Changes of copper speciation in maize rhizosphere soil

Chemical forms of copper in the rhizosphere and bulk soil of maize were investigated using rhizobox cultivation and sequential extraction techniques. The copper accumulations were also determined. The results demonstrated that there were continuous changes in copper fractionation within the maize rhizosphere. Initially, the amount of exchangeable copper increased before dropping below the initial level after 40 days or so. Carbonate associated copper followed a similar trend of change, but with a slower pace than the exchangeable copper. The increase in carbonate associated copper only become evident after 30 days, with the net loss occurring after 60 days. There were also initial increases in oxide bound copper as well as decreases in the organic matter associated copper, both followed by a turnover after 40-50 days. The accumulation of copper in the maize plant was found to be biomass dependent. The amount of accumulated copper absorbed in the plant material exceeded the initial quantity of the exchangeable copper in the soil, revealing a transformation from less bioavailable to more bioavailable fractions. During cultivation, decreases in redox potential and increases in pH, dissolved organic carbon (DOC), and microbial activity in the maize rhizosphere were observed. The change in copper speciation may result from root-induced changes in DOC, redox potential, and microbial activity in the rhizosphere.     

Uranium transport around the reactor zone at Bangombé and Okélobondo (Oklo): examples of hydrogeological and geochemical model integration and data evaluation

The sites at Bangombé and Okélobondo (Oklo) in Gabon provide a unique opportunity to study the behaviour of products from natural nuclear reactions in the vicinity of reactor zones which were active around two billion years ago. The Commission of the European Communities initiated the Oklo Natural Analogue Programme. One of the principal aims was to study indications of present time migration of elements from the reactor zones under ambient conditions. The hydrogeological and hydrochemical data from the Oklo sites were modelled in order to better understand the geochemical behaviour of radionuclides in the natural system, by using independent models and by comparing the modelling outcome. Two modelling approaches were used: M3 code (hydrochemical mixing and mass balance model), developed by the Swedish Nuclear Fuel and Waste Management Company (SKB) and HYTEC (reactive transport model) developed by Ecole des Mines de Paris. Two different reactor zones were studied: Bangombé, a shallow site, the reactor being at 11 m depth, and OK84 at Okélobondo, situated at about 450 m depth, more comparable with a real repository location. This allowed the validation of modelling tools in two different sedimentary environments: one shallow, with a more homogeneous layering situated in an area of meteoric alteration, and the other offering the opportunity to study radionuclide migration from the reaction zone over a distance of 450 m through very heterogeneous sedimentary layers. The modeling results indicate that the chemical reactions retarding radionuclide transport are very different at the two sites. At Bangombé, the decomposition of organic material consumes oxygen and at Okélobondo the oxygen is consumed by inorganic reactions resulting, in both cases, in uranium retardation. Both modelling approaches (statistic with M3 code and deterministic with HYTEC code) could describe this situation. The goal of this exercise is to test codes which can help to describe and understand the processes taking place at the sites, validate the models with in situ data, and thus build confidence in the tools used for future site characterization. Ultimately, this allows identifying and selecting processes and parameters that can be used as input into repository performance assessment calculations and modelling exercises.     

Metal ion removal from water by sorption on paper mill sludge

Chromatographic columns packed with paper mill sludge are employed for metal ion recovery from water. The breakthrough curves show that cadmium, copper, lead and silver are removed from acid solutions (pH 2, 4); the affinity series is Pb(II)>Cu(II)>Ag(I)>Cd(II). Both the amount of metal retained and the metal-matrix interaction are pH dependent; the sorptive capacity increases with increasing pH. When the metals are present together at the same initial concentrations a competition among the different ions occurs although the affinity order remains unchanged. In metal recovery from the paper mill sludge column, the total amount of the cadmium and copper is displaced by HCl 1.0 M, 65% of the lead by HCl 0.1 M and 75% of the silver by HNO(3) 0.1 M. More than 95% of copper and lead and less than 20% of cadmium were recovered with HCl 0.1 M when the metals were present at the same time.     

Can aquatic distribution of human pharmaceuticals be related to pharmacological data?

The recognition of pharmaceuticals as significant environmental contaminants has only been a recent phenomenon. Therefore there is a paucity of data relating to the fate and effects of pharmaceuticals once they enter an aquatic receiving system. The amount of work that needs to be done in terms of risk assessment for pharmaceuticals required by regulatory agencies is substantial. This paper has determined the environmental partitioning coefficient (K_d) of 13 diverse human pharmaceuticals in three model systems of differing combinations of solid phases and solutions. The K_d values were then compared with distribution values of the pharmaceuticals in the human body determined from pharmacological studies. This was done to assess the functional relationship between K_d and distribution values in the human body (V_D). K_d values ranged from 3 to 2450 L kg⁻¹. Regression coefficients ranged from r² = 0.62–0.72, indicating that V_D values are a useful indicator for the K_d values of the tested pharmaceuticals within the batch sorption systems. The relationship between K_d and V_D should therefore be further explored to determine whether this relationship can be applied to a broader range of pharmaceuticals in more diverse environmental systems. Exploiting available human pharmacological data in such a way would be of great benefit in prioritising human pharmaceuticals as environmental contaminants in the risk assessment process.     

Development of a microscale emission factor model for particulate matter for predicting real-time motor vehicle emissions

The U.S. Environmental Protection Agency's National Exposure Research Laboratory is pursuing a project to improve the methodology for modeling human exposure to motor vehicle emissions. The overall project goal is to develop improved methods for modeling the source through the air pathway to human exposure in significant exposure microenvironments. Current particulate matter (PM) emission models, particle emission factor model (used in the United States, except California) and motor vehicle emission factor model (used in California only), are suitable only for county-scale modeling and emission inventories. There is a need to develop a site-specific real-time emission factor model for PM emissions to support human exposure studies near roadways. A microscale emission factor model for predicting site-specific real-time motor vehicle PM (MicroFacPM) emissions for total suspended PM, PM less than 10 microm aerodynamic diameter, and PM less than 2.5 microm aerodynamic diameter has been developed. The algorithm used to calculate emission factors in MicroFacPM is disaggregated, and emission factors are calculated from a real-time fleet, rather than from a fleet-wide average estimated by a vehicle-miles-traveled weighting of the emission factors for different vehicle classes. MicroFacPM requires input information necessary to characterize the site-specific real-time fleet being modeled. Other variables required include average vehicle speed, time and day of the year, ambient temperature, and relative humidity.     

Sustainable watershed management: an international multi-watershed case study

Global freshwater resources are being increasingly polluted and depleted, threatening sustainable development and human and ecosystem health. Utilizing case studies from 4 different watersheds in the United States, Japan, Switzerland, and Brazil, this paper identifies the most relevant sustainability deficits and derives general vectors for more sustainable water management. As a consequence of the demographic and economic developments experienced in the last few decades, each watershed has suffered declines in water quality, streamflow and biotic resources. However, the extent and the cultural perception of these water-related problems vary substantially in the different watersheds, leading to specific water-management strategies. In industrialized countries, exemplified by the US, Switzerland, and Japan, these strategies have primarily consisted of finance- and energy-intensive technologies, allowing these countries to meet water requirements while minimizing human health risks. But, from a sustainability point of view, such strategies, relying on limited natural resources, are not long-term solutions. For newly industrialized countries such as Brazil, expensive technologies for water management are often not economically feasible, thus limiting the extent to which newly industrialized and developing countries can utilize the expertise offered by the industrialized world. Sustainable water management has to be achieved by a common learning process involving industrialized, newly industrialized, and developing countries, following general sustainability guidelines as exemplified in this paper.     

Local-scale fluxes of carbon dioxide in urban environments: methodological challenges and results from Chicago

Much attention is being directed to the measurement and modeling of surface-atmosphere exchanges of CO2 for different surface types. However, as yet, few measurements have been conducted in cities, even though these environments are widely acknowledged to be major sources of anthropogenic CO2. This paper highlights some of the challenges facing micrometeorologists attempting to use eddy covariance techniques to directly monitor CO2 fluxes in urban environments, focusing on the inherent variability within and between urban areas, and the importance of scale and the appropriate height of measurements. Results from a very short-term study of CO2 fluxes, undertaken in Chicago, Illinois in the summer of 1995, are presented. Mid-afternoon minimum CO2 concentrations and negative fluxes are attributed to the strength of biospheric photosynthesis and strong mixing of local anthropogenic sources in a deep mixed layer. Poor night-time atmospheric mixing, lower mixed layer depths, biospheric respiration, and continued missions from mobile and fixed anthropogenic sources, account for the night-time maxima in CO2 concentrations. The need for more, longer-term, continuous eddy covariance measurements is stressed.     

Effects of clearfelling on stream and soil water aluminium chemistry in three UK forests

Data are presented demonstrating how clearfelling has changed soil and stream water aluminium chemistry. For soil waters, a strong empirical relationship was observed between inorganic aluminium (Al(inorg)) and total inorganic anion (TIA) concentrations. Before felling, chloride and sulphate accounted for the largest proportion of the TIA concentration. After felling, in soils where nitrification was active, nitrate became increasingly important. Where this led to an increase in TIA, Al(inorg) concentrations increased. Over five years, nitrate concentrations have fallen, along with TIA, resulting in a sympathetic decline in Al(inorg). Streams draining clearfelled areas initially became more acid, although chloride and sulphate concentrations decreased. Stream water nitrate concentrations increased soon after felling and remained higher than controls for up to four years. While nitrate concentrations were high, Al(inorg) remained unchanged. Subsequently, as nitrate and TIA decreased, Al(inorg) also declined to concentrations below those in the control stream. Clearfelling upland forests will not necessarily result in immediate improvements in water quality, although long-term benefits may be seen before canopy-closure of the next crop.     

Deposition of atmospheric ammonia to moorlands

Micrometeorological methods were applied to measure fluxes of atmospheric ammonia (NH3) to moorlands. Measurements were made in a wide variety of surface conditions and included both Calluna vulgaris (L.) Hull and Eriophorum vaginatum L. dominated sites. NH3 was found to deposit rapidly to all the sites investigated, providing large deposition velocities (Vd, typically 10-40 mm s(-1)) and usually minimal surface resistances (rc). A small number of measurements were made in frozen conditions and suggest a possible exception to this pattern with mean rc of 50-200 s m(-1). The effect of vegetation drying was also investigated and a possible increase in rc observed, though this was small (< 10 s m(-1)). The results are interpreted in terms of the processes controlling exchange; it is shown that NH3 deposition is predominantly to the leaf surfaces and that the net NH3 compensation point approaches zero. Annual estimates show that dry deposition of NH3 is a major source of atmospheric nitrogen to moorland ecosystems. For two typical UK sites subject to background air concentrations, NH3 dry deposition is of similar magnitude to equivalent NH4+ inputs in wet deposition. In the vicinity of emission sources, NH3 dry deposition is expected to dominate inputs of atmospheric nitrogen.     

Cadmium availability to the cyanobacterium Synechocystis aquatilis in solutions containing chloride

Availability of cadmium to Synechocystis aquatilis (estimated by 109Cd sorption and cadmium toxicity-14C method) in solutions containing cadmium and complexing (KCl) or non-complexing (KNO3) salts, in the range of 0-0.5 m was investigated. Both cadmium surface adsorption and transport into the cells were lower in solutions containing cadmium chloride complexes (CdCl+, CdCl2, CdCl3-) than in those containing cadmium in the form of Cd2+. Also, cadmium toxicity in solutions of higher KCl concentrations, in which CdCl+ and CdCl2 forms predominated, was significantly limited.