Performance of passive sampling with low-density polyethylene membranes for the estimation of freely dissolved DDx concentrations in lake environments.

Laboratory and field studies were used to evaluate the performance of low-density polyethylene (PE) passive samplers for assessing the freely dissolved concentrations of DDT and its degradates (DDD and DDE, together referred to as DDx) in an Italian lake environment. We tested commercially available 25 µm thick PE sheets as well as specially synthesized, 10 µm thick PE films which equilibrated with their surroundings more quickly. We measured PE-water partitioning coefficients (Kpew) of the 10 µm thick PE films, finding good correspondence with previously reported values for thicker PE. Use of the 10 µm PE for ex situ sampling of a lake sediment containing DDx in laboratory tumbling experiments showed repeatability of ±15% (= standard deviation/mean). Next, we deployed replicate 10 µm and 25 µm PE samplers (N = 4 for 10 d and for 30 d) in the water and sediment of a lake located in northern Italy; the results showed dissolved DDx concentrations in the picogram/L range in porewater and the bottom water. Values deduced from 10 µm thick PE films compared well (95% of all comparison pairs matched within a factor of 5) with those obtained using PE films of 25 µm thickness when dissolved DDx concentrations were estimated using performance reference compound (PRC) corrections, whether left at the bed-water interface for 10 or 30 days. These results demonstrated the potential of this sampling method to provide estimation of the truly dissolved DDx concentrations, and thereby the mobile and bio-available fractions in both surface waters and sediment beds.

Characterization of bio-oil from hydrothermal liquefaction of organic waste by NMR spectroscopy and FTICR mass spectrometry.

Solid wastes of organic origins are potential feedstocks for the production of liquid biofuels, which could be suitable alternatives to fossil fuels for the transport and heating sectors, as well as for industrial use. By hydrothermal liquefaction, the wet biomass is partially transformed into a water-immiscible, oil-like organic matter called bio-oil. In this study, an integrated NMR spectroscopy/mass spectrometry approach has been developed for the characterization of the hydrothermal liquefaction of bio-oil at the molecular level. (1)H and (13)C NMR spectroscopy were used for the identification of functional groups and gauging the aromatic carbon content in the mixture. GC-MS analysis revealed that the volatile fraction was rich in fatty acids, as well as in amides and esters. High-resolution Fourier-transform ion cyclotron resonance mass spectrometry (FTICR-MS) has been applied in a systematic way to fully categorize the bio-oil in terms of different classes of components, according to their molecular formulas. Most importantly, for the first time, by using this technique, and for the liquefaction bio-oil characterization in particular, FT-MS data have been used to develop a methodology for the determination of the aromatic versus aliphatic carbon and nitrogen content. It is well known that, because they resist hydrogenation and represent sources of polluting species, both aromatic molecules and nitrogen-containing species raise concerns for subsequent upgrading of bio-oil into a diesel-like fuel.

Pyrene and benzo(a)pyrene metabolism by an Aspergillus terreus strain isolated from a polycylic aromatic hydrocarbons polluted soil.

A strain of Aspergillus terreus was isolated from a polycyclic aromatic hydrocarbons (PAHs) polluted soil. The metabolism of pyrene and benzo(a)pyrene by this fungus was investigated in liquid submerged culture added of 50 and 25 ppm respectively of each compound. Depletion of pyrene and Benzo(a)pyrene was evident during the first stages of growth and was 60% and 27.5% respectively of the added amount after nine days of culture. Solvent extracts of the fermentation broth and mycelium were analysed for presence of metabolites by HPLC-MS technique. Under the present cultural conditions pyrene was mainly metabolised to pyrenylsulfate similarly to benzo(a)pyrene that led to benzo(a)pyrenylsulfate. The structure of 1-pyrenilsulfate was determined after purification of extracts and H-NMR analysis. The result show that the isolated A. terreus strain metabolises PAHs by reaction similar to those previously reported for non lignolinolytic fungi with a mechanism that suggests the hydroxylation by a cytochrome P-450 monooxygenase followed by conjugation with sulfate ion.