Spatial representation of in-stream sediment phosphorus release combining channel network approaches and in-situ experiments.

Impairment of rivers by elevated phosphorus (P) concentration is an issue often studied at outlets of mesoscale catchments. Our objective was to evaluate within-catchment spatio-temporal processes along connected reaches to understand processes of internal P loading associated with sediment input, accumulations in channels and sediment-water column P exchange. Our overall hypothesis was that heterogeneous sediment residence within the channel of a 52 km2 mixed land cover catchment resulted in key zones for sediment-water P exchange. We evaluated the channel network through ground-survey, spatial data methods establishing connectivity and energy gradients. This gave a background to understand sampling of sediments and P release/uptake to the water column using 90 s in-situ resuspension isolating a portion of streambed over five sets of three-location transects in May (spring storms, recent active erosion) and September (summer low flow, longer sediment residence). Simple transect position models (top, mid, bottom) predicted increased sediment resuspension yields and P contents in lower settings. Sediment P release following resuspension were mean (and range) 0.5 (-0.8 to 1.8) and 0.5 (-2.5 to 3.6) mg soluble reactive P/m2 bed in May and September, respectively, strengthening generally down the transects but inconsistently. Relationships (log form) showed a steepening rise in fine sediments, P content, background and disturbance-released dissolved P, with specific stream power < 40 W/m2. In-situ methods showed sediments dominantly (12 cases May, 13 cases Sep) as P sources capable of influencing dissolved P concentrations and with potential explanation that heterogeneous locations of internal P loading influence the systems longer-term observed P trends. Combining channel network, stream power assessment and in-situ sorption studies improved the understanding of influential zones of sediment-water P exchange within this mesoscale catchment. Such methods have potential to inform P model development and management.

Phosphorus leaching from riparian soils with differing management histories under three grass species.

Plants release carbon-based exudates from their roots into the rhizosphere to increase phosphorus (P) supply to the soil solution. However, if more P than required is brought into solution, additional P could be available for leaching from riparian soils. To investigate this further, soil columns containing a riparian arable and buffer strip soil, which differed in organic matter contents, were sown with three common agricultural and riparian grass species. The P loads in leachate were measured and compared with those from unplanted columns, which were 0.17 ± 0.01 and 0.89 ± 0.04 mg kg-1 for the arable and buffer strip soil, respectively. A mixture of ryegrass and red fescue significantly (p ≤ .05) increased dissolved inorganic P loads in leachate from the arable (0.23 ± 0.01 mg kg-1 ) and buffer strip soil (1.06 ± 0.05 mg kg-1 ), whereas barley significantly reduced P leaching from the buffer strip soil (0.53 ± 0.08 mg kg-1 ). This was dependent on the dissolved organic C released under different plant species and on interactions with soil management history and biogeochemical conditions, rather than on plant uptake of P and accumulation into biomass. This suggested that the amount and forms of P present in the soil and the ability of the plants to mobilize them could be key factors in determining how plants affect leaching of soil P. Selecting grass species for different stages of buffer strip development, basing species selection on root physiological traits, and correcting soil nutrient stoichiometry in riparian soils through vegetative mining could help to lower this contribution.

Modeling the Ecological Impact of Phosphorus in Catchments with Multiple Environmental Stressors.

The broken phosphorus (P) cycle has led to widespread eutrophication of freshwaters. Despite reductions in anthropogenic nutrient inputs that have led to improvement in the chemical status of running waters, corresponding improvements in their ecological status are often not observed. We tested a novel combination of complementary statistical modeling approaches, including random-effect regression trees and compositional and ordinary linear mixed models, to examine the potential reasons for this disparity, using low-frequency regulatory data available to catchment managers. A benthic Trophic Diatom Index (TDI) was linked to potential stressors, including nutrient concentrations, soluble reactive P (SRP) loads from different sources, land cover, and catchment hydrological characteristics. Modeling suggested that SRP, traditionally considered the bioavailable component, may not be the best indicator of ecological impacts of P, as shown by a stronger and spatially more variable negative relationship between total P (TP) concentrations and TDI. Nitrate-N ( < 0.001) and TP ( = 0.002) also showed negative relationship with TDI in models where land cover was not included. Land cover had the strongest influence on the ecological response. The positive effect of seminatural land cover ( < 0.001) and negative effect of urban land cover ( = 0.030) may be related to differentiated bioavailability of P fractions in catchments with different characteristics (e.g., P loads from point vs. diffuse sources) as well as resilience factors such as hydro-morphology and habitat condition, supporting the need for further research into factors affecting this stressor-response relationship in different catchment types. Advanced statistical modeling indicated that to achieve desired ecological status, future catchment-specific mitigation should target P impacts alongside multiple stressors.

Simultaneous Quantification of Soil Phosphorus Labile Pool and Desorption Kinetics Using DGTs and 3D-DIFS.

The buffering of phosphorus concentrations in soil solution by the soil-solid phase is an important process for providing plant root access to nutrients. Accordingly, the size of labile solid phase-bound phosphorus pool and the rate at which it can resupply phosphorous into the dissolved phase can be important variables in determining when the plant availability of the nutrient may be limited. The phosphorus labile pool (Plabile) and its desorption kinetics were simultaneously evaluated in 10 agricultural UK soils using the diffusive gradients in thin-films (DGT) technique. The DGT-induced fluxes in the soil and sediments model (DIFS) was fitted to the time series of DGT deployments (1-240 h), which allowed the estimation of Plabile, and the system response time ( Tc). The Plabile concentration was then compared to that obtained by several soil P extracts including Olsen P, FeO-P, and water extractable P, in order to assess if the data from these analytical procedures can be used to represent the labile P across different soils. The Olsen P concentration, commonly used as a representation of the soil labile P pool, overestimated the desorbable P concentration by 6-fold. The use of this approach for the quantification of soil P desorption kinetic parameters found a wide range of equally valid solutions for Tc. Additionally, the performance of different DIFS model versions working in different dimensions (1D, 2D, and 3D) was compared. Although all models could provide a good fit to the experimental DGT time series data, the fitted parameters showed a poor agreement between different model versions. The limitations of the DIFS model family are associated with the assumptions taken in the modeling approach and the three-dimensional (3D) version is here considered to be the most precise among them.

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.

Is Green Manure from Riparian Buffer Strip Species an Effective Nutrient Source for Crops?

Agriculture needs to reduce inputs of inorganic fertilizers and close the loop on nutrients that can otherwise become environmental pollutants. This can be achieved by promoting recycling of nutrients within the agricultural landscape. We investigated the extent to which plants found in riparian buffer zones have the potential to provide nutrients to crops as a green manure, through plant growth and decomposition studies. Under controlled conditions, species typical of Scottish riparian buffer strips were tested for their ability to accumulate biomass and nutrients in tissue under N- and P-replete conditions and whether this ability enhanced the utility of the resulting green manure in promoting crop growth. In this proof-of-concept study, we found that green manure derived from riparian buffer strips did not effectively replace inorganic fertilizer and only had a significant positive effect on growth, yield, and nutrient accumulation in barley ( L.) when it was integrated with the addition of inorganic fertilizers. The individual species tested varied in the amount of P they accumulated in their tissue (1.38-52.73 mg P plant), but individual species did not differ in their ability to promote yield when used as a green manure. Our results indicate that selecting certain species in the buffer strip on the basis of their nutrient accumulating abilities is not an effective way to increase the utility of buffer strip green manure as a nutrient source for crops.

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.

Potential tracers for tracking septic tank effluent discharges in watercourses.

Septic tank effluent (STE) contributes to catchment nutrient and pollutant loads. To assess the role of STE discharges in impairment of surface water, it is essential to identify the sources of pollution by tracing contaminants in watercourses. We examined tracers that were present in STE to establish their potential for identifying STE contamination in two stream systems (low and high dilution levels) against the background of upstream sources. The studied tracers were microbial, organic matter fluorescence, caffeine, artificial sweeteners and effluent chemical concentrations. The results revealed that tracer concentration ratios Cl/EC, Cl/NH4-N, Cl/TN, Cl/TSS, Cl/turbidity, Cl/total coliforms, Cl/sucralose, Cl/saccharin and Cl/Zn had potential as tracers in the stream with low dilution level (P < 0.05). Fluorescence spectroscopy could detect STE inputs through the presence of the tryptophan-like peak, but was limited to water courses with low level of dilution and was positively correlated with stream Escherichia coli (E. coli) and soluble reactive phosphorus (SRP). The results also suggested that caffeine and artificial sweeteners can be suitable tracers for effluent discharge in streams with low and high level of dilution. Caffeine and saccharin were positively correlated with faecal coliforms, E. coli, total P and SRP, indicating their potential to trace discharge of a faecal origin and to be a marker for effluent P. Caffeine and SRP had similar attenuation behaviour in the receiving stream waters suggesting caffeine's potential role as a surrogate indicator for the behaviour of P downstream of effluent inputs. Taken together, results suggest that a single tracer alone was not sufficient to evaluate STE contamination of watercourses, but rather a combination of multiple chemical and physical tracing approaches should be employed. A multiple tracing approach would help to identify individual and cumulative STE inputs that pose risks to stream waters in order to prioritise and target effective mitigation measures.

Response-based selection of barley cultivars and legume species for complementarity: Root morphology and exudation in relation to nutrient source.

Phosphorus (P) and nitrogen (N) use efficiency may be improved through increased biodiversity in agroecosystems. Phenotypic variation in plants' response to nutrient deficiency may influence positive complementarity in intercropping systems. A multicomponent screening approach was used to assess the influence of P supply and N source on the phenotypic plasticity of nutrient foraging traits in barley (H. vulgare L.) and legume species. Root morphology and exudation were determined in six plant nutrient treatments. A clear divergence in the response of barley and legumes to the nutrient treatments was observed. Root morphology varied most among legumes, whereas exudate citrate and phytase activity were most variable in barley. Changes in root morphology were minimized in plants provided with ammonium in comparison to nitrate but increased under P deficiency. Exudate phytase activity and pH varied with legume species, whereas citrate efflux, specific root length, and root diameter lengths were more variable among barley cultivars. Three legume species and four barley cultivars were identified as the most responsive to P deficiency and the most contrasting of the cultivars and species tested. Phenotypic response to nutrient availability may be a promising approach for the selection of plant combinations for minimal input cropping systems.

Removal and attenuation of sewage effluent combined tracer signals of phosphorus, caffeine and saccharin in soil.

Contaminants in septic tank effluent (STE) are expected to be removed by the soil system before discharging to the environment. However, potential contaminants such as phosphorus (P), caffeine and artificial sweeteners do find their way to watercourses impacting aquatic eco systems. In this study, the attenuation of STE P, caffeine and saccharin were investigated in untreated soil and in soil with reduced microbial activity, in aqueous solutions and in the complex matrix of STE. Time series sorption and desorption experiments using batch equilibrium and a column experiment of STE P attenuation were conducted. The results revealed that the soil distribution coefficients (Kd) were: P 81.57 > caffeine 22.16 > saccharin 5.98 cm3/g, suggesting greater soil affinity to P adsorption. The data revealed that 80% of saccharin and 33% of caffeine attenuation was associated with microbial activities rather than adsorption processes. However, a complete removal of saccharin and caffeine did not occur during the equilibration period, suggesting their leaching potential. The dominant mechanism of P attenuation was adsorption (chemical and physical), yielding P retention of >73% and 35% for P in aqueous solution and in STE matrix, respectively, for batch equilibrium. The soil in the column acted as effluent P sink retaining 125 µg P/g soil of effluent P. The attenuation of P, caffeine and saccharin in the aqueous solution was greater than in STE, suggesting that the complex composition of STE reduced soil adsorption ability, and that other substances present in STE may be competing for soil binding sites. The data revealed that caffeine and P had similarities in the interaction with soils and thus caffeine may be considered as a STE tracer of anthropogenic source of P in receiving waters.

Organic Acids Regulation of Chemical-Microbial Phosphorus Transformations in Soils.

We have used an integrated approach to study the mobility of inorganic phosphorus (P) from soil solid phase as well as the microbial biomass P and respiration at increasing doses of citric and oxalic acid in two different soils with contrasting agronomic P status. Citric or oxalic acids significantly increased soil solution P concentrations for doses over 2 mmol kg-1. However, low organic acid doses (<2 mmol kg-1) were associated with a steep increase in microbial biomass P, which was not seen for higher doses. In both soils, treatment with the tribasic citric acid led to a greater increase in soil solution P than the dibasic oxalic acid, likely due to the rapid degrading of oxalic acids in soils. After equilibration of soils with citric or oxalic acids, the adsorbed-to-solution distribution coefficient (Kd) and desorption rate constants (k-1) decreased whereas an increase in the response time of solution P equilibration (Tc) was observed. The extent of this effect was shown to be both soil and organic acid specific. Our results illustrate the critical thresholds of organic acid concentration necessary to mobilize sorbed and precipitated P, bringing new insight on how the exudation of organic acids regulate chemical-microbial soil phosphorus transformations.

A Holistic Approach to Understanding the Desorption of Phosphorus in Soils.

The mobility and resupply of inorganic phosphorus (P) from the solid phase were studied in 32 soils from the UK. The combined use of diffusive gradients in thin films (DGT), diffusive equilibration in thin films (DET) and the "DGT-induced fluxes in sediments" model (DIFS) were adapted to explore the basic principles of solid-to-solution P desorption kinetics in previously unattainable detail. On average across soil types, the response time (Tc) was 3.6 h, the desorption rate constant (k-1) was 0.0046 h(-1), and the desorption rate was 4.71 nmol l(-1) s(-1). While the relative DGT-induced inorganic P flux responses in the first hour is mainly a function of soil water retention and % Corg, at longer times it is a function of the P resupply from the soil solid phase. Desorption rates and resupply from solid phase were fundamentally influenced by P status as reflected by their high correlation with P concentration in FeO strips, Olsen, NaOH-EDTA and water extracts. Soil pH and particle size distribution showed no significant correlation with the evaluated mobility and resupply parameters. The DGT and DET techniques, along with the DIFS model, were considered accurate and practical tools for studying parameters related to soil P desorption kinetics.

Septic tank discharges as multi-pollutant hotspots in catchments.

Small point sources of pollutants such as septic tanks are recognised as significant contributors to streams' pathogen and nutrient loadings, however there is little data in the UK on which to judge the potential risks that septic tank effluents (STEs) pose to water quality and human health. We present the first comprehensive analysis of STE to help assess multi-pollutant characteristics, management-related risk factors and potential tracers that might be used to identify STE sources. Thirty-two septic tank effluents from residential households located in North East of Scotland were sampled along with adjacent stream waters. Biological, physical, chemical and fluorescence characterisation was coupled with information on system age, design, type of tank, tank management and number of users. Biological characterisation revealed that total coliforms and Escherichia coli (E. coli) concentration ranges were: 10(3)-10(8) and 10(3)-10(7)MPN/100 mL, respectively. Physical parameters such as electrical conductivity, turbidity and alkalinity ranged 160-1730 µS/cm, 8-916 NTU and 15-698 mg/L, respectively. Effluent total phosphorus (TP), soluble reactive P (SRP), total nitrogen (TN) and ammonium-N (NH4-N) concentrations ranged 1-32, <1-26, 11-146 and 2-144 mg/L, respectively. Positive correlations were obtained between phosphorus, sodium, potassium, barium, copper and aluminium. Domestic STE may pose pollution risks particularly for NH4-N, dissolved P, SRP, copper, dissolved N, and potassium since enrichment factors were >1651, 213, 176, 63, 14 and 8 times that of stream waters, respectively. Fluorescence characterisation revealed the presence of tryptophan peak in the effluent and downstream waters but not detected upstream from the source. Tank condition, management and number of users had influenced effluent quality that can pose a direct risk to stream waters as multiple points of pollutants.

The composition, leaching, and sorption behavior of some alternative sources of phosphorus for soils.

Concerns about the sustainability of inorganic fertilizers necessitate the characterization of alternative P source materials for agronomic P-efficiencies and P losses via leaching. Firstly, this study examined nutrient compositions including P speciation of seven soil amendments: sewage sludge (SS), anaerobic digestate (AD), green compost (GC), food waste compost (FWC), chicken manure (CM), biochar, and seaweed. Secondly, soil P leaching and availability was studied on a subset of four materials (SS, AD, GC, and CM). Sorption of extracts onto columns of a test soil showed strong P retention for SS and compost, but weak P sorption for CM and especially AD, suggesting short-term leaching risks for soil applied AD. Limited P desorption with water or citrate indicated sorbed P was strongly fixed, potentially limiting crop availability. These data indicate that variation in P forms and environmental behavior should be understood to maximize P usage, but minimize leaching and soil P accumulation. Hence, different alternative P source materials need differing recommendations for their agronomic management.

The contribution of household chemicals to environmental discharges via effluents: combining chemical and behavioural data.

Increased concentrations and loads of soluble, bioavailable forms of phosphorus (P) are a major cause of eutrophication in streams, rivers and lakes in many countries around the world. To implement P control measures, it is essential to identify P sources and their relative load contributions. A proportion of P loading generated from household wastewaters is derived from detergents yet the P compositions of the range of domestic detergents and their usage is poorly understood. To quantify P loads from household detergents, we analysed a large range of detergents and cleaning products commonly available in the UK and Europe, comparing regular and eco-labelled products. Chemical data were coupled with survey results on typical household detergents preferences and usage (n = 95 households). We also determined whether the major and trace element signatures of these household detergents could potentially be used as anthropogenic tracers in watercourses. The greatest P concentrations were found for regular dishwasher detergents (43-131 mg P/g detergent) whilst the range of P in eco-labelled dishwasher detergents was much lower (0.7-9.1 mg P/g detergent). Other household cleaning groups contained relatively smaller P concentrations. Considering the survey results, detergents' total P loading generated from one household using either regular or eco labelled products, was 0.414 and 0.021 kg P/year, respectively. Given a household occupancy of 2.7, the P load from all detergent use combined was 0.154 kg P/person/year of which the dishwasher contribution was 0.147 kg P/person/year. In terms of elemental signatures, (DWD) dishwasher detergents were significantly (P-value <0.001) different from other household cleaning products in their As, Na, TP, Si, Sr, SRP, Ti, Zn and Zr signatures. Na, P and B were all positively correlated with each other, indicating their potential use as a tracer suite for septic tank effluent in combination with other indices. We conclude that forthcoming legislation for reducing P contents in domestic laundry detergents will not address the dominant environmental P load from DWD and studies such as this are important in promoting and allowing scenarios of benefits from future legislation for DWD.

Relationships between soil physicochemical, microbiological properties, and nutrient release in buffer soils compared to field soils.

The retention of nutrients in narrow, vegetated riparian buffer strips (VBS) is uncertain and underlying processes are poorly understood. Evidence suggests that buffer soils are poor at retaining dissolved nutrients, especially phosphorus (P), necessitating management actions if P retention is not to be compromised. We sampled 19 buffer strips and adjacent arable field soils. Differences in nutrient retention between buffer and field soils were determined using a combined assay for release of dissolved P, N, and C forms and particulate P. We then explored these differences in relation to changes in soil bulk density (BD), moisture, organic matter by loss on ignition (OM), and altered microbial diversity using molecular fingerprinting (terminal restriction fragment length polymorphism [TRFLP]). Buffer soils had significantly greater soil OM (89% of sites), moisture content (95%), and water-soluble nutrient concentrations for dissolved organic C (80%), dissolved organic N (80%), dissolved organic P (55%), and soluble reactive P (70%). Buffer soils had consistently smaller bulk densities than field soils. Soil fine particle release was generally greater for field than buffer soils. Significantly smaller soil bulk density in buffer soils than in adjacent fields indicated increased porosity and infiltration in buffers. Bacterial, archaeal, and fungal communities showed altered diversity between the buffer and field soils, with significant relationships with soil BD, moisture, OM, and increased solubility of buffer nutrients. Current soil conditions in VBS appear to be leading to potentially enhanced nutrient leaching via increasing solubility of C, N, and P. Manipulating soil microbial conditions (by management of soil moisture, vegetation type, and cover) may provide options for increasing the buffer storage for key nutrients such as P without increasing leaching to adjacent streams.

Phosphorus retention and remobilization in vegetated buffer strips: a review.

Diffuse pollution remains a major threat to surface waters due to eutrophication caused by phosphorus (P) transfer from agricultural land. Vegetated buffer strips (VBSs) are increasingly used to mitigate diffuse P losses from agricultural land, having been shown to reduce particulate P transfer. However, retention of dissolved P (DP) has been lower, and in some cases VBSs have increased delivery to surface waters. The aims of this review were (i) to develop a conceptual model to enhance the understanding of VBS functioning in terms of DP, (ii) to identify key processes within the model that affect DP retention and delivery, and (iii) to explore evidence for the controls on these processes. A greater understanding in these areas will allow the development of management strategies that enhance DP retention. We found evidence of a surface layer in buffer strip soils that is enriched in soluble P compared with adjacent agricultural land and may be responsible for the reported increased DP delivery. Through increased biological activity in VBSs, plants and microorganisms may assimilate P from particulates retained in the VBSs or native soil P and remobilize this P in a more soluble form. These conclusions are based on a limited amount of research, and a better understanding of biogeochemical cycling of P in buffer strip soils is required.

Vegetated buffer strips can lead to increased release of phosphorus to waters: a biogeochemical assessment of the mechanisms.

Establishing vegetated buffer strips (VBS) between cropland and watercourses is currently promoted as a principal control of diffuse pollution transport. However, we lackthe mechanistic understanding to evaluate P retention in VBS and predict risks of P transport to aquatic ecosystems. We observed that VBS establishment led to enhanced rates of soil P cycling, increasing soil P solubility and the potential amount leached to watercourses. Soil in VBS, relative to adjacentfields, had increased inorganic P solubility indices, dissolved organic P, phosphatase enzyme activity, microbial diversity, and biomass P. Small relative increases in the pool of soil P rendered labile had disproportionate effects on the P available for leaching. We propose a mechanism whereby the establishment of VBS on previous agricultural land causes a diversifying plant-microbial system which can access previous immobilized soil P from past fertilization or trapped sediment P. Laboratory experiments suggested that sediment-P inputs to VBS were insufficient alone to increase P solubility without biological cycling. Results showthat VBS management may require strategies, for example, harvesting vegetation, to offset biochemical processes that can increase the susceptibility of VBS soil P to move to adjoining streams.