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.

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 .

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.

Celebrating the 350th Anniversary of Phosphorus Discovery: A Conundrum of Deficiency and Excess.

2019 will be the 350th anniversary of the discovery of phosphorus (P) by the alchemist Henning Brandt. This perspective traces the historical threads that P has weaved through the fabric of our society and identifies challenges to improve P stewardship in the future and for our future. A century after Brandt's discovery, P was identified in bone ash, which became the primary source of P until guano and ultimately rock P was mined to provide the various mineral formulations used today. Owing to limited supplies, a strategic shift in resource management ethics-from exploiting to conserving P resources-is needed. In agriculture, remedial strategies should consider when conservation practices can transition from P sinks to sources; however, a broader, long-term strategy for P stewardship is needed. This must include educing P loss in food and other wastes, ecovering P from waste streams, eusing P generated beneficial by-products, and estructuring production systems. A key action to enact such changes will be collaboration across all sectors of society and the supply chain, from field to fork and beyond. As this will likely increase the cost of food, fiber, and feed production, it will require an innovative mix of public and private initiatives.

A review of regulations and guidelines related to winter manure application.

Winter manure application elevates nutrient losses and impairment of water quality as compared to manure applications in other seasons. In conjunction with reviewing global distribution of animal densities, we reviewed worldwide mandatory regulations and voluntary guidelines on efforts to reduce off-site nutrient losses associated with winter manure applications. Most of the developed countries implement regulations or guidelines to restrict winter manure application, which range from a regulative ban to guidelines based upon weather and field management conditions. In contrast, developing countries lack such official directives, despite an increasing animal production industry and concern over water quality. An analysis of five case studies reveals that directives are derived from a common rationale to reduce off-site manure nutrient losses, but they are also affected by local socio-economic and biophysical considerations. Successful programs combine site-specific management strategies along with expansion of manure storage to offer farmers greater flexibility in winter manure management.

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.

Evaluation of Phosphorus Site Assessment Tools: Lessons from the USA.

Critical source area identification through phosphorus (P) site assessment is a fundamental part of modern nutrient management planning in the United States, yet there has been only sparse testing of the many versions of the P Index that now exist. Each P site assessment tool was developed to be applicable across a range of field conditions found in a given geographic area, making evaluation extremely difficult. In general, evaluation with in-field monitoring data has been limited, focusing primarily on corroborating manure and fertilizer "source" factors. Thus, a multiregional effort (Chesapeake Bay, Heartland, and Southern States) was undertaken to evaluate P Indices using a combination of limited field data, as well as output from simulation models (i.e., Agricultural Policy Environmental eXtender, Annual P Loss Estimator, Soil and Water Assessment Tool [SWAT], and Texas Best Management Practice Evaluation Tool [TBET]) to compare against P Index ratings. These comparisons show promise for advancing the weighting and formulation of qualitative P Index components but require careful vetting of the simulation models. Differences among regional conclusions highlight model strengths and weaknesses. For example, the Southern States region found that, although models could simulate the effects of nutrient management on P runoff, they often more accurately predicted hydrology than total P loads. Furthermore, SWAT and TBET overpredicted particulate P and underpredicted dissolved P, resulting in correct total P predictions but for the wrong reasons. Experience in the United States supports expanded regional approaches to P site assessment, assuming closely coordinated efforts that engage science, policy, and implementation communities, but limited scientific validity exists for uniform national P site assessment tools at the present time.

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.

Evaluation of the APEX Model to Simulate Runoff Quality from Agricultural Fields in the Southern Region of the United States.

The Agricultural Policy Environmental eXtender (APEX) model has been widely applied to assess phosphorus (P) loss in runoff water and has been proposed as a model to support practical decisions regarding agricultural P management, as well as a model to evaluate tools such as the P Index. The aim of this study is to evaluate the performance of APEX to simulate P losses from agricultural systems to determine its potential use for refinement or replacement of the P Index in the southern region of the United States. Uncalibrated and calibrated APEX model predictions were compared against measured water quality data from row crop fields in North Carolina and Mississippi and pasture fields in Arkansas and Georgia. Calibrated models satisfactorily predicted event-based surface runoff volumes at all sites (Nash-Sutcliffe efficiency [NSE] > 0.47, |percent bias [PBIAS]| < 34) except Arkansas (NSE < 0.11, |PBIAS| < 50) but did not satisfactory simulate sediment, dissolved P, or total P losses in runoff water. The APEX model tended to underestimate dissolved and total P losses from fields where manure was surface applied. The model also overestimated sediments and total P loads during irrigation events. We conclude that the capability of APEX to predict sediment and P losses is limited, and consequently so is the potential for using APEX to make P management recommendations to improve P Indices in the southern United States.

Short-term Forecasting Tools for Agricultural Nutrient Management.

The advent of real-time, short-term farm management tools is motivated by the need to protect water quality above and beyond the general guidance offered by existing nutrient management plans. Advances in high-performance computing and hydrologic or climate modeling have enabled rapid dissemination of real-time information that can assist landowners and conservation personnel with short-term management planning. This paper reviews short-term decision support tools for agriculture that are under various stages of development and implementation in the United States: (i) Wisconsin's Runoff Risk Advisory Forecast (RRAF) System, (ii) New York's Hydrologically Sensitive Area Prediction Tool, (iii) Virginia's Saturated Area Forecast Model, (iv) Pennsylvania's Fertilizer Forecaster, (v) Washington's Application Risk Management (ARM) System, and (vi) Missouri's Design Storm Notification System. Although these decision support tools differ in their underlying model structure, the resolution at which they are applied, and the hydroclimates to which they are relevant, all provide forecasts (range 24-120 h) of runoff risk or soil moisture saturation derived from National Weather Service Forecast models. Although this review highlights the need for further development of robust and well-supported short-term nutrient management tools, their potential for adoption and ultimate utility requires an understanding of the appropriate context of application, the strategic and operational needs of managers, access to weather forecasts, scales of application (e.g., regional vs. field level), data requirements, and outreach communication structure.

Southern Phosphorus Indices, Water Quality Data, and Modeling (APEX, APLE, and TBET) Results: A Comparison.

Phosphorus (P) Indices in the southern United States frequently produce different recommendations for similar conditions. We compared risk ratings from 12 southern states (Alabama, Arkansas, Florida, Georgia, Kentucky, Louisiana, Mississippi, North Carolina, Oklahoma, South Carolina, Tennessee, and Texas) using data collected from benchmark sites in the South (Arkansas, Georgia, Mississippi, North Carolina, Oklahoma, and Texas). Phosphorus Index ratings were developed using both measured erosion losses from each benchmark site and Revised Universal Soil Loss Equation 2 predictions; mostly, there was no difference in P Index outcome. The derived loss ratings were then compared with measured P loads at the benchmark sites by using equivalent USDA-NRCS P Index ratings and three water quality models (Annual P Loss Estimator [APLE], Agricultural Policy Environmental eXtender [APEX], and Texas Best Management Practice Evaluation Tool [TBET]). Phosphorus indices were finally compared against each other using USDA-NRCS loss ratings model estimate correspondence with USDA-NRCS loss ratings. Correspondence was 61% for APEX, 48% for APLE, and 52% for TBET, with overall P index correspondence at 55%. Additive P Indices (Alabama and Texas) had the lowest USDA-NRCS loss rating correspondence (31%), while the multiplicative (Arkansas, Florida, Louisiana, Mississippi, South Carolina, and Tennessee) and component (Georgia, Kentucky, and North Carolina) indices had similar USDA-NRCS loss rating correspondence-60 and 64%, respectively. Analysis using Kendall's modified Tau suggested that correlations between measured and calculated P-loss ratings were similar or better for most P Indices than the models.

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.

Spatially-Distributed Cost-Effectiveness Analysis Framework to Control Phosphorus from Agricultural Diffuse Pollution.

Best management practices (BMPs) for agricultural diffuse pollution control are implemented at the field or small-watershed scale. However, the benefits of BMP implementation on receiving water quality at multiple spatial is an ongoing challenge. In this paper, we introduce an integrated approach that combines risk assessment (i.e., Phosphorus (P) index), model simulation techniques (Hydrological Simulation Program-FORTRAN), and a BMP placement tool at various scales to identify the optimal location for implementing multiple BMPs and estimate BMP effectiveness after implementation. A statistically significant decrease in nutrient discharge from watersheds is proposed to evaluate the effectiveness of BMPs, strategically targeted within watersheds. Specifically, we estimate two types of cost-effectiveness curves (total pollution reduction and proportion of watersheds improved) for four allocation approaches. Selection of a ''best approach" depends on the relative importance of the two types of effectiveness, which involves a value judgment based on the random/aggregated degree of BMP distribution among and within sub-watersheds. A statistical optimization framework is developed and evaluated in Chaohe River Watershed located in the northern mountain area of Beijing. Results show that BMP implementation significantly (p >0.001) decrease P loss from the watershed. Remedial strategies where BMPs were targeted to areas of high risk of P loss, deceased P loads compared with strategies where BMPs were randomly located across watersheds. Sensitivity analysis indicated that aggregated BMP placement in particular watershed is the most cost-effective scenario to decrease P loss. The optimization approach outlined in this paper is a spatially hierarchical method for targeting nonpoint source controls across a range of scales from field to farm, to watersheds, to regions. Further, model estimates showed targeting at multiple scales is necessary to optimize program efficiency. The integrated model approach described that selects and places BMPs at varying levels of implementation, provides a new theoretical basis and technical guidance for diffuse pollution management in agricultural watersheds.

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.

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.

Implementing agricultural phosphorus science and management to combat eutrophication.

Experience with implementing agricultural phosphorus (P) strategies highlights successes and uncertainty over outcomes. We examine case studies from the USA, UK, and Sweden under a gradient of voluntary, litigated, and regulatory settings. In the USA, voluntary strategies are complicated by competing objectives between soil conservation and dissolved P mitigation. In litigated watersheds, mandated manure export has not wrought dire consequences on poultry farms, but has adversely affected beef producers who fertilize pastures with manure. In the UK, regulatory and voluntary approaches are improving farmer awareness, but require a comprehensive consideration of P management options to achieve downstream reductions. In Sweden, widespread subsidies sometime hinder serious assessment of program effectiveness. In all cases, absence of local data can undermine recommendations from models and outside experts. Effective action requires iterative application of existing knowledge of P fate and transport, coupled with unabashed description and demonstration of tradeoffs to local stakeholders.

Managing agricultural phosphorus for water quality: lessons from the USA and China.

The accelerated eutrophication of freshwaters and to a lesser extent some coastal waters is primarily driven by phosphorus (P) inputs. While efforts to identify and limit point source inputs of P to surface waters have seen some success, nonpoint sources remain difficult to identify, target, and remediate. As further improvements in wastewater treatment technologies becomes increasingly costly, attention has focused more on nonpoint source reduction, particularly the role of agriculture. This attention was heightened over the last 10 to 20 years by a number of highly visible cases of nutrient-related water quality degradation; including the Lake Taihu, Baltic Sea, Chesapeake Bay, and Gulf of Mexico. Thus, there has been a shift to targeted management of critical sources of P loss. In both the U.S. and China, there has been an intensification of agricultural production systems in certain areas concentrate large amounts of nutrients in excess of local crop and forage needs, which has increased the potential for P loss from these areas. To address this, innovative technologies are emerging that recycle water P back to land as fertilizer. For example, in the watershed of Lake Taihu, China one of the largest surface fresh waters for drinking water supply in China, local governments have encouraged innovation and various technical trials to harvest harmful algal blooms and use them for bio-gas, agricultural fertilizers, and biofuel production. In any country, however, the economics of remediation will remain a key limitation to substantial changes in agricultural production.