The roles of dissolved organic matter (DOM) in microbial processes and nutrient cycles depend on its composition, which requires detailed measurements and analyses. We introduce a package for R, called staRdom (“spectroscopic analysis of DOM in R”), to analyze DOM spectroscopic data (absorbance and fluorescence), which is key to deliver fast insight into DOM composition of many samples. staRdom provides functions that standardize data preparation and analysis of spectroscopic data and are inspired by practical work. The user can perform blank subtraction, dilution correction, Raman normalization, scatter removal and interpolation, and fluorescence normalization. The software performs parallel factor analysis (PARAFAC) of excitation–emission matrices (EEMs), including peak picking of EEMs, and calculates fluorescence indices, absorbance indices, and absorbance slope indices from EEMs and absorbance spectra. A comparison between PARAFAC solutions by staRdom in R compared with drEEM in MATLAB showed nearly identical solutions for most datasets, although different convergence criteria are needed to obtain similar results and interpolation of missing data is important when working with staRdom. In conclusion, staRdom offers the opportunity for standardized multivariate decomposition of spectroscopic data without requiring software licensing fees and presuming only basic R knowledge.
13 March 2023 in Environmental Science & Technology
High-frequency water quality measurements in streams and rivers have expanded in scope and sophistication during the last two decades. Existing technology allows in situ automated measurements of water quality constituents, including both solutes and particulates, at unprecedented frequencies from seconds to subdaily sampling intervals. This detailed chemical information can be combined with measurements of hydrological and biogeochemical processes, bringing new insights into the sources, transport pathways, and transformation processes of solutes and particulates in complex catchments and along the aquatic continuum. Here, we summarize established and emerging high-frequency water quality technologies, outline key high-frequency hydrochemical data sets, and review scientific advances in key focus areas enabled by the rapid development of high-frequency water quality measurements in streams and rivers. Finally, we discuss future directions and challenges for using high-frequency water quality measurements to bridge scientific and management gaps by promoting a holistic understanding of freshwater systems and catchment status, health, and function.
Agriculture delivers significant amounts of dissolved organic matter (DOM) to streams, thereby changing the composition and biodegradability of the aquatic DOM. This study focuses on the interactive effects of DOM quality and biofilm composition on the degradation of DOM in a laboratory flume experiment. Half of the flumes were exposed to light to stimulate algal growth, the other half was shaded. Leachates of deciduous leaves, maize leaves, and cow dung were added to the flumes in a single pulse and changes of DOC (dissolved organic carbon) and nutrient concentrations, DOM composition (absorbance and fluorescence data), chlorophyll-a concentrations, bacterial abundances, and enzymatic activities were recorded over a week. DOM was taken up with rates of 50, 109, and 136 µg DOC L−1 h−1 for dung, leaf, and maize leachates, respectively, in the light flumes and 37, 80, and 170 µg DOC L−1 h−1 in the dark flumes. DOC uptake correlated strongly with initial SRP (soluble reactive phosphorus) and DOC concentrations, but barely with DOM components and indices. Algae mostly stimulated the microbial DOC uptake, but the effects differed among differently aged biofilms. We developed a conceptual model of intrinsic (DOM quality) and external (environmental) controlling factors on DOM degradation, with the microbial community acting as biotic filter.
Besides the importance of dissolved organic matter (DOM) in soil biogeochemical processes, there is still a debate on how agricultural intensification affects the leaching of terrestrial DOM into adjacent aquatic ecosystems. In order to close this linkage, we conducted a short-term (45 day) lysimeter experiment with silt loam and sandy loam undisturbed/intact soil cores. Mineral (calcium ammonium nitrate) or organic (pig slurry) fertilizer was applied on the soil surface with a concentration equivalent to 130 kg N ha−1. On average, amounts of leached DOC over 45 days ranged between 20.4 mg (silt loam, mineral fertilizer) and 34.4 mg (sandy loam, organic fertilizer). Both, mineral and organic fertilization of a silt loam reduced concentration of dissolved organic carbon (DOC) in the leachate and shifted its composition towards a microbial-like signature (BIX) with a higher aromaticity (Fi) and a lower molecular size (E2:E3). However, in sandy loam only mineral fertilization affected organic matter leaching. There, lowered DOC concentrations with a smaller molecular size (E2:E3) could be detected. The overall effect of fertilization on DOC leaching and DOM composition was interrelated with soil texture and limited to first 12 days. Our results highlight the need for management measures, which prevent or reduce fast flow paths leading soil water directly into aquatic systems, such as surface flow, fast subsurface flow, or drainage water.
Uptake and release patterns of dissolved organic matter (DOM) compounds and co-transported nutrients are entangled, and the current literature does not provide a consistent picture of the interactions between the retention processes of DOM fractions. We performed plateau addition experiments with five different complex DOM leachates in a small experimental stream impacted by diffuse agricultural pollution. The study used a wide range of DOM qualities by including leachates of cow dung, pig dung, corn leaves, leaves from trees, and whole nettle plants. We measured changes in nutrient and dissolved organic carbon (DOC) concentrations along the stream course and determined DOM fractions by fluorescence measurements and parallel factor (PARAFAC) decomposition. To assess the influences of hydrological transport processes, we used a 1D hydrodynamic model. We developed a non-linear Bayesian approach based on the nutrient spiralling concept, which we named the “interactions in nutrient spirals using Bayesian regression” (INSBIRE) approach. This approach can disentangle complex interactions of biotic and abiotic drivers of reactive solutes' uptake in multi-component DOM sources. It can show the variability of the uptake velocities and quantify their uncertainty distributions. Furthermore, previous knowledge of nutrient spiralling can be included in the model using prior probability distributions. We used INSBIRE to assess interactions of compound-specific DOM and nutrient spiralling metrics in our experiment. Bulk DOC uptake varied among sources, showing decreasing uptake velocities in the following order: corn > pig dung > leaves > nettles > cow dung. We found no correlations between bulk DOC uptake and the amounts of protein-like compounds or co-leached soluble reactive phosphorus (SRP). The fastest uptake was observed for SRP and the tryptophan-like component, while the other DOM components' uptake velocities more or less resembled that of the bulk DOC. Almost all DOM components showed a negative relationship between uptake and concentration, known as efficiency loss. Furthermore, we observed a few negative and (weak) positive interactions between the uptake and the concentration of different components, such as a decreased uptake of protein-like compounds at high concentrations of a high-molecular-weight humic-like compound. We also found an influence of the wetted width on the uptake of SRP and a microbially derived humic substance, which indicates the importance of the sediment–water interface for P and humic C cycling in the studied stream. Overall, we show that bulk DOC is a weak predictor of DOC uptake behaviour for complex DOM leachates. Individual DOM compound uptake, including co-leached nutrients, is controlled by both internal (quality-related) and external (environmental) factors within the same aquatic ecosystem. We conclude that the cycling of different C fractions and their mutual interaction with N and P uptake in streams is a complex, non-linear problem, which can only be assessed with advanced non-linear approaches, such as the presented INSBIRE approach.