Surface retention and photochemical reactivity of the diphenylether herbicide oxyfluorfen

The photochemical behavior of oxyfluorfen [2-chloro-1-(3-etoxy-4-nitrophenoxy)-4-(trifluoromethyl) benzene] on two Greek soils was investigated. Soils were sampled from Nea Malgara and Preveza regions, characterized by a different organic matter content. Soils were spiked with the diphenyl-ether herbicide and irradiation experiments were performed either in the laboratory with a solar simulator (xenon lamp) or outside, under natural sunlight irradiation; other soil samples were kept in the dark to control the retention reaction. Kinetic parameters of both retention and photochemical reactions were calculated using zero-, first- and second- (Langmuir-Hinshelwood) order equations, and best fit was checked through statistical analysis. The soil behaviors were qualitatively similar but quantitatively different, with the soil sampled from the Nea Malgara region much more sorbent as compared with Preveza soil. All studied reactions followed second-order kinetics and photochemical reactions were influenced by retaining capability of the soils. The contributions of the photochemical processes to the global dissipation rates were also calculated. Two main metabolites were identified as 2-chloro-1-(3-ethoxy-4-hydroxyphenoxy)-4-(trifluoromethyl)benzene and 2-chloro-1- (3-hydroxy-4-nitrophenoxy)-4-(trifluoromethyl)benzene.     

Polychlorinated biphenyls in contaminated soil samples evaluated by GC-ECD with dual-column and GC-HRMS

We present and compare results obtained from the analysis of polychlorinated biphenyls (PCBs) of a limited number of contaminated soil samples collected in three areas of Basilicata region (south of Italy). The levels of PCBs were evaluated by using two analytical methods: (i) parallel dual-column gas-chromatography with dual electron capture detectors (GC-ECD) and (ii) gas-chromatography coupled to high-resolution mass spectrometry (GC-HRMS) via electron impact ionization (EI) in the multiple ion monitoring mode (MIM, two ions per compound). Two extraction methods prior to sample cleanup were also examined: microwave-assisted extraction (MAE) and ultrasonic-assisted extraction (UAE). The MAE was the extraction procedure adopted using acetone/n-hexane (1:1, v/v) as it is mainly characterized by higher sample throughput and allowed reduced consumption of organic solvents. While extraction and analysis of spiked soil samples showed the applicability of both methods, systematic differences between the results were obtained for the sum of PCBs as a result of some non-detected congeners by GC-ECD compared with GC-HRMS. Indeed, high resolution MS using EI mode (electron energy 40eV) with a resolving power of 10,000 provides additional information about the contamination pattern. The GC-ECD screening of 11 soil samples led to just one sample non-compliant to as it was close to the guide value for soils fixed by the Italian legislation (i.e., 60ppb for private or urban soil). Using GC-HRMS, the amount of all PCBs found ranged from 5.4 to 127ppb with five soil samples non-compliant to the guide value. The number of identified congeners ranged from 1 to 9 and 9 to 18 using dual-column GC-ECD and GC-HRMS, respectively.     

Gas- and particle-phase distribution of polycyclic aromatic hydrocarbons in two-stroke, 50-cm3 moped emissions

Gas- and particle-phase polycyclic aromatic hydrocarbons (PAHs) concentrations evaluated in the exhaust of 10 two-stroke, 50-cm³ mopeds belonging to three different levels of emission legislation (EURO-0, EURO-1 and EURO-2) were used to assess the prevalent mechanism driving the gas/particle partitioning of PAHs in moped exhaust. Sampling was performed on a dynamometer bench both during the “cold-start” and the “hot” phases of the ECE-47 driving cycle. Gas and particulate phase PAHs were collected on polyurethane foam (PUF) plugs and 47-mm Pallflex T60A20 filters, respectively, under isokinetic conditions by using sampling probes inserted into the dilution tunnel of a Constant Volume Sampling – Critical Flow Venturi (CVS–CFV) system.The results show that semi-volatile PAHs were predominantly partitioned to the particle phase. The soluble organic fraction (SOF) of the collected particulates ranged between 72 and 98%. Measured total suspended particulate matter normalized partition coefficients (K_p) were predicted within a factor of 3–5 by assuming absorption into the organic fraction according to a model developed by Harner and Bidleman [Harner, T., Bidleman, T.F., 1998. Octanol–air partition coefficient for describing particle/gas partitioning of aromatic compounds in urban air. Environmental Science & Technology 32, 1494–1502.]. This suggests that the gas/particle partitioning in moped exhaust is mainly driven by the high fraction of organic matter of the emitted particles and that absorption could be the main partitioning mechanism of PAHs.     

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.