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.     

Predicting logP of pesticides using different software

We compared experimental and calculated logP values using a data set of 235 pesticides and experimental values from four different sources: The Pesticide Manual, Hansch Manual, ANPA and KowWin databases. LogP were calculated with four softwares: HyperChem, Pallas, KowWin and TOPKAT. Crossed comparison of the experimental and calculated values proved useful, especially for pesticides. These are harder to study than simpler organic compounds. Structurally they are complex, heterogeneous and similar to drugs from a chemical point of view. They offer an interesting way to verify the goodness of the different methods. Other studies compared several logP predictors using a single set of experimental values taken as a reference. Here we discuss the utility of the different logP predictors, with reference to experimental data found in different databases. This offers three advantages: (1) it avoids bias due to the assumption that one single data set is correct; (2) a given predictor can be developed on the same data set used for evaluation; (3) it takes account of experimental variability and can compare it with the predictor's variability. In our study Pallas and KowWin gave the best results for prediction, followed by TOPKAT.     

Photodegradation of Pyrimethanil induced by iron(III) in aqueous solutions

In this study an abiotic process was suggested to evaluate the behaviour of Pyrimethanil (antibotrytic fungicide) in real matrices. This process consists of a photodegradation of the fungicide carried out in the presence of iron(III) in three types of buffer; acetate, phosphate and citrate. The experimental results show that the nature of buffered solutions influences both the rate of disappearance of Pyrimethanil and, in the case of citrate, also the kind of by-products formed during the photodegradation process. For each case examined, the breakdown products were identified by using liquid chromatography (LC) or gas chromatography (GC), coupled with mass spectrometry (MS). The degradation pathways of the fungicide were proposed and the relative kinetic constants were evaluated. The abiotic photodegradation process shows the possibility of different pathways for Pyrimethanil degradation in environmental matrices such as the soil, plants and foodstuffs, where iron (free and/or bonded) is a natural component.     

Air quality research: perspective from climate change modelling research

A major component of climate change is a manifestation of changes in air quality. This paper explores the question of air quality from the climate change modelling perspective. It reviews recent research advances on the cause-effect relationships between atmospheric air composition and climate change, primarily based on the Intergovernmental Panel on Climate Change (IPCC) assessment of climate change over the past decade. There is a growing degree of confidence that the warming world over the past century was caused by human-related changes in the composition of air. Reliability of projections of future climate change is highly dependent on future emission scenarios that have been identified that in turn depend on a multitude of complicated interacting social-economic factors. Anticipated improvements in the performance of climate models is a major source of optimism for better climate projections in the future, but the real benefits of its contribution will be closely coupled with other sources of uncertainty, and in particular emission projections.     

New international long-term ecological research on air pollution effects on the Carpathian Mountain forests,Central Europe

An international cooperative project on distribution of ozone in the Carpathian Mountains, Central Europe was conducted from 1997 to 1999. Results of that project indicated that in large parts of the Carpathian Mountains, concentrations of ozone were elevated and potentially phytotoxic to forest vegetation. That study led to the establishment of new long-term studies on ecological changes in forests and other ecosystems caused by air pollution in the Retezat Mountains, Southern Carpathians, Romania and in the Tatra Mountains, Western Carpathians on the Polish-Slovak border. Both of these important mountain ranges have the status of national parks and are Man & the Biosphere Reserves. In the Retezat Mountains, the primary research objective was to evaluate how air pollution may affect forest health and biodiversity. The main research objective in the Tatra Mountains was to evaluate responses of natural and managed Norway spruce forests to air pollution and other stresses. Ambient concentrations of ozone (O(3)), sulfur dioxide (SO(2)), nitrogen oxides (NO(x)) as well as forest health and biodiversity changes were monitored on densely distributed research sites. Initial monitoring of pollutants indicated low levels of O(3), SO(2), and NO(x) in the Retezat Mountains, while elevated levels of O(3) and high deposition of atmospheric sulfur (S) and nitrogen (N) have characterized the Tatra Mountains. In the Retezat Mountains, air pollution seems to have little effect on forest health; however, there was concern that over a long time, even low levels of pollution may affect biodiversity of this important ecosystem. In contrast, severe decline of Norway spruce has been observed in the Tatra Mountains. Although bark beetle seems to be the immediate cause of that decline, long-term elevated levels of atmospheric N and S depositions and elevated O(3) could predispose trees to insect attacks and other stresses. European and US scientists studied pollution deposition, soil and plant chemistry, O(3)-sensitive plant species, forest insects, and genetic changes in the Retezat and Tatra Mountains. Results of these investigations are presented in a GIS format to allow for a better understanding of the changes and the recommendations for effective management in these two areas.     

Activity of glutathione S-transferase in Spodoptera exigua larvae exposed to cadmium and zinc in two subsequent generations

The aim of our study was to establish changes in activity of important in detoxification enzyme-glutathione S-transferase (GST): in alimentary tract, fat body and Malpighian tubules of Spodoptera exigua larvae being under cadmium and zinc exposure through the first as well as the second generation. There was registered enhancement of the enzyme activity in the fat body and the Malpighian tubules caused by zinc as well as its decrease in the Malpighian tubules under cadmium action. Amounts of metals in the alimentary tract were either several times higher than in the diet ingested by larvae or than in the fat body. Metal concentration in the fat body correlated with the level of the enzyme activity (positive correlation for zinc and negative for cadmium). The effect of metal action differentiated dependently on time exposition.     

Flooding patterns of the Okavango Wetland in Botswana between 1972 and 2000

The inundated area of the Okavango Delta changes annually and interannually. The variability relates to regional precipitation over the catchment area in the Angolan highlands, and to local rainfall. The patterns of the wetland were captured using more than 3000 satellite images for the period 1972 to 2000, near daily NOAA AVHRR data for 1985-2000, and less frequent images of the Landsat sensors from 1972 onwards. One AVHRR image for every 10-day period was classified into land and water using an unsupervised classification method. Evaluation against Landsat TM and ERS2-ATSR data indicate an agreement of 89% for the size of estimated inundation area. Results show that the wetland area has varied between approximately 2450 km2 and 11400 km2 during the last 30 years.     

In vitro and in vivo studies of lead immobilization by synthetic hydroxyapatite

Apatite appears a useful compound for removing lead from water, due to its ability to immobilize the metal by precipitation. In dilute solution, dissolved hydroxyapatite [HA, Ca1O(P04)6(OH)2] provided phosphates that were reactive with aqueous lead (molar ratio HA/Pb= 1/10) forming precipitates at around pH 6. These dissolved at a more acidic pH (3). Solid HA in contact with Pb2+ions, led to the formation of pyromorphite [Pblo(P04)6(OH)2], identified by X-ray diffraction and insoluble at pH tested (3-8). The amount of pyromorphite increased with the weight ratio of HA/Pb. When this one increased from 1 to 1000, lead precipitated as pyromorphite rose from 19 to 99%. In vivo experiments on rats confirmed the in vitro results. In fact, lead bioavailability assessed by intestinal perfusion was unchanged in the presence of dissolved HA, whereas it was significantly lower in the presence of solid HA, evaluated by gastric intubation, at a weight ratio equal to 10 (amount of lead absorbed decreased by 60%). Apatite could bean effective means of immobilizing lead in drinking or sewage, since accidental pyromorphite ingestion does not yield bioavailable lead.     

Behavior of a surface applied radionuclide and a dye tracer in structured and repacked soil monoliths

There has been increasing evidence in recent years about the impact of soil structure on vadose zone hydrology and the distribution of surface applied chemical substances. We have carried out a combined dye and radionuclide tracer study on two monoliths from the same location, one structured and one repacked, as part of an ongoing study to investigate the link between preferential flow, leaching of surface applied substances and their distribution within the soil.A tracer solution containing 1300 Bq/L (58)Co and 0.31 micromol/L Sulforhodamine B (SB) was added with roughly constant irrigation during a period of three weeks. The dye served as a tracer for water movement within the soil and thus allowed linkage of the radiotracer ((58)Co) with the flow pattern. Both were monitored in the outflow and measured within profile sections after monolith disassembly. Preferential flow in the structured monolith promoted the bypass and transport of both tracers, although transport was impeded at depths greater than 30 cm by compacted soil and reduced hydraulic conductivity. Eighty four percent of radiocobalt and 8% of SB were found in the upper 4 cm of the structured monolith. The homogenized monolith, on the other hand, showed mostly chromatographic infiltration and a more efficient soil filtering capacity with 91% of radiocobalt and 20% SB residing in the upper 4 cm. Furthermore no tracer was found in the outflow of the homogenized monolith during normal to high irrigation or at greater depth within the monolith. We have related flow characteristics and sorption of radiotracers by quantifying dye distributions and radionuclide activities throughout the profiles. Activities within the flow paths are up to 20-times higher than those measured in the soil matrix, and a fraction of radiocobalt follows the dye tracer in spite of cobalt's low mobility. The dye can thus be used to trace radionuclide distribution within the soil block.     

Availability of 99Tc in undisturbed soil cores

Models for safety assessment of radioactive waste repositories need accurate values of the soil-to-plant transfer of radionuclides. In oxidizing environments, (99)Tc is expected to occur as pertechnetate ((99)TcO(4)(-)). Due to its high mobility, leaching of this element in the field might be important, potentially affecting the reliability of estimated transfer parameters of (99)Tc as measured in closed experimental systems such as hydroponics or pot experiments. The aim of this experiment was to measure the leaching of (99)Tc in undisturbed irrigated soil cores under cultivation as well as plant uptake and to study the possible competition between the two transfer pathways. Undisturbed soil cores (50 x 50 cm) were sampled from a Rendzic Leptosol (R), a colluvial Fluvic Cambisol (F) and a Dystric Cambisol (D) using PVC tubes (three cores sampled per soil type). Each core was equipped with a leachate collector at the bottom, allowing the monitoring of (99)Tc leaching through the cores. Cores were placed in a greenhouse and maize (Zea mays L., cv. DEA, Pioneer) was sown. After 135 d, maize was harvested and radioactivity determined in both plant and water samples. Results showed that during the growing period, leaching of (99)Tc was limited, due to the high evapotranspiration rate of maize. After harvest, leaching of (99)Tc went on because of the absence of evapotranspiration. Effective uptake (EU) of (99)Tc in leaves and grains was calculated. EU reached 70% of the input in the leaves and was not significantly different among soils. These results confirmed those obtained from pot experiments, even though leaching was allowed to occur in close-to-reality hydraulical conditions. As a consequence, it was concluded that pot experiments are an adequate surrogate for more complex "close-to-reality" experimental systems for measuring transfer factors.