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.

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.

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.

Phosphorus mirabilis: Illuminating the Past and Future of Phosphorus Stewardship.

After its discovery in 1669, phosphorus (P) was named ("the miraculous bearer of light"), arising from the chemoluminescence when white P is exposed to the atmosphere. The metaphoric association between P and light resonates through history: from the discovery of P at the start of the Enlightenment period to the vital role of P in photosynthetic capture of light in crop and food production through to new technologies, which seek to capitalize on the interactions between novel ultrathin P allotropes and light, including photocatalysis, solar energy production, and storage. In this introduction to the special section "Celebrating the 350th Anniversary of Discovering Phosphorus-For Better or Worse," which brings together 22 paper contributions, we shine a spotlight on the historical and emerging challenges and opportunities in research and understanding of the agricultural, environmental, and societal significance of this vital element. We highlight the role of P in water quality impairment and the variable successes of P mitigation measures. We reflect on the need to improve P use efficiency and on the kaleidoscope of challenges facing efficient use of P. We discuss the requirement to focus on place-based solutions for developing effective and lasting P management. Finally, we consider how cross-disciplinary collaborations in P stewardship offer a guiding light for the future, and we explore the glimmers of hope for reconnecting our broken P cycle and the bright new horizons needed to ensure future food, water, and bioresource security for growing global populations.

Future Phosphorus: Advancing New 2D Phosphorus Allotropes and Growing a Sustainable Bioeconomy.

With more than 40 countries currently proposing to boost their national bioeconomies, there is no better time for a clarion call for a "new" bioeconomy, which, at its core, tackles the current disparities and inequalities in phosphorus (P) availability. Existing biofuel production systems have widened P inequalities and contributed to a linear P economy, impairing water quality and accelerating dependence on P fertilizers manufactured from finite nonrenewable phosphate rock reserves. Here, we explore how the emerging bioeconomy in novel, value-added, bio-based products offers opportunities to rethink our stewardship of P. Development of integrated value chains of new bio-based products offers opportunities for codevelopment of "P refineries" to recover P fertilizer products from organic wastes. Advances in material sciences are exploiting unique semiconductor and opto-electrical properties of new "two-dimensional" (2D) P allotropes (2D black phosphorus and blue phosphorus). These novel P materials offer the tantalizing prospect of step-change innovations in renewable energy production and storage, in biomedical applications, and in biomimetic processes, including artificial photosynthesis. They also offer a possible antidote to the P paradox that our agricultural production systems have engineered us into, as well as the potential to expand the future role of P in securing sustainability across both agroecological and technological domains of the bioeconomy. However, a myriad of social, technological, and commercialization hurdles remains to be crossed before such an advanced circular P bioeconomy can be realized. The emerging bioeconomy is just one piece of a much larger puzzle of how to achieve more sustainable and circular horizons in our future use of P.

The Role of Field-Scale Management on Soil and Surface Runoff C/N/P Stoichiometry.

Agricultural runoff is an important contributor to water quality impairment. This study was conducted to evaluate the potential role of field-scale management on carbon (C), nitrogen (N), and phosphorus (P) stoichiometry in soils and runoff from agricultural fields. Cultivated and pasture fields at the Riesel watersheds in central Texas were used for this analysis, and nutrients were transformed to evaluate relative to the Redfield ratio (106 C/16 N/1 P). Using the Redfield ratio, all soil samples were P depleted relative to C and N. The majority of stormflow and baseflow runoff samples contained 9 to 19% Redfield N relative to C and P. Shifting from inorganic fertilizer application to poultry litter as a fertilizer source resulted in increased absolute C, N, and P concentrations in stormflow and baseflow runoff. Increasing rates of poultry litter application increased the Redfield P relative to Redfield C, whereas Redfield N remained relatively constant at roughly 9 to 11% in stormflow runoff from cultivated fields. This study shows how land use and management can affect C/N/P stoichiometry in stormflow and baseflow runoff.

Phosphorus footprint in China over the 1961-2050 period: Historical perspective and future prospect.

The phosphorus footprint (PF) is a novel concept to analyze human burdens on phosphorus resources. However, research on PF approach is still limited, and current several PF studies include incomplete phosphorus sources and have limited quantitative interpretation about the drivers of PF changes, which can help understand future trends of PF. This study develops a more comprehensive PF model by considering crop, livestock and aquatic food, and non-food goods, which covers the mainly phosphorus containing products consumed by human. The model is applied to quantify China's PF from 1961 to 2014, and the results of the model are also used to analyze the factors driving the PF changes and explored China's PF scenarios for 2050 using an econometric analysis model (STIRPAT). The result shows that China's PF increased over 11-fold, from 0.9 to 10.6 Tg between 1961 and 2014. The PF of livestock food dominated China's PF, accounting for 57% of the total in 1961 and 45% in 2014. The key factors driving the increase in China's PF are the increase in population and urbanization rate, with contributions of 38% and 33%, respectively. We showed that in the baseline scenario, China's PF would increase by 70% during 2014-2050 and cause the depletion of China's phosphate reserves in 2045. However, in the best case scenario, China's PF would decrease by 15% in 2050 compared with that in 2014, and it would have 50% of current phosphate reserve remaining by 2050. Several mitigation measures are then proposed by considering China's realities from both production and consumption perspective, which can provide valuable policy insights to other rapid developing countries to mitigate the P footprint.

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.

Future agriculture with minimized phosphorus losses to waters: Research needs and direction.

The series of papers in this issue of AMBIO represent technical presentations made at the 7th International Phosphorus Workshop (IPW7), held in September, 2013 in Uppsala, Sweden. At that meeting, the 150 delegates were involved in round table discussions on major, predetermined themes facing the management of agricultural phosphorus (P) for optimum production goals with minimal water quality impairment. The six themes were (1) P management in a changing world; (2) transport pathways of P from soil to water; (3) monitoring, modeling, and communication; (4) importance of manure and agricultural production systems for P management; (5) identification of appropriate mitigation measures for reduction of P loss; and (6) implementation of mitigation strategies to reduce P loss. This paper details the major challenges and research needs that were identified for each theme and identifies a future roadmap for catchment management that cost-effectively minimizes P loss from agricultural activities.

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.

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.

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.

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.

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.

Internal loading of phosphorus in a sedimentation pond of a treatment wetland: effect of a phytoplankton crash.

Sedimentation ponds are widely believed to act as a primary removal process for phosphorus (P) in nutrient treatment wetlands. High frequency in-situ P, ammonium (NH(4)(+)) and dissolved oxygen measurements, alongside occasional water quality measurements, assessed changes in nutrient concentrations and productivity in the sedimentation pond of a treatment wetland between March and June. Diffusive equilibrium in thin films (DET) probes were used to measure in-situ nutrient and chemistry pore-water profiles. Diffusive fluxes across the sediment-water interface were calculated from the pore-water profiles, and dissolved oxygen was used to calculate rates of primary productivity and respiration. The sedimentation pond was a net sink for total P (TP), soluble reactive P (SRP) and NH(4)(+) in March, but became subject to a net internal loading of TP, SRP and NH(4)(+) in May, with SRP concentrations increasing by up to 41µM (1300µl(-1)). Reductions in chlorophyll a and dissolved oxygen concentrations also occurred at this time. The sediment changed from a small net sink of SRP in March (average diffusive flux: -8.2µmolm(-2)day(-1)) to a net source of SRP in June (average diffusive flux: +1324µmolm(-2)day(-1)). A diurnal pattern in water column P concentrations, with maxima in the early hours of the morning, and minima in the afternoon, occurred during May. The diurnal pattern and release of SRP from the sediment were attributed to microbial degradation of diatom biomass, causing reduction of the dissolved oxygen concentration and leading to redox-dependent release of P from the sediment. In June, 2.7mol-Pday(-1) were removed by photosynthesis and 23mol-Pday(-1) were supplied by respiration in the lake volume. SRP was also released through microbial respiration within the water column, including the decomposition of algal matter. It is imperative that consideration to internal recycling is given when maintaining sedimentation ponds, and before the installation of new ponds designed to treat nutrient waste.