Evaluation of diffusive gradients in thin-films using a Diphonix® resin for monitoring dissolved uranium in natural waters

Commercially available Diphonix® resin (TrisKem International) was evaluated as a receiving phase for use with the diffusive gradients in thin-films (DGT) passive sampler for measuring uranium. This resin has a high partition coefficient for actinides and is used in the nuclear industry. Other resins used as receiving phases with DGT for measuring uranium have been prone to saturation and significant chemical interferences. The performance of the device was evaluated in the laboratory and in field trials. In laboratory experiments uptake of uranium (all 100% efficiency) by the resin was unaffected by varying pH (4–9), ionic strength (0.01–1.00 M, as NaNO3) and varying aqueous concentrations of Ca2+ (100–500 mg L−1) and HCO3− (100–500 mg L−1). Due to the high partition coefficient of Diphonex®, several elution techniques for uranium were evaluated. The optimal eluent mixture was 1 M NaOH/1 M H2O2, eluting 90% of the uranium from the resin. Uptake of uranium was linear (R2 = 0.99) over time (5 days) in laboratory experiments using artificial freshwater showing no saturation effects of the resin. In field deployments (River Lambourn, UK) the devices quantitatively accumulated uranium for up to 7 days. In both studies uptake of uranium matched that theoretically predicted for the DGT. Similar experiments in seawater did not follow the DGT theoretical uptake and the Diphonix® appeared to be capacity limited and also affected by matrix interferences. Isotopes of uranium (U235/U238) were measured in both environments with a precision and accuracy of 1.6–2.2% and 1.2–1.4%, respectively. This initial study shows the potential of using Diphonix®-DGT for monitoring of uranium in the aquatic environment

Na+-H+ exchange activity in brush-border membrane vesicles isolated from chick small intestine

This study was undertaken to investigate the presence of a Na+{single bond}H+ antiporter in brush-border membrane vesicles (BBMV) isolated from chick small intestine. An outwardly directed proton gradient (pH 5.5 inside, 7.5 outside) stimulated Na+ uptake into BBMV and resulted in a transient accumulation. No accumulation was observed in the absence of a proton gradient. Voltage clamping the membrane with K+ and valinomycin decreased the Na+ overshoot. Amiloride inhibited pH gradient-driven Na+ uptake in a dose-dependent manner with an IC50 of 44 μM. The relationship between pH gradient-driven Na+ uptake and external Na+ concentration followed simple, saturating Michaelis-Menten kinetics. Eadie-Hofstee analysis of the pH gradient-driven Na+ uptake indicated a single transport system with a Vmax of 33 nmol/mg protein per 15 s and a Km for Na+ of 12 mM. The initial rate of pH-driven Na+ uptake increased as the intravesicular pH decreased, with a Hill coefficient close to 1. These findings indicate that BBMV isolated from chicken small intestine posses a Na+{single bond}H+ exchanger. This exchanger does not appear to be the one involved in cell pH regulation.Dirección General de Investigaciones Científicas y Técnicas PB89-061

Species sensitivity of zeolite minerals for uptake of mercury solutes

The uptake of inorganic Hg2+ and organometallic CH3Hg+ from aqueous solutions by 11 different natural zeolites has been investigated using a batch distribution coefficient (Kd) method and supported by a preliminary voltammetric study. The effect of mercury concentration on theKd response is shown over an environmentally appropriate concentration range of 0.1-5 ppm inorganic and organometallic Hg using a batch factor of 100 ml g−1 and 20 h equilibration. Analcime and a Na-chabazite displayed the greatest methylmercury uptakes (Kd values at 1.5 ppm of 4023 and 3456, respectively), with mordenite as the smallest at 578. All uptake responses were greater for methylmercury than for the inorganic mercuric nitrate solutions, suggesting a distinctive sensitivity of zeolites to reaction with different types of solute species. It is likely that this sensitivity is attributable to the precise nature of the resultant Hg-zeolite bonds. Additionally, both the Si-Al ratio and the Na content of the initial natural zeolite samples are shown to influence the Kd responses, with positive correlations between Kd and Na content for all zeolites excluding mordenite

Organics Substantially Reduce HO2 Uptake Onto Aerosols Containing Transition Metal ions

A HO2 mass accommodation coefficient of α = 0.23 ± 0.07 was measured onto sub-micron copper (II) doped ammonium sulphate aerosols at a relative humidity of 60 ± 3 %, at 293 ± 2 K and at an initial HO2 concentration of ~ 1 × 109 molecule cm-3 using an aerosol flow tube coupled to a sensitive Fluorescence Assay by Gas Expansion (FAGE) HO2 detection system. The effect upon the HO2 uptake coefficient γ of adding different organic species (malonic acid, citric acid, 1,2 diaminoethane, tartronic acid, ethylenediaminetetraacetic acid (EDTA) and oxalic acid) into the copper (II) doped aerosols was investigated. The HO2 uptake coefficient decreased steadily from the mass accommodation value to γ = 0.008 ± 0.009 when EDTA was added in a one-to-one molar ratio with the copper (II) ions, and to γ = 0.003 ± 0.004 when oxalic acid was added into the aerosol in a ten-to-one molar ratio with the copper (II). EDTA binds strongly to copper (II) ions potentially making them unavailable for catalytic destruction of HO2, and could also be acting as a surfactant or changing the viscosity of the aerosol. The addition of oxalic acid to the aerosol potentially forms low-volatility copper-oxalate complexes that reduce the uptake of HO2 either by changing the viscosity of the aerosol or causing precipitation out of the aerosol forming a coating. It is likely that there is a high enough oxalate to copper (II) ion ratio in many types of atmospheric aerosols to decrease the HO2 uptake coefficient. No observable change in the HO2 uptake coefficient was measured when the other organic species (malonic acid, citric acid, 1,2 diaminoethane and tartronic acid) were added in a ten-to-one molar ratio with the copper (II) ions

Hydro-chemical modelling of in situ behaviour of bituminized radioactive waste in Boom Clay

The hydro-chemical (CH) interaction between swelling Eurobitum bituminized radioactive waste (BW) and Boom Clay was investigated to assess the feasibility of geological disposal for the long-term management of this waste. First, the long-term behaviour of BW in contact with water was studied. A CH formulation of chemically and hydraulically coupled flow processes in porous materials containing salt crystals is discussed. The formulation incorporates the strong dependence of the osmotic efficiency of the bitumen membrane on porosity and assumes the existence of high salt concentration gradients that are maintained for a long time and that influence the density and motion of the fluid. The impacts of temporal and spatial variations of key transport parameters (i.e. osmotic efficiency (s), intrinsic permeability (k), diffusion, etc.) were investigated. Porosity was considered the basic variable. For BW porosity varies in time because of the water uptake and subsequent processes (i.e. dissolution of salt crystals, swelling of hydrating layers, compression of highly leached layers). New expressions of s and k describing the dependence of these parameters on porosity are proposed. Several cases were analysed. The numerical analysis was proven to be able to furnish a satisfactory representation of the main observed patterns of the behaviour in terms of osmotic-induced swelling, leached mass of NaNO3 and progression of the hydration front when heterogeneous porosity and crystal distributions have been assumed. Second, the long-term behaviour of real Eurobitum drums in disposal conditions, and in particular its interaction with the surrounding clay, was investigated. Results of a CH analysis are presented.Peer ReviewedPostprint (published version

Development and critical evaluation of a generic 2-D agro-hydrological model (SMCR_N) for the responses of crop yield and nitrogen composition to nitrogen fertilizer

Models play an important role in optimizing fertilizer use in agriculture to maintain sustainable crop production and to minimize the risk to the environment. In this study, we present a new Simulation Model for Crop Response to Nitrogen fertilizer (SMCR_N). The SMCR_N model, based on the recently developed model EU-Rotate_N for the N-economies of a wide range of crops and cropping systems, includes new modules for the estimation of N in the roots and an associated treatment of the recovery of soil mineral N by crops, for the reduction of growth rates by excessive fertilizer-N, and for the N mineralization from soil organic matter. The validity of the model was tested against the results from 32 multi-level fertilizer experiments on 16 different crop species. For this exercise none of the coefficients or parameters in the model was adjusted to improve the agreement between measurement and simulation. Over the practical range of fertilizer-N levels model predictions were, with few exceptions, in good agreement with measurements of crop dry weight (excluding fibrous roots) and its %N. The model considered that the entire reduction of soil inorganic N during growth was due to the sum of nitrate leaching, retention of N in fibrous roots and N uptake by the rest of the plant. The good agreement between the measured and simulated uptakes suggests that in this arable soil, losses of N from other soil processes were small. At high levels of fertilizer-N yields were dominated by the negative osmotic effect of fertilizer-N and model predictions for some crops were poor. However, the predictions were significantly improved by using a different value for the coefficient defining the osmotic effect for saline sensitive crops. The developed model SMCR_N uses generally readily available inputs, and is more mechanistic than most agronomic models and thus has the potential to be used as a tool for optimizing fertilizer practice

Long-term fate of sewage-sludge derived cadmium in arable soils

The focus of this work was to improve knowledge of the long-term fate of cadmium supplied to arable soils by sewage sludge. Emphasis was placed on measured and modelled changes in the solubility and mobility of cadmium, resulting from long-term turnover of both sludge-derived and inherent organic matter of the soil. Measurements were conducted in a long-term sludge supplied field experiment, situated at Ultuna (60°N, 17°E), started in 1956. Furthermore, batch studies on soil samples and modelling exercises in WHAM were performed in order to study the speciation of cadmium in the soil-solution system. A comprehensive model -the SLAM model- was developed to increase the understanding of the influence of soil and sludge adsorption characteristics on cadmium solubility and bioavailability, and the migration rate of cadmium in soil profiles. The long-term sludge supplies had increased the solubility of cadmium, measured in crop cadmium concentration, as an effect of enhanced acidification and increased Cd concentration in the soil. A low Cd migration was measured, attributed to non-equilibrium Cd concentration in percolating water, a high cadmium sorption capacity in the subsoil and root driven Cd circulation in the soil profile. No increased Cd sorption capacity was measured in the sludge supplied soil, despite the almost doubled soil organic matter content. This might be partly attributed to the higher iron oxide and hydroxide concentration measured in the sludge, forming more stable complexes with soil humic compounds compared to cadmium complexes with soil humic compounds. A Monte-Carlo analysis of the SLAM model suggested that the major parameters affecting leaching and crop uptake of cadmium were the cadmium loading and the partitioning coefficient for sludge-derived inorganic material and parameters controlling the effect of pH on sorption. Long-term scenario simulations in SLAM identified critical factors influencing plant cadmium uptake: the cadmium concentration in the sludge, the adsorption capacity of the sludge in relation to the adsorption capacity of native soil and the proportion of the sludge adsorption capacity contributed by the inorganic fraction

On the implications of aerosol liquid water and phase separation for modeled organic aerosol mass

Water is an important component of PM2.5 Many traditional SOA species are highly soluble and thus can be considered extractable Water can influence the partitioning of compounds traditionally considered insoluble in models Organic aerosol takes up water according to RH Organic aerosol interacts with inorganic water Deviations in ideality (solubility) must be considered

The performance of the EU-Rotate_N model in predicting the growth and nitrogen uptake of rotations of field vegetable crops in a Mediterranean environment

The EU-Rotate_N model was developed as a tool to estimate the growth and nitrogen (N) uptake of vegetable crop rotations across a wide range of European climatic conditions and to assess the economic and environmental consequences of alternative management strategies. The model has been evaluated under field conditions in Germany and Norway and under greenhouse conditions in China. The present work evaluated the model using Italian data to evaluate its performance in a warm and dry environment. Data were collected from four 2-year field rotations, which included lettuce (Lactuca sativa L.), fennel (Foeniculum vulgare Mill.), spinach (Spinacia oleracea L.), broccoli (Brassica oleracea L. var. italica Plenck) and white cabbage (B. oleracea convar. capitata var. alba L.); each rotation used three different rates of N fertilizer (average recommended N1, assumed farmer's practice N2=N1+0·3×N1 and a zero control N0). Although the model was not calibrated prior to running the simulations, results for above-ground dry matter biomass, crop residue biomass, crop N concentration and crop N uptake were promising. However, soil mineral N predictions to 0·6 m depth were poor. The main problem with the prediction of the test variables was the poor ability to capture N mineralization in some autumn periods and an inappropriate parameterization of fennel. In conclusion, the model performed well, giving results comparable with other bio-physical process simulation models, but for more complex crop rotations. The model has the potential for application in Mediterranean environments for field vegetable production