Analysis of reactive phosphorus treatment by filter materials at the edge of tile-drained agricultural catchments: A global view of the current status and challenges.

Phosphorus losses from agriculture have long generated concern due to the ecological impact on surface waters. Here tile-drained agricultural catchments are a critical source for concentrating and transporting phosphorus bioavailable forms or dissolved reactive phosphorus (DRP). Hence, edge-of-field technologies have been introduced to reduce DRP loads. Filter systems have received special attention due to their targeted approach using a permeable filter material (FM) rich in DRP sorbents. This review explores the performance and applicability of FMs in the aforementioned context because of the growing number of studies. An overall analysis revealed that sorption is preferable to precipitation for DRP retention at the edge-of-field, and that FM pH and particle size affect sorption properties and subsequently DRP retention and lifetime. Thus, FMs with predominant amounts of iron and/or aluminium can be recommended. Such materials generally have an appreciable availability of DRP binding sites, strong bonds with DRP and short reaction times, as well as low desorption, which lead to good operation. On the other hand, FMs with predominant amounts of calcium and/or magnesium are restricted to catchments with favourable conditions unless they have optimal reactivity for DRP. The review also found that hydraulic retention time plays a key role in the performance and applicability of FMs, especially in those dependent on precipitation reactions. Therefore, it is crucial that FMs are designed, constructed and managed according to the catchment conditions-including normally varying flow rates and DRP concentrations-in order to ensure successful operation. This reflects in long-term, high and steady net DRP retention along with low costs, thus improving the FM cost-effectiveness, besides discharging non-harmful effluents to aquatic ecosystems.

Combining Laser-Induced Breakdown Spectroscopy (LIBS) and Visible Near-Infrared Spectroscopy (Vis-NIRS) for Soil Phosphorus Determination.

Conventional wet chemical methods for the determination of soil phosphorus (P) pools, relevant for environmental and agronomic purposes, are labor-intensive. Therefore, alternative techniques are needed, and a combination of the spectroscopic techniques-in this case, laser-induced breakdown spectroscopy (LIBS)-and visible near-infrared spectroscopy (vis-NIRS) could be relevant. We aimed at exploring LIBS, vis-NIRS and their combination for soil P estimation. We analyzed 147 Danish agricultural soils with LIBS and vis-NIRS. As reference measurements, we analyzed water-extractable P (Pwater), Olsen P (Polsen), oxalate-extractable P (Pox) and total P (TP) by conventional wet chemical protocols, as proxies for respectively leachable, plant-available, adsorbed inorganic P, and TP in soil. Partial least squares regression (PLSR) models combined with interval partial least squares (iPLS) and competitive adaptive reweighted sampling (CARS) variable selection methods were tested, and the relevant wavelengths for soil P determination were identified. LIBS exhibited better results compared to vis-NIRS for all P models, except for Pwater, for which results were comparable. Model performance for both the LIBS and vis-NIRS techniques as well as the combined LIBS-vis-NIR approach was significantly improved when variable selection was applied. CARS performed better than iPLS in almost all cases. Combined LIBS and vis-NIRS models with variable selection showed the best results for all four P pools, except for Pox where the results were comparable to using the LIBS model with CARS. Merging LIBS and vis-NIRS with variable selection showed potential for improving soil P determinations, but larger and independent validation datasets should be tested in future studies.

Long-term phosphorus removal by Ca and Fe-rich drainage filter materials under variable flow and inlet concentrations.

Phosphorus (P) losses from tile-drained agricultural fields may degrade surface water quality by accelerating eutrophication. Among the different edge-of-field technologies, compact filter systems using different filter materials have been identified as potentially effective solutions for removing P from drainage water before discharge downstream. This study investigated the long-term (>696 days) P removal efficiency of 5 different filter materials in a column setup, using artificial drainage water (pH 6). Filter materials included two iron-based granulates (calcinated diatomaceous earth (CDE), ferric hydroxide granules (CFH)), and three calcium-based granulates (seashells, limestone, calcinated silicate/calcium oxide (Filtralite-P)). Experiments were performed under variable flow rates (0.037 and 1.52 L h-1; hydraulic retention time of 26-43 min and 18-30 h) and inlet P concentrations (0.14 and 0.7 mg L-1). An overall analysis revealed that the Fe-based materials achieved higher P retention than Ca-based materials. In particular, CFH was capable of retaining 99 and 98 % of the high and low inlet P concentrations, respectively. Conversely, limestone retained only 25 % of the high P load. CDE performed moderately well, independently of the inlet P concentration. Filtralite-P and Seashells performed well at high inlet P concentration but relatively poorly at low P concentration. The sensitivity of filter material P removal efficiency to variations in P loading was generally lowest for CFH and highest for limestone.

Predicting phosphorus losses with the PLEASE model on a local scale in Denmark and the Netherlands.

To reduce losses from agricultural soils to surface water, mitigation options have to be implemented as a local scale. For a cost-effective implementation of these measures, an instrument to identify critical areas for P leaching is indispensable. In many countries, P-index methods are used to identify areas as risk for P losses to surface water. In flat areas, where losses by leaching are dominant, these methods have their limitations because leaching is often not described in detail, PLEASE, is a simple mechanistic model designed to stimulate P Losses by leaching at the field scale using a limited amount of local field data. In this study, PLEASE, was applied to 17 lowland sites in Denmark and 14 lowland sites in the Netherlands. Results show that the simple model simulated measured fluxes and concentrations in water from pipe drains, suction cups, and groundwater quite well. The modeling efficiency ranged from 0.92 for modeling total-P fluxes to 0.36 fr modeling concentrations in groundwater. Poor results were obtained for heavy clay soils and eutrophic peat soils, where fluxes and concentration were strongly underestimated by the model. The poot performance for the heavy clay soil can be explained by the transport of P through macropores to the drain pipes and the underestimation of overland flow on this heavy-textured soil. In the eutrophic peat soils, fluxes were underestimated due to the release of P from deep soil layers.

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.

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.

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.

An Assessment of the Multifunctionality of Integrated Buffer Zones in Northwestern Europe.

Integrated buffer zones (IBZs) have recently been introduced in the Northwestern Europe temperate zone to improve delivery of ecosystem services compared with the services associated with long-established vegetated buffer zones. A common feature of all the studied IBZ sites is that tile drainage, which previously discharged directly into the streams, is now intercepted within the IBZ. Specifically, the design of IBZs combines a pond, where soil particles present in drain water or surface runoff can be deposited, and a planted subsurface flow infiltration zone. Together, these two components should provide an optimum environment for microbial processes and plant uptake of nutrients. Nutrient reduction capacities, biodiversity enhancement, and biomass production functions were assessed with different emphasis across 11 IBZ sites located in Denmark, Great Britain, and Sweden. Despite the small size of the buffer zones (250-800 m) and thus the small proportion of the drained catchment (mostly <1%), these studies cumulatively suggest that IBZs are effective enhancements to traditional buffer zones, as they (i) reduce total N and P loads to small streams and rivers, (ii) act as valuable improved habitats for aquatic and amphibian species, and (iii) offer economic benefits by producing fast-growing wetland plant biomass. Based on our assessment of the pilot sites, guidance is provided on the implementation and management of IBZs within agricultural landscapes.

Mapping areas at risk of diffuse phosphorus losses to water: a pilot study of Lake Haderslev Dam, Denmark.

Haderslev Dam is a 272 ha lake in southern Denmark with a high recreational value. For decades the lake has been severely eutrophicated due to excessive phosphorus loading. Major point sources were cut off in the early 1990s and an upstream wetland was recreated. However, the ecological quality remains unsatisfactory. In this study we estimate the importance of agriculture on diffuse phosphorus (P) input to the lake by modelling combined with independent estimates for contributions from scattered dwellings not connected to a sewer and from background losses. We apply a newly developed Danish P index to the lake catchment for mapping of risk areas for diffuse phosphorus losses. For risk areas we suggest mitigation measures and estimate the effect of the mitigation measures on the total P loading of the lake as well as the associated costs.