Electrochemical oxidation of benzene on boron-doped diamond electrodes

This work presents an electrochemical investigation of the benzene oxidation process in aqueous solution on boron-doped diamond (BDD) electrodes. Additionally, in order to determine the main products generated during the oxidation process, electrolysis and high performance liquid chromatography experiments were carried out. The complete degradation of this compound was performed aiming to a further application in waste water treatment. The cyclic voltammetry studies indicate that benzene is irreversibly oxidized in acid medium (H₂SO₄ 0.5 M) on the BDD electrode surface at 2.0 V versus Ag/AgCl in a diffusion controlled process. During the cycling, other products are generated, and a pair of peaks was observed that can be associated with the oxi-reduction of anyone of the following species: hydroquinone, benzoquinone, resorcinol or catechol. The electrolysis experiments were carried out at 2.4 and 2.5 V on the BDD electrode surface in a solution containing 1 × 10⁻² M of benzene (below the saturation concentration in aqueous solution), for 3 and 5 h, respectively. The main products measured were: hydroquinone, resorcinol, p-benzoquinone, catechol and phenol. The complete electrochemical benzene degradation was performed in the electrolysis experiments using a rotating BDD disc electrode (2.5 V for 5 h) and the main products detected were all measured at concentrations lower than 10⁻⁵ M in this condition. The boron-doped diamond electrode had proved to be a valuable tool for the electrochemical degradation of the benzene, a very stable chemical compound.     

Landscape-scale spatial distribution of the Lanner Falcon (Falco biarmicus feldeggii) breeding population in Italy

Falco biarmicus feldeggii is one of the most threatened taxa in Europe. Its global population is estimated at a few hundred pairs unequally scattered in a vast and fragmented area stretching from Sicily to the Caspian Sea. Most recent counts showed that Italy hosts a large part (>25%) of the whole population. Consequently, Italian authorities promoted a national action plan. In this framework, we carried out the first national survey for the Lanner Falcon in Italy (2003-2004). Our study area covered the whole breeding range, i.e., Sicily and the Italian peninsula (n = 2909 cells 10 x 10 km). When possible, we considered also additional information from previous regional investigations (1993-2001). First, we estimated size and distribution of each breeding subpopulation. Then, we tried to identify, at landscape level, the main environmental features linked to the spatial distribution of the nesting sites. We found the Lanner Falcon in 184 cells (6.4% of the total grid map), but we estimated no more than 140-172 pairs (70-80 of which are in Sicily) in the same breeding season. Higher levels of isolation characterize the continental breeding cells whereas in Sicily cells are much more clustered. Altitude is the main factor influencing cell aggregations in Italy; nevertheless, other environmental variables, such as climate, precipitation, and vegetation may be important. Our results show that the conservation measures adopted in Italy are somewhat inadequate given the low number of breeding pairs included in protected areas (23%-28%). Many small and scattered special areas of conservation (SAC) devoted to conserve priority habitats fit the irregular spatial aggregations of Lanner Falcon sites better than several large special protection areas (SPA).     

Development of a new automated clean-up system for the simultaneous analysis of polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs) and 'dioxin-like' polychlorinated biphenyls (dl-PCB) in flue gas emissions by GPC-SPE

A comprehensive clean-up method for quantitative analysis of polychlorinated biphenyls (PCBs) and polychlorinated dibenzo-p-dioxins and dibenzo-furans (PCDD/Fs) in one single extract of environmental samples was developed. Since the chemical nature and toxicity of planar PCBs are similar to those of PCDD/Fs, dioxin-like PCBs and PCDD/Fs are often surveyed together in their exposure assessments. The development of a method for the simultaneous analysis of PCBs and PCDD/Fs in environmental samples is invaluable. The automated clean-up system evaluated in this work consists of three additional steps after traditional extraction: the chromatography on gel permeation (GPC), the concentration of the solvent through the use of an in-line evaporation module and the further purification and separation of PCDDs/Fs and dl-PCBs on an alumina cartridge in the 'SPE module'. In this work, three fly ash samples from an interlaboratory study with different PCDD/F and PCB levels were Soxhlet-extracted and then cleaned up using an automated system. PCDD/Fs and PCBs were determined using isotope dilution and high resolution gas chromatography/high resolution mass spectrometry. The determined values of 17 PCDD/Fs were consistent with the certified values and the relative standard deviations (RSDs) of the determined values were less than 20%. The recoveries of (13)C labeled PCDD/Fs and planar PCBs, and their RSDs were within the ranges specified in EPA1613 and 1668a methods, respectively. An accurate and reliable method was successfully developed and can be used in the simultaneous analysis of PCDD/Fs and planar PCBs in environmental samples.     

Soils and sediments of the Thua Thien-Hue Province (central Vietnam): recognizing trace element sources and the likely influence of natural events

Trace element concentrations have been measured in soil and sediment samples taken from the Thua Thien Hue (TT-H) Province and the Tam Giang-Cau Hai (TG-CH) Lagoon in 2002 and 2004. Results show that the lagoon is only slightly contaminated by elements such as Ag, Cd, Cr, Cu, Ni, Pb and Zn, whereas As, probably naturally enriched in this Asian region, reaches values above the lowest internationally accepted sediment quality guidelines. Concentrations in soils are ascribable to natural sources and distributions in the TG-CH Lagoon are mainly influenced by river inputs, with Ag and Cd undergoing estuarine desorption processes. However, concentration-depth profiles of most trace elements in sediments show a recent increasing trend that might be linked to the economic development of the area. The comparison of porosity and (210)Pb depth profiles (confirmed also by Cd and As) from repeated samplings of the same core locations in the TG-CH Lagoon seems to account for a loss of 5-10 cm of surficial sediment that took place during the time interval between the two samplings. It is hypothesized that extreme meteorological events (e.g. a major typhoon that hit the area in November 2003) could be responsible for such sediment displacement.     

Habitat Mosaic, Wildlife Availability, and Hunting in the Tropical Forest of Calakmul, Mexico

Abstract: Habitat loss and subsistence hunting are two of the main activities that affect wildlife in frontier areas. We compared subsistence hunting patterns in four villages with different ethnic composition and degree of habitat disturbance in the vicinity of Calakmul Biosphere Reserve, Campeche, Mexico. We also compared differences between some of these villages in harvest composition and prey availability to determine hunting preferences. We used a Landsat TM satellite image to analyze the degree of disturbance around the villages. We conducted periodic surveys of subsistence hunting and prey availability. Wildlife availability was assessed monthly on nine transects (3000 m) established in the vicinity of three villages. The relative amount of disturbed habitat was smaller in an indigenous Maya village ( IV ) and larger in a mestizo village ( MV ). The two mixed-composition villages ( MCVs) had intermediate levels of disturbance. Ten species, four large and six small, of birds and mammals accounted for 97% of the hunting records. Hunting was more intense in IV and less intense in MCV1. The three village types had different hunting preferences. The habitat-mosaic composition in the vicinity of the villages influenced prey availability and subsistence-hunting preferences. Changes in the habitat mosaic were caused by the size of the holding and by ethnic composition. In spite of longer settlement time, the habitat mosaic in the vicinity of IV was less transformed than that of the other sites. Their larger holding size and greater diversity of economic activities may explain why the Mayas at IV have transformed the landscape less than the other groups and can hunt more and larger prey.     

Seasonal and pluri-annual variability of sediment accumulation and organic matter fluxes in the Northwestern Adriatic shelf and its relationship with the frontal system

Twenty eight short sediment cores, collected along six transects in two areas influenced by the frontal system formed by the Po River, were analysed for Th and Cs in order to improve our knowledge on short time scale sediment deposition, accumulation and mixing. Sedimentological and mineralogical parameters were also analysed._ The decreasing Cs activities and C/N values in surface sediments indicate a decreasing input of terrestrial material during the study period. Furthermore, low excess thorium activities and inventories at some sites, together with low sedimentary organic matter concentrations in the southern area, suggest that the productivity in summer 1997 was lower than in 1996. Temporal and spatial shifts of the front exert a strong influence on short time scale deposition of particulate matter in the northern area, while the front position is more stable in the southern area, influencing both seasonal and interannual deposition._ The comparison between apparent seasonal and pluri-annual accumulation rates suggests, for the northern area, a sedimentation pattern characterized by temporal deposition of material on to the sea floor, with periodical resuspension. The net apparent accumulation is 0.1-0.4 r g r cm r yr. The same occurs for the southern area, where values are higher, probably due to the longer persistence of the frontal system in the same area over the years. Here, both seasonal and pluri-annual deposition showed the same pattern, but seasonal values were two to three times higher with a net apparent accumulation rate of 0.3-0.8 r g r cm r yr. Organic carbon and nitrogen concentrations are generally less than 1.3 and 0.2% d.w., with lower values in the southern area. By contrast, mass fluxes showed higher values in the southern area, while the rate of removal over a pluri-annual time scale is generally high.     

Effects of female mating status on copulation behaviour and sperm expenditure in the freshwater crayfish <Emphasis Type="Italic">Austropotamobius italicus</Emphasis>

Sperm competition models predict that males should adjust their sperm expenditure according to the risk and/or intensity of sperm competition. In this paper, we analysed copulatory behaviour of both sexes and sperm expenditure in relation to female mating status (virgin or mated) in the freshwater crayfish Austropotamobius italicus, a species where males have been reported to feed on and remove sperm laid by other males. The same females were allowed to be inseminated sequentially by two males, and we compared the sexual behaviours of partners between the first (virgin females) and the second mating (mated females). We found that female resistance did not differ between the first and the second mating, nor males refused or took more time to mount a mated female. However, when mating with a mated female, males reached an effective copulation position significantly later. This occurred because second-mating males removed, by eating, all or most spermatophores previously deposited by first males. As removal was often incomplete, this resulted in a larger amount of sperm being deposited on female ventral parts after the second mating, although second males did not allocate more sperm to mated females than first males did. Thus, the peculiar mode of sperm competition, where males remove previously deposited sperm, and the consequent predictable strong last male prevalence in paternity likely led to the observed lack of adjustment of sperm expenditure to female mating status in this species.     

Element accumulation performance of living and dead lichens in a large-scale transplant application

Environmental Science and Pollution Research - In bioaccumulation studies, sample devitalization through acid washing or oven drying is commonly applied to enhance the element accumulation...     

Contamination by chlorinated pesticides, PCBs and PBDEs in Atlantic spotted dolphin (Stenella frontalis) in western South Atlantic

Chlorinated pesticides, PCBs and PBDEs were analysed in nine blubber samples of Atlantic spotted dolphins, Stenella frontalis, incidentally captured during fishing operations in southern and southeastern Brazil between 2005 and 2007. The majority of compounds analysed were detected, suggesting widespread contamination over the region. Although the samples came from a location far from main coastal industrial areas, the results revealed an influence from such sources. Therefore, levels of PCBs (774-23 659 ng g⁻¹ lipid wt.) and PBDEs (23-1326 ng g⁻¹ lipid wt.) detected seem to be related to the movement of individuals throughout near-shore and offshore waters. The sample from a lactating female exhibited a lower level of contamination and a distinct pattern, indicating selective transfer favouring less lipophilic compounds.     

Seasonal Fluctuations in the Nutritional Value of Particulate Organic Matter in A Lagoon

Water samples were collected on a fortnightly basis in the lagoon of S. Gilla (Sardinia, Mediterranean Sea) in order to study seasonal nutritional fluctuations of particulate organic matter. the lagoon is characterized by high quantities of suspended matter throughout the year. Thermohaline conditions had no effect on particulate matter quantity and composition, but the quantity as well as quality of suspended particles was drastically affected by the wind, the major effecter of sediment resuspension. As a result of sediment resuspension, seston was always richer in inorganic fraction. However, throughout the year of investigation, most particulate organic carbon was quite appealing for filter feeding communities, although the best POM quality was available during phytoplankton blooming. the phytoplankton pool of suspended matter was just a small fraction of the bulk, accounting for only 13% on average of particulate organic carbon. in terms of energy available in the seston, the highest amount was stored in organic matter heterotrophic fraction, whilst the smallest was to be found in living phytoplankton.