Sediment analysis to support the recent glacial origin of DDT pollution in Lake Iseo (Northern Italy)

In the present study, a depth-related distribution of Persistent Organic Pollutants (POPs) in sediments of Lake Iseo, one of the major southern Alpine Italian lakes, is reported in order to further test the hypothesis of melting Alpine glaciers as a secondary source of contamination. In a previous paper, a “glacier contamination hypothesis” was suggested to explain the unexpected contamination of the biota of Lake Iseo, mainly fed by the Alpine melting ice.The sediment core analyses covered around the last 50 years. The organic matter profile evaluated as a Loss-On-Ignition percentage indicated transition of the basin from an oligotrophic to a mesotrophic status at around the early 1970s, but there was no evidence of the shift to eutrophy in the 1980s. Among DDTs, pp’DDE was the predominant metabolite, accounting on average for 79.4% of the total DDT concentrations and ranging from 6.4 to 447.5 ng g⁻¹ d.w. PCBs ranged from 5.0 to 163.7 ng g⁻¹ d.w. The maximum PCB concentrations were found in sediment layers corresponding to the 1970s when the highest production and use of these compounds occurred in Italy. In contrast, concentrations of DDTs showed a sharp increase from the early 1990s, long after their agricultural use was banned in Italy. This delayed pollution provides support for the hypothesis that the recent retreat of glaciers represents a secondary pollution source for old pesticides that were stored in the ice at the time of their use in agriculture.     

Estimation of measurement uncertainty associated to the determination of pesticide residues: a case study

In the analytical analysis the measurement uncertainty is a quantitative indicator of the confidence describing the range around a reported or experimental result within which the true value can be expected. Several approaches can be used to estimate the measurement uncertainty associated to the analysis of pesticide residues: a) the top-down, the estimation can be referred to default values; b) the bottom-up the estimation is related to the uncertainty sources. Concerning the bottom-up approach, the following contributions have been investigated: weight of sample, calibration solutions, final volume of sample and intermediate repeatability studies. The commodity/residue combination selected in this study was celery/tau-fluvalinate pesticide. Tau-fluvalinate is a broad-spectrum insecticide in the pyrethroid class of pesticides. The Maximum Residue Limit (MRL) of tau-fluvalinate in celery has been set at 0.01 mg/kg. The tau- Fluvalinate showed two chromatographic peaks. Since the individual standards are not available, the two peaks were integrated separately and the instrumental responses were added. The total residue was calculated on the basis of resulted peaks. The present work aims to compare the uncertainty estimated by experimental data using repeated analysis (n = 12) of a real sample and a spiked sample. The relative expanded uncertainty for two data set, incurred and spiked, was 22 % and 20 %, respectively. No differences were observed from repeated determinations of real samples and spiked samples.     

Modelling the biphasic sorption of simazine,imidacloprid, and boscalid in water/soil systems

The sorption kinetics of simazine (6-chloro-N,N′-diethyl-1,3,5-triazine-2,4-diamine), imidacloprid (1-(6-chloro-3-pyridylmethyl)-N-nitroimidazolidin-2-ylideneamine), and boscalid (2-chloro-N-(4′-chlorobiphenyl-2-yl)nicotinamide), three pesticides of wide use in agriculture, was determined in five different water/soil systems over a time interval from the initial few seconds to about 1 month. In all the experiments, sorption kinetics showed a biphasic pattern characterized by an initial, relatively short phase with a high sorption rate and a later phase with much a lower sorption rate. Initial sorption capacity increased with soil organic carbon content and with sorbate hydrophobicity. We postulate that the first phase of the process involves a fast second-order sorption reaction on superficial sites of soil particles, whereas the second phase depends on diffusion-controlled migration to internal binding sites. A kinetic equation based on this hybrid model accurately fitted all data sets. Less satisfactory results were obtained employing the pseudo-first order, pseudo-second order, Elovich, two site non-equilibrium, or Weber-Morris equation. The superior performance of the hybrid model for describing boscalid sorption probably reflects the high hydrophobic character and consequent low diffusion rates of this compound. The accuracy of modelling was in any case strongly dependent on the time interval considered.     

Degradation of clofibric acid in acidic aqueous medium by electro-Fenton and photoelectro-Fenton

Acidic aqueous solutions of clofibric acid (2-(4-chlorophenoxy)-2-methylpropionic acid), the bioactive metabolite of various lipid-regulating drugs, have been degraded by indirect electrooxidation methods such as electro-Fenton and photoelectro-Fenton with Fe(2+) as catalyst using an undivided electrolytic cell with a Pt anode and an O(2)-diffusion cathode able to electrogenerate H(2)O(2). At pH 3.0 about 80% of mineralization is achieved with the electro-Fenton method due to the efficient production of oxidant hydroxyl radical from Fenton's reaction between Fe(2+) and H(2)O(2), but stable Fe(3+) complexes are formed. The photoelectro-Fenton method favors the photodecomposition of these species under UVA irradiation, reaching more than 96% of decontamination. The mineralization current efficiency increases with rising metabolite concentration up to saturation and with decreasing current density. The photoelectro-Fenton method is then viable for treating acidic wastewaters containing this pollutant. Comparative degradation by anodic oxidation (without Fe(2+)) yields poor decontamination. Chloride ion is released during all degradation processes. The decay kinetics of clofibric acid always follows a pseudo-first-order reaction, with a similar rate constant in electro-Fenton and photoelectro-Fenton that increases with rising current density, but decreases at greater metabolite concentration. 4-Chlorophenol, 4-chlorocatechol, 4-chlororesorcinol, hydroquinone, p-benzoquinone and 1,2,4-benzenetriol, along with carboxylic acids such as 2-hydroxyisobutyric, tartronic, maleic, fumaric, formic and oxalic, are detected as intermediates. The ultimate product is oxalic acid, which forms very stable Fe(3+)-oxalato complexes under electro-Fenton conditions. These complexes are efficiently photodecarboxylated in photoelectro-Fenton under the action of UVA light.     

The role of zooplankton in DDT biomagnification in a pelagic food web of Lake Maggiore (Northern Italy)

Background  

In the present study, we report the analytical results of pp′DDT, pp′DDE and pp′DDD determination in lake water, plankton and zooplanktivorous fish of Lake Maggiore (Northern Italy), rather recently polluted by DDT of industrial origin, in order to understand the bottom-up pollution transfer among the abiotic and biotic components of the lake ecosystem.     

Contribution of vehicular traffic and industrial facilities to PM10 concentrations in a suburban area of Caserta (Italy)

PM10 levels have been recorded in the suburban area of Caserta (Italy) from February to October 2012. The daily limit was exceeded in 13 % of the determinations, with no significant difference between weekdays and weekends. Benzo[a]pyrene concentrations were in the range 0.01–0.46 ng/m³, thus, never exceeding the National Standard. The B(a)P-eq was 0.20 ng/m³. PM10 peaks were associated with wind from east–northeast. The same was observed for Ca concentrations, whereas no relation with wind direction was observed for organic pollutants. The results point to a local limestone quarry and cement factory as the likely major source of PM10 pollution in the area investigated.     

Geochemical and ecological significance of soil lipids under Rhododendron ponticum stands

The bio-geographical significance of Rhododendron ponticum spp. baeticum (Ericaceae) as a relict species is well recognized. However, out of its native habitat it is an invasive exotic considered a major threat to natural ecosystems in areas of Atlantic Western Europe. The studies on the impact of Rhododendron influence on soil organic matter composition and associated ecological implications, i.e. presence of bioactive compounds with ecological significance, are limited. This work describes the soil lipid assemblage in three sites under Rhododendron stands and adjacent sites with deciduous oak (Quercus canariensis), both in their native habitats in Southern Spain (Sierra de Luna, Cádiz). The results are discussed in terms of organic matter dynamics and the presence of molecules that may be associated with Rhododendron invasive success. The soils are acid Xerochrepts formed on siliceous sands. Composite soil samples were taken at two depths (0?C10?cm and 10?C20?cm) and soxhlet extracted with a dichloromethane-methanol mixture (3:1). Soil lipid assemblage was studied by GC/MS after fractionation and appropriate derivatization of extracts. The qualitative chemical composition of soil extractable lipids under Rhododendron is reported here for the first time. Our results show that soil n-alkane and fatty acid distributions are compatible with an input from plant epicuticular waxes, as well as with the occurrence of selective preservation of long-chain fatty acids with depth. The pattern of short-chain n-alkanes found in surface samples indicates an anthropogenic contamination threat from nearby industrialized areas of ??Campo de Gibraltar??. The presence of branched iso and anteiso C₁₅ and C₁₇, ??-hydroxy fatty acids and the sterol brassicasterol points to high microbial soil activity. Finally, the pentacyclic triterpenes taraxerone and taraxerol were detected in soils with Rhododendron but not with Quercus. These are known bio-active plant compounds and could be related with the effectiveness of Rhododendron as an invasive exotic species.     

Free-ranging dogs’ lifetime estimated by an approach for long-term survival data with dependent censoring

Environmental and Ecological Statistics - Populations of free-ranging dogs are still a matter of concern in developing countries. The presence of stray dogs is associated with environmental and...