Effect of pH on the development of acidic sites in clayey and sandy loam Oxisol from the Cerrado Region, Brazil

Titration curves were determined for soil from horizon samples of a clayey and a sandy loam Oxisol by (a) adding NaOH to soil suspensions and (b) incubating moist soils with Ca(OH)(2). The organic fraction was primarily responsible for buffering in both soils. Humic acids were more important than fulvic acids in buffering against NaOH additions. With Ca(OH)(2), greater buffer capacities were found due to carboxyl sites, primarily on fulvic acids, becoming complexed with Ca2+ so that in the clay soil humic and fulvic acids were equally important as buffering components while fulvic acids were more important in the sandy loam soil. The buffer capacity of organic matter against Ca(OH)(2) additions was 1.1 mol(c) kg(-1) pH(-1). In the incubated soils, exchangeable cations were also determined and changes in the amounts of exchangeable and non-exchangeable Ca2+ acidity and effective cation exchange capacity were calculated. Up to half the added Ca2+ became complexed and was nonexchangeable. Aluminum complexed by organic matter appears to be an important buffering component, together with non exchangeable H+. With the increase of pH the dissociated sites from the carboxyl groups could complex Ca2+. (c) 2005 Elsevier B.V. All rights reserved.

Acid-base reactions between an acidic soil and plant residues

The elemental composition of residues of maize (Zea mays), sorghum (S. bicolor), groundnuts (Arachis hypogea), soya beans (Glycine max), leucaena (L. leucocephala), gliricidia (G. sepium), and sesbania (S. sesban) was determined as a basis for examining their alkalinity when incorporated into an acidic Zambian Ferralsol. Potential (ash) alkalinity, available alkalinity by titration to pH 4 and soluble alkalinity (16 It water extract titrated to pH 4) were measured. Potential alkalinity ranged from 3 73 (maize) to 1336 (groundnuts) mmol kg(-1) and was equivalent to the excess of their cation charge over inorganic anion charge. Available alkalinity was about half the potential alkalinity. Cations associated with organic anions are the source of alkalinity. About two thirds of the available alkalinity is soluble. Residue buffer curves were determined by titration with H2SO4 to pH 4. Soil buffer capacity measured by addition of NaOH was 12.9 mmol kg(-1) pH(-1). Soil and residue (10 g:0.25 g) were shaken in solution for 24 h and suspension pH values measured. Soil pH increased from 4.3 to between 4.6 (maize) and 5.2 (soyabean) and the amounts of acidity neutralized (calculated from the rise in pH and the soil buffer capacity) were between 3.9 and 11.5 mmol kg(-1), respectively. The apparent base contributions by the residues (calculated from the buffer curves and the fall in pH) ranged between 105 and 350 mmol kg(-1) of residue, equivalent to 2.6 and 8.8 mmol kg(-1) of soil, respectively. Therefore, in contact with soil acidity, more alkalinity becomes available than when in contact with H2SO4 solution. Available alkalinity (to pH 4) would be more than adequate to supply that which reacts with soil but soluble alkalinity would not. It was concluded that soil Al is able to displace cations associated with organic anions in the residues which are not displaced by H+, or that residue decomposition may have begun in the soil suspension releasing some of the non-available alkalinity. Soil and four of the residues were incubated for 100 days and changes in pH, NH4+ and NO3- concentrations measured. An acidity budget equated neutralized soil acidity with residue alkalinity and base or acid produced by N transformations. Most of the potential alkalinity of soyabean and leucaena had reacted after 14 days, but this only occurred after 100 days for gliricidia, and for maize only the available alkalinity reacted. For gliricidia and leucaena, residue alkalinity was primarily used to react with acidity produced by nitrification. Thus, the ability of residues to ameliorate acidity depends not only on their available and potential alkalinity but also on their potential to release mineral N. (C) 2004 Elsevier B.V. All rights reserved.

Utilisation by upland rice of plant residue- and fertiliser-phosphorus in two tropical acid soils

A dual isotopic technique was used to assess the effects of soil type, and residues of Gliricidia sepium, without and with added fertiliser-P on the utilisation of P. Upland rice (Oryza sativa) was grown for 70 days in two tropical acid soils of different P sorbing capacity and P status. Uniformly P-32-labelled soils were treated with inorganic fertiliser-P tagged with P-33, Gliricidia sepium residue applied at planting and 3 weeks earlier, and in a combination of fertiliser-P and Gliricidia applied at and 3 weeks before planting. There were significant responses of shoot and root weights, and total P uptake to Gliricidia- and/or fertiliser-P addition in the Ultisol (low P status) but not the Oxisol (high P status), suggesting that P in the latter soil was not yield limiting, despite the high standard P requirement. Similarly, incorporation of Gliricidia three weeks before planting further increased shoot weight only in the Ultisol. There were generally higher proportions, quantities and percent utilisations of the Gliricidia- P and fertiliser-P in the Ultisol than in the Oxisol. Gliricidia significantly increased the utilisation of fertiliser-P only in the Ultisol. However, early application of Gliricidia increased Gliricidia- P but not fertiliser-P utilisation in the Ultisol. Added fertiliser-P did not influence Gliricidia- P utilisation.

Physico-chemical controls on phosphorus cycling in two lowland streams. Part 1 - the water column

This paper investigates phosphorus (P) transport and transformation dynamics in two contrasting sub-catchments of the River Kennel, England. Samples were collected daily under baseflow and hourly under stormflow conditions using autosamplers for 2 years and analysed for a range of determinands (full P fractionation, suspended sediment (SS), cations, pH, alkalinity, temperature and oxygen). Concentrations of SRP, SUP, PP and SS were higher in the flashy River Enborne (means of 0.186, 0.071, 0.101 and 34 mg l(-1), respectively) than the groundwater-fed River Lambourn (0.079, 0.057, 0.028 and 9 mg l(-1), respectively). A seasonal trend in the daily P dataset was evident, with lower concentrations during intermediate flows and the spring (caused by a dilution effect and macrophyte uptake) than during baseflow conditions. However, in the hourly P dataset, highest concentrations were observed during storm events in the autumn and winter (reflecting higher scour with increased capacity to entrain particles). Storm events were more significant in contributing to the total P load in the River Enborne than the River Lambourn, especially during August to October, when dry antecedent conditions were observed in the catchment. Re-suspension of P-rich sediment that accumulated within the channel during summer low flows might account for these observations. It is suggested that a P-calcite co-precipitation mechanism was operating during summer in the River Lambourn, while adsorption by metal oxyhydroxide groups was an important mechanism controlling P fractionation in the River Enborne. The influence of flow conditions and channel storage/release mechanisms on P dynamics in these two lowland rivers is assessed. (C) 2004 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.

The effect of soil phosphorus on particulate phosphorus in land runoff

Accumulation of surplus phosphorus (P) in the soil and the resulting increased transport of P in land runoff contribute to freshwater eutrophication. The effects of increasing soil P (19–194 mg Olsen-P (OP) kg−1) on the concentrations of particulate P (PP), and sorption properties (Qmax, k and EPCo) of suspended solids (SS) in overland flow from 15 unreplicated field plots established on a dispersive arable soil were measured over three monitoring periods under natural rainfall. Concentrations of PP in plot runoff increased linearly at a rate of 2.6 μg litre−1 per mg OP kg−1 of soil, but this rate was approximately 50% of the rate of increase in dissolved P (< 0.45 μm). Concentrations of SS in runoff were similar across all plots and contained a greater P sorption capacity (mean + 57%) than the soil because of enrichment with fine silt and clay (0.45–20 μm). As soil P increased, the P enrichment ratio of the SS declined exponentially, and the values of P saturation (Psat; 15–42%) and equilibrium P concentration (EPCo; 0.7–5.5 mg litre−1) in the SS fell within narrower ranges compared with the soils (6–74% and 0.1–10 mg litre−1, respectively). When OP was < 100 mg kg−1, Psat and EPCo values in the SS were smaller than those in the soil and vice-versa, suggesting that eroding particles from soils with both average and high P fertility would release P on entering the local (Rosemaund) stream. Increasing soil OP from average to high P fertility increased the P content of the SS by approximately 10%, but had no significant (P > 0.05) effect on the Psat, or EPCo, of the SS. Management options to reduce soil P status as a means of reducing P losses in land runoff and minimizing eutrophication risk may therefore have more limited effect than is currently assumed in catchment management.

Layer-by-layer electrostatic entrapment of protein molecules on superparamagnetic nanoparticle: new strategy to enhance adsorption capacity and maintain biological activity

There is a recent interest to use inorganic-based magnetic nanoparticles as a vehicle to carry biomolecules for various biophysical applications, but direct attachment of the molecules is known to alter their conformation leading to attenuation in activity. In addition, surface immobilization has been limited to monolayer coverage. It is shown that alternate depositions of negatively charged protein molecules, typically bovine serum albumin (BSA) with a positively charged aminocarbohydrate template such as glycol chitosan (GC) on magnetic iron oxide nanoparticle surface as a colloid, are carried out under pH 7.4. Circular dichroism (CD) clearly reveals that the secondary structure of the entrapped BSA sequential depositions in this manner remains totally unaltered which is in sharp contrast to previous attempts. Probing the binding properties of the entrapped BSA using small molecules (Site I and Site II drug compounds) confirms for the first time the full retention of its biological activity as compared with native BSA, which also implies the ready accessibility of the entrapped protein molecules through the porous overlayers. This work clearly suggests a new method to immobilize and store protein molecules beyond monolayer adsorption on a magnetic nanoparticle surface without much structural alteration. This may find applications in magnetic recoverable enzymes or protein delivery.

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 relationship between diffuse spectral reflectance of the soil and its cation exchange capacity is scale-dependent

Diffuse reflectance spectroscopy (DRS) is increasingly being used to predict numerous soil physical, chemical and biochemical properties. However, soil properties and processes vary at different scales and, as a result, relationships between soil properties often depend on scale. In this paper we report on how the relationship between one such property, cation exchange capacity (CEC), and the DRS of the soil depends on spatial scale. We show this by means of a nested analysis of covariance of soils sampled on a balanced nested design in a 16 km × 16 km area in eastern England. We used principal components analysis on the DRS to obtain a reduced number of variables while retaining key variation. The first principal component accounted for 99.8% of the total variance, the second for 0.14%. Nested analysis of the variation in the CEC and the two principal components showed that the substantial variance components are at the > 2000-m scale. This is probably the result of differences in soil composition due to parent material. We then developed a model to predict CEC from the DRS and used partial least squares (PLS) regression do to so. Leave-one-out cross-validation results suggested a reasonable predictive capability (R2 = 0.71 and RMSE = 0.048 molc kg− 1). However, the results from the independent validation were not as good, with R2 = 0.27, RMSE = 0.056 molc kg− 1 and an overall correlation of 0.52. This would indicate that DRS may not be useful for predictions of CEC. When we applied the analysis of covariance between predicted and observed we found significant scale-dependent correlations at scales of 50 and 500 m (0.82 and 0.73 respectively). DRS measurements can therefore be useful to predict CEC if predictions are required, for example, at the field scale (50 m). This study illustrates that the relationship between DRS and soil properties is scale-dependent and that this scale dependency has important consequences for prediction of soil properties from DRS data

Decomposition and phosphorus release from organic residues as affected by residue quality and added inorganic phosphorus

The combined use of organic residue and inorganic fertiliser-phosphorus (P) is appropriate in meeting both the short and long-term P requirement of crops. To assess the influence of added inorganic fertiliser-P on the processes of decomposition and P release from the residue and the relationships with quality, prunings of Gliricidia sepium, Leucaena leucocephela, Senna siamea, Acacia mangium and Paraserienthus falcataria were incubated without and with added inorganic fertiliser-P for 56 days. Soil was added only as inoculum. Decomposition rate and amounts of acid extractable-P (P release) were in the same order: G. sepium > S. siamea > L. leucocepheta > P falcataria > A. mangium. Unlike the other residues, A. mangium released no P despite the loss of half its mass during the 8 weeks of incubation. The residue P content correlated with P release. However, decomposition rate did not correlate with residue P content but with the lignin, polyphenol and cellulose content, and ratios to P. These ratios were negatively correlated with P release suggesting that lignin and polyphenol contents influence P release more when the residue-P content is low. Results suggest that rate of decomposition influences the release of P. The critical residue P content for P release was estimated to be 0.12% < P < 0.19%. Added P had no effect on decomposition and P release from the residues.

A comparison of diatom phosphorus transfer functions and export coefficient models as tools for reconstructing lake nutrient histories

1. We compared the baseline phosphorus (P) concentrations inferred by diatom-P transfer functions and export coefficient models at 62 lakes in Great Britain to assess whether the techniques produce similar estimates of historical nutrient status. 2. There was a strong linear relationship between the two sets of values over the whole total P (TP) gradient (2-200 mu g TP L-1). However, a systematic bias was observed with the diatom model producing the higher values in 46 lakes (of which values differed by more than 10 mu g TP L-1 in 21). The export coefficient model gave the higher values in 10 lakes (of which the values differed by more than 10 mu g TP L-1 in only 4). 3. The difference between baseline and present-day TP concentrations was calculated to compare the extent of eutrophication inferred by the two sets of model output. There was generally poor agreement between the amounts of change estimated by the two approaches. The discrepancy in both the baseline values and the degree of change inferred by the models was greatest in the shallow and more productive sites. 4. Both approaches were applied to two lakes in the English Lake District where long-term P data exist, to assess how well the models track measured P concentrations since approximately 1850. There was good agreement between the pre-enrichment TP concentrations generated by the models. The diatom model paralleled the steeper rise in maximum soluble reactive P (SRP) more closely than the gradual increase in annual mean TP in both lakes. The export coefficient model produced a closer fit to observed annual mean TP concentrations for both sites, tracking the changes in total external nutrient loading. 5. A combined approach is recommended, with the diatom model employed to reflect the nature and timing of the in-lake response to changes in nutrient loading, and the export coefficient model used to establish the origins and extent of changes in the external load and to assess potential reduction in loading under different management scenarios. 6. However, caution must be exercised when applying these models to shallow lakes where the export coefficient model TP estimate will not include internal P loading from lake sediments and where the diatom TP inferences may over-estimate TP concentrations because of the high abundance of benthic taxa, many of which are poor indicators of trophic state.

Physico-chemical controls on phosphorus cycling in two lowland streams. Part 2 - The sediment phase

This article investigates the temporal and spatial controls on sediment-phosphorus (P) dynamics in two contrasting sub-catchments of the River Kennet, England. Suspended sediment (collected under representative flow conditions) and size-fractionated bedload (collected weekly for one year) from the Rivers Lambourn and Enborne was analysed for a range of physico-chemical determinands. Total P concentrations were highest in the most mobile fractions of sediment: suspended sediment, fine silt and clay and organic matter (mean concentrations of 1758, 1548 and 1440 mug P g(-1) dry sediment, respectively). Correlation analysis showed significant relationships between total P and total iron (n = 110), total manganese (n = 110), organic matter (n = 110) and specific surface area (n = 28) in the Lambourn (r(2) 0.71, 0.68, 0.62 and 0.52, respectively) and between total P and total iron (n = 110), total manganese (n = 110) and organic matter (n = 110) in the Enborne (r(2) 0.74, 0.85 and 0.68, respectively). These data highlight the importance of metal oxyhydroxide adsorption of P on fine particulates and organic matter. However, high total P concentrations in the granule gravel and coarse sand size fraction during the summer period (mean concentration 228 mug P g(-1) dry sediment) also highlight the role of calcite co-precipitation on P dynamics in the Lambourn. P to cation ratios in Lambourn sediment indicated that fine silt and clay and granule gravel and coarse sand size fractions were potential sources of P release to the water column during specific periods of the summer and autumn. In the Enborne, however, only the granule gravel and coarse sand size fraction had high ratios and a slow, constant release of P was observed. In addition, scanning electron microscopy work confirmed the association of P with calcite in the Lambourn and P with iron on clay particles in the Enborne. The study highlighted the importance of the chemical and physical properties of the sediment in influencing the mechanisms controlling P storage and release within river channels. (C) 2004 Elsevier B.V. All rights reserved.

Response of organically managed grassland to available phosphorus and potassium in the soil and supplementary fertilization: field trials using grass-clover leys cut for silage

Effective use and recycling of manures together with occasional and judicious use of supplementary fertilizing materials forms the basis for management of phosphorus (P) and potassium (K) within organic farming systems. Replicated field trials were established at three sites across the UK to compare the supply of P and K to grass-clover swards cut for silage from a range of fertilizing materials, and to assess the usefulness of routine soil tests for P and K in organic farming systems. None of the fertilizing materials (farmyard manure, rock phosphate, Kali vinasse, volcanic tuff) significantly increased silage yields, nor was P offtake increased. However, farmyard manure and Kali vinasse proved effective sources of K to grass and clover in the short to medium term. Available P (measured as Olsen-P) showed no clear relationship with crop P offtake in these trials. In contrast, available K (measured by ammonium nitrate extraction) proved a useful measurement to predict K availability to crops and support K management decisions.

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.

Zinc tolerance in wheat cultivars as affected by varying levels of phosphorus

The effect of zinc-phosphorus (Zn-P) interaction on Zn efficiency of six wheat cultivars was studied. The higher dry matter yields were observed when Zn was applied at 5 mu g g(-1) soil than with no Zn application. Phosphorus applications also increased dry matter yield up to the application of 25 mu g P g(-1) soil. The dry matter yield was significantly lower at the P rate of 250 mu g g(-1) soil. At the Zn-deficient level, the Zn-efficient cultivars had higher Zn concentrations in the shoots. Zinc concentrations in all cultivars increased when the P level in the soil was increased from 0 to 25 mu g P g(-1) soil except for the cv. Durati, in which Zn concentrations decreased with increases in P levels. However, when ZnxP interactions were investigated, it was observed that at a Zn-deficient level, Zn concentrations in the plant shoot decreased with each higher level of P, and more severe Zn deficiency was observed at P level of 250 mu g g(-1) soil.