Advances in Catchment Science, Hydrochemistry, and Aquatic Ecology Enabled by High-Frequency Water Quality Measurements.

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.

Coupling High-Frequency Stream Metabolism and Nutrient Monitoring to Explore Biogeochemical Controls on Downstream Nitrate Delivery.

Instream biogeochemical process measurements are often short-term and localized. Here we use in situ sensors to quantify the net effects of biogeochemical processes on seasonal patterns in baseflow nitrate retention at the river-reach scale. Dual-station high-frequency in situ nitrate measurements, were coupled with high-frequency measurements of stream metabolism and dissolved inorganic carbon, in a tributary of the Buffalo National River, Arkansas. Nitrate assimilation was calculated from net primary production, and combined with mass-balance measurements, to estimate net nitrification and denitrification. The combined net effects of these instream processes (assimilation, denitrification, and nitrification) removed >30-90% of the baseflow nitrate load along a 6.5 km reach. Assimilation of nitrate by photoautotrophs during spring and early summer was buffered by net nitrification. Net nitrification peaked during the spring. After midsummer, there was a pronounced switch from assimilatory nitrate uptake to denitrification. There was clear synchronicity between the switch from nitrate assimilation to denitrification, a reduction in river baseflows, and a shift in stream metabolism from autotrophy to heterotrophy. The results show how instream nitrate retention and downstream delivery is driven by seasonal shifts in metabolic pathways; and how continuous in situ stream sensor networks offer new opportunities for quantifying the role of stream biota in the dynamics, fate, and transport of nitrogen in fluvial systems.

Increased Soluble Phosphorus Loads to Lake Erie: Unintended Consequences of Conservation Practices?

Cumulative daily load time series show that the early 2000s marked a step-change increase in riverine soluble reactive phosphorus (SRP) loads entering the Western Lake Erie Basin from three major tributaries: the Maumee, Sandusky, and Raisin Rivers. These elevated SRP loads have been sustained over the last 12 yr. Empirical regression models were used to estimate the contributions from (i) increased runoff from changing weather and precipitation patterns and (ii) increased SRP delivery (the combined effects of increased source availability and/or increased transport efficiency of labile phosphorus [P] fractions). Approximately 65% of the SRP load increase after 2002 was attributable to increased SRP delivery, with higher runoff volumes accounting for the remaining 35%. Increased SRP delivery occurred concomitantly with declining watershed P budgets. However, within these watersheds, there have been long-term, largescale changes in land management: reduced tillage to minimize erosion and particulate P loss, and increased tile drainage to improve field operations and profitability. These practices can inadvertently increase labile P fractions at the soil surface and transmission of soluble P via subsurface drainage. Our findings suggest that changes in agricultural practices, including some conservation practices designed to reduce erosion and particulate P transport, may have had unintended, cumulative, and converging impacts contributing to the increased SRP loads, reaching a critical threshold around 2002.

The Pivotal Role of Phosphorus in a Resilient Water-Energy-Food Security Nexus.

We make the case that phosphorus (P) is inextricably linked to an increasingly fragile, interconnected, and interdependent nexus of water, energy, and food security and should be managed accordingly. Although there are many other drivers that influence water, energy, and food security, P plays a unique and under-recognized role within the nexus. The P paradox derives from fundamental challenges in meeting water, energy, and food security for a growing global population. We face simultaneous dilemmas of overcoming scarcity of P to sustain terrestrial food and biofuel production and addressing overabundance of P entering aquatic systems, which impairs water quality and aquatic ecosystems and threatens water security. Historical success in redistributing rock phosphate as fertilizer to enable modern feed and food production systems is a grand societal achievement in overcoming inequality. However, using the United States as the main example, we demonstrate how successes in redistribution of P and reorganization of farming systems have broken local P cycles and have inadvertently created instability that threatens resilience within the nexus. Furthermore, recent expansion of the biofuels sector is placing further pressure on P distribution and availability. Despite these challenges, opportunities exist to intensify and expand food and biofuel production through recycling and better management of land and water resources. Ultimately, a strategic approach to sustainable P management can help address the P paradox, minimize tradeoffs, and catalyze synergies to improve resilience among components of the water, energy, and food security nexus.

Phosphorus retention and remobilization along hydrological pathways in karst terrain.

Karst landscapes are often perceived as highly vulnerable to agricultural phosphorus (P) loss, via solution-enlarged conduits that bypass P retention processes. Although attenuation of P concentrations has been widely reported within karst drainage, the extent to which this results from hydrological dilution, rather than P retention, is poorly understood. This is of strategic importance for understanding the resilience of karst landscapes to P inputs, given increasing pressures for intensified agricultural production. Here hydrochemical tracers were used to account for dilution of P, and to quantify net P retention, along transport pathways between agricultural fields and emergent springs, for the karst of the Ozark Plateau, midcontinent USA. Up to ∼ 70% of the annual total P flux and ∼ 90% of the annual soluble reactive P flux was retained, with preferential retention of the most bioavailable (soluble reactive) P fractions. Our results suggest that, in some cases, karst drainage may provide a greater P sink than previously considered. However, the subsequent remobilization and release of the retained P may become a long-term source of slowly released "legacy" P to surface waters.

Potential drivers of changing ecological conditions in English and Welsh rivers since 1990.

River invertebrate communities across Europe have been changing in response to variations in water quality over recent decades, but the underlying drivers are difficult to identify because of the complex stressors and environmental heterogeneity involved. Here, using data from ∼4000 locations across England and Wales, collected over 29 years, we use three approaches to help resolve the drivers of spatiotemporal variation in the face of this complexity: i) mapping changes in invertebrate richness and community composition; ii) structural equation modelling (SEM) to distinguish land cover, water quality and climatic influences; and iii) geographically weighted regression (GWR) to identify how the apparent relationships between invertebrate communities and abiotic variables change across the area. Mapping confirmed widespread increases in richness and the proportion of pollution-sensitive taxa across much of England and Wales. It also revealed regions where pollution-sensitive taxa or overall richness declined, the former primarily in the uplands. SEMs confirmed strong increases in average biochemical oxygen demand and nutrient concentrations related to urban and agricultural land cover, but only a minority of land cover's effect upon invertebrate communities was explained by average water chemistry, highlighting potential factors such as episodic extremes or emerging contaminants. GWR identified strong geographical variation in estimated relationships between macroinvertebrate communities and environmental variables, with evidence that the estimated negative impacts of nutrients and water temperature were increasing through time. Overall the results are consistent with widespread biological recovery of Britain's rivers from past gross organic pollution, whilst highlighting declines in some of the most diverse and least impacted streams. Modelling points to a complex and changing set of drivers, highlighting the multifaceted impacts of catchment land cover and the evolving role of different stressors, with the relationship to gross organic pollution weakening, whilst estimated nutrient and warming effects strengthened.

Phosphorus legacy: overcoming the effects of past management practices to mitigate future water quality impairment.

The water quality response to implementation of conservation measures across watersheds has been slower and smaller than expected. This has led many to question the efficacy of these measures and to call for stricter land and nutrient management strategies. In many cases, this limited response has been due to the legacies of past management activities, where sinks and stores of P along the land-freshwater continuum mask the effects of reductions in edge-of-field losses of P. Accounting for legacy P along this continuum is important to correctly apportion sources and to develop successful watershed remediation. In this study, we examined the drivers of legacy P at the watershed scale, specifically in relation to the physical cascades and biogeochemical spirals of P along the continuum from soils to rivers and lakes and via surface and subsurface flow pathways. Terrestrial P legacies encompass prior nutrient and land management activities that have built up soil P to levels that exceed crop requirements and modified the connectivity between terrestrial P sources and fluvial transport. River and lake P legacies encompass a range of processes that control retention and remobilization of P, and these are linked to water and sediment residence times. We provide case studies that highlight the major processes and varying timescales across which legacy P continues to contribute P to receiving waters and undermine restoration efforts, and we discuss how these P legacies could be managed in future conservation programs.

Phosphorus mitigation to control river eutrophication: murky waters, inconvenient truths, and "postnormal" science.

This commentary examines an "inconvenient truth" that phosphorus (P)-based nutrient mitigation, long regarded as the key tool in eutrophication management, in many cases has not yet yielded the desired reductions in water quality and nuisance algal growth in rivers and their associated downstream ecosystems. We examine why the water quality and aquatic ecology have not recovered, in some case after two decades or more of reduced P inputs, including (i) legacies of past land-use management, (ii) decoupling of algal growth responses to river P loading in eutrophically impaired rivers; and (iii) recovery trajectories, which may be nonlinear and characterized by thresholds and alternative stable states. It is possible that baselines have shifted and that some disturbed river environments may never return to predisturbance conditions or may require P reductions below those that originally triggered ecological degradation. We discuss the practical implications of setting P-based nutrient criteria to protect and improve river water quality and ecology, drawing on a case study from the Red River Basin in the United States. We conclude that the challenges facing nutrient management and eutrophication control bear the hallmarks of "postnormal" science, where uncertainties are large, management intervention is urgently required, and decision stakes are high. We argue a case for a more holistic approach to eutrophication management that includes more sophisticated regime-based nutrient criteria and considers other nutrient and pollutant controls and river restoration (e.g., physical habitat and functional food web interactions) to promote more resilient water quality and ecosystem functioning along the land-freshwater continuum.

Exploring how organic matter controls structural transformations in natural aquatic nanocolloidal dispersions.

The response of the dispersion nanostructure of surface river bed sediment to the controlled removal and readdition of natural organic matter (NOM), in the absence and presence of background electrolyte, was examined using the technique of small-angle neutron scattering (SANS). Partial NOM removal induced aggregation of the mineral particles, but more extensive NOM removal restored colloidal stability. When peat humic acid (PHA) was added to a NOM-deficient sediment concentration-related structural transformations were observed: at 255 mg/L PHA aggregation of the nanocolloid was actually enhanced, but at 380 mg/L PHA disaggregation and colloidal stability were promoted. The addition of 2 mM CaCl(2) induced mild aggregation in the native sediment but not in sediments with added PHA, suggesting that the native NOM and the PHA respond differently to changes in ionic strength. A first attempt at using SANS to directly characterize the thickness and coverage of an adsorbed PHA layer in a natural nanocolloid is also presented. The results are discussed in the context of a hierarchical aquatic colloidal nanostructure, and the implications for contemporary studies of the role of dissolved organic carbon (DOC) in sustaining the transport of colloidal iron in upland catchments.

Within-river phosphorus retention: accounting for a missing piece in the watershed phosphorus puzzle.

The prevailing "puzzle" in watershed phosphorus (P) management is how to account for the nonconservative behavior (retention and remobilization) of P along the land-freshwater continuum. This often hinders our attempts to directly link watershed P sources with their water quality impacts. Here, we examine aspects of within-river retention of wastewater effluent P and its remobilization under high flows. Most source apportionment methods attribute P loads mobilized under high flows (including retained and remobilized effluent P) as nonpoint agricultural sources. We present a new simple empirical method which uses chloride as a conservative tracer of wastewater effluent, to quantify within-river retention of effluent P, and its contribution to river P loads, when remobilized under high flows. We demonstrate that within-river P retention can effectively mask the presence of effluent P inputs in the water quality record. Moreover, we highlight that by not accounting for the contributions of retained and remobilized effluent P to river storm-flow P loads, existing source apportionment methods may significantly overestimate the nonpoint agricultural sources and underestimate wastewater sources in mixed land-use watersheds. This has important implications for developing effective watershed remediation strategies, where remediation needs to be equitably and accurately apportioned among point and nonpoint P contributors.

High-frequency phosphorus monitoring of the River Kennet, UK: are ecological problems due to intermittent sewage treatment works failures?

The River Kennet in southern England has exhibited excessive benthic algal growth and associated ecological problems, such as loss of macrophytes and invertebrates, since the 1980s. These ecological problems were attributed to regular peaks in phosphorus concentration, which were widely attributed to intermittent failures of the Marlborough sewage treatment works (STW). This study deployed high-frequency phosphorus auto-analysers to monitor the total reactive phosphorus (TRP) concentrations of Marlborough STW final effluent and the downstream River Kennet at hourly and 30 minute resolution respectively, between 2008 and 2009. This monitoring confirmed that the Marlborough STW was operating well within its 1000 µg l⁻¹ annual mean total phosphorus consent limit, with mean total P and soluble reactive P concentrations of 675 and 345 µg l⁻¹ respectively. There were two occasions where effluent TRP concentration exceeded 1000 µg l⁻¹, and only one of these resulted in a peak in TRP concentration of over 100 µg l⁻¹ in the River Kennet at Mildenhall. The other nine peaks of over 100 µg l⁻¹ in the River Kennet during the monitoring period were associated with storm events, indicating that diffuse-source inputs and remobilisation of stored within-channel phosphorus were the cause of the peaks in river concentration, rather than Marlborough STW. The value of high-frequency environmental monitoring and the problems associated with using nutrient auto-analysers in the field are discussed. Seasonal phosphorus consents for STWs could provide a useful and cost effective means to improve both water quality and river ecology in the upper River Kennet.

River metabolic fingerprints and regimes reveal ecosystem responses to enhanced wastewater treatment.

Although many studies have examined how improvements in wastewater treatment impact river nutrient concentrations and loads, there has been much less focus on measuring river metabolism to evaluate the wider aquatic ecosystem benefits of reducing nutrient inputs to rivers. The objectives of this study were to evaluate the effects of enhanced wastewater treatment (nitrification) on river metabolism in the Grand River, Canada's largest river draining into Lake Erie. Metabolic fingerprints and regimes (calculated from high-frequency dissolved oxygen [DO] measurements) were used to visualize whole-river ecosystem functional responses to these wastewater treatment upgrades. There was a 60% reduction in ecosystem respiration during summer, in response to reductions in effluent total ammonia inputs, causing a shift from net heterotrophy to net autotrophy, and contraction of river metabolic fingerprints. This resulted in major improvements in summer DO concentrations, with reductions in the percentage of days during summer that DO minima fell below water-quality guidelines for protection of aquatic early life stages, from 88% to ≤16%. The results also point to potential cascading impacts on coupled phosphorus and nitrogen cycles, which may generate further improvements in river water quality. During the summer, high rates of river metabolism and nutrient retention may result in measured water-column nutrient concentrations potentially underestimating nutrient pressures. This study also demonstrates the value of combining river metabolism with nutrient monitoring for a more holistic understanding of the role of nutrients in river ecosystem health and function.

Quantifying phosphorus retention and release in rivers and watersheds using extended end-member mixing analysis (E-EMMA).

Extended end-member mixing analysis (E-EMMA) is presented as a novel empirical method for exploring phosphorus (P) retention and release in rivers and watersheds, as an aid to water-quality management. E-EMMA offers a simple and versatile tool that relies solely on routinely measured P concentration and flow data. E-EMMA was applied to two river systems: the Thames (U.K.) and Sandusky River (U.S.), which drain similar watershed areas but have contrasting dominant P sources and hydrology. For both the Thames and Sandusky, P fluxes at the watershed outlets were strongly influenced by processes that retain and cycle P. However, patterns of P retention were markedly different for the two rivers, linked to differences in P sources and speciation, hydrology and land use. On an annual timescale, up to 48% of the P flux was retained for the Sandusky and up to 14% for the Thames. Under ecologically critical low-flow periods, up to 93% of the P flux was retained for the Sandusky and up to 42% for the Thames. In the main River Thames and the Sandusky River, in-stream processes under low flows were capable of regulating the delivery of P and modifying the timing of delivery in a way that may help to reduce ecological impacts to downstream river reaches, by reducing ambient P concentrations at times of greatest river eutrophication risk. The results also suggest that by moving toward cleaner rivers and improved ecosystem health, the efficiency of P retention may actually increase.

Aluminium in UK rivers: a need for integrated research related to kinetic factors, colloidal transport, carbon and habitat.

Dissolved aluminium concentrations ([Al]) in the <0.45 µm filtered fraction are described for 54 UK river sites covering rural, acidic/acid sensitive, agricultural and urban typologies, and wide pH range (4 to 11). High [Al] occurred under acidic conditions and for acid runoff neutralised by bicarbonate rich groundwater. Thermodynamic analysis indicates Al hydroxide/hydroxy-silicate oversaturation at circumneutral pH across the rivers, but undersaturation at lower/higher pH. The oversaturation reflects in part the presence of Al bearing colloids as indicated by (1) [Al] being correlated with components associated with both lithogenic (Fe, Ti and lanthanides) colloids and organic carbon, (2) baseflow studies using cross-flow ultrafiltration and (3) comparison of our data with Acid Waters Monitoring Network (AWMN) information on labile and non-labile Al. Tree harvesting and emission reductions of SO(x) in acidic and acid sensitive catchments in mid-Wales led to acidification reversal, lower [Al] and changing [H(+)] - [Al] relationships. The [Al] decline was confined to acidic conditions while [Al] increased during the later part of the monitoring period with a peak around 2002 for moorland and forested systems. Colloidal production across the flow range was indicated late in the record by comparison of our data with information collected by the AWMN for a site in mid-Wales. This production seems interlinked with organic carbon and with dissolved CO(2) changes. In order for further understanding of Al hydrogeochemistry in river systems there is a need to integrate research that moves from equilibrium to kinetic and colloidal consideration including the critical issues of organic and inorganic controls within the context of bioavailability and aquatic stress. The colloidal Al may well be of low environmental concern to fish and other factors such as habitat may well be critical.

Sediment phosphorus buffering in streams at baseflow: A meta-analysis.

Phosphorus (P) pollution of surface waters remains a challenge for protecting and improving water quality. Central to the challenge is understanding what regulates P concentrations in streams. This quantitative review synthesizes the literature on a major control of P concentrations in streams at baseflow-the sediment P buffer-to better understand streamwater-sediment P interactions. We conducted a global meta-analysis of sediment equilibrium phosphate concentrations at net zero sorption (EPC0 ), which is the dissolved reactive P (DRP) concentration toward which sediments buffer solution DRP. Our analysis of 45 studies and >900 paired observations of DRP and EPC0 showed that sediments often have potential to remove or release P to the streamwater (83% of observations), meaning that "equilibrium" between sediment and streamwater is rare. This potential for P exchange is moderated by sediment and stream characteristics, including sorption affinity, stream pH, exchangeable P concentration, and particle sizes. The potential for sediments to modify streamwater DRP concentrations is often not realized owing to other factors (e.g., hydrologic interactions). Sediment surface chemistry, hyporheic exchange, and biota can also influence the potential exchange of P between sediments and the streamwater. Methodological choices significantly influenced EPC0 determination and thus the estimated potential for P exchange; we therefore discuss how to measure and report EPC0 to best suit research objectives and aid in interstudy comparison. Our results enhance understanding of the sediment P buffer and inform how EPC0 can be effectively applied to improve management of aquatic P pollution and eutrophication.

Towards resolving the phosphorus chaos created by food systems.

The chaotic distribution and dispersal of phosphorus (P) used in food systems (defined here as disorderly disruptions to the P cycle) is harming our environment beyond acceptable limits. An analysis of P stores and flows across Europe in 2005 showed that high fertiliser P inputs relative to productive outputs was driving low system P efficiency (38 % overall). Regional P imbalance (P surplus) and system P losses were highly correlated to total system P inputs and animal densities, causing unnecessary P accumulation in soils and rivers. Reducing regional P surpluses to zero increased system P efficiency (+ 16 %) and decreased total P losses by 35 %, but required a reduction in system P inputs of ca. 40 %, largely as fertiliser. We discuss transdisciplinary and transformative solutions that tackle the P chaos by collective stakeholder actions across the entire food value chain. Lowering system P demand and better regional governance of P resources appear necessary for more efficient and sustainable food systems.

Biogeochemical and climate drivers of wetland phosphorus and nitrogen release: Implications for nutrient legacies and eutrophication risk.

The dynamics and processes of nutrient cycling and release were examined for a lowland wetland-pond system, draining woodland in southern England. Hydrochemical and meteorological data were analyzed from 1997 to 2017, along with high-resolution in situ sensor measurements from 2016 to 2017. The results showed that even a relatively pristine wetland can become a source of highly bioavailable phosphorus (P), nitrogen (N), and silicon (Si) during low-flow periods of high ecological sensitivity. The drivers of nutrient release were primary production and accumulation of biomass, which provided a carbon (C) source for microbial respiration and, via mineralization, a source of bioavailable nutrients for P and N co-limited microorganisms. During high-intensity nutrient release events, the dominant N-cycling process switched from denitrification to nitrate ammonification, and a positive feedback cycle of P and N release was sustained over several months during summer and fall. Temperature controls on microbial activity were the primary drivers of short-term (day-to-day) variability in P release, with subdaily (diurnal) fluctuations in P concentrations driven by water body metabolism. Interannual relationships between nutrient release and climate variables indicated "memory" effects of antecedent climate drivers through accumulated legacy organic matter from the previous year's biomass production. Natural flood management initiatives promote the use of wetlands as "nature-based solutions" in climate change adaptation, flood management, and soil and water conservation. This study highlights potential water quality trade-offs and shows how the convergence of climate and biogeochemical drivers of wetland nutrient release can amplify background nutrient signals by mobilizing legacy nutrients, causing water quality impairment and accelerating eutrophication risk.