Natural attenuation of diesel aliphatic hydrocarbons in contaminated agricultural soil

A diesel fuel spill at a concentration of 1 L m(-2) soil was simulated on a 12 m(2) plot of agricultural land, and natural attenuation of aliphatic hydrocarbons was monitored over a period of 400 days following the spill after which the aliphatic hydrocarbon concentrations were found to be below the legal contamination threshold for soil. The main fraction of these compounds (95%) remained at the surface layer (0-10 cm). Shortly after the spill (viz. between days 0 and 18), evaporation was the main origin of the dramatic decrease in pollutant concentrations in the soil. Thereafter, soil microorganisms used aliphatic hydrocarbons as sources of carbon and energy, as confirmed by the degradation ratios found. Soil quality indicators, soil microbial biomass and dehydrogenase activity, regained their original levels about 200 days after the spill.     

Mixture toxicity of the antifouling compound irgarol to the marine phytoplankton species Dunaliella tertiolecta

This study examined the toxicity of irgarol, individually and in binary mixtures with three other pesticides (the fungicide chlorothalonil, and the herbicides atrazine and 2,4-D), to the marine phytoplankton species Dunaliella tertiolecta. Standard 96-h static algal bioassays were used to determine pesticide effects on population growth rate. Irgarol significantly inhibited D. tertiolecta growth rate at concentrations > or = 0.27 micro g/L. Irgarol was significantly more toxic to D. tertiolecta than the other pesticides tested (irgarol 96 h EC50 = 0.7 micro g/L; chlorothalonil 96 h EC50 = 64 micro g/L; atrazine 96 h EC50 = 69 micro g/L; 2,4-D 96 h EC50 = 45,000 micro g/L). Irgarol in mixture with chlorothalonil exhibited synergistic toxicity to D. tertiolecta, with the mixture being approximately 1.5 times more toxic than the individual compounds. Irgarol and atrazine, both triazine herbicides, were additive in mixture. The toxicity threshold of 2,4-D was much greater than typical environmental levels and would not be expected to influence irgarol toxicity. Based on these interactions, overlap of certain pesticide applications in the coastal zone may increase the toxicological risk to resident phytoplankton populations.     

Maternal transfer of organochlorine compounds to oocytes in wild and farmed gilthead sea bream (Sparus aurata)

To investigate the transfer of lipophilic organochlorine compounds to the gonads in gilthead sea bream females, liver and oocytes from wild and farmed females, just before spawning, were analysed by gas chromatography coupled to tandem mass spectrometry after clean-up of the fatty extracts by normal phase HPLC. This analytical methodology allowed us to achieve limits of detection of around 0.1 ng/g. Data obtained show that the chemicals studied are transferred from the liver to oocytes in ratios up to 0.51. In general this means that less than a half of pollutant load is transferred from liver to oocytes. A significant correlation (p<0.05) between log K(ow) and ratios (oocytes/liver) was found. Compounds with larger Log K(ow) present lower lipid-based concentration ratios (oocytes/liver). We have inferred that the reason the fugacity model is not accomplished is specifically dependent on the vitellogenesis process, which involves the transfer of lipids from the liver to oocytes in teleostei. No significant differences (t-Student) have been found between wild and farmed females transfer ratios (oocytes/liver).     

Relations between PM10 composition and cell toxicity: a multivariate and graphical approach

Previous studies have used particle mass and size as metrics to link airborne particles with deleterious health effects. Recent evidence suggests that particle composition can play an important role in PM-toxicity; however, little is known about the specific participation of components (individually or acting in groups) present in such a complex mixture that accounts for toxicity. This work explores relationships among PM(10) components in order to identify their covariant structure and how they vary in three sites in Mexico City. Relationships between PM(10) with cell toxicity and geographical location were also explored. PM(10) was analyzed for elemental composition, organic and elemental carbon, endotoxins and the induction of inhibition of cell proliferation, IL-6, TNFalpha and p53. PM(10) variables were evaluated with principal component analysis and one-way ANOVA. The inhibition of cell proliferation, IL-6 and TNFalpha were evaluated with factorial ANOVA and p53 with the Welch test. The results indicate that there is heterogeneity in particle mass, composition and toxicity in samples collected at different sites. Multivariate analysis identified three major groups: (1) S/K/Ca/Ti/Mn/Fe/Zn/Pb; (2) Cl/Cr/Ni/Cu; and (3) endotoxins, organic and elemental carbon. Groups 1 and 3 showed significant differences among sites. Factorial ANOVA modeling indicated that cell proliferation was affected by PM concentration; TNFalpha and IL-6 by the interaction of concentration and site, and p53 was different by site. Radial plots suggest the existence of complex interactions between components, resulting in characteristic patterns of toxicity by site. We conclude that interactions of PM(10) components determine specific cellular outcomes.     

Stable isotope determination in wild and farmed gilthead sea bream (Sparus aurata) tissues from the western Mediterranean

Stable isotopes of carbon and nitrogen (delta(13)C and delta(15)N) have been determined in wild and farmed gilthead sea bream (Sparus aurata) samples of white and red muscle, liver, gills and gonads. First, delta(13)C and delta(15)N values were determined in samples with and without lipid removal to check the possible effect of lipid content on the stable isotope values of the different tissues studied. Differences were found for delta(13)C in all tissues studied apart from white muscle of wild fish, the tissue with the lowest lipid content. For delta(15)N values no differences were found in wild fish tissues. Liver from farmed fish showed lower delta(15)N value after lipid removing. Further conclusions were based on results obtained from lipid-free samples. delta(13)C of cultured fish tissues showed a mean depletion of 2.9+/-0.4 per thousand compared to wild specimens, suggesting different sources of carbon in the diet, probably due to the feed used during sea-cage culture. Cultured gilthead sea bream tissues were significantly more enriched in nitrogen than wild specimens by an average of 1.5+/-0.2 per thousand in white muscle, indicating a slight increase in the trophic level. Determination of stable isotope signatures of gilthead sea bream tissues allows clear discrimination between wild and cultured sea bream, and characterisation of differences in diet and feeding conditions in any tissue studied.     

Analysis of Products Generated from the Thermal and Catalytic Degradation of Pure and Waste Polyolefins using Py-GC/MS

The possibility of transforming waste plastics into valuable hydrocarbons via catalytic cracking and reforming is attracting increasing interest. Pyrolysis coupled with Gas Chromatographic separation and Mass Spectrometry detection (Py-GC/MS) has been used in this work to study the product selectivity of various catalysts in the conversion of pure and residual polyethylene samples into hydrocarbon products. Five acid solids of comparable aluminium contents but different textural and acid properties were tested as catalysts, including three zeolites (standard ZSM-5, nanocrystalline n-ZSM-5 and Beta) and two mesostructured solids (Al-MCM-41 and Al-SBA-15). Thermal cracking of the pure and residual polymers generated a similar range of products to each other, with a high proportion of linear paraffins and olefins of varying lengths. The presence of zeolitic materials resulted in complete elimination of heavy linear products, an increase in the light hydrocarbon fraction and a marked selectivity towards the formation of single-ring aromatic species, particularly benzene, toluene and xylene. Aromatic formation was particularly notable with the small crystal size n-ZSM-5 (aromatic selectivity up to 53.9%) and less marked in the case of standard ZSM-5 (up to 36.4%) and Beta zeolite (up to 35.0%). Mesostructured catalysts like Al-MCM-41 and Al-SBA-15 favoured the production of light C₂–C₅ hydrocarbons (up to 57.9%) while the formation of aromatic products was significantly lower than with zeolitic materials. The paper examines the extent and the causes for this product selectivity and discusses its connection with the acid and textural properties of each catalyst. It was also observed that, under the experimental conditions employed, the products generated were not significantly affected by the nature and origin of the polymers employed.     

Effect of Decalin Solvent on the Thermal Degradation of HDPE

The thermal cracking of HDPE in presence of different amounts of decalin was studied and compared with the reaction carried out in the absence of solvent. The decalin favours the mass and heat transfer during the reaction. In addition, it modifies the thermal degradation mechanism, which facilitates the formation of specific products. The use of decalin substantially increases the C₅–C₃₂ yield in comparison with the solventless reaction. In all cases, linear hydrocarbons such as n-paraffins, α-olefins and α,ω-dienes were detected. Increasing the decalin/plastic ratio led to enhanced α-olefin and n-paraffins yields, but the increase was more significant in the case of α-olefins, which are valuable compounds useful as raw chemicals. A reaction mechanism was proposed to explain the results obtained in presence of decalin. In these reactions, intramolecular radical transfer, secondary radical β-scission and hydrogen transfer from both decalin to intermediate radicals and from the polymer chain to regenerate the decalin play a significant role in determining the plastic conversion and the relative amounts of each product.