Historical marine ecology: examining the role of fisheries in changes in North Sea benthos

The organisms living on and in the sea floor, the benthos, represent an important ecological group. Although some (shellfish) have an economic value, most do not, and so little long-term data are available. We have identified three sources of historic benthic data for the North Sea, a regional sea that has been subjected to multiple human impacts for at least several hundred years. Each dataset has its limitations, but by their use together some issues emerge. Wider community shifts were observed in the shorter term and a number of extirpations at the scale of the North Sea were seen over longer time scales. The extirpated taxa share a number of characteristics consistent with an effect of fisheries such as fragile morphology. We must concentrate now on furthering our understanding of the ecological significance of shifts in dominance of particular functional units and protecting those habitats and species most vulnerable to fisheries-driven extirpation.     

Effect of modified Fenton treatment on the thermal behavior of contaminated harbor sediments

This study presents the results of experimental Fenton-like treatments conducted on marine sediment slurries (2g sediment vs. 20 ml liquid). The sediment was collected in a harbor situated in a high density industrial area, characterized by a great hydrocarbon C>12 and PAHs contamination. The investigated parameters were: the H(2)O(2) dose, the reagent's pH and the effect of a phosphate salt and ferrous iron addition. To evaluate sediment's characteristics COD, particle size, thermogravimetric and differential thermal analyses were performed under N(2) and O(2) atmosphere while dissolved organic carbon and COD analyses were performed on the filtrate. Results indicate that the treatment was able to change the organic matter to a less hydrophobic state, to destroy part of the organic carbon (up to 78% decrease of the 200-400 degrees C labile organic matter), to lower the COD of the sediment (60% COD removal maximum) and to increase the cumulated distribution undersize. In addition as the treated sediment showed easier-to-handle characteristics, reduced caking and lower aggregation capacity, the modified Fenton treatment could also be considered a pre-treatment of a successive thermal treatment.     

Assessment of the effects of soil PAH accumulation by a battery of ecotoxicological tests

Surface soils were collected at remote, urban and industrial sites in the Southern of Italy in order to evaluate PAH concentrations and assess the toxic effects by a battery of ecotoxicological tests. The tests were performed on whole soils and on both organic and aqueous extracts. Further goal of this study was to integrate the results coming from each test and matrix in a synthetic toxicity index. The highest summation sigmaPAH concentrations were measured at the industrial soil, although this one did not show an high ecotoxicological risk. Among the performed tests, the phytotoxicity tests showed the highest sensitivity. For whole soil, the worst case always has been represented by test through bacteria. Our results could represent the first step toward the selection of a proper battery to characterize the soil ecotoxicological risk.     

Significance of urinary arsenic speciation in assessment of seafood ingestion as the main source of organic and inorganic arsenic in a population resident near a coastal area

In order to characterize the different sources of exposure to arsenic (As), urinary excretion of total As, the sum of inorganic As+MMA+DMA determined by the hydride generation-atomic absorption spectrophotometry technique, and the species As(3), As(5), monomethylarsonic acid (MMA), dimethylarsinic acid (DMA) and arsenobetaine were determined in 49 workers at a steel foundry, with presumed occupational exposure to As, and 50 subjects from the general population, all males. No evidence of occupational exposure to As resulted from environmental monitoring performed in the foundry, although the analysis of minerals used as raw materials showed the presence of As, particularly in fossils and fine ores. The urinary concentrations of As(3), MMA, DMA, the sum of inorganic As+MMA+DMA and total As were not different in the two groups, while arsenobetaine appeared significantly higher in the controls than in the workers. The different species of urinary As were all significantly correlated. Urinary excretion of As(3) was associated with the consumption of mineral water and with residence in an industrial zone, while MMA, DMA, arsenobetaine, the sum of inorganic As+MMA+DMA and total As urinary excretion were associated with the consumption of crustaceans and/or shellfish 3 days or less before urine collection. Multiple regression analysis confirmed these results. In conclusion, in populations with a high consumption of seafood, living in areas characterized by coastal/marine As pollution, only speciation of As can identify a prevalent role of environmental sources, like the consumption of seafood contaminated by As, in determining urinary As excretion, and exclude an occupational origin of the exposure.     

Structure characterization and thermal stabilities of the isomers of the brominated flame retardant 1,2-dibromo-4-(1,2-dibromoethyl)cyclohexane

1,2-Dibromo-4-(1,2-dibromoethyl)cyclohexane (TBECH) is used primarily as an additive flame retardant. 1H NMR spectroscopy and an X-ray structure determination have revealed that a technical mixture consists largely of two (of the four possible) diastereomers, rac-(1R,2R)-1,2-dibromo-(4S)-4-((1S)-1,2-dibromoethyl)cyclohexane (alpha-TBECH) and rac-(1R,2R)-1,2-dibromo-(4S)-4-((1R)-1,2-dibromoethyl)cyclohexane (beta-TBECH), in a mole ratio of approximately 1:1. The two other possible isomers, gamma- and delta-TBECH, were not detected in a technical mixture. The TBECH isomers are thermally sensitive and can easily interconvert at temperatures of 125 degrees C. A thermal equilibrium mixture of alpha-, beta-, gamma- and delta-TBECH consists of approximately 33%, 33%, 17% and 17% of these isomers, respectively. Separation of all four TBECH diastereomers, with minimal thermal interconversion of the isomers, was achieved by careful selection of GC-capillary column length and injector temperature. Although technical TBECH does not contain the gamma- and delta-isomers, they may still be relevant environmental contaminants since manufacturing processes utilize thermal processes which may induce their formation.     

Photodegradation of the steroid hormones 17beta-estradiol (E2) and 17alpha-ethinylestradiol (EE2) in dilute aqueous solution

The photochemical transformation of natural estrogenic steroid 17beta-estradiol (E2) and the synthetic oral contraceptive 17alpha-ethinylestradiol (EE2) has been studied in dilute non buffered aqueous solution (pH 5.5-6.0) upon monochromatic (254 nm) and polychromatic (lambda>290 nm) irradiation. Upon irradiation at 254 nm, the quantum yields of E2 and EE2 photolysis were similar and evaluated to be 0.067+/-0.007 and 0.062+/-0.007, respectively. Upon polychromatic excitation, and by using phenol as chemical actinometer, the photolysis efficiencies have been determined to be 0.07+/-0.01 and 0.08+/-0.01 for E2 and EE2, respectively. For both estrogens, photodegradation by-products were identified with GC/MS and LC/MS. In a first step, a model compound--5,6,7,8-tetrahydro-2-naphthol (THN)--, which represents the photoactive phenolic group, was used to obtain basic photoproduct structural informations. Numerous primary and secondary products were observed, corresponding to hydroxylated phenolic- or quinone-type compounds.     

Solubility of toluene, benzene and TCE in high-microbial concentration systems

We report measurements of solubility limits for benzene, toluene, and TCE in systems that contain varying levels of biomass up to 0.13 g mL⁻¹ for TCE and 0.25 g mL⁻¹ for benzene and toluene. The solubility limit increased from 21 to 48 mM when biomass (in the form of yeast) was added to aqueous batch systems containing benzene. The toluene solubility limit increased from 4.9 to greater than 20 mM. For TCE, the solubility increased from 8 mM to more than 1000 mM. Solubility for TCE (trichloroethylene) was most heavily impacted by biomass levels, changing by two orders of magnitude as the microbial concentrations approach those in biofilms.     

Modelling of stable isotope fractionation by methane oxidation and diffusion in landfill cover soils

A technique to measure biological methane oxidation in landfill cover soils that is gaining increased interest is the measurement of stable isotope fractionation in the methane. Usually to quantify methane oxidation, only fractionation by oxidation is taken into account. Recently it was shown that neglecting the isotope fractionation by diffusion results in underestimation of the methane oxidation. In this study a simulation model was developed that describes gas transport and methane oxidation in landfill cover soils. The model distinguishes between (12)CH(4), (13)CH(4), and (12)CH(3)D explicitly, and includes isotope fractionation by diffusion and oxidation. To evaluate the model, the simulations were compared with column experiments from previous studies. The predicted concentration profiles and isotopic profiles match the measured ones very well, with a root mean square deviation (RMSD) of 1.7vol% in the concentration and a RMSD of 0.8 per thousand in the delta(13)C value, with delta(13)C the relative (13)C abundance as compared to an international standard. Overall, the comparison shows that a model-based isotope approach for the determination of methane oxidation efficiencies is feasible and superior to existing isotope methods.     

Toluene removal biofilter modeling: Optimization and case study

Based on the model proposed by De Visscher and Van Cleemput for methane oxidation in landfill cover soils, a simulation model for biofiltration of toluene-contaminated air has been developed for biofilters with substrate inhibition. A convenient way to optimize biofilter performance was developed assuming Haldane kinetics. It was calculated that for a typical oilsands operation emitting 200 ton of toluene annually, 90% of the toluene can be removed by a 740 m³ biofilter, if the waste gas sent to the biofilter has a toluene concentration of 2.25 g m⁻³. The optimal initial concentration increases with increasing target efficiency.