Total Phosphorus Determination in Soils Using Laser-Induced Breakdown Spectroscopy: Evaluating Different Sources of Matrix Effects.

Laser-induced breakdown spectroscopy (LIBS) is a potential alternative to wet chemical methods for total soil phosphorus determination, but matrix effects related to physical and chemical sample properties need to be further understood. The aim of this study was to explore matrix effects linked to particle size distribution and chemical form of phosphorus on LIBS response and the ability of LIBS to predict total phosphorus in a range of different soil types. Univariate calibration curves were developed by spiking the soils with increasing doses of phosphorus, and limits of detection for LIBS determined phosphorous (P) (LIBS-P) were calculated. Different particle size distributions in otherwise identical soils were obtained by four milling treatments and effects of chemical form of phosphorus were examined by spiking soils with identical amounts of phosphorus in different chemical compounds. The LIBS-P response showed a high correlation (R2 > 0.99) with total phosphorus for all soils. Yet, the sensitivity of LIBS differed significantly among soils, as the slope of the calibration curves increased with increasing sand content, resulting in estimated limits of detection of 10 mg kg-1 for the sandiest and 122 mg · kg-1 for the most clayey soils. These limits indicate that quantitative evaluation of total phosphorus in sandy and loamy sandy soils by LIBS is feasible, since they are lower than typical total phosphorus concentrations in soil. A given milling treatment created different particle size distributions depending on soil type, and consequently different LIBS-P results. Thus, procedures that specify the required degree of homogenization of soil samples prior to analysis are needed. Sieving after milling could be an option, but that should be tested. The soils spiked with Fe(III) phosphate, potassium phosphate and phytic acid had similar LIBS-P, except for soils with hydroxyapatite, which resulted in markedly lower response. These results suggested that matrix effects related to the chemical nature of phosphorus would be minor for non-calcareous soils in humid regions, where apatites comprise only a small fraction of total phosphorus. Strategies to overcome matrix effects related to particle size and content of apatite-phosphorus by combining multivariate models and soil type groupings should be further investigated.

A Global Perspective on Integrated Strategies to Manage Soil Phosphorus Status for Eutrophication Control without Limiting Land Productivity.

Unnecessary accumulation of phosphorus (P) in agricultural soils continues to degrade water quality and linked ecosystem services. Managing both soil loss and soil P fertility status is therefore crucial for eutrophication control, but the relative environmental benefits of these two mitigation measures, and the timescales over which they occur, remain unclear. To support policies toward reduced P loadings from agricultural soils, we examined the impact of soil conservation and lowering of soil test P (STP) in different regions with intensive farming (Europe, the United States, and Australia). Relationships between STP and soluble reactive P concentrations in land runoff suggested that eutrophication control targets would be more achievable if STP concentrations were kept at or below the current recommended threshold values for fertilizer response. Simulations using the Annual P Loss Estimator (APLE) model in three contrasting catchments predicted total P losses ranging from 0.52 to 0.88 kg ha depending on soil P buffering and erosion vulnerability. Drawing down STP in all catchment soils to the threshold optimum for productivity reduced catchment P loss by between 18 and 40%, but this would take between 30 and 40+ years. In one catchment, STP drawdown was more effective in reducing P loss than erosion control, but combining both strategies was always the most effective and more rapid than erosion control alone. By accounting for both soil P buffering interactions and erosion vulnerability, the APLE model quickly provided reliable information on the magnitude and time frame of P loss reduction that can be realistically expected from soil and STP management. Greater precision in the sampling, analysis, and interpretation of STP, and more technical innovation to lower agronomic optimum STP concentrations on farms, is needed to foster long-term sustainable management of soil P fertility in the future.

Management Options to Reduce Phosphorus Leaching from Vegetated Buffer Strips.

Vegetated buffer strips (VBS) between agricultural areas and surface waters are important retention areas for eroded particulate P through which they may obtain critically high degrees of P saturation imposing high risk of soluble P leaching. We tested topsoil removal and three harvesting frequencies (once, twice, or four times per year) of natural buffer vegetation to reduce P leaching with the aim to offset erosional P accumulation and high degrees of P saturation. We used a simple numerical time-step model to estimate changes in VBS soil P levels with and without harvest. Harvesting offset erosional deposition as it resulted in an annual ammonium oxalate-extractable P reduction of 0.3 to 2.8% (25-cm topsoil content) in soils of the VBS and thus, with time, reduced potential P leaching below a baseline of 50 µg L. Topsoil removal only marginally reduced potential leaching at two sites and not anywhere near this baseline. The harvest frequency only marginally affected the annual P removal, making single annual harvests the most economical. We estimate 50 to 300 yr to reach the P leaching baseline, due to substantial amounts of P accumulated in the soils. Even in high-erosion-risk situations in our study, harvesting reduced soil P content and the P leaching risk. We suggest harvesting as a practical and efficient management to combat P leaching from agricultural VBS, not just for short-term reductions of dissolved P, but also for reductions of the total soil P pool and for possible multiple benefits for VBS.

High plant availability of phosphorus and low availability of cadmium in four biomass combustion ashes.

For biomass combustion to become a sustainable energy production system, it is crucial to minimise landfill of biomass ashes, to recycle the nutrients and to minimise the undesirable impact of hazardous substances in the ash. In order to test the plant availability of phosphorus (P) and cadmium (Cd) in four biomass ashes, we conducted two pot experiments on a P-depleted soil and one mini-plot field experiment on a soil with adequate P status. Test plants were spring barley and Italian ryegrass. Ash applications were compared to triple superphosphate (TSP) and a control without P application. Both TSP and ash significantly increased crop yields and P uptake on the P-depleted soil. In contrast, on the adequate-P soil, the barley yield showed little response to soil amendment, even at 300-500kgPha(-1) application, although the barley took up more P at higher applications. The apparent P use efficiency of the additive was 20% in ryegrass - much higher than that of barley for which P use efficiencies varied on the two soils. Generally, crop Cd concentrations were little affected by the increasing and high applications of ash, except for relatively high Cd concentrations in barley after applying 25Mgha(-1) straw ash. Contrarily, even modest increases in the TSP application markedly increased Cd uptake in plants. This might be explained by the low Cd solubility in the ash or by the reduced Cd availability due to the liming effect of ash. High concentrations of resin-extractable P (available P) in the ash-amended soil after harvest indicate that the ash may also contribute to P availability for the following crops. In conclusion, the biomass ashes in this study had P availability similar to the TSP fertiliser and did not contaminate the crop with Cd during the first year.

Stewardship to tackle global phosphorus inefficiency: The case of Europe.

The inefficient use of phosphorus (P) in the food chain is a threat to the global aquatic environment and the health and well-being of citizens, and it is depleting an essential finite natural resource critical for future food security and ecosystem function. We outline a strategic framework of 5R stewardship (Re-align P inputs, Reduce P losses, Recycle P in bioresources, Recover P in wastes, and Redefine P in food systems) to help identify and deliver a range of integrated, cost-effective, and feasible technological innovations to improve P use efficiency in society and reduce Europe's dependence on P imports. Their combined adoption facilitated by interactive policies, co-operation between upstream and downstream stakeholders (researchers, investors, producers, distributors, and consumers), and more harmonized approaches to P accounting would maximize the resource and environmental benefits and help deliver a more competitive, circular, and sustainable European economy. The case of Europe provides a blueprint for global P stewardship.

Characterization of leached phosphorus from soil, manure, and manure-amended soil by physical and chemical fractionation and Diffusive Gradients in Thin films (DGT).

We are challenged to date to fully understand mechanisms controlling phosphorus (P) mobilization in soil. In this study we evaluated physical properties, chemical reactivity, and potential bioavailability of P mobilized in soil during a leaching event and examined how the amounts and properties of leached P were influenced by surface application of cattle manure. Leaching experiments on manure itself, and on intact soil columns (14.1 cm inner dia., 25 cm height) before and after manure application, were carried out at an irrigation rate of 1 mm h(-1) for 48 h. High concentrations of dissolved reactive P (DRP) were found in manure leachates (up to 32 mg L(-1)), whereas concentrations of P in soil leachates were low both before and after manure application (around 0.04 mg L(-1) before application and up to 0.4 mg L(-1) afterward). This result indicates that the soil retained most of the P added with manure. Manure particles themselves were also largely retained by the soil. Combined physical (centrifugation) and chemical (molybdate reactiveness) fractionation of leached P showed that leachates in the manure treated soils were dominated by dissolved unreactive P (DUP), mainly originating from manure. However, centrifugation only removed a small fraction of total particles from the leachates, indicating that the so-called dissolved fraction may be associated with low density particulate matter. Deployment of Diffusive Gradients in Thin films (DGT) devices in the leachates proved to be a good approach for measuring reactive P in soil leachates. The results indicated that total reactive P (TRP) gave a better estimate of potentially bioavailable P than both total P (TP) and DRP in these experiments.

Interactions between soil texture and placement of dairy slurry application: II. Leaching of phosphorus forms.

Managing phosphorus (P) losses in soil leachate folllowing land application of manure is key to curbing eutrophication in many regions. We compared P leaching from columns of variably textured, intact soils (20 cm diam., 20 cm high) subjected to surface application or injection of dairy cattle (Bos taurus L.) manure slurry. Surface application of slurry increased P leaching losses relative to baseline losses, but losses declined with increasing active flow volume. After elution of one pore volume, leaching averaged 0.54 kg P ha(-1) from the loam, 0.38 kg P ha(-1) from the sandy loam, and 0.22 kg P ha(-1) from the loamy sand following surface application. Injection decreased leaching of all P forms compared with surface application by an average of 0.26 kg P ha(-1) in loam and 0.23 kg P ha(-1) in sandy loam, but only by 0.03 kg P ha(-1) in loamy sand. Lower leaching losses were attributed to physical retention of particulate P and dissolved organic P, caused by placing slurry away from active flow paths in the fine-textured soil columns, as well as to chemical retention of dissolved inorganic P, caused by better contact between slurry P and soil adsorption sites. Dissolved organic P was less retained in soil after slurry application than other P forms. On these soils with low to intermediate P status, slurry injection lowered P leaching losses from clay-rich soil, but not from the sandy soils, highlighting the importance of soil texture in manageing P losses following slurry application.

International phosphorus workshop: diffuse phosphorus loss to surface water bodies--risk assessment, mitigation options, and ecological effects in river basins.

Agriculture is a major source of P to the aquatic environment in many countries. Although efforts have been made to improve the P utilization in agricultural production, which is reflected in modestly declining P surpluses in many countries, increasing agricultural P surpluses are still observed in some countries. The IPW5 Special Submission included in this issue addresses and discusses four key topics that emerged from the workshop: (i) managing agricultural P losses-effectiveness, uncertainties, and costs; (ii) P modeling at different scales; (iii) functioning of riparian buffers; (iv) ecological responses to P loadings and impacts of climate change. Each of these four topics interacts with each other as well as with the four tiers of the P Transfer Continuum (Source, Mobilization, Transport, and Ecological Effects). In this review paper we highlight the main outcomes of the workshop and the special collection of eight papers. Moreover, we identify the main gaps in our knowledge and future research directions on P, which are linked to important issues such as addressing scale effects, improved P models with the ability to quantify uncertainty, the linking of P losses with ecological effects, and climate change.

Critical evaluation of the implementation of mitigation options for phosphorus from field to catchment scales.

Nutrient regulations have been developed over the past decades to limit anthropogenic inputs of phosphorus (P) to surface waters. All of the regulations were promulgated in response to decreased water quality, which was at least partially associated with agricultural non-point source pollution. Improvements in water quality can take years, so the impacts of these regulations on water quality can not always be seen. Denmark has had nutrient management regulations aimed at achieving mass balance of P for 20 yr, and although great progress has been made, an average surplus of 11 kg P ha(-1) remains. Northern Ireland is also trying to move toward mass balance, but decreases in inorganic P fertilizer use have been undermined by an increase in the use of feed concentrates. In the Chesapeake Bay watershed, which covers several states in the USA, a variety of best management practices are starting to have an effect on P losses from agriculture, but water quality has only improved slightly. Impairment to the supply of drinking water to the City of Tulsa Oklahoma led to a lawsuit that has greatly affected the management of poultry litter in the supplying watershed. This paper discusses the different regulations that have developed in these four regions, evaluates the strategies used to prevent non-point source pollution of P, reports impacts on water quality, and looks for lessons that can be learned as we move forward.