstrating that these quantities are primarily driven by site or area specific factors. The analysis of isotope data presented here provides important constraints on isotope variation in North American biomes and the timescales of water movement through NEON study sites. 

Abstract Sampling intervals of precipitation geochemistry measurements are often coarser than those required by fine-scale hydrometeorological models. This study presents a statistical method to temporally downscale geochemical tracer signals in precipitation so that they can be used in high-resolution, tracer-enabled applications. In this method, we separated the deterministic component of the time series and the remaining daily stochastic component, which was approximated by a conditional multivariate Gaussian distribution. Specifically, statistics of the stochastic component could be explained from coarser data using a newly identified power-law decay function, which relates data aggregation intervals to changes in tracer concentration variance and correlations with precipitation amounts. These statistics were used within a copula framework to generate synthetic tracer values from the deterministic and stochastic time series components based on daily precipitation amounts. The method was evaluated at 27 sites located worldwide using daily precipitation isotope ratios, which were aggregated in time to provide low resolution testing datasets with known daily values. At each site, the downscaling method was applied on weekly, biweekly and monthly aggregated series to yield an ensemble of daily tracer realizations. Daily tracer concentrations downscaled from a biweekly series had average (+/- standard deviation) absolute errors of 1.69‰ (1.61‰) for δ 2 H and 0.23‰ (0.24‰) for δ 18 O relative to observations. The results suggest coarsely sampled precipitation tracers can be accurately downscaled to daily values. This method may be extended to other geochemical tracers in order to generate downscaled datasets needed to drive complex, fine-scale models of hydrometeorological processes. 

Abstract The National Ecological Observatory Network (NEON) provides open-access measurements of stable isotope ratios in atmospheric water vapor (δ²H, δ¹⁸O) and carbon dioxide (δ¹³C) at different tower heights, as well as aggregated biweekly precipitation samples (δ²H, δ¹⁸O) across the United States. These measurements were used to create the NEON Daily Isotopic Composition of Environmental Exchanges (NEON-DICEE) dataset estimating precipitation (P; δ²H, δ¹⁸O), evapotranspiration (ET; δ²H, δ¹⁸O), and net ecosystem exchange (NEE; δ¹³C) isotope ratios. Statistically downscaled precipitation datasets were generated to be consistent with the estimated covariance between isotope ratios and precipitation amounts at daily time scales. Isotope ratios in ET and NEE fluxes were estimated using a mixing-model approach with calibrated NEON tower measurements. NEON-DICEE is publicly available on HydroShare and can be reproduced or modified to fit user specific applications or include additional NEON data records as they become available. The NEON-DICEE dataset can facilitate understanding of terrestrial ecosystem processes through their incorporation into environmental investigations that require daily δ²H, δ¹⁸O, and δ¹³C flux data.