Colloidal mercury (Hg) distribution in soil samples by sedimentation field-flow fractionation coupled to mercury cold vapour generation atomic absorption spectroscopy

Diverse analytical techniques are available to determine the particle size distribution of potentially toxic elements in matrices of environmental interest such as soil, sediments, freshwater and groundwater. However, a single technique is often not exhaustive enough to determine both particle size distribution and element concentration. In the present work, the investigation of mercury in soil samples collected from a polluted industrial site was performed by using a new analytical approach which makes use of sedimentation field-flow fractionation (SdFFF) coupled to cold vapour generation electrothermal atomic absorption spectroscopy (CV-ETAAS). The Hg concentration in the SdFFF fractions revealed a broad distribution from about 0.1 to 1 μm, roughly following the particle size distributions, presenting a maximum at about 400-700 nm in diameter. A correlation between the concentration of Hg in the colloidal fraction and organic matter (O.M.) content in the soil samples was also found. However, this correlation is less likely to be related to Hg sorption to soil O.M. but rather to the presence of colloidal mercuric sulfide particles whose size is probably controlled by the occurrence of dissolved O.M. The presence of O.M. could have prevented the aggregation of smaller particles, leading to an accumulation of mercuric sulfides in the colloidal fraction. In this respect, particle size distribution of soil samples can help to understand the role played by colloidal particles in mobilising mercury (also as insoluble compounds) and provide a significant contribution in determining the environmental impact of this toxic element.     

Chemometric data analysis application to Sparus aurata samples from two offshore farming plants along the Apulian (Italy) coastline

The levels of polychlorodibenzo-p-dioxins (PCDDs), polychlorodibenzofurans (PCDFs), dioxin-like polychlorobiphenyls (DL-PCBs), non-dioxin-like polychlorobiphenyls (NDL-PCBs), and polybromodiphenyl ethers (PBDEs) in fish collected from two marine offshore farming plants were determined. Each sample was constituted by specimens of the same size collected at the same time in four different seasons along the farming year. The feeds given were of industrial origin and the plants were positioned in two different sites respectively exposed to different environmental characteristics. A chemometric approach was applied to interpret the subtle differences observed in fish body burdens across the three chemical groups taken into consideration. The approach consisted in a stepwise multivariate process including a hierarchical cluster analysis (CA) and a linear discriminant analysis (DA). The two main clusters determined by CA were subjected to the canonical DA, backward and forward selection procedures to select the best discriminative functions. A clear temporal and spatial discrimination was found among the samples. Across the three chemical groups, the monthly separation seemed to depend on the growth process and the main exposure was due to the feed. In addition, the two plants differed significantly from the environmental point of view and the most important discriminating group of chemicals were the NDL-PCBs. The approach resulted really effective in discriminating the subtle differences and in individuating suggestions to improve the quality of culturing conditions.     

Environmental ozone exposure and oxidative DNA damage in adult residents of Florence, Italy

In 71 adults residing in Florence, Italy, enrolled in a prospective study, we investigated the correlation between individual levels of oxidative DNA damage detected by the Comet assay in circulating lymphocytes, and a specific ozone exposure score calculated in 10 different time-windows (0-5 to 0-90 days) before blood drawing, based on daily measurements provided by the local environmental monitoring system.Overall, statistically significant positive correlations between average ozone concentrations and DNA damage emerged in almost all time-windows considered; correlations were more evident among males, non-smokers, and traffic-exposed workers. Multivariate regression analyses taking into account selected individual characteristics, showed an independent effect on DNA damage of average ozone concentrations in the last 60-90 days before blood drawing. Local residents showed a divergent pattern with correlations restricted to shorter time-windows.Our results suggest that ozone concentrations at ground levels modulate oxidative DNA damage in circulating lymphocytes of residents of polluted areas.     

Mechanochemistry of ibuprofen pharmaceutical

In this paper mechanochemistry has been studied in view of possible application to detoxification of expired pharmaceuticals. The experiments have been carried out with a commercial medication containing ibuprofen ((RS)-2-(4-(2-methylpropyl)phenyl)propanoic acid) which has been submitted to prolonged milling up to 40 h. When Al(OH)₃ is used as co-reagent, the first degradation step induced by the mechanochemical treatment is an acid-base reaction with the ibuprofen carboxylic acid group. The subsequent degradation follows a complex pathway leading to 1-(4-isobutylphenyl)ethanone, 1-isobutyl-4-vinylbenzene and 2-(4-(3-methylbutan-2-yl)phenyl)propan-1-ol after 10 h milling and, in addition, 1-(4-acetylphenyl)-2-methylpropan-1-one, 1-(4-(1-hydroxy-2-methylpropyl)phenyl)ethanone and 1-(4-(2-hydroxy-2-methylpropyl)phenyl)ethanone after 40 h milling. The degradation reaction path and products have been identified by means of FT-IR spectroscopy, thin layer chromatography, NMR spectroscopy, mass spectroscopy and elemental analysis. The observed ibuprofen decarboxylation makes the drug simultaneously lose both its pharmaceutical activity and toxicity.     

Effects of Equilibration Temperature on PM10 Concentrations from the TEOM Method in the Lower Fraser Valley

ABSTRACT

This study investigated the effect of equilibration temperature on PM₁₀ concentrations from the tapered element oscillating microbalance (TEOM) method by operating collocated TEOM monitors at different equilibration temperatures in an airshed (the Lower Fraser Valley, British Columbia). This airshed contained an abundance of par-ticulate semivolatile material (PSVM). For the period when three collocated TEOM monitors were operated, the PM₁₀ from the monitor at an equilibration temperature of 30 ° C was 2.5 μ g/m³ (22%) and 1.7 (17%) μ g/m³ higher, on average, than the PM₁₀ from monitors at 50 and 40 ° C, respectively, and the differences were proportional to the ambient PM₁₀ loading. Greater volatilization of PSVM in the TEOM monitors at higher equilibration temperatures may have been a cause of the differences.     

Polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs) in milk from Italian women living in Rome and Venice

The levels of selected polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs) were measured in human milk samples from the areas of Venice and Rome, primarily in order to characterize the current levels of infant exposure to PCBs and PBDEs due to breast feeding in Italy. Sixteen non-dioxin-like PCBs, including the traditional indicator congeners, and 11 PBDEs, comprising the relevant PBDE-47, PBDE-99, and PBDE-153, were determined. Congeners were selected for analysis according to their relative abundance in human tissues, toxicological relevance, and diffusion in the environment. Dietary habits of the milk donors were recorded by questionnaires; mothers of the Venice area were classified into three groups according to their consumption of local fish, molluscs, and other fishery products. Sigma(16)(PCBs) and Sigma(11)(PBDEs) (ng g(-1) fat) for the areas of Venice and Rome were respectively, 250-390 and 240, and 1.6-2.8 and 4.1. An increase of fish and fishery product consumption could not be associated with an increase of PCB and PBDE levels in milk.     

Particle-phase Polycyclic Aromatic Hydrocarbon Emissions from Non-catalysed, In-use Four-stroke Scooters

Metals and radionuclide levels in marine birds of the Aleutians are of interest because they are part of subsistence diets of the Aleut people, and can also serve as indicators of marine pollution. We examined geographic and species-specific variations in concentrations of radionuclides in birds and their eggs from Amchitka, the site of underground nuclear tests from 1965 to 1971, and Kiska Islands (a reference site) in the Aleutians, and the levels of lead, mercury and cadmium in eggs. In 2004 we collected common eiders (Somateria mollissima), tufted puffins (Fratercula cirrhata), pigeon guillemot (Cepphus columba) and glaucous-winged gulls (Larus glaucescens) from Amchitka and Kiska, and eggs from eiders and gulls from the two island. We also collected one runt bald eagle (Haliaeetus leucocephalus) chick from both Amchitka and Kiska Islands. For most species, the levels of radionuclide isotopes were below the minimum detectable activity levels (MDA). Out of 74 cesium-137 analyses, only one composite (gulls) was above the MDA, and out of 14 composites tested for plutonium (Pu-239, 240), only one exceeded the MDA (a guillemots). Three composites out of 14 tested had detectable uranium-238. In all cases, the levels were low and close to the MDAs, and were below those reported for other seabirds. There were significant interspecific differences in metal levels in eggs: gulls had significantly higher levels of cadmium and mercury than the eiders, and eiders had higher levels of lead than gulls. There were few significant differences as a function of island, but eiders had significantly higher levels of cadmium in eggs from Kiska, and gulls had significantly higher levels of mercury on Kiska. The levels of cadmium and mercury in eggs of eiders and gulls from this study were above the median for cadmium and mercury from studies in the literature. The levels of mercury in eggs are within the range known to affect avian predators, but seabirds seem less vulnerable to mercury than other birds. However, the levels of mercury are within the action levels for humans, suggesting some cause for concern if subsistence Aleuts eat a large quantity of eggs.     

Coal fly ash as raw material for the manufacture of geopolymer-based products

In this work coal fly ash has been employed for the synthesis of geopolymers. Two different systems with silica/alumina ratios stoichiometric for the formation of polysialatesiloxo (PSS, SiO2/Al2O3=4) and polysialatedisiloxo (PSDS, SiO2/Al2O3=6) have been prepared. The alkali metal hydroxide (NaOH or KOH) necessary to start polycondensation has been added in the right amount as concentrated aqueous solution to each of the two systems. The concentration of each alkali metal solution has been adjusted in order to have the right liquid volume to ensure constant workability. The systems have been cured at four different temperatures (25, 40, 60, and 85 degrees C) for several different times depending on the temperature (16-672 h at 25 degrees C; 72-336 h at 40 degrees C; 16-120 h at 60 degrees C and 1-6h at 85 degrees C). The products obtained in the different experimental conditions have been submitted to the quantitative determination of the extent of polycondensation through mass increase and loss on ignition, as well as to qualitative characterization by means of FT-IR spectroscopy. Furthermore, physico-structural and mechanical characterization has been carried out through microscopic observations and the determination of unconfined compressive strength, elasticity modulus, apparent density, porosity and specific surface area. The results have indicated that the systems under investigation are suited for the manufacture of pre-formed building blocks at room temperature.     

Equilibrium disorders in workers exposed to mixed solvents

Background. Organic solvents cause diseases of the vestibular system. However, little is known regarding the correlation between vestibular damage and exposure to organic solvents below threshold limit values. The best measure by which to evaluate vestibular disorders is static and dynamic posturography. Objective. The aim of this study was to evaluate equilibrium disorders via static and dynamic posturography in workers without clear symptoms and exposed to low doses of mixed solvents. Methods. 200 subjects were selected. Using an Otometrics device (Madsen, Denmark), all subjects endured static and dynamic posturography testing with both eyes-open and eyes-closed conditions. Results were compared with a control group of unexposed individuals. Result. Based on the obtained data, the following results can be drawn: (a) subjects exposed to mixtures of solvents show highly significant differences regarding all static and dynamic posturography parameters in comparison to the control group; (b) posturography testing has proven to be a valid means by which to detect subliminal equilibrium disorders in subjects exposed to solvents. Conclusion. We can confirm that refinery workers exposed to mixtures of solvents can present subliminal equilibrium disorders. Early diagnosis of the latter is made possible by static and dynamic posturography.