Chlorpyrifos-methyl dissipation in a small adjacent water body following application to citrus

Chlorpyrifos-methyl use in citrus, vineyards and vegetables is extensive and it has become an essential component of pest control in Southern European regions. The objective of this study was to assess surface water and sediment exposure to chlorpyrifos-methyl (RELDAN 22) under field conditions in a citrus orchard in Sicily (Italy). Pesticide drift loadings were measured in a small surface water body situated 0.5-1.0 m from the edge of the treated field. Measured drift values after the application were between 0.04% and 0.19% of the theoretical applied dose and were highly variable. However, the loadings were lower than those measured by other authors, also lower than predicted by regulatory drift models (95th percentile) typically used for aquatic risk assessment in Europe. Most of the variability occurred due to fluctuating wind speed and direction. In water samples collected in the surface water adjacent to the target field, chlorpyrifos-methyl was detected immediately after application, with concentrations ranging from less than the limit of quantification of the analytical method (0.05 microg/l) to a maximum of 0.08 microg/l. Predicted environmental concentrations in water, using the TOXSWA model, were similar to the measured data when measured drift data from the field experiment were used as inputs.     

Fine structure and X-ray microanalysis of a red macrophyte cultured under cadmium stress

Thalli of the red alga Audouinella saviana were exposed to 600 microM Cd2+ (LC50), 1000 microM Cd2+ and 1500 microM Cd2+ (final concentrations) for 5, 10 and 15 days (each dose) by adding cadmium nitrate to the culture medium. Untreated thalli were set in triplicate as controls for each experiment. Ultrastructural modifications due to cadmium ad/absorption were observed by TEM/SEM electron microscopy. SEM-EDS X-ray microanalysis, definining the accumulation sites, was performed on cryoprepared samples. TEM studies showed striking changes in the plasmalemma of treated algae, which became irregular and convoluted. Electron-transparent exocytic vesicles, possibly related to cell wall polysaccharide synthesis, were observed. The appearance of ribosomes and Golgi bodies, not significantly present in the cytoplasms of untreated cells, suggested enhanced protein and carbohydrate biosynthesis. The cell walls lost their initial grooves and became smooth and thick. More or less electron-dense vesicular systems were formed. Electron-dense sphaeroids occurred in the plasmalemma-cell wall interface, in the cell wall itself and in nearby vesicular membrane systems. Many small vacuoles containing large metal complexes were formed. Complexes were then sequestered into a large vacuole. SEM observations demonstrated that the cell wall and the membrane systems were the most involved in the defense responses. EDS-X-ray microanalysis confirmed the presence of cadmium in these compartments. Chloroplasts, where no Cd2+ signal was detected, were the least affected organelles, showing only a partial disorganization after lengthy exposure to high Cd2+ concentrations.     

Electrochemical analysis of endosulfan using a C18-modified carbon-paste electrode

Successful applications of different analytical procedures to determine quantitatively endosulfan and its metabolites in aqueous media can be found in recent literature. Fundamentally, they have made use of solid-phase extraction (SPE) and gas (GC) or liquid chromatography (LC), sometimes coupled to mass spectrometry (MS). In this paper, a new and alternative methodology to determine quantitatively endosulfan in aqueous media is reported. A C18-modified carbon-paste electrode has been used to determine voltammetrically endosulfan, despite its unfavourable electrochemical properties and behaviour. The methodology proposed is based on the decrease experienced by the peak intensity corresponding to voltammetric signals of Cu(II) when successive and constant additions of endosulfan are carried out. This decrease is directly proportional to the concentration of endosulfan what allows to perform an indirect quantification of the pesticide. The detection limit obtained is 40 ng l⁻¹, this value being under the limits specified by European norms and EPA reports.     

Methane oxidation and attenuation of sulphur compounds in landfill top cover systems: Lab-scale tests

In this study,a top cover system is investigated as a control for emissions during the aftercare of new landfills and for old landfills where biogas energy production might not be profitable.Different materials were studied as landfill cover system in lab-scale columns:mechanical–biological pretreated municipal solid waste(MBP);mechanical–biological pretreated biowaste(PB);fine(PBS_f)and coarse(PBS_c)mechanical–biological pretreated mixtures of biowaste and sewage sludge,and natural soil(NS).The effectiveness of these materials in removing methane and sulphur compounds from a gas stream was tested,even coupled with activated carbon membranes.Concentrations of CO_2,CH_4,O_2,N_2,H_2S and mercaptans were analysed at different depths along the columns.Methane degradation was assessed using mass balance and the results were expressed in terms of methane oxidation rate(MOR).The highest maximum and mean MOR were observed for MBP(17.2 g CH_4/m~2/hr and 10.3 g CH_4/m~2/hr,respectively).Similar values were obtained with PB and PBS_c.The lowest values of MOR were obtained for NS(6.7 g CH_4/m~2/hr)and PBS_f(3.6 g CH_4/m~2/hr),which may be due to their low organic content and void index,respectively.Activated membranes with high load capacity did not seem to have an influence on the methane oxidation process:MBP coupled with 220 g/m~2and 360 g/m~2membranes gave maximum MOR of 16.5 g CH_4/m~2/hr and 17.4 g CH_4/m~2/hr,respectively.Activated carbon membranes proved to be very effective on H_2S adsorption.Furthermore,carbonyl sulphide,ethyl mercaptan and isopropyl mercaptan seemed to be easily absorbed by the filling materials.     

Interaction between Fe-cyanide complex and humic acids

The fate of cyanides in soil is strongly influenced by the formation of Fe cyanides, which can interact with organic and inorganic colloids and precipitate as stable compounds. Scarce information is available on the capacity of humic acids to interact with cyano-complexes and thus affect the leaching and prevent the risk of contamination of watertable. Here we show that interaction between humic acids (HAs) and ferricyanide complex led to a formation of ferricyanide-humo micelles, and that the interaction did not imply changes in the original structure of ferricyanide complex.     

Mate preferences by male guppies (Poecilia reticulata) in relation to the risk of sperm competition

We investigated male mate preferences in relation to the perceived risk of sperm competition in the guppy (Poecilia reticulata), a freshwater fish with a promiscuous mating system. Our laboratory experiments revealed that male mate choice behaviour is not influenced by the presence of rival males that are merely in close proximity to a potential mate, as there was no significant difference in the amount of time that males spent with females that were recently either alone or in close proximity to four rival males. Male mate choice behaviour was, however, strongly influenced by the presence of rival males in a second experiment, where those rivals were permitted to copulate with one of the females. In that situation, males spent significantly more time with, and directed significantly more sigmoid courtship displays toward, females that they had recently seen alone compared to females they had seen receiving forced copulations from up to four rival males. Our results therefore indicate that male guppies are sensitive to the risk of sperm competition and alter their mate choice behaviour in an adaptive fashion.Communicated by K. Lindström     

Ecotoxicity in Aliivibrio fischeri of Ibuprofen,Omeprazole and their Mixtures

The acute ecotoxic effects of ibuprofen and omeprazole and their mixture have been measured using Aliivibrio fischeri as a biomodel. The toxic effects were also tested after 5 days, and an effect-driven approach was used to analyse the results. The toxic effects of the mixtures were compared with the predictions obtained using concentration addition and independent action mathematical methods.

According to the Passino and Smith classification, the results indicate that ibuprofen can be considered slightly toxic (10<EC₅₀ <100?mg?L^-1), while omeprazole can be denoted as moderately toxic (1<EC₅₀ <10?mg?L^-1) to Aliivibrio fischeri. An overestimation of the actual ecotoxic effect of the mixture was found when the concentration addition and independent action methods were applied. Finally, the effect-driven approach indicated that the transformation products of the studied drugs should be prioritized for risk assessment purposes.     

Monitoring trace metals in urban aerosols from Buenos Aires city. Determination by plasma-based techniques

A study was undertaken, within the framework of a 3 years national project, to assess the content of 13 elements in airborne particulate matter collected in representative zones of the metropolitan area of Buenos Aires. The sampling strategy followed consisted in collecting simultaneously 67 samples of PM10 particulate matter in 9 sampling sites covering an area of about 30 km2 during one week. The collection was performed on ash-free fibre-glass filters using high volume samplers. A combination of aqua regia and perchloric acid was used for leaching metals from filters. Key elements, namely Al, Ca, Cu, Fe, Mn, Mo, Ni, Pb, S, Sb, Sn, Zn and Zr, were determined by inductively coupled plasma-optical emission spectrometry (ICP-OES) and inductively coupled plasma-mass spectrometry (ICP-MS) at micro g g(-1) and ng g(-1) levels. Analyte concentration varied from 130 ng g(-1)(Mo) to over 30%(Ca). Multivariate statistical analysis was performed on the data set including the measured elemental compositions for the monitored period. The atmospheric concentration found for Pb confirms the decreasing levels of this element since the introduction of unleaded gasoline in 1995: 88 ng m(-3)(2001) < 220 ng m(-3)(1997) < 3900 ng m(-3)(1994). The average S concentration above 3 microg m(-3) is somehow unexpectedly high for Buenos Aires since the relatively low S content of liquid fuels and the massive usage of natural gas imply low emissions of this element from combustion activities. To the best of our knowledge, S concentrations are reported for the first time for this city.     

Arsenic biomonitoring using a hyperaccumulator fern (Pteris vittata)

Samples of Pteris vittata L. (brake fern or ladder brake) collected in Genova and in areas outside urban centres, have been analysed for arsenic content in order to assess if hyper accumulating plants are suitable for monitoring purposes. Hyper accumulation ability of the Ligurian fern populations was evaluated by analysing specimens grown with hydroponic media added with As(v). Arsenic concentrations in the range 2-310 microg g(-1) dry weight have been measured in samples collected in different sites along the Ligurian coast. Arsenic concentrations in fern fronds correlate with the estimated arsenic emission in the area, verifying the applicability of P. vittata as an arsenic biomonitor.