Intermediate distributions and primary yields of phenolic products in nitrobenzene degradation by Fenton's reagent

Nitrobenzene thermal degradation was investigated using the Fenton reagent in different experimental conditions. Reaction products were analyzed by HPLC, GC-MS, LC-MS and IC. The products obtained at different nitrobenzene conversion degrees show that degradation mainly involves successive hydroxylation steps of the aromatic ring and its subsequent opening followed by oxidation of corresponding aliphatic compounds. Our results show as primary reaction products: 4-nitrophenol, 3-nitrophenol, 2-nitrophenol, phenol and 1,3-dinitrobenzene, indicating that both hydroxylation and nitration reactions are involved. The formation of phenolic products can be explained by postulating an initial step of HO() addition to nitrobenzene ring. The mechanisms of primary reaction pathways are discussed and a detailed kinetic analysis to obtain the true primary yields of phenolic products is proposed. The relative yields observed for nitrophenol isomers do not follow the expected orientation according to deactivating characteristics of the nitro group but significantly depend on Fe(+2), Fe(+3), H(2)O(2) and O(2) concentrations. The understanding of the effect of reaction conditions on the relative product distribution benefits the application of Fenton and Fenton-like systems to waste water treatment.     

Biochemical mechanisms of resistance in Daphnia magna exposed to the insecticide fenitrothion

Resistance to fenitrothion and enzyme activities associated with the toxicity and metabolism of organophosphorus insecticides were measured in three genetically unique Daphnia magna clones collected from rice fields of Delta del Ebro (NE Spain) during the growing season and a lab sensitive clone. The studied clones showed up to sixfold differences in resistance to fenitrothion. The lack of correlation between in vitro sensitivity of acetylcholinesterase (AChE) to fenitrooxon and resistance to fenitrothion indicated that insensitivity of AChE to the most active oxon metabolite was not involved in the observed differences in resistance. Inhibition of mixed- function oxidases (MFOs) by piperonyl butoxide (PBO) increased the tolerance to fenitrothion by almost 20-fold in all clones without altering their relative ranking of resistance. Conversely, when exposed to fenitrooxon, the studied clones showed similar levels of tolerance, thus indicating that clonal differences in the conversion of fenitrothion to fenitrooxon by MFOs were involved in the observed resistance patterns. Despite that resistant clones showed over 1.5 higher activities of carboxilesterase (CbE) than sensitive ones, toxicity tests with 2-(O-cresyl)-4H-1,3,2-benzodioxaphosphorin-2 oxide, which is a specific inhibitor of these enzymes, evidenced that this system only contributed marginally to the observed clonal differences in tolerance. Glutathione-S-transferases activity (GST) varied across clones but not under exposure to fenitrothion, and was only related with tolerance levels in the field clones. In summary, our results indicate that MFO mediated differences on the bio-activation of the phosphorotionate OP pesticide to its active oxon metabolite contributed mostly in explaining the observed moderate levels of resistance, whereas the activities of CbE and GST had only a marginal role.     

Sub-soil contamination due to oil spills in six oil-pipeline pumping stations in northern Mexico

Mexico has a very important oil industry, comprehending the exploration, production, transformation, storage and distribution of crude oil and its fractions. Petroleos Mexicanos (PEMEX) is a state-owned monopoly in charge of these activities. Oil and oil-products transport is an extremely crucial operation for the cycle production-transformation-distribution. Pipeline system transport crude oil and sub-products along the country (including liquids, gases and mixtures). It has been reported that more than 30% of the oil ducts in Mexico have been operating for over 30 years, although their lifetime has been calculated in 25-30 years. This work is aimed at characterizing a zone around six oil-pipeline pumping stations located at northern Mexico. The specific places to evaluate soil contamination were (1) the distribution head of the Gomez Palacio (GOPA) pumping station; (2) the north side of the old ditch, the API oil separator and the wastewater zones of the Jimenez (JIM) pumping station; (3) the pumping stations of Ceballos (CE), Peronal (PER), Simon Bolivar (SIBO), and Mayran (MAY). The study comprehended sampling of the areas, delimitation of contamination in the vertical and horizontal extension, analysis of the sampled soils, regarding TPH and, in some cases, the 16 PAHs considered as a priority by USEPA, calculation of areas and volumes contaminated (according to the Mexican legislation, specifically NOM-EM-138-ECOL-2002) and, finally, a proposal for the best remediation techniques suitable for the encountered contamination levels and the localization of contaminants. In general, TPHs were found in all the pumping stations analyzed in this study. Regarding maximal TPHs concentrations at the stations, their order of contamination was as follows: SIBO>CE>PER>MAY>JIM>GOPA. PAHs were found only in a few points at concentrations above the detection limit. At the Jimenez, Gomez Palacio, Peronal, and Ceballos stations, only one point, with PAHs values over the detection limit was found, whereas two points were found at Mayran, and finally at the Simon Bolivar station there were four points with measurable amounts of PAHs. Given the areas and volumes that need to be treated (32835 m3), as well as the physical position of contaminants, it is considered that excavation of the contaminated soil is feasible and the cleaning process could be soil washing assisted with surfactants, though bioremediation should not been discharged as a possible remediation technique.     

Influence of the chemical structure on mobility of PCB congeners in female and male sardine (Sardina pilchardus) from Portuguese coast

Concentrations of 30 polychlorinated biphenyl congeners (CBs) were determined in muscle, liver and gonad tissues of female and male sardines (Sardina pilchardus) collected in February-May 2000 and September-January 2001 from purse seine vessels operating around Peniche, Portugal. The determined CBs were aggregated in four groups (I, II, III and IV), according to similarities of their chemical structures. Muscle and liver of males contained significantly higher concentrations of groups I and II than females during the final period of spawning (February-April). A less contrast was observed for the groups III and IV. This seasonal fluctuation associated with the spawning indicates that female sardines regulate the excess of CBs sequestrated during fatten period. On the contrary, levels of groups I and II were higher in males than in females indicating slower mobility of these compounds as lipids were consumed during the final period of spawning. The deficient regulation of those CBs in muscle of male sardines can not be attributed to selective transfer to gonads and subsequent excretion. Although the full explanation was not found for the different mobility of PCBs with the gender, the results provide evidence of slower elimination of group I and II congeners in male sardines.     

Mercury and selenium in blue shark (Prionace glauca, L. 1758) and swordfish (Xiphias gladius, L. 1758) from two areas of the Atlantic Ocean

Muscle, liver and stomach contents of 64 blue sharks and 52 swordfishes, caught between September 2004 and February 2005 near the Azores (area A) and the Equator (area E), were analysed for mercury and selenium. Levels of mercury were relatively high (blue shark: 0.032-2.5microgg(-1); swordfish: 0.031-9.8microgg(-1)) and comparable to values reported in the literature. However, mercury and organic mercury concentrations in muscle and liver of specimens from E were significantly higher than those from A. A similar trend was registered in stomach contents, suggesting higher uptake of Hg in specimens from E. This difference was also observed in the relationship between concentration in muscle and size, indicating a higher accumulation rate in specimens from E. The accumulation of Se in the liver of both species showed a positive correlation with inorganic mercury concentrations, pointing to a detoxifying mechanism of organic mercury in these species through Se-Hg liasons.     

A participatory decision making framework for artisanal fisheries collaborative governance: Insights from management committees in Chile

Fisheries management is increasingly transitioning towards collaborative governance. Collaborative systems depend on stakeholders’ capacity to design and implement legitimate and scientifically robust management plans within collective action arenas. Here we propose that collaborative governance outcomes, in fisheries management, will benefit from using structured participatory decision making frameworks that enhance deliberative thinking among stakeholders. We tested our approach in the artisanal fishery of Chile, an important producer of marine resources. Recently in 2013, Chile made important changes to fisheries policies by creating multi-sectorial management committees to manage de facto open access fishing areas. We applied a structured decision making framework to inform the restructuring of a management plan within a committee. As a result, we identified goals,objectives and indicators, including social, economic, biological and ecological dimensions; we explored tradeoffs, assessing the relative importance of the objectives; finally, we created scenarios and prioritized alternatives, reflecting on the interplay between self-regulation and government control. Members of the management committee were able to rationalize the different steps of the framework and identify ways forward which highlighted the importance of self-regulation in comparison to central authorities’ control. We concluded that structured decision making promotes spaces for rational analysis of alternatives costs and benefits. Promoting deliberative thinking in fisheries management can improve equity, legitimacy and sustainability of collaborative governance.     

Sorption interactions between imazaquin and a humic acid extracted from a typical Brazilian oxisol

Soil sorption of most hydrophobic organic compounds (e.g., nonpolar pesticides) is directly related to soil organic matter (SOM) content. Humic substances are the major SOM components, containing carboxylic, phenolic, amine, quinone, and other functional groups, and specific structural configurations. In this paper, sorption interactions between imazaquin (2-[4,5-dydro-4-methyl-4-(1-methylethyl)-5-oxo-1H- imidazol-2-yl]-3-quinoline-carboxylic acid) herbicide (IM) and a humic acid (HA) extracted from a typical Brazilian Oxisol were studied with electron paramagnetic resonance (EPR) and Fourier-transform infrared (FTIR) spectroscopic techniques. A polarographic technique was used to quantify sorption. The IM amount sorbed on the HA was much higher than that on the whole soil within the pH range studied, emphasizing the prominent role played by SOM on IM sorption. Moreover, IM sorption increased as the soil-solution pH decreased. This enhancement in sorption was attributed to the hydrophobic affinity of the herbicide by the HA and to the electrostatic interaction between the protonated quinoline group of IM and the negative sites of the HA. Hydrophobic regions in the HA's interior at low pH (< 5.0) were recently demonstrated by an EPR detectable spin-label molecule. The FTIR and EPR spectroscopy and polarography data indicated weak interaction between IM and the soil and its HA, involving hydrogen bonding, proton transfer, and cation exchange (at low pH), and mainly hydrophobic interactions. However, no strong reaction mechanism, such as charge transfer, was involved. In addition, this research suggested that soil amendment with organic material might increase magnitude of IM sorption, consequently avoiding leaching and carryover problems usually found for mobile and persistent herbicides such as imazaquin.