Development of a methodology to investigate the importance of chemical speciation on the bioavailability of contaminants to Eisenia andrei

The uptake of metals by earthworms occurs predominantly via the soil pore water, or via an uptake route which is related to the soil pore water metal concentration. However, it has been suggested that the speciation of the metal is also important. A novel technique is described which exposes Eisenia andrei Bouche to contaminant bearing solutions in which the chemical factors affecting its speciation may be individually and systematically manipulated. In a preliminary experiment, the LC50 for copper nitrate was 0.046 mg l(-1) (95 % confidence intervals: 0.03 and 0.07 mg l(-1)). There was a significant positive correlation between earthworm mortality and bulk copper concentration in solution (R-2 = 0.88, P less than or equal to 0.001), and a significant positive increase in earthworm tissue copper concentration with increasing copper concentration in solution (R-2 = 0.97, P less than or equal to 0.001). It is anticipated that quantifying the effect of soil solution chemical speciation on copper bioavailability will provide an excellent aid to understanding the importance of chemical composition and the speciation of metals, in the calculation of toxicological parameters.

Is the OECD acute worm toxicity test environmentally relevant? The effect of mineral form on calculated lead toxicity

In a series of experiments the toxicity of lead to worms in soil was determined following the draft OECD earthworm reproduction toxicity protocol except that lead was added as solid lead nitrate, carbonate and sulphide rather than as lead nitrate solution as would normally be the case. The compounds were added to the test soil to give lead concentrations of 625-12500 pg Pb g-1 of soil. Calculated toxicities of the lead decreased in the order nitrate > carbonate > sulphide, the same order as the decrease in the solubility of the metal compounds used. The 7-day LC50 (lethal concentration when 50% of the population is killed) for the nitrate was 5321 +/- 275 mug Pb g(-1) of soil and this did not change with time. The LC50 values for carbonate and sulphide could not be determined at the concentration ranges used. The only parameter sensitive enough to distinguish the toxicities of the three compounds was cocoon (egg) production. The EC50S for cocoon production (the concentration to produce a 50% reduction in cocoon production) were 993, 8604 and 10 246 mug Pb g(-1) of soil for lead nitrate, carbonate and sulphide, respectively. Standard toxicity tests need to take into account the form in which the contaminant is present in the soil to be of environmental relevance. (C) 2002 Elsevier Science Ltd. All rights reserved.

The influence of time on lead toxicity and bioaccumulation determined by the OECD earthworm toxicity test

Internationally agreed standard protocols for assessing chemical toxicity of contaminants in soil to worms assume that the test soil does not need to equilibrate with the chemical to be tested prior to the addition of the test organisms and that the chemical will exert any toxic effect upon the test organism within 28 days. Three experiments were carried out to investigate these assumptions. The first experiment was a standard toxicity test where lead nitrate was added to a soil in solution to give a range of concentrations. The mortality of the worms and the concentration of lead in the survivors were determined. The LC(50)s for 14 and 28 days were 5311 and 5395 mug(Pb) g(soil)(-1) respectively. The second experiment was a timed lead accumulation study with worms cultivated in soil containing either 3000 or 5000 mug(Pb) g(soil)(-1). The concentration of lead in the worms was determined at various sampling times. Uptake at so' Sol both concentrations was linear with time. Worms in the 5000 mug g(-1) soil accumulated lead at a faster rate (3.16 mug Pb g(tissue)(-1) day(-1)) tiss than those in the 3000 mug g(-1) soil (2.21 mug Pb-tissue g(-1) day(-1)). The third experiment was a timed experiment with worms cultivated in tiss soil containing 7000 mugPb g(soil)(-1). Soil and lead nitrate solution were mixed and stored at 20 degreesC. Worms were added at various times over a 35-day period. The time to death increased from 23 h, when worms were added directly after the lead was added to the soil, to 67 It when worms were added after the soil had equilibrated with the lead for 35 days. In artificially Pb-amended soils the worms accumulate Pb over the duration of their exposure to the Pb. Thus time limited toxicity tests may be terminated before worm body load has reached a toxic level. This could result in under-estimates of the toxicity of Pb to worms. As the equilibration time of artificially amended Pb-bearing soils increases the bioavailability of Pb decreases. Thus addition of worms shortly after addition of Pb to soils may result in the over-estimate of Pb toxicity to worms. The current OECD acute worm toxicity test fails to take these two phenomena into account thereby reducing the environmental relevance of the contaminant toxicities it is used to calculate. (C) 2002 Elsevier Science Ltd. All rights reserved.

Modelling stream and soil water nitrate dynamics during experimentally increased nitrogen deposition in a coniferous forest catchment at Gardsjon, Sweden

Increased atmospheric deposition of inorganic nitrogen (N) may lead to increased leaching of nitrate (NO3-) to surface waters. The mechanisms responsible for, and controls on, this leaching are matters of debate. An experimental N addition has been conducted at Gardsjon, Sweden to determine the magnitude and identify the mechanisms of N leaching from forested catchments within the EU funded project NITREX. The ability of INCA-N, a simple process-based model of catchment N dynamics, to simulate catchment-scale inorganic N dynamics in soil and stream water during the course of the experimental addition is evaluated. Simulations were performed for 1990-2002. Experimental N addition began in 1991. INCA-N was able to successfully reproduce stream and soil water dynamics before and during the experiment. While INCA-N did not correctly simulate the lag between the start of N addition and NO 2 3 breakthrough, the model was able to simulate the state change resulting from increased N deposition. Sensitivity analysis showed that model behaviour was controlled primarily by parameters related to hydrology and vegetation dynamics and secondarily by in-soil processes.

Nitrate transport in Chalk catchments: monitoring, modelling and policy implications

Rising nitrate levels have been observed in UK Chalk catchments in recent decades, with concentrations now approaching or exceeding legislated maximum values in many areas. In response, strategies seeking to contain concentrations through appropriate land management are now in place. However, there is an increasing consensus that Chalk systems, a predominant landscape type over England and indeed northwest Europe, can retard decades of prior nitrate loading within their deep unsaturated zones. Current levels may not fully reflect the long-term impact of present-day practices, and stringent land management controls may not be enough to avert further medium-term rises. This paper discusses these issues in the context of the EU Water Framework Directive, drawing on data from recent experimental work and a new model (INCA-Chalk) that allows the impacts of different land use management practices to be explored. Results strongly imply that timelines for water quality improvement demanded by the Water Framework directive are not realistic for the Chalk, and give an indication of time-scales over which improvements might be achieved. However, important unresolved scientific issues remain, and further monitoring and targeted data collection is recommended to reduce prediction uncertainties and allow cost effective strategies for mitigation to be designed and implemented. (C) 2007 Elsevier Ltd. 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.

An application of the GLUE methodology for estimating the parameters of the INCA-N model

The conceptual and parameter uncertainty of the semi-distributed INCA-N (Integrated Nutrients in Catchments-Nitrogen) model was studied using the GLUE (Generalized Likelihood Uncertainty Estimation) methodology combined with quantitative experimental knowledge, the concept known as 'soft data'. Cumulative inorganic N leaching, annual plant N uptake and annual mineralization proved to be useful soft data to constrain the parameter space. The INCA-N model was able to simulate the seasonal and inter-annual variations in the stream-water nitrate concentrations, although the lowest concentrations during the growing season were not reproduced. This suggested that there were some retention processes or losses either in peatland/wetland areas or in the river which were not included in the INCA-N model. The results of the study suggested that soft data was a way to reduce parameter equifinality, and that the calibration and testing of distributed hydrological and nutrient leaching models should be based both on runoff and/or nutrient concentration data and the qualitative knowledge of experimentalist. (c) 2006 Elsevier B.V. All rights reserved.

Integrated Nitrogen CAtchment model (INCA) applied to a tropical catchment in the Atlantic Forest, Sao Paulo, Brazil

Stream-water flows and in-stream nitrate and ammonium concentrations in a small (36.7 ha) Atlantic Forest catchment were simulated using the Integrated Nitrogen in CAtchments (INCA) model version 1.9.4. The catchment, at Cunha, is in the Serra do Mar State Park, SE Brazil and is nearly pristine because the nearest major conurbations, Sao Paulo and Rio, are some 450 km distant. However, intensive farming may increase nitrogen (N) deposition and there are growing pressures for urbanisation. The mean-monthly discharges and NO3-N concentration dynamics were simulated adequately for the calibration and validation periods with (simulated) loss rates of 6.55 kg.ha(-1) yr(-1) for NO3-N and 3.85 kg.ha(-1) yr(-1) for NH4-N. To investigate the effects of elevated levels of N deposition in the future, various scenarios for atmospheric deposition were simulated; the highest value corresponded to that in a highly polluted area of Atlantic Forest in Sao Paulo City. It was found that doubling the atmospheric deposition generated a 25% increase in the N leaching rate, while at levels approaching the highly polluted Sao Paulo deposition rate, five times higher than the current rate, leaching increased by 240%, which would create highly eutrophic conditions, detrimental to downstream water quality. The results indicate that the INCA model can be useful for estimating N concentration and fluxes for different atmospheric deposition rates and hydrological conditions.

Plant roots release phospholipid surfactants that modify the physical and chemical properties of soil

Plant root mucilages contain powerful surfactants that will alter the interaction of soil solids with water and ions, and the rates of microbial processes. The lipid composition of maize, lupin and wheat root mucilages was analysed by thin layer chromatography and gas chromatography-mass spectrometry. A commercially available phosphatidylcholine (lecithin), chemically similar to the phospholipid surfactants identified in the mucilages, was then used to evaluate its effects on selected soil properties. The lipids found in the mucilages were principally phosphatidylcholines, composed mainly of saturated fatty acids, in contrast to the lipids extracted from root tissues. In soil at low tension, lecithin reduced the water content at any particular tension by as much as 10 and 50% in soil and acid-washed sand, respectively. Lecithin decreased the amount of phosphate adsorption in soil and increased the phosphate concentration in solution by 10%. The surfactant also reduced net rates of ammonium consumption and nitrate production in soil. These experiments provide the first evidence we are aware of that plant-released surfactants will significantly modify the biophysical environment of the rhizosphere.

Uneven distribution of nutrients in the root zone affects the incidence of blossom end rot and concentration of calcium and potassium in fruits of tomato

Tomato plants ( Lycopersicon esculentum Mill. var. DRK) were grown hydroponically to determine the effect of an uneven distribution of nutrients in the root zone on blossomend rot (BER) and Ca and K concentrations in the fruits. The plants were grown in rockwool with their root system divided into two portions. Each portion was irrigated with nutrient solutions with either the same or the different electrical conductivity (EC) in the range 0 to 6 dS m(-1). Solutions with high EC supplied to both sides of the root system significantly increased the incidence of BER. However, when only water or a solution of low EC was supplied to one portion, BER was reduced by 80%. Fruit yields were significantly higher ( P < 0.01) for plants that received solutions of the uneven EC treatments (6/0 or 4.5/0 EC treatment). Plants supplied with solutions of uneven EC generally had higher leaf and fruit concentrations of Ca but lower concentrations of K than those supplied with solutions of high EC. There was no difference in Ca concentration at the distal end of young fruits of the uneven EC treatment but it was reduced in the high EC treatments. The concentration of K in the mature fruits of the uneven EC treatments was lower than that of the high EC treatments and higher or similar that of the 3/3 or 2.5/2.5 EC treatments ( controls). A clear relationship was found between the incidence of BER and the exudation rate. High rate of xylem exudation was observed in the uneven EC treatments. Reduction of BER in the uneven EC treatments is most likely to be the effect of high exudation rate on Ca status in the young fruits. It was concluded that high EC of solution had positive effects on Ca concentration and incidence of BER provided that nutrient solution with low EC or water is supplied to the one portion of the root system.

Modeling the Stream Water Nitrate Dynamics in 60,000-km(2) European Catchment, the Garonne, Southwest France

The spatial and temporal dynamics in the stream water NO3-N concentrations in a major European river-system, the Garonne (62,700 km(2)), are described and related to variations in climate, land management, and effluent point-sources using multivariate statistics. Building on this, the Hydrologiska Byrans Vattenbalansavdelning (HBV) rainfall-runoff model and the Integrated Catchment Model of Nitrogen (INCA-N) are applied to simulate the observed flow and N dynamics. This is done to help us to understand which factors and processes control the flow and N dynamics in different climate zones and to assess the relative inputs from diffuse and point sources across the catchment. This is the first application of the linked HBV and INCA-N models to a major European river system commensurate with the largest basins to be managed tinder the Water Framework Directive. The simulations suggest that in the lowlands, seasonal patterns in the stream water NO3-N concentrations emerge and are dominated by diffuse agricultural inputs, with an estimated 75% of the river load in the lowlands derived from arable farming. The results confirm earlier European catchment studies. Namely, current semi-distrubuted catchment-scale dynamic models, which integrate variations in land cover, climate, and a simple representation of the terrestrial and in-stream N cycle, are able to simulate seasonal NO3-N patterns at large spatial (> 300 km(2)) and temporal (>= monthly) scales using available national datasets.

Towards an improved understanding of the nitrate dynamics in lowland, permeable river-systems: Applications of INCA-N

The Integrated Catchment Model of Nitrogen (INCA-N) was applied to the Lambourn and Pang river-systems to integrate current process-knowledge and available-data to test two hypotheses and thereby determine the key factors and processes controlling the movement of nitrate at the catchment-scale in lowland, permeable river-systems: (i) that the in-stream nitrate concentrations were controlled by two end-members only: groundwater and soil-water, and (ii) that the groundwater was the key store of nitrate in these river-systems. Neither hypothesis was proved true or false. Due to equifinality in the model structure and parameters at least two alternative models provided viable explanations for the observed in-stream nitrate concentrations. One model demonstrated that the seasonal-pattern in the stream-water nitrate concentrations was controlled mainly by the mixing of ground- and soil-water inputs. An alternative model demonstrated that in-stream processes were important. It is hoped further measurements of nitrate concentrations made in the catchment soil- and ground-water and in-stream may constrain the model and help determine the correct structure, though other recent studies suggest that these data may serve only to highlight the heterogeneity of the system. Thus when making model-based assessments and forecasts it is recommend that all possible models are used, and the range of forecasts compared. In this study both models suggest that cereal production contributed approximately 50% the simulated in-stream nitrate toad in the two catchments, and the point-source contribution to the in-stream load was minimal. (c) 2006 Elsevier B.V. All rights reserved.

Selenium supplementation of lactating dairy cows: Effect on selenium concentration in blood, milk, urine and feces

The objectives were to determine effects of graded levels of selenized yeast derived from a specific strain of Saccharomyces cerevisiae (CNCM I-3060) on animal performance and in selenium concentrations in the blood, milk, feces, and urine of dairy cows compared with sodium selenite; and to provide preliminary data on the proportion of selenium as selenomethionine in the milk and blood. Twenty Holstein cows were used in a 5 × 5 Latin square design study in which all cows received the same total mixed rations, which varied only in source or concentration of dietary selenium. There were 5 experimental treatments. Total dietary selenium of treatment 1, which received no added selenium, was 0.15 mg/kg of dry matter, whereas values for treatments 2, 3, and 4, derived from selenized yeast, were 0.27, 0.33, and 0.40 mg/kg of dry matter, respectively. Treatment 5 contained 0.25 mg of selenium obtained from sodium selenite/kg of dry matter. There were no significant treatment effects on animal performance, and blood chemistry and hematology showed few treatment effects. Regression analysis noted significant positive linear effects of increasing dietary selenium derived from selenized yeast on selenium concentrations in the milk, blood, urine, and feces. In addition, milk selenium results indicated improved bioavailability of selenium from selenized yeast, compared with sodium selenite. Preliminary analyses showed that compared with sodium selenite, the use of selenized yeast increased the concentration of selenomethionine in the milk and blood. There was no indication of adverse effects on cow health associated with the use of selenized yeast.