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The article discusses the significance of fluorescence spectroscopy to determine the effectiveness of water treatment to remove organic matter (OM) characterization. It analyzes the fluorescence data of purified and raw water that were gathered from 16 drinking water treatment processes. It reveals that the application was significantly related to OM removal and could produce accurate quantification of OM fractions.

Climate change is expected to significantly deteriorate water quality in heavily managed agricultural landscapes, however, the exact mechanisms of these impacts are unknown. In this study we adopted a modelling approach to predict the multiple effects of climate change on hydrological and biogeochemical responses for dominant solutes and particulates in two agriculture-dominated temperate headwater catchments. We used climatic projections from three climatic models to simulate future flows, mobilisation and delivery of solutes and particulates. This allowed an examination of potential drivers by identifying changes in flow pathway distribution and key environmental variables. We found that future climate conditions will lead to a general increase in stream discharge as well as higher concentrations and loads of solutes and particulates. However, unlike previous studies, we observed a higher magnitude of change during the warmer part of the year. These changes will reduce the relative importance of winter flows on solute and particulate transport, leading to both higher and more evenly distributed concentrations and loads between seasons. We linked these changes to the higher importance of superficial flow pathways of tile and surface runoff driven by more rapid transition from extremely wet to dry conditions. Overall, the observed increase in solute and particulate mobilisation and delivery will lead to widespread water quality deterioration. Mitigation of this deterioration would require adequate management efforts to address the direct and indirect negative effects on stream biota and water scarcity., 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 The Authors. Published by Elsevier B.V. All rights reserved.)

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.)

Agricultural headwaters are positioned at the interface between terrestrial and aquatic ecosystems and, therefore, at the margins of scientific disciplines. They are deemed devoid of biodiversity and too polluted by ecologists, overlooked by hydrologists, and are perceived as a nuisance by landowners and water authorities. While agricultural streams are widespread and represent a major habitat in terms of stream length, they remain understudied and thereby undervalued. Agricultural headwater streams are significantly modified and polluted but at the same time are the critical linkages among land, air, and water ecosystems. They exhibit the largest variation in streamflow, water quality, and greenhouse gas emission with cascading effects on the entire stream networks, yet they are underrepresented in monitoring, remediation, and restoration. Therefore, we call for more intense efforts to characterize and understand the inherent variability and sensitivity of these ecosystems to global change drivers through scientific and regulatory monitoring and to improve their ecosystem conditions and functions through purposeful and evidence-based remediation.

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.

Heavily modified headwater streams and open ditches carry high nitrogen loads from agricultural soils that sustain eutrophication and poor water quality in downstream aquatic ecosystems. To remediate agricultural streams and reduce the export of nitrate (NO 3 - ), phosphorus and suspended sediments, two-stage ditches with constructed floodplains can be implemented as countermeasures. By extending hydrological connectivity between the stream channel and riparian corridor within constructed floodplains, these remediated ditches enhance the removal of NO 3 - via the microbial denitrification process. Ten remediated ditches were paired with upstream trapezoidal ditches in Sweden across different soils and land uses to measure the capacity for denitrification and nitrous oxide (N 2 O) production and yields under denitrifying conditions in stream and floodplain sediments. To examine the controls for denitrification, water quality was monitored monthly and flow discharge continuously along reaches. Floodplain sediments accounted for 33 % of total denitrification capacity of remediated ditches, primarily controlled by inundation and stream NO 3 - concentrations. Despite reductions in flow-weighted NO 3 - concentrations along reaches, NO 3 - removal in remediated ditches via denitrification can be masked by inputs of NO 3 - -rich groundwaters, typical of intensively managed agricultural landscapes. Although N 2 O production rates were 50 % lower in floodplains compared to the stream, remediated ditches emitted more N 2 O than conventional trapezoidal ditches. Higher denitrification rates and reductions of N 2 O proportions were predicted by catchments with loamy soils, higher proportions of agricultural land use and lower floodplain elevations. For realizing enhanced NO 3 - removal from floodplains and avoiding increased N 2 O emissions, soil type, land use and the design of floodplains need to be considered when implementing remediated streams. Further, we stress the need for assessing the impact of stream remediation in the context of broader catchment processes, to determine the overall potential for improving water quality., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personalrelationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 The Authors. Published by Elsevier B.V. All rights reserved.)

Despite our growing understanding of the global carbon cycle, scientific consensus on the drivers and mechanisms that control dissolved organic carbon (DOC) turnover in aquatic systems is lacking, hampered by the mismatch between research that approaches DOC reactivity from either intrinsic (inherent chemical properties) or extrinsic (environmental context) perspectives. Here we propose a conceptual view of DOC reactivity in which the combination of intrinsic and extrinsic factors controls turnover rates and determines which reactions will occur. We review three major types of reactions (biological, photochemical, and flocculation) from an intrinsic chemical perspective and further define the environmental features that modulate the expression of chemically inherent reactivity potential. Finally, we propose hypotheses of how extrinsic and intrinsic factors together shape patterns in DOC turnover across the land-to-ocean continuum, underscoring that there is no intrinsic DOC reactivity without environmental context. By acknowledging the intrinsic-extrinsic control duality, our framework intends to foster improved modeling of DOC reactivity and its impact on ecosystem services., (© 2022 The Authors. Ecology published by Wiley Periodicals LLC on behalf of The Ecological Society of America.)

The Arctic environment harbors a complex mosaic of mercury (Hg) and carbon (C) reservoirs, some of which are rapidly destabilizing in response to climate warming. The sources of riverine Hg across the Mackenzie River basin (MRB) are uncertain, which leads to a poor understanding of potential future release. Measurements of dissolved and particulate mercury (DHg, PHg) and carbon (DOC, POC) concentration were performed, along with analyses of Hg stable isotope ratios (incl. ∆ 199 Hg, δ 202 Hg), radiocarbon content (∆ 14 C) and optical properties of DOC of river water. Isotopic ratios of Hg revealed a closer association to terrestrial Hg reservoirs for the particulate fraction, while the dissolved fraction was more closely associated with atmospheric deposition sources of shorter turnover time. There was a positive correlation between the ∆ 14 C-OC and riverine Hg concentration for both particulate and dissolved fractions, indicating that waters transporting older-OC ( 14 C-depleted) also contained higher levels of Hg. In the dissolved fraction, older DOC was also associated with higher molecular weight, aromaticity and humic content, which are likely associated with higher Hg-binding potential. Riverine PHg concentration increased with turbidity and SO 4 concentration. There were large contrasts in Hg concentration and OC age and quality among the mountain and lowland sectors of the MRB, which likely reflect the spatial distribution of various terrestrial Hg and OC reservoirs, including weathering of sulfate minerals, erosion and extraction of coal deposits, thawing permafrost, forest fires, peatlands, and forests. Results revealed major differences in the sources of particulate and dissolved riverine Hg, but nonetheless a common positive association with older riverine OC. These findings reveal that a complex mixture of Hg sources, supplied across the MRB, will contribute to future trends in Hg export to the Arctic Ocean under rapid environmental changes., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have influence the work reported in this paper., (Copyright © 2021 The Authors. Published by Elsevier B.V. All rights reserved.)

Agricultural land use covers almost half of the EU territory and reducing nutrient and pesticide losses to freshwaters is central to existing EU policy. However, the progress of improving freshwater quality and reducing eutrophication is slow and lags behind targets. The Green Deal is a key element of the EU plans to implement the United Nation's Sustainable Development Goals. Here, we discuss the opportunities that the Green Deal and associated strategies may provide for the achievement of the water quality goals of the Water Framework Directive in agricultural landscapes. We welcome Green Deal's aspirational stated goals. However, the reliance of mitigation of diffuse agricultural pollution on the reform of the Common Agricultural Policy represents grave risks for practical implementation and the achievement of the Green Deal objectives. We also argue that the new strategies should be targeted at tackling and understanding the sources of water quality problems along the full pollution continuum. To maximise the opportunities for tackling diffuse pollution from agricultural land use and achieving the delayed water quality targets, we stress that a range of targeted new instruments will be needed to close the gaps in the pollution continuum 'from source to impact'. These gaps include: (I) smart and standardised monitoring of the impacts of proposed eco-schemes and agri-environment-climate measures, (ii) active restoration of agricultural streams and ditches and their floodplains to reduce secondary pollution sources, (iii) options to draw down nutrient levels to or below the agronomic optimum that reduce legacy sources, (iv) integrating farm-scale and catchment-scale analysis of trade-offs in reducing different pollutants and their combined effects, and finally (v) accounting for emerging pressures to freshwater quality due to climate change. Incorporation of the pollution continuum framework into tackling diffuse agricultural pollution will ensure that the European water-related policy goals are achieved., Competing Interests: Declaration of competing interest The authors express no conflict of interest including any financial and personal relationships with other people or organizations that could inappropriately influence (bias) their work., (Copyright © 2021 The Authors. Published by Elsevier B.V. All rights reserved.)

Nutrient losses from headwater catchments (<50 km 2 ) cause eutrophication problems downstream. Catchment properties are strongly reflected in the levels of nutrient concentrations in headwater streams. Based on measurements of total and dissolved nitrogen (TN, DN) and phosphorus (TP, DP) in 235 small headwater streams, we showed that proportion of arable land in a catchment had the strongest positive effect on nutrient concentrations, with coefficient of determination (R 2 ) of 0.54, 0.64, 0.45, and 0.51 for TN, DN, TP, and DP, respectively. In contrast, increased proportion of forest and wetland led to lower nutrient concentrations in streams. The geological composition of catchments had a major influence on the soil properties. In turn, certain soil properties, such as clay content and content of aluminum (Al), an important binding agent of P, influenced losses of particulate P (PP) and DP, respectively. Consequently, by using soil properties as a link between geology and water quality, areas potentially sensitive to nutrient losses were identified by classifying bedrock categories into three geological groups. Approximately 25% of Swedish arable land was identified as potentially sensitive. Sensitive catchments were found in regions with sedimentary bedrock and showed higher concentrations of dissolved nutrient fractions even when the proportion of agricultural land was small, indicating higher background concentrations., 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 © 2021 The Authors. Published by Elsevier B.V. All rights reserved.)

Combating eutrophication requires changes in land and water management in agricultural catchments and implementation of mitigation measures to reduce phosphorus (P), nitrogen (N) and suspended sediment (SS) losses. To date, such mitigation measures have been built in many agricultural catchments, but there is a lack of studies evaluating their effectiveness. Here we evaluated the effectiveness of mitigation measures in a clay soil-dominated headwater catchment by combining the evaluation of long-term and high-frequency data with punctual measurements upstream and downstream of three mitigation measures: lime-filter drains, a two-stage ditch, and a sedimentation pond. Long-term hydrochemical data at the catchment outlet showed a significant decrease in P (-15%) and SS (-28%) and an increase in nitrate nitrogen (NO-N, +13%) concentrations. High-frequency (hourly) measurements with a wet-chemistry analyzer (total and reactive P) and optical sensor (NO-N and SS) showed that the catchment is an abundant source of nutrients and sediments and that their transport is exacerbated by prolonged drought and resuspension of stream sediments during storm events. Lime-filter drains showed a decrease in SS by 76% and total P by 80% and an increase in NO-N by 45% compared with traditional drains, potentially indicating pollution swapping. The effectiveness of two-stage ditch and sedimentation pond was less evident and depended on the prevalent hydrometeorological conditions that drove the resuspension of bed sediments and associated sediment-bound P transport. These results suggest that increased frequency of prolonged drought due to changing weather patterns and resuspension of SS and sediment-bound P during storm events can override the generally positive effect of mitigation measures., (© 2019 The Author(s).)

Recent technological breakthroughs of optical sensors and analysers have enabled matching the water quality measurement interval to the time scales of stream flow changes and led to an improved understanding of spatially and temporally heterogeneous sources and delivery pathways for many solutes and particulates. This new ability to match the chemograph with the hydrograph has promoted renewed interest in the concentration-discharge (c-q) relationship and its value in characterizing catchment storage, time lags and legacy effects for both weathering products and anthropogenic pollutants. In this paper we evaluated the stream c-q relationships for a number of water quality determinands (phosphorus, suspended sediments, nitrogen) in intensively managed agricultural catchments based on both high-frequency (sub-hourly) and long-term low-frequency (fortnightly-monthly) routine monitoring data. We used resampled high-frequency data to test the uncertainty in water quality parameters (e.g. mean, 95th percentile and load) derived from low-frequency sub-datasets. We showed that the uncertainty in water quality parameters increases with reduced sampling frequency as a function of the c-q slope. We also showed that different sources and delivery pathways control c-q relationship for different solutes and particulates. Secondly, we evaluated the variation in c-q slopes derived from the long-term low-frequency data for different determinands and catchments and showed strong chemostatic behaviour for phosphorus and nitrogen due to saturation and agricultural legacy effects. The c-q slope analysis can provide an effective tool to evaluate the current monitoring networks and the effectiveness of water management interventions. This research highlights how improved understanding of solute and particulate dynamics obtained with optical sensors and analysers can be used to understand patterns in long-term water quality time series, reduce the uncertainty in the monitoring data and to manage eutrophication in agricultural catchments., (Copyright © 2018 Elsevier B.V. All rights reserved.)

In agricultural catchments, diffuse nutrient fluxes (mainly nitrogen N and phosphorus P), are observed to pollute receiving waters and cause eutrophication. Organic matter (OM) is important in mediating biogeochemical processes in freshwaters. Time series of the variation in nutrient and OM loads give insights into flux processes and their impact on biogeochemistry but are costly to maintain and challenging to analyse for elements that are highly reactive in the environment. We evaluated the capacity of the automated monitoring to capture typically low baseflow concentrations of the reactive forms of nutrients and OM: total reactive phosphorus (TRP), nitrate nitrogen (NO 3 -N) and tryptophan-like fluorescence (TLF). We compared the performance of in situ monitoring (wet chemistry analyser, UV-vis and fluorescence sensors) and automated grab sampling without instantaneous analysis using autosamplers. We found that automatic grab sampling shows storage transformations for TRP and TLF and do not reproduce the diurnal concentration pattern captured by the in situ analysers. The in situ TRP and fluorescence analysers respond to temperature variation and the relationship is concentration-dependent. Accurate detection of low P concentrations is particularly challenging due to large errors associated with both the in situ and autosampler measurements. Aquatic systems can be very sensitive to even low concentrations of P typical of baseflow conditions. Understanding transformations and measurement variability in reactive forms of nutrients and OM associated with in situ analysis is of great importance for understanding in-stream biogeochemical functioning and establishing robust monitoring protocols., (Copyright © 2016 Elsevier B.V. All rights reserved.)

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.)

We evaluate different frequencies of riverine nutrient concentration measurement to interpret diffuse pollution in agricultural catchments. We focus on three nutrient fractions, nitrate-nitrogen (NO3-N), total reactive phosphorus (TRP) and total phosphorus (TP) observed using conventional remote laboratory-based, low-frequency sampling and automated, in situ high-frequency monitoring. We demonstrate the value of low-frequency routine nutrient monitoring in providing long-term data on changes in surface water and groundwater nutrient concentrations. By contrast, automated high-frequency nutrient observations provide insight into the fine temporal structure of nutrient dynamics in response to a full spectrum of flow dynamics. We found good agreement between concurrent in situ and laboratory-based determinations for nitrate-nitrogen (Pearson's R = 0.93, p < 0.01). For phosphorus fractions: TP (R = 0.84, p < 0.01) and TRP (R = 0.79, p < 0.01) the relationships were poorer due to the underestimation of P fractions observed in situ and storage-related changes of grab samples. A detailed comparison between concurrent nutrient data obtained by the hourly in situ automated monitoring and weekly-to-fortnightly grab sampling reveals a significant information loss at the extreme range of nutrient concentration for low-frequency sampling.

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.)

Monthly raw and clarified water samples were obtained for 16 UK surface water treatment works. The fluorescence excitation-emission matrix (EEM) technique was used for the assessment of total organic carbon (TOC) removal and organic matter (OM) characterisation. The impact of algae presence in water on TOC removal, and its relationship with fluorescence, was analysed. Fluorescence peak C intensity was found to be a sensitive and reliable measure of OM content. Fluorescence peak C emission wavelength and peak T intensity (reflecting the degree of hydrophobicity and the microbial fraction, respectively) were found to characterize the OM; the impact of both on TOC removal efficiency was apparent. OM fluorescence properties were shown to predict TOC removal, and identify spatial and temporal variations. Previous work indicates that the trihalomethane (THM) concentration of treated water can be predicted from the raw water TOC concentration. The simplicity, sensitivity, speed of analysis and low cost, combined with potential for incorporation into on-line monitoring systems, mean that fluorescence spectroscopy offers a robust analytical technique to be used in conjunction with, or in place of, other approaches to OM characterisation and THM formation prediction.