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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 usedmore »to quantitatively predict the presence/absence of various sources at trace levels in the environment.« less

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.

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‰) formore »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.« less