Search

To improve water quality and reduce instream erosion, floodplain remediation along agricultural streams can provide multiple ecosystem services through biogeochemical and fluvial processes. During floodplain inundation, longer water residence time and periodic anoxic conditions can lead to increased nitrogen (N) removal through denitrification but also mobilization of phosphorus (P), impeding overall water quality improvements. To investigate the capacity for N and P processing in remediated streams, we measured potential denitrification and nitrous oxide production and yields together with potential P desorption and P fractions in floodplain and stream sediments in ten catchments in Sweden. Sediment P desorption was measured as equilibrium P concentration, using P isotherm incubations. Denitrification rates were measured with the acetylene inhibition method. Sediment nutrient process rates were combined with hydrochemical monitoring along remediated streams and their paired upstream control reaches of trapezoidal shape to determine the impact of floodplains on water quality. The correlation between floodplain denitrification rates and P desorption (r = 0.53, p = 0.02) revealed a trade-off between soluble reactive P (SRP) and nitrate removal, driven by stream water connectivity to floodplains. Nitrous oxide production was not affected by differences in P processing, but nitrous oxide yields decreased with higher denitrification and P desorption. The release of SRP from floodplains (0.03 ± 0.41 mg P kg - 1 day - 1) was significantly lower than from trapezoidal stream banks (0.38 ± 0.37 mg P kg - 1 day - 1), predicted by long-term SRP concentrations in stream water and floodplain inundation frequency. The overall impact of SRP release from floodplains on stream SRP concentrations in remediated reaches was limited. However, the remediated reaches showing increased stream SRP concentrations were also frequently inundated and had higher labile P content and coarse soil texture in floodplain sediments. To fully realize the potential for water quality improvements with constructed floodplains in agricultural streams, the promotion of denitrification through increased inundation should be balanced against the risk of P release from sediments, particularly in streams with high SRP inputs., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024. Published by Elsevier Ltd.)

The ability of WHAM VII and NICA-Donnan models to predict free-ion activities of Cu in natural waters was examined from two perspectives, (i) the presence of EDTA and NTA contaminants, (ii) the need to improve estimates of HA and FA concentrations. Potentiometric responses of a Cu(II) ion-selective electrode were investigated in five assays containing dissolved organic matter (DOM) isolated from a series of polluted (urban) and relatively unpolluted (upland) streams in northern England. The [Cu]/[DOC] ratio in these assays spanned an environmentally realistic range of ∼1-500 μmol/g. Reasonably good agreement between measured and predicted Cu(2+) activities was obtained with both WHAM VII and NICA-Donnan models, assuming 65% of DOM as fulvic acid and including the measured EDTA and NTA concentrations, but generally the models overestimated the activities by a factor of ∼2. In contrast, the models over-predicted the Cu(2+) activities by up to 2 orders of magnitude at low [Cu]/[DOC] ratios in urban waters if anthropogenic ligands were not included in the model simulations. Three-dimensional fluorescence excitation-emission matrix (EEM) spectroscopy was used to measure the functional properties of the isolated DOM and to estimate the fractions of FA and HA present. Using these fractions in the models gave improvements in predictions compared to the 65% FA assumption, as shown by higher correlations, reduced error and reduced bias. These results highlight various issues with the use of the available speciation models for predicting free ion concentrations in natural waters, such as the use of the Biotic Ligand Model (BLM) for the derivation of environmental standards. It is clearly necessary to measure EDTA and NTA in waters with urban influences, while fluorescence measurements offer the possibility of appreciably improving the accuracy of predictions., (Copyright © 2014 Elsevier Ltd. All rights reserved.)

The fluorescence intensity of dissolved organic matter (DOM) in aqueous samples is known to be highly influenced by temperature. Although several studies have demonstrated the effect of thermal quenching on the fluorescence of DOM, no research has been undertaken to assess the effects of temperature by combining fluorescence excitation - emission matrices (EEM) and parallel factor analysis (PARAFAC) modelling. This study further extends previous research on thermal quenching by evaluating the impact of temperature on the fluorescence of DOM from a wide range of environmental samples, in the range 20 °C - 0 °C. Fluorescence intensity increased linearly with respect to temperature decrease at all temperatures down to 0 °C. Results showed that temperature affected the PARAFAC components associated with humic-like and tryptophan-like components of DOM differently, depending on the water type. The terrestrial humic-like components, C1 and C2 presented the highest thermal quenching in rural water samples and the lowest in urban water samples, while C3, the tryptophan-like component, and C4, a reprocessed humic-like component, showed opposite results. These results were attributed to the availability and abundance of the components or to the degree of exposure to the heat source. The variable thermal quenching of the humic-like components also indicated that although the PARAFAC model generated the same components across sites, the DOM composition of each component differed between them. This study has shown that thermal quenching can provide additional information on the characteristics and composition of DOM and highlighted the importance of correcting fluorescence data collected in situ., (Copyright © 2014 Elsevier Ltd. All rights reserved.)

Real-time fluorescence monitoring has been mostly performed in marine systems, with little progress being made in the application of fluorescence excitation-emission matrix (EEM) spectroscopy, especially for freshwater monitoring. This paper presents a two weeks experiment where real-time fluorescence EEM data have been obtained for Bourn Brook, Birmingham, UK, using an in-situ fibre-optic probe. Fluorescence EEMs were measured every 3 min for two weeks, with control 'grab' samples every hour analyzed for fluorescence EEMs as well as pH, conductivity and dissolved organic carbon. Comparison of real-time and control samples showed an excellent agreement, with no evidence of fibre-optic probe fouling. EEMs of different character were identified using self-organizing maps, which demonstrated seven clusters of fluorescence EEMs which related to the intensity of fluorescence and relative intensities of peak T(1) and T(2) vs. peak C and peak A fluorescence. Fluorescence intensity of peaks A and C were observed to increase with rainfall, and a diesel pollution event was detected through an increase in T(2) fluorescence., (Copyright © 2010 Elsevier Ltd. All rights reserved.)