Phosphorus dynamics and export in streams draining micro-catchments: Development of empirical models

Annual total phosphorus (TP) export data from 108 European micro-catchments were analyzed against descriptive catchment data on climate (runoff), soil types, catchment size, and land use. The best possible empirical model developed included runoff, proportion of agricultural land and catchment size as explanatory variables but with a low explanation of the variance in the dataset (R-2 = 0.37). Improved country specific empirical models could be developed in some cases. The best example was from Norway where an analysis of TP-export data from 12 predominantly agricultural micro-catchments revealed a relationship explaining 96% of the variance in TP-export. The explanatory variables were in this case soil-P status (P-AL), proportion of organic soil, and the export of suspended sediment. Another example is from Denmark where an empirical model was established for the basic annual average TP-export from 24 catchments with percentage sandy soils, percentage organic soils, runoff, and application of phosphorus in fertilizer and animal manure as explanatory variables (R-2 = 0.97).

Mitigation of diffuse phosphorus pollution during rewetting of fen peat soils: A trans-European case study

Intensive cultivation of fen peat soils (Eutric Histosols) for agricultural purposes, started in Europe about 250 years ago, resulting in decreased soil fertility, increased oxidation of peat and corresponding CO2-emissions to the atmosphere, nutrient transfer to aquatic ecosystems and losses in the total area of the former native wetlands. To prevent these negative environmental effects set-aside programs and rewetting measures were promoted in recent years. Literature results and practical experiences showed that large scale rewetting of intensively used agricultural Histosols may result in the mobilisation of phosphorus (P), its transport to adjacent surface waters and an accelerated eutrophication risk. The paper summarises results from an international European Community sponsored research project and demonstrates how results obtained at different scales and from different scientific disciplines were compiled to derive a strategy to carry out rewetting measures. A decision support system (DSS) for a hydrologically sensitive area in the Droemling catchment in north-eastern Germany was developed and is presented as a tool to regulate rewetting in order to control P release. It is demonstrated that additional laboratory experiments to identify essential processes of P release during rewetting and the site-specific management of the water table, the involvement of specific knowledge and experience of the stakeholders are necessary to develop an applicable DSS. The presented DSS is practically used to prevent freshwater resources from diffuse P pollution.

Phosphorus dynamics in the ditch system of a restored peat wetland

The restoration of wetlands as bird habitats often involves the maintenance of a fluctuating water regime by careful, localised ditch water management using pumps and sluices. However, there is evidence in the literature to Suggest that alternate flood/drainage cycles can accelerate nutrient cycling and transport within the soil and, therefore, pose a threat to water quality through the process of eutrophication. This study focused on the dynamics and losses of soil P in a recently re-wetted, eutrophic fen peat developed on alluvium ill South west England. During the 2-year Study (2001 and 2002), soil water tensiometry revealed that the field water table (fluctuating annually between +20 and 60 cm relative to ground level) was extensively influenced across most of the 8.4 ha field site by the management of the adjacent ditch water levels. This conservation-led, prescribed water balance was facilitated by the high hydraulic conductivity (1.1 x 10(-s) ms(-1)) of the lower (70-140 cm), degraded layer of peat. However, only during a 7-day period of water table drawdown by intermittent pump drainage, approximately 45 g ha(-1) of dissolved reactive P (DRP) entered the pumped ditch from the field via this degraded layer. Summer rainfall events >35 mm d(-1) also coincided with significant peaks ill ditch water P concentration (up to 200 mu g L-1 DRP). Even larger peaks (Up to 700 mu g L-1 DRP) Occurred With the annual onset of autumn reflooding. These episodic P loss events pose a serious potential threat to biological water quality. (C) 2009 Elsevier B.V. All rights reserved.

Effect of ammonium and nitrate on indigenous mycorrhizal infection, rhizosphere pH change, and phosphorus uptake by sorghum

Sorghum (Sorghum bicolor L.) plants were grown in split pots in three Rothamsted soils with different soil pH values and phosphorus (P) contents. Ammonium addition resulted in higher plant dry weight and P content than comparable nitrate treatments. The pH of soils in the rhizosphere (0.51-mm average thickness) differed from the bulk soil depending on nitrogen (N) form and level. Ammonium application resulted in a pH decrease, but nitrate application slightly increased pH. To examine the effect of rhizosphere acidification on mobilization of phosphate, 0.5 M NaHCO3 extractable phosphate was measured. The lowering rhizosphere pH enhanced the solubility of P in the soil and maybe availability of P to plants. Rhizosphere-P depletion increased with increasing ammonium supply, but when N was supplied as nitrate, P depletion was not related to increasing nitrate supply. Low P status Hoosfield soils developed mycorrhizal infection., and as a result, P inflow was increased. Geescroft soil, which initially had a high P status, did not develop mycorrhizal infection, and P inflow was much smaller and was unaffected by N treatments. Therefore, plant growth and P uptake were influenced by both rhizosphere pH and indigenous mycorrhizal infection.

Effect of mycorrhizae and pH change at the root-soil interface on phosphorus uptake by Sorghum using a rhizocylinder technique

Sorghum (Sorghum bicolor) was grown for 40 days in. rhizocylinder (a growth container which permitted access to rh zosphere and nonrhizosphere soil), in two soils of low P status. Soils were fertilized with different rates of ammonium and nitrate and supplemented with 40 mg phosphorus (P) kg(-1) and inoculated with either Glomus mosseae (Nicol. and Gerd.) or nonmycorrhizal root inoculum.. N-serve (2 mg kg(-1)) was added to prevent nitrification. At harvest, soil from around the roots was collected at distances of 0-5, 5-10, and 10-20 mm from the root core which was 35 mm diameter. Sorghum plants, with and without mycorrhiza, grew larger with NH4+ than with NO3- application. After measuring soil pH, 4 3 suspensions of the same sample were titrated against 0.01 M HCl or 0.01 M NaOH until soil pH reached the nonplanted pH level. The acid or base requirement for each sample was calculated as mmol H+ or OFF kg(-1) soil. The magnitude of liberated acid or base depended on the form and rate of nitrogen and soil type. When the plant root was either uninfected or infected with mycorrhiza., soil pH changes extended up to 5 mm from the root core surface. In both soils, ammonium as an N source resulted in lower soil pH than nitrate. Mycorrhizal (VAM) inoculation did not enhance this difference. In mycorrhizal inoculated soil, P depletion extended tip to 20 mm from the root surface. In non-VAM inoculated soil P depletion extended up to 10 mm from the root surface and remained unchanged at greater distances. In the mycorrhizal inoculated soils, the contribution of the 0-5 mm soil zone to P uptake was greater than the core soil, which reflects the hyphal contribution to P supply. Nitrogen (N) applications that caused acidification increased P uptake because of increased demand; there is no direct evidence that the increased uptake was due to acidity increasing the solubility of P although this may have been a minor effect.

Comparison of ammonium lactate, sodium bicarbonate and double calcium lactate methods for extraction of phosphorus from wetland peat soils

Procedures for routine analysis of soil phosphorus (P) have been used for assessment of P status, distribution and P losses from cultivated mineral soils. No similar studies have been carried out on wetland peat soils. The objective was to compare extraction efficiency of ammonium lactate (PAL), sodium bicarbonate (P-Olsen), and double calcium lactate (P-DCaL) and P distribution in the soil profile of wetland peat soils. For this purpose, 34 samples of the 0-30, 30-60 and 60-90 cm layers were collected from peat soils in Germany, Israel, Poland, Slovenia, Sweden and the United Kingdom and analysed for P. Mean soil pH (CaCl2, 0.01 M) was 5.84, 5.51 and 5.47 in the 0-30, 30-60 and 60-90 cm layers, respectively. The P-DCaL was consistently about half the magnitude of either P-AL or P-Olsen. The efficiency of P extraction increased in the order P-DCaL < P-AL &LE; P-Olsen, with corresponding means (mg kg(-1)) for all soils (34 samples) of 15.32, 33.49 and 34.27 in 0-30 cm; 8.87, 17.30 and 21.46 in 30-60 cm; and 5.69, 14.00 and 21.40 in 60-90 cm. The means decreased with depth. When examining soils for each country separately, P-Olsen was relatively evenly distributed in the German, UK and Slovenian soils. P-Olsen was linearly correlated (r = 0.594, P = 0.0002) with pH, whereas the three P tests (except P-Olsen vs P-DCaL) significantly correlated with each other (P = 0.017850.0001). The strongest correlation (r = 0.617, P = 0.0001) was recorded for P-AL vs P-DCaL) and the two methods were inter-convertible using a regression equation: P-AL = -22.593 + 5.353 pH + 1.423 P-DCaL, R-2 = 0.550.

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.

Adsorption of water vapor by bare soil in an olive grove in southern Spain

Data for water vapor adsorption and evaporation are presented for a bare soil (sandy loam, clay content 15%) in a southern Spanish olive grove. Water losses and gains were measured using eight high-precision minilysimeters, placed around an olive tree, which had been irrigated until the soil reached field capacity (similar to 0.22 m(3) m(-3)). They were subsequently left to dry for 10 days. A pair of lysimeters was situated at each of the main points of the compass (N, E, S, W), at a distance of 1 m (the inner set of lysimeters; ILS) and 2 m (the outer set of lysimeters; OLS), respectively, from the tree trunk. Distinct periods of moisture loss (evaporation) and moisture gain (vapor adsorption) could be distinguished for each day. Vapor adsorption often started just after noon and generally lasted until the (early) evening. Values of up to 0.7 mm of adsorbed water per day were measured. Adsorption was generally largest for the OLS (up to 100% more on a daily basis), and increased during the dry down. This was mainly the result of lower OLS surface soil moisture contents (period-average absolute difference similar to 0.005 m(3) m(-3)), as illustrated using various analyses employing a set of micrometeorological equations describing the exchange of water vapor between bare soil and the atmosphere. These analyses also showed that the amount of water vapor adsorbed by soils is very sensitive to changes in atmospheric forcing and surface variables. The use of empirical equations to estimate vapor adsorption is therefore not recommended.

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.

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.

Influence of adsorption geometry in the heterogeneous enantioselective catalytic hydrogenation of a prototypical enone

Asymmetric catalysis is of paramount importance in organic synthesis and, in current practice, is achieved by means of homogeneous catalysts. The ability to catalyze such reactions heterogeneously would have a major impact both in the research laboratory and in the production of fine chemicals and pharmaceuticals, yet heterogeneous asymmetric hydrogenation of C═C bonds remains hardly explored. Very recently, we demonstrated how chiral ligands that anchor robustly to the surface of Pd nanoparticles promote asymmetric catalytic hydrogenation: ligand rigidity and stereochemistry emerged as key factors. Here, we address a complementary question: how does the enone reactant adsorb on the metal surface, and what implications does this have for the enantiodifferentiating interaction with the surface-tethered chiral modifiers? A reaction model is proposed, which correctly predicts the identity of the enantiomer experimentally observed in excess.

Sewage effluent clean-up reduces phosphorus but not phytoplankton in lowland chalk stream (River Kennet, UK) impacted by water mixing from adjacent canal

Information is provided on phosphorus in the River Kennet and the adjacent Kennet and Avon Canal in southern England to assess their interactions and the changes following phosphorus reductions in sewage treatment work (STW) effluent inputs. A step reduction in soluble reactive phosphorus (SRP) concentration within the effluent (5 to 13 fold) was observed from several STWs discharging to the river in the mid-2000s. This translated to over halving of SRP concentrations within the lower Kennet. Lower Kennet SRP concentrations change from being highest under base-flow to highest under storm-flow conditions. This represented a major shift from direct effluent inputs to a within-catchment source dominated system characteristic of the upper part to the catchment. Average SRP concentrations in the lower Kennet reduced over time towards the target for good water quality. Critically, there was no corresponding reduction in chlorophyll-a concentration, the waters remaining eutrophic when set against standards for lakes. Following the up gradient input of the main water and SRP source (Wilton Water), SRP concentrations in the canal reduced down gradient to below detection limits at times near its junction with the Kennet downstream. However, chlorophyll concentrations in the canal were in an order of magnitude higher than in the river. This probably resulted from long water residence times and higher temperatures promoting progressive algal and suspended sediment generations that consumed SRP. The canal acted as a point source for sediment, algae and total phosphorus to the river especially during the summer months when boat traffic disturbed the canal's bottom sediments and the locks were being regularly opened. The short-term dynamics of this transfer was complex. For the canal and the supply source at Wilton Water, conditions remained hypertrophic when set against standards for lakes even when SRP concentrations were extremely low.