Field and Laboratory Tests of Flow-Proportional Passive Samplers for Determining Average Phosphorus and Nitrogen Concentration in Rivers

Flow responsive passive samplers offer considerable potential in nutrient monitoring in catchments; bridging the gap between the intermittency of grab sampling and the high cost of automated monitoring systems. A commercially available passive sampler was evaluated in a number of river systems encapsulating a gradient in storm response, combinations of diffuse and point source pressures, and levels of phosphorus and nitrogen concentrations. Phosphorus and nitrogen are sequestered to a resin matrix in a permeable cartridge positioned in line with streamflow. A salt tracer dissolves in proportion to advective flow through the cartridge. Multiple deployments of different cartridge types were undertaken and the recovery of P and N compared with the flow-weighted mean concentration (FWMC) from high-resolution bank-side analysers at each site. Results from the passive samplers were variable and largely underestimated the FWMC derived from the bank-side analysers. Laboratory tests using ambient river samples indicated good replication of advective throughflow using pumped water, although this appeared not to be a good analogue of river conditions where flow divergence was possible. Laboratory tests also showed good nutrient retention but not elution and these issues appeared to combine to limit the utility in ambient river systems at the small catchment scale.

Optimization of the electrodialytic phosphorus recovery from sewage sludge ash

Phosphorus (P) is becoming a scarce element due to the decreasing availability of primary sources. Therefore, recover P from secondary sources, e.g. waste streams, have become extremely important. Sewage sludge ash (SSA) is a reliable secondary source of P. The use of SSAs as a direct fertilizer has very restricted legislation due to the presence of inorganic contaminants. Furthermore, the P present in SSAs is not in a plant-available form. The electrodialytic (ED) process is one of the methods under development to recover P and simultaneously remove heavy metals. The present work aimed to optimize the P recovery through a 2 compartment electrodialytic cell. The research was divided in three independent phases. In the first phase, ED experiments were carried out for two SSAs from different seasons, varying the duration of the ED process (2, 4, 6 and 9 days). During the ED treatment the SSA was suspended in distilled water in the anolyte, which was separated from the catholyte by a cation exchange membrane. From both ashes 90% of P was successfully extracted after 6 days of treatment. Regarding the heavy metals removal, one of the SSAs had a better removal than the other. Therefore, it was possible to conclude that SSAs from different seasons can be submitted to ED process under the same parameters. In the second phase, the two SSAs were exposed to humidity and air prior to ED, in order to carbonate them. Although this procedure was not successful, ED experiments were carried out varying the duration of the treatment (2 and 6 days) and the period of air exposure that SSAs were submitted to (7, 14 and 30 days). After 6 days of treatment and 30 days of air exposure, 90% of phosphorus was successfully extracted from both ashes. No differences were identified between carbonated and non-carbonated SSAs. Thus, SSAs that were exposed to the air and humidity, e.g. SSAs stored for 30 days in an open deposit, can be treated under the same parameters as the SSAs directly collected from the incineration process. In the third phase, ED experiments were carried out during 6 days varying the stirring time (0, 1, 2 and 4 h/day) in order to investigate if energy can be saved on the stirring process. After 6 days of treatment and 4 h/day stirring, 80% and 90% of P was successfully extracted from SSA-A and SSA-B, respectively. This value is very similar to the one obtained for 6 days of treatment stirring 24 h/day.

Intervariability of Phosphorus Speciation in Selected Mangrove Ecosystems Around the Greater Cochin

Mangrove forests are best developed on tropical shorelines where there is an extensive intertidal zone, with an abundant supply of fine-grained sediment. It receives a mixture of liable and refractory organic and inorganic phosphorus compounds from the overlying water and the surrounding landmasses. Organic phosphorus is not available for mangrove plant nutrition. While inorganic phosphate represents the largest potential pool of plant-available and which are bound in the form of Ca, Fe and Al phosphate. It deals with the scientific investigations on mangrove systems in the Kerala coastline and to investigate nutrient distribution of mangrove ecosystems of greater Cochin area. It discusses the description of study areas such as Murikkumpadam-Vypeen Island and Aroor. Then it deals with the spatial and seasonal distribution of dissolved ammonia, nitrite, nitrate, inorganic phosphate, organic phosphate and the total phosphorus in surface waters of mangrove fringed creeks. Then it discusses the geochemical compositions of mangrove-fringed sediments and also the chemical speciation of phosphorus in sediment cores.

Effects of fertility management strategies on phosphorus bioavailability in four West African soils

Low phosphorus (P) in acid sandy soils of the West African Sudano-Sahelian zone is a major limitation to crop growth. To compare treatment effects on total dry matter (TDM) of crops and plant available P (P-Bray and isotopically exchangeable P), field experiments were carried out for 2 years at four sites where annual rainfall ranged from 560 to 850 mm and topsoil pH varied between 4.2 and 5.6. Main treatments were: (i) crop residue (CR) mulch at 500 and 2000 kg ha^-1, (ii) eight different rates and sources of P and (iii) cereal/legume rotations including millet (Pennisetum glaucum L.), sorhum [Sorghum bicolor (L.) Moench], cowpea (Vigna unguiculata Walp.) and groundnut (Arachis hypogaea L.). For the two Sahelian sites with large CR-induced differences in TDM, mulching did not modify significantly the soils' buffering capacity for phosphate ions but led to large increases in the intensity factor (C_p) and quantity of directly available soil P (E_1min). In the wetter Sudanian zone lacking effects of CR mulching on TDM mirrored a decline of E_1min with CR. Broadcast application of soluble single superphosphate (SSP) at 13 kg P ha^-1 led to large increases in C_p and quantity of E_1min at all sites which translated in respective TDM increases. The high agronomic efficiency of SSP placement (4 kg P ha^-1) across sites could be explained by consistent increases in the quantity factor which confirms the power of the isotopic exchange method in explaining management effects on crop growth across the region.

Efficient phosphorus application strategies for increased crop production in sub-Saharan West Africa

Comparable data are lacking from the range of environments found in sub-Saharan West Africa to draw more general conclusions about the relative merits of locally available rockphosphate (RockP) in alleviating phosphorus (P) constraints to crop growth. To fill this gap, a multi-factorial field experiment was conducted over 4 years at eight locations in Niger, Burkina Faso and Togo. These ranged in annual rainfall from 510 to 1300 mm. Crops grown were pearl millet (Pennisetum glaucum L.), sorghum (Sorghum bicolor (L.) Moench) and maize (Zea mays L.) either continuously or in rotation with cowpea (Vigna unguiculata Walp.) and groundnut (Arachis hypogaea L.). Crops were subjected to six P fertiliser treatments comprising RockP and soluble P at different rates and combined with 0 and 60 kg N ha^-1. For legumes, time trend analyses showed P-induced total dry matter (TDM) increases between 28 and 72% only with groundnut. Similarly, rotation-induced raises in cereal TDM compared to cereal monoculture were only observed with groundnut. For cereals, at the same rate of application, RockP was comparable to single superphosphate (SSP) only at two millet sites with topsoil pH-KCl <4.2 and annual average rainfall >600 mm. Across the eight sites NPK placement at 0.4 g P per hill raised average cereal yields between 26 and 220%. This was confirmed in 119 on-farm trials revealing P placement as a promising strategy to overcome P deficiency as the regionally most growth limiting nutrient constraint to cereals.

Uncertainty assessment of a process-based integrated catchment model of phosphorus

Despite the many models developed for phosphorus concentration prediction at differing spatial and temporal scales, there has been little effort to quantify uncertainty in their predictions. Model prediction uncertainty quantification is desirable, for informed decision-making in river-systems management. An uncertainty analysis of the process-based model, integrated catchment model of phosphorus (INCA-P), within the generalised likelihood uncertainty estimation (GLUE) framework is presented. The framework is applied to the Lugg catchment (1,077 km2), a River Wye tributary, on the England–Wales border. Daily discharge and monthly phosphorus (total reactive and total), for a limited number of reaches, are used to initially assess uncertainty and sensitivity of 44 model parameters, identified as being most important for discharge and phosphorus predictions. This study demonstrates that parameter homogeneity assumptions (spatial heterogeneity is treated as land use type fractional areas) can achieve higher model fits, than a previous expertly calibrated parameter set. The model is capable of reproducing the hydrology, but a threshold Nash-Sutcliffe co-efficient of determination (E or R 2) of 0.3 is not achieved when simulating observed total phosphorus (TP) data in the upland reaches or total reactive phosphorus (TRP) in any reach. Despite this, the model reproduces the general dynamics of TP and TRP, in point source dominated lower reaches. This paper discusses why this application of INCA-P fails to find any parameter sets, which simultaneously describe all observed data acceptably. The discussion focuses on uncertainty of readily available input data, and whether such process-based models should be used when there isn’t sufficient data to support the many parameters.

The Phosphorus Indicators Tool: a simple model of diffuse P loss from agricultural land to water

The Phosphorus Indicators Tool provides a catchment-scale estimation of diffuse phosphorus (P) loss from agricultural land to surface waters using the most appropriate indicators of P loss. The Tool provides a framework that may be applied across the UK to estimate P loss, which is sensitive not only to land use and management but also to environmental factors such as climate, soil type and topography. The model complexity incorporated in the P Indicators Tool has been adapted to the level of detail in the available data and the need to reflect the impact of changes in agriculture. Currently, the Tool runs on an annual timestep and at a 1 km(2) grid scale. We demonstrate that the P Indicators Tool works in principle and that its modular structure provides a means of accounting for P loss from one layer to the next, and ultimately to receiving waters. Trial runs of the Tool suggest that modelled P delivery to water approximates measured water quality records. The transparency of the structure of the P Indicators Tool means that identification of poorly performing coefficients is possible, and further refinements of the Tool can be made to ensure it is better calibrated and subsequently validated against empirical data, as it becomes available.

Uncertainties in annual riverine phosphorus load estimation: Impact of load estimation methodology, sampling frequency, baseflow index and catchment population density

Models developed to identify the rates and origins of nutrient export from land to stream require an accurate assessment of the nutrient load present in the water body in order to calibrate model parameters and structure. These data are rarely available at a representative scale and in an appropriate chemical form except in research catchments. Observational errors associated with nutrient load estimates based on these data lead to a high degree of uncertainty in modelling and nutrient budgeting studies. Here, daily paired instantaneous P and flow data for 17 UK research catchments covering a total of 39 water years (WY) have been used to explore the nature and extent of the observational error associated with nutrient flux estimates based on partial fractions and infrequent sampling. The daily records were artificially decimated to create 7 stratified sampling records, 7 weekly records, and 30 monthly records from each WY and catchment. These were used to evaluate the impact of sampling frequency on load estimate uncertainty. The analysis underlines the high uncertainty of load estimates based on monthly data and individual P fractions rather than total P. Catchments with a high baseflow index and/or low population density were found to return a lower RMSE on load estimates when sampled infrequently than those with a tow baseflow index and high population density. Catchment size was not shown to be important, though a limitation of this study is that daily records may fail to capture the full range of P export behaviour in smaller catchments with flashy hydrographs, leading to an underestimate of uncertainty in Load estimates for such catchments. Further analysis of sub-daily records is needed to investigate this fully. Here, recommendations are given on load estimation methodologies for different catchment types sampled at different frequencies, and the ways in which this analysis can be used to identify observational error and uncertainty for model calibration and nutrient budgeting studies. (c) 2006 Elsevier B.V. All rights reserved.

Phosphorus sorption and availability in soils amended with animal manures and sewage sludge

Soils that receive large applications of animal wastes and sewage sludge are vulnerable to releasing environmentally significant concentrations of dissolved P available to subsurface flow owing to the gradual saturation of the soil's P sorption capacity. This study evaluated P sorption (calculated from Langmuir isotherms) and availability of P (as CaCl2-P and resin P) in soils incubated for 20 d with poultry litter, poultry manure, cattle slurry, municipal sewage sludge, or KH2PO4, added on a P-equivalent basis (100 mg P kg(-1)). All the P sources had a marked negative effect on P sorption and a positive effect on P availability in all soils. In the cattle slurry- and KH2PO4- treated soils, the decreases in P sorption maximum (19-66%) and binding energy (25-89%) were consistently larger than the corresponding decreases (7-41% and 11-30%) in poultry litter-, poultry manure-, and sewage sludge-treated soils. The effects of cattle slurry and KH2PO4 on P availability were, in most cases, larger than those of the other P sources. In the poultry litter, poultry manure, and sewage sludge treatments, the increase in soil solution P was inversely related (R-2 = 0.75) to the input of Ca from these relatively high Ca (13.5-42 g kg(-1)) sources. Correlation analyses implied that the magnitude of the changes in P sorption and availability was not related to the water-extractable P content of the P sources. Future research on the sustainable application of organic wastes to agricultural soils needs to consider the non-P- as well as P-containing components of the waste.

Evaluation of two hybrid metric-conceptual models, for simulating phosphorus transfer from agricultural land in the river enborne, a lowland UK catchment

Across Europe, elevated phosphorus (P) concentrations in lowland rivers have made them particularly susceptible to eutrophication. This is compounded in southern and central UK by increasing pressures on water resources, which may be further enhanced by the potential effects of climate change. The EU Water Framework Directive requires an integrated approach to water resources management at the catchment scale and highlights the need for modelling tools that can distinguish relative contributions from multiple nutrient sources and are consistent with the information content of the available data. Two such models are introduced and evaluated within a stochastic framework using daily flow and total phosphorus concentrations recorded in a clay catchment typical of many areas of the lowland UK. Both models disaggregate empirical annual load estimates, derived from land use data, as a function of surface/near surface runoff, generated using a simple conceptual rainfall-runoff model. Estimates of the daily load from agricultural land, together with those from baseflow and point sources, feed into an in-stream routing algorithm. The first model assumes constant concentrations in runoff via surface/near surface pathways and incorporates an additional P store in the river-bed sediments, depleted above a critical discharge, to explicitly simulate resuspension. The second model, which is simpler, simulates P concentrations as a function of surface/near surface runoff, thus emphasising the influence of non-point source loads during flow peaks and mixing of baseflow and point sources during low flows. The temporal consistency of parameter estimates and thus the suitability of each approach is assessed dynamically following a new approach based on Monte-Carlo analysis. (c) 2004 Elsevier B.V. All rights reserved.

Dissolution of phosphorus from animal bone char in 12 soils

Heat-treated animal bone char (ABC) has not previously been evaluated for its potential as a phosphorus (P) fertilizer. ABC, Gafsa phosphate rock (GPR) and triple superphosphate fertilizer (TSP) were incubated in 12 soils. Dissolved-P was assessed by extraction with NaOH and bioavailability with the Olsen extractant. The rate of P dissolution from ABC was described almost equally well by the Elovich and Power equations. After 145 days, the fraction of P dissolved ranged from 0 to 73% and to 56% for ABC and GPR, respectively. The most important soil properties determining P dissolution from ABC were pH and P sorption. P dissolution was not significant at soil pH > 6.1 (ABC) and > 5 (GPR) and the lower the pH, the greater the Dissolved-P. Dissolved-P also correlated positively and significantly with inorganic P sorption, measured by the Freundlich isotherm and the P sorption index of Bache and Williams (1971). Soil pH and P sorption index could be combined in multiple regression equations that use readily measured soil properties to predict the potential for ABC dissolution in a soil. Dissolution of P from GPR correlated with soil pH and exchangeable acidity. In comparison with GPR, ABC was a better source of available P, assessed by Olsen-P. In most soils, ABC increased Olsen-P immediately after application, including soils of relatively high pH in which GPR was ineffective. ABC is a P fertilizer of solubility intermediate between GPR and TSP.

Predicting the profile of nutrients available for absorption: from nutrient requirement to animal response and environmental impact

Current feed evaluation systems for dairy cattle aim to match nutrient requirements with nutrient intake at pre-defined production levels. These systems were not developed to address, and are not suitable to predict, the responses to dietary changes in terms of production level and product composition, excretion of nutrients to the environment, and nutrition related disorders. The change from a requirement to a response system to meet the needs of various stakeholders requires prediction of the profile of absorbed nutrients and its subsequent utilisation for various purposes. This contribution examines the challenges to predicting the profile of nutrients available for absorption in dairy cattle and provides guidelines for further improved prediction with regard to animal production responses and environmental pollution. The profile of nutrients available for absorption comprises volatile fatty acids, long-chain fatty acids, amino acids and glucose. Thus the importance of processes in the reticulo-rumen is obvious. Much research into rumen fermentation is aimed at determination of substrate degradation rates. Quantitative knowledge on rates of passage of nutrients out of the rumen is rather limited compared with that on degradation rates, and thus should be an important theme in future research. Current systems largely ignore microbial metabolic variation, and extant mechanistic models of rumen fermentation give only limited attention to explicit representation of microbial metabolic activity. Recent molecular techniques indicate that knowledge on the presence and activity of various microbial species is far from complete. Such techniques may give a wealth of information, but to include such findings in systems predicting the nutrient profile requires close collaboration between molecular scientists and mathematical modellers on interpreting and evaluating quantitative data. Protozoal metabolism is of particular interest here given the paucity of quantitative data. Empirical models lack the biological basis necessary to evaluate mitigation strategies to reduce excretion of waste, including nitrogen, phosphorus and methane. Such models may have little predictive value when comparing various feeding strategies. Examples include the Intergovernmental Panel on Climate Change (IPCC) Tier II models to quantify methane emissions and current protein evaluation systems to evaluate low protein diets to reduce nitrogen losses to the environment. Nutrient based mechanistic models can address such issues. Since environmental issues generally attract more funding from governmental offices, further development of nutrient based models may well take place within an environmental framework.

Contributing understanding of mitigation options for phosphorus and sediment to a review of the efficacy of contemporary agricultural stewardship measures

Experiences from the Mitigation Options for Phosphorus and Sediment (MOPS) projects, which aim to determine the effectiveness of measures to reduce pollutant loading from agricultural land to surface waters, have been used to contribute to the findings of a recent paper (Kay et al., 2009, Agricultural Systems, 99, 67–75), which reviewed the efficacy of contemporary agricultural stewardship measures for ameliorating the water pollution problems of key concern to the UK water industry. MOPS1 is a recently completed 3-year research project on three different soil types in the UK, which focused on mitigation options for winter cereals. MOPS1 demonstrated that tramlines can be the major pathway for sediment and nutrient transfer from arable hillslopes, and that although minimum tillage, crop residue incorporation, contour cultivation, and beetle banks also have potential to be cost-effective mitigation options, tramline management is the one of the most promising treatments for mitigating diffuse pollution losses, as it was able to reduce sediment and nutrient losses by 72–99% in four out of five site years trialled. Using information from the MOPS projects, this paper builds on the findings of Kay et al. to provide an updated picture of the evidence available and the immediate needs for research in this area.

Elevated atmospheric CO2 changes phosphorus fractions in soils under a short rotation poplar plantation (EuroFACE)

Future high levels of atmospheric carbon dioxide (CO2) may increase biomass production of terrestrial plants and hence plant requirements for soil mineral nutrients to sustain a greater biomass production. Phosphorus (P), an element essential for plant growth, is found in soils both in inorganic and in organic forms. In this work, three genotypes of Populus were grown under ambient and elevated atmospheric CO2 concentrations (FACE) for 5 years. An N fertilisation treatment was added in years 4 and 5 after planting. Using a fractionation scheme, total P was sequentially extracted using H2O, NaOH, HCl and HNO3, and P determined as both molybdate (Mo) reactive and total P. Molybdate-reactive P is defined as mainly inorganic but also some labile organic P which is determined by Vanado-molybdophosphoric acid colorimetric methods. Organic P was also measured to assess all plant available and weatherable P pools. We tested the hypotheses that higher P demand due to increased growth is met by a depletion of easily weatherable soil P pools, and that increased biomass inputs increases the amount of organic P in the soil. The concentration of organic P increased under FACE, but was associated with a decrease in total soil organic matter. The greatest increase in the soil P due to elevated CO2 was found in the HCl-extractable P fraction in the non-fertilised treatment. In the NaOH-extractable fraction the Mo-reactive P increased under FACE, but total P did not differ between ambient and FACE. The increase in both the NaOH- and HCl-extractable fractions was smaller after N addition. The results showed that elevated atmospheric CO2 has a positive effect on soil P availability rather than leading to depletion.We suggest that the increase in the NaOH- and HCl-extractable fractions is biologically driven by organic matter mineralization, weathering and mycorrhizal hyphal turnover.

Determining the cost of in-field mitigation options to reduce sediment and phosphorus loss

The Mitigation Options for Phosphorus and Sediment (MOPS) project investigated the effectiveness of within-field control measures (tramline management, straw residue management, type of cultivation and direction, and vegetative buffers) in terms of mitigating sediment and phosphorus loss from winter-sown combinable cereal crops using three case study sites. To determine the cost of the approaches, simple financial spreadsheet models were constructed at both farm and regional levels. Taking into account crop areas, crop rotation margins per hectare were calculated to reflect the costs of crop establishment, fertiliser and agro-chemical applications, harvesting, and the associated labour and machinery costs. Variable and operating costs associated with each mitigation option were then incorporated to demonstrate the impact on the relevant crop enterprise and crop rotation margins. These costs were then compared to runoff, sediment and phosphorus loss data obtained from monitoring hillslope-length scale field plots. Each of the mitigation options explored in this study had potential for reducing sediment and phosphorus losses from arable land under cereal crops. Sediment losses were reduced from between 9 kg ha−1 to as much as 4780 kg ha−1 with a corresponding reduction in phosphorus loss from 0.03 kg ha−1 to 2.89 kg ha−1. In percentage terms reductions of phosphorus were between 9% and 99%. Impacts on crop rotation margins also varied. Minimum tillage resulted in cost savings (up to £50 ha−1) whilst other options showed increased costs (up to £19 ha−1 for straw residue incorporation). Overall, the results indicate that each of the options has potential for on-farm implementation. However, tramline management appeared to have the greatest potential for reducing runoff, sediment, and phosphorus losses from arable land (between 69% and 99%) and is likely to be considered cost-effective with only a small additional cost of £2–4 ha−1, although further work is needed to evaluate alternative tramline management methods. Tramline management is also the only option not incorporated within current policy mechanisms associated with reducing soil erosion and phosphorus loss and in light of its potential is an approach that should be encouraged once further evidence is available.