Isomer specific syntheses of chlorinated catechols and guaiacols relevant to pulp bleaching

A variety of chlorinated catechols and guaiacols relevant to pulp bleaching were synthesized by employing fundamental differences in the acidities of phenolic hydroxyl groups in chlorinated catechols, and directive effects in guaiacols.     

Do vesicle cells of the red alga Asparagopsis (Falkenbergia stage) play a role in bromocarbon production?

The Rhodophyceae (red algae) are an established source of volatile halocarbons in the marine environment. Some species in the Bonnemaisoniaceae have been reported to contain large amounts of halogens in structures referred to as vesicle cells, suggesting involvement of these specialised cells in the production of halocarbons. We have investigated the role of vesicle cells in the accumulation and metabolism of bromide in an isolate of the red macroalga Asparagopsis (Falkenbergia stage), a species known to release bromocarbons. Studies of laboratory-cultivated alga, using light microscopy, revealed a requirement of bromide for both the maintenance and formation of vesicle cells. Incubation of the alga in culture media with bromide concentrations below 64 mgl(-1) (the concentration of Br(-) in seawater) resulted in a decrease in the proportion of vesicle cells to pericentral cells. The abundance of vesicle cells was correlated with bromide concentration below this level. Induction of vesicle cell formation in cultures of Falkenbergia occurred at concentrations as low as 8 mgl(-1), with the abundance of vesicle cells increasing with bromide concentration up to around 100 mgl(-1). Further studies revealed a positive correlation between the abundance of vesicle cells and dibromomethane and bromoform production. Interestingly, however, whilst dibromomethane production was stimulated by the presence of bromide in the culture media, bromoform release remained unaffected suggesting that the two compounds are formed by different mechanisms.     

Cadmium,chromium and lead contamination of Athene noctua,the little owl,of Bologna and Parma,Italy

A study was conducted to determine cadmium, chromium and lead concentrations in liver and brain of 52 little owls (Athene noctua) from two provinces of Emilia Romagna region, with the aim of furnishing indirect information concerning contamination of their habitat, also considering possible environmental dispersion of the metals. Metal analysis was performed by atomic absorption spectrophotometry with graphite furnace. Variance analysis with sampling area, gender and age shows that no statistical difference was found for gender, while a significant difference (P<0.05) was found for cadmium and lead, but not for chromium, when sampling areas and age were of concern. For all metals highest mean concentrations were found in liver (170 ppb for cadmium, 297 ppb for chromium and 312 ppb for lead). These levels can be considered as indicative of chronic exposure to low and "background" amounts of pollutants and they are of no toxicological concern, as they are always well below the toxic thresholds defined for each metal. The present study can be considered as a starting point for further analyses, aimed to the definition of any possible subtle effect (e.g. effects on enzymes activity) and of any possible correlation between levels of pollutants and appearance of possible adverse effects. It also furnished useful data for diagnostic cases and potentially for monitoring local contamination.     

Explaining Agricultural Expansion, Resource Booms and Growth in Latin America

The following paper examines the main factors determining long-run agricultural land expansion in Latin America compared to other tropical regions. Given the importance of natural resource-based sectors for most economies in Latin America, the impact of price-induced "resource booms" on economic growth in the region is explored. In addition, the paper examines whether there is an inherent "boom and bust" pattern of economic development associated with agricultural land expansion in Latin America, and the extent to which economic policies in the region exacerbate this problem. The paper concludes by examining the role of targeted policies in alleviating the structural obstacles to Latin American agricultural and economic development.     

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.     

Use of chemical cues in detection of conspecific predators and prey by newts, <Emphasis Type="Italic">Notophthalmus viridescens</Emphasis>

Summary. Detection of heterospecific predators and prey via chemical cues is well known, but only a few studies have examined the potential for such discrimination in cannibalistic systems. In newts, Notophthalmus viridescens, adults are opportunistic predators of conspecific larvae. I used a laboratory bioassay to determine whether larvae and adults distinguish between chemical stimuli from members of the different age classes. Larvae distinguished between chemical stimuli from larvae and adults by decreasing their activity only following exposure to stimuli from adults. Decreased activity is consistent with an antipredator response in many prey species, including larval newts. In contrast, adults increased their activity and increased time spent in open areas in response to stimuli from larvae, but not to stimuli from adults. Increased activity is consistent with a feeding response; adults also showed increased activity and increased time in open areas in response to chemical stimuli from familiar heterospecific prey (brine shrimp). The proximate cue that allowed the newts to distinguish between the different age classes is not associated with short-term dietary differences because all stimulus animals were fed the same prey. Stimulus strength was controlled by diluting the stimulus solutions according to the volume of the stimulus animal. Therefore, there appear to be intrinsic differences in the chemical signatures of larval and adult newts.     

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.     

Simulating endosulfan transport in runoff from cotton fields in Australia with the GLEAMS model

Endosulfan (6,7,8,9,10,10-hexachloro-1,5,5a,6,9,9a-hexahydro-6,9methano-2,4,3-benzodioxathiepin 3-oxide), a pesticide that is highly toxic to aquatic organisms, is widely used in the cotton (Gossypium hirsutum L.) industry in Australia and is a risk to the downstream riverine environment. We used the GLEAMS model to evaluate the effectiveness of a range of management scenarios aimed at minimizing endosulfan transport in runoff at the field scale. The field management scenarios simulated were (i) Conventional, bare soil at the beginning of the cotton season and seven irrigations per season; (ii) Improved Irrigation, irrigation amounts reduced and frequency increased to reduce runoff from excess irrigation; (iii) Dryland, no irrigation; (iv) Stubble Retained, increased soil cover created by retaining residue from the previous crop or a specially planted winter cover crop; and (v) Reduced Sprays, a fewer number of sprays. Stubble Retained was the most effective scenario for minimizing endosulfan transport because infiltration was increased and erosion reduced, and the stubble intercepted and neutralized a proportion of the applied endosulfan. Reducing excess irrigation reduced annual export rates by 80 to 90%, but transport in larger storm events was still high. Reducing the number of pesticide applications only reduced transport when three or fewer sprays were applied. We conclude that endosulfan transport from cotton farms can be minimized with a combination of field management practices that reduce excess irrigation and concentration of pesticide on the soil at any point in time; however, discharges, probably with endosulfan concentrations exceeding guideline values, will still occur in storm events.     

Endosulfan transport: I. Integrative assessment of airborne and waterborne pathways

To reduce endosulfan (C9H6O3Cl6S; 6,7,8,9,10,10-hexachloro-1,5, 5a,6,9,9a-hexahydro-6,9-methano-2,4,3-benzodioxathiepin 3-oxide) contamination in rivers and waterways, it is important to know the relative significances of airborne transport pathways (including spray drift, vapor transport, and dust transport) and waterborne transport pathways (including overland and stream runoff). This work uses an integrated modeling approach to assess the absolute and relative contributions of these pathways to riverine endosulfan concentrations. The modeling framework involves two parts: a set of simple models for each transport pathway, and a model for the physical and chemical processes acting on endosulfan in river water. An averaging process is used to calculate the effects of transport pathways at the regional scale. The results show that spray drift, vapor transport, and runoff are all significant pathways. Dust transport is found to be insignificant. Spray drift and vapor transport both contribute low-level but nearly continuous inputs to the riverine endosulfan load during spraying season in a large cotton (Gossypium hirsutum L.)-growing area, whereas runoff provides occasional but higher inputs. These findings are supported by broad agreement between model predictions and observed typical riverine endosulfan concentrations in two rivers.