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.

Comparing an Annual and a Daily Time-Step Model for Predicting Field-Scale Phosphorus Loss.

A wide range of mathematical models are available for predicting phosphorus (P) losses from agricultural fields, ranging from simple, empirically based annual time-step models to more complex, process-based daily time-step models. In this study, we compare field-scale P-loss predictions between the Annual P Loss Estimator (APLE), an empirically based annual time-step model, and the Texas Best Management Practice Evaluation Tool (TBET), a process-based daily time-step model based on the Soil and Water Assessment Tool. We first compared predictions of field-scale P loss from both models using field and land management data collected from 11 research sites throughout the southern United States. We then compared predictions of P loss from both models with measured P-loss data from these sites. We observed a strong and statistically significant ( < 0.001) correlation in both dissolved (ρ = 0.92) and particulate (ρ = 0.87) P loss between the two models; however, APLE predicted, on average, 44% greater dissolved P loss, whereas TBET predicted, on average, 105% greater particulate P loss for the conditions simulated in our study. When we compared model predictions with measured P-loss data, neither model consistently outperformed the other, indicating that more complex models do not necessarily produce better predictions of field-scale P loss. Our results also highlight limitations with both models and the need for continued efforts to improve their accuracy.

Surface runoff and tile drainage transport of phosphorus in the midwestern United States.

The midwestern United States offers some of the most productive agricultural soils in the world. Given the cool humid climate, much of the region would not be able to support agriculture without subsurface (tile) drainage because high water tables may damage crops and prevent machinery usage in fields at critical times. Although drainage is designed to remove excess soil water as quickly as possible, it can also rapidly transport agrochemicals, including phosphorus (P). This paper illustrates the potential importance of tile drainage for P transport throughout the midwestern United States. Surface runoff and tile drainage from fields in the St. Joseph River Watershed in northeastern Indiana have been monitored since 2008. Although the traditional concept of tile drainage has been that it slowly removes soil matrix flow, peak tile discharge occurred at the same time as peak surface runoff, which demonstrates a strong surface connection through macropore flow. On our research fields, 49% of soluble P and 48% of total P losses occurred via tile discharge. Edge-of-field soluble P and total P areal loads often exceeded watershed-scale areal loadings from the Maumee River, the primary source of nutrients to the western basin of Lake Erie, where algal blooms have been a pervasive problem for the last 10 yr. As farmers, researchers, and policymakers search for treatments to reduce P loading to surface waters, the present work demonstrates that treating only surface runoff may not be sufficient to reach the goal of 41% reduction in P loading for the Lake Erie Basin.

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.

Effects of long-term poultry litter application on phosphorus soil chemistry and runoff water quality.

Continuous application of poultry litter (PL) significantly changes many soil properties, including soil test P (STP); Al, Fe, and Ca concentrations; and pH, which can affect the potential for P transport in surface runoff water. We conducted rainfall simulations on three historically acidic silt loam soils in Arkansas, Missouri, and Virginia to establish if long-term PL applications would affect soil inorganic P fractions and the resulting dissolved reactive P (DRP) in runoff water. Soil samples (0-5 cm depth) were taken to find sites ranging in Mehlich-3 STP from 20 to 1154 mg P kg. Simulated rainfall events were conducted on 3-m plots at 6.7 cm h, and runoff was collected for 30 min. Correlation between Mehlich-3 and runoff DRP indicated a linear relationship to 833 mg Mehlich-3 P kg. As Mehlich-3 STP increased, a concomitant increase in soil pH and Ca occurred on all soils. Soil P fractionation demonstrated that, as Mehlich-3 STP generally increased above 450 mg P kg (from high to very high), the easily soluble and loosely bound P fractions decreased by 3 to 10%. Water-insoluble complexes of P bound to Al and Ca were the main drivers in the reduction of DRP in runoff, accounting for up to 43 and 38% of total P, respectively. Basing runoff DRP concentration projections solely on Mehlich-3 STP may overestimate runoff P losses from soils receiving long-term PL applications due to dissolution of water-insoluble Ca-P compounds.

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.

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.

Using a phosphorus loss model to evaluate and improve phosphorus indices.

In most states, the phosphorus (P) index (PI) is the adopted strategy for assessing a field's vulnerability to P loss; however, many state PIs have not been rigorously evaluated against measured P loss data to determine how well the PI assigns P loss risk-a major reason being the lack of field data available for such an analysis. Given the lack of P loss data available for PI evaluation, our goal was to demonstrate how a P loss model can be used to evaluate and revise a PI using the Pennsylvania (PA) PI as an example. Our first objective was to compare two different formulations-multiplicative and component-for calculating a PI. Our second objective was to evaluate whether output from a P loss model can be used to improve PI weighting by calculating weights for modified versions of the PA PI from model-generated P loss data. Our results indicate that several potential limitations exist with the original multiplicative index formulation and that a component formulation is more consistent with how P loss is calculated with P loss models and generally provides more accurate estimates of P loss. Moreover, using the PI weights calculated from the model-generated data noticeably improved the correlation between PI values and a large and diverse measured P loss data set. The approach we use here can be used with any P loss model and PI and thus can serve as a guide to assist states in evaluating and modifying their PI.

Change point analysis of phosphorus trends in the Illinois River (Oklahoma) demonstrates the effects of watershed management.

Detecting water quality improvements following watershed management changes is complicated by flow-dependent concentrations and nonlinear or threshold responses that are difficult to detect with traditional statistical techniques. In this study, we evaluated the long-term trends (1997-2009) in total P (TP) concentrations in the Illinois River of Oklahoma, and some of its major tributaries, using flow-adjusted TP concentrations and regression tree analysis to identify specific calendar dates in which change points in P trends may have occurred. Phosphorus concentrations at all locations were strongly correlated with stream flow. Flow-adjusted TP concentrations increased at all study locations in the late 1990s, but this trend was related to a change in monitoring practices where storm flow samples were specifically targeted after 1998. Flow-adjusted TP concentrations decreased in the two Illinois River sites after 2003. This change coincided with a significant decrease in effluent TP concentrations originating with one of the largest municipal wastewater treatment facilities in the basin. Conversely, flow-adjusted TP concentrations in one tributary increased, but this stream received treated effluent from a wastewater facility where effluent TP did not decrease significantly over the study period. Results of this study demonstrate how long-term trends in stream TP concentrations are difficult to quantify without consistent long-term monitoring strategies and how flow adjustment is likely mandatory for examining these trends. Furthermore, the study demonstrates how detecting changes in long-term water quality data sets requires statistical methods capable of identifying change point and nonlinear responses.

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.

Critical source area management of agricultural phosphorus: experiences, challenges and opportunities.

The concept of critical source areas of phosphorus (P) loss produced by coinciding source and transport factors has been studied since the mid 1990s. It is widely recognized that identification of such areas has led to targeting of management strategies and conservation practices that more effectively mitigate P transfers from agricultural landscapes to surface waters. Such was the purpose of P Indices and more complex nonpoint source models. Despite their widespread adoption across the U.S., a lack of water quality improvement in certain areas (e.g. Chesapeake Bay Watershed and some of its tributaries) has challenged critical source area management to be more restrictive. While the role of soil and applied P has been easy to define and quantify, representation of transport processes still remains more elusive. Even so, the release of P from land management and in-stream buffering contribute to a legacy effect that can overwhelm the benefits of critical source area management, particularly as scale increases (e.g. the Chesapeake Bay). Also, conservation tillage that reduces erosion can lead to vertical stratification of soil P and ultimately increased dissolved P loss. Clearly, complexities imparted by spatially variable landscapes, climate, and system response will require iterative monitoring and adaptation, to develop locally relevant solutions. To overcome the challenges we have outlined, critical source area management must involve development of a 'toolbox' that contains several approaches to address the underlying problem of localized excesses of P and provide both spatial and temporal management options. To a large extent, this may be facilitated with the use of GIS and digital elevation models. Irrespective of the tool used, however, there must be a two-way dialogue between science and policy to limit the softening of technically rigorous and politically difficult approaches to truly reducing P losses.

Estimating dissolved phosphorus losses from legacy sources in pastures: The limits of soil tests and small-scale rainfall simulators.

A legacy of using P fertilizers on grazed pastures has been enhanced soil fertility and an associated increased risk of P loss in runoff. Rainfall simulation has been extensively used to develop relationships between soil test P (STP) and dissolved P (DP) in runoff as part of modeling efforts scrutinizing the impact of legacy P. This review examines the applicability of rainfall simulation to draw inferences related to legacy P. Using available literature, we propose a mixing layer model with chemical transfer to describe DP mobilization from pasture soils where readily available P in the mixing layer is rapidly exhausted and contact time controls DP concentrations responsible for subsequent DP mobilization. That conceptual model was shown to be consistent with field monitoring data and then used to assess the likely effect of rainfall simulation protocols on DP mobilization, highlighting the influence of soil preparation, scale and measurement duration, and, most important, hydrology that can facilitate the physical transport of P into and out of surface flow. We conclude that rainfall simulation experimental protocols can have severe limitations for developing relationships between DP in runoff and STP that are subsequently used to estimate legacy P contributions to downstream water resources.

Evaluating the success of phosphorus management from field to watershed.

Studies have demonstrated some P loss reduction following implementation of remedial strategies at field scales. However, there has been little coordinated evaluation of best management practices (BMPs) on a watershed scale to show where, when, and which work most effectively. Thus, it is still difficult to answer with a degree of certainty, critical questions such as, how long before we see a response and where would we expect to observe the greatest or least response? In cases where field and watershed scales are monitored, it is not uncommon for trends in P loss to be disconnected. We review case studies demonstrating that potential causes of the disconnect varies, from competing sources of P at watershed scales that are not reflected in field monitoring to an abundance of sinks at watershed scales that buffer field sources. To be successful, P-based mitigation strategies need to occur iteratively, involve stakeholder driven programs, and address the inherent complexity of all P sources within watersheds.

Nitrogen fate in drainage ditches of the coastal plain after dredging.

Drainage ditches are a key conduit of nitrogen (N) from agricultural fields to surface water. The effect of ditch dredging, a common practice to improve drainage, on the fate of N in ditch effluent is not well understood. This study evaluated the effect of dredging on N transport in drainage ditches of the Delmarva Peninsula. Sediments from two ditches draining a single field were collected (0-5 cm) to represent conditions before and after dredging. Sediments were packed in 10-m-long recirculating flumes and subjected to a three-phase experiment to assess the sediment's role as a sink or source of ammonium (NH4) and nitrate (NO3). Under conditions of low initial NH4-N and NO3-N concentrations in flume water, sediment from the undredged ditch released 113 times more NO3-N to water than did sediment from the dredged ditch. When flume water was spiked with NH4-N and NO3-N to simulate increases in N concentrations from drainage and runoff from adjacent fields, NO3-N in flume water increased during 48 h compared with the initial spiked concentration, while NH4-N decreased. These simultaneous changes were attributed to nitrification, with 23% more NO3-N observed in flume water with undredged ditch sediment compared with dredged ditch sediment. Replacing the N-spiked water with deionized water resulted in two times more NO3-N released from the undredged ditch sediment than the dredged ditch sediment. These results suggest that ditch sediments could represent significant stores of N and that dredging could greatly affect the ditch sediment's ability to temporarily assimilate N input from field drainage.

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.

Development of PLEAD: A Database Containing Event-based Runoff Phosphorus Loadings from Agricultural Fields.

Computer models are commonly used for predicting risks of runoff P loss from agricultural fields by enabling simulation of various management practices and climatic scenarios. For P loss models to be useful tools, however, they must accurately predict P loss for a wide range of climatic, physiographic, and land management conditions. A complicating factor in developing and evaluating P loss models is the relative scarcity of available measured field data that adequately capture P losses before and after implementing management practices in a variety of physiographic settings. Here, we describe the development of the P Loss in runoff Events from Agricultural fields Database (PLEAD)-a compilation of event-based, field-scale dissolved and/or total P loss runoff loadings from agricultural fields collected at various research sites located in the US Heartland and southern United States. The database also includes runoff and erosion rates; soil-test P; tillage practices; planting and harvesting rates and practices; fertilizer application rate, method, and timing; manure application rate, method, and timing; and livestock grazing density and timing. In total, >1800 individual runoff events-ranging in duration from 0.4 to 97 h-have been included in the database. Event runoff P losses ranged from <0.05 to 1.3 and 3.0 kg P ha for dissolved and total P, respectively. The data contained in this database have been used in multiple research studies to address important modeling questions relevant to P management planning. We provide these data to encourage additional studies by other researchers. The PLEAD database is available at .