Degradation of some biorecalcitrant pesticides by homogeneous and heterogeneous photocatalytic ozonation

Photo-Fenton/ozone (PhFO) and TiO2-photocatalysis/ozone (PhCO) coupled systems are used as advanced oxidation processes for the degradation of the following biorecalcitrant pesticides: alachlor, atrazine, chlorfenvinfos, diuron, isoproturon and pentachlorophenol. These organic compounds are considered Priority Hazardous Substances by the Water Framework Directive of the European Commission. The degradation process of the different pesticides, that occurs through oxidation of the organic molecules by means of their reaction with generated OH radical, follows a first and zero-order kinetics, when PhFO and PhCO are applied, respectively. These two Advanced Oxidation Processes, together with the traditional ozone+UV, have been used to investigate TOC reduction of the different pesticide aqueous solutions. The best results of pesticide mineralization are obtained when PhFO is applied; with the use of this advanced oxidation process the aqueous pesticide solutions become detoxyfied except in the case of atrazine and alachlor aqueous solutions for which no detoxification is achieved at the experimental conditions used in the work, at least after 2 and 3 h of treatment, respectively.     

Biomonitoring of trace metals in a mine-polluted estuarine system (Spain)

In this paper, we examine metal concentrations in the water and in the crustacean Balanus balanoides from the Huelva estuary, one of the most polluted estuaries in Europe. Metal levels in waters are very high, especially those of Zn, Fe and Cu. Zn presents the highest concentrations, with a mean value of 690 microg l-1 in 2001 and 301 microg l-1 in 2002. As the water flows down through the estuary toward the sea, the metal concentrations drop sharply and the pH rises. The metal concentrations in balanoides tissues are, in general, very high, undoubtedly due to the high metal pollution of the water where it lives. Metal concentrations in Balanus balanoides tissues behave similarly to those in the water, reaching maximums in the upper part of the estuary and diminishing as we approach the sea. The element that reaches the highest levels in Balanus balanoides is Zn, with a mean value of 54.6 g kg-1 in 2001 and 29.9 g kg-1 in 2002, followed by Cu and Fe. There is a significant correlation (p<0.01) for concentrations of Cd, Cu, Fe, Mn, Ni and Zn in Balanus balanoides relative to their concentration in waters. Barnacles showed a great capacity to accumulate metals, especially Zn, Cu and Fe. Based on the results obtained, we can conclude that Balanus balanoides is a good tool for monitoring trace metals in the Huelva estuary.     

Oxidative damage to Pseudomonas aeruginosa ATCC 27833 and Staphylococcus aureus ATCC 24213 induced by CuO-NPs

Environmental Science and Pollution Research - The cytotoxicity of nanoparticles (NPs) and their properties are important issues in nanotechnology research. Particularly, NPs affect the metabolism...     

The effect of helpers on artificially increased brood size in sociable weavers (Philetairus socius)

In cooperatively breeding birds, the presence of helpers is expected to increase the reproductive success of the breeding pair. However, some studies fail to find this effect. A positive effect of helpers may be restricted to cases in which a breeding pair has a poor likelihood of raising the entire brood on its own, as would be the case under stressful environmental conditions or with enlarged brood sizes. We conducted brood size manipulations in a cooperative breeder, the sociable weaver, Philetairus socius, to investigate the relationship between the difficulty of raising nestlings and the effort and impact of helpers. Overall, sociable weavers did not work harder to raise the enlarged broods. However, the presence of helpers significantly increased the feeding rates at enlarged nests, but not controls. This was insufficient to prevent generalised brood reduction in enlarged broods, whether attended by pairs alone or with helpers. Nonetheless, the presence of helpers was associated with decreased nestling mortality and an increase in the numbers of young fledged. Our results suggest that groups are better able to respond to the needs of enlarged broods than pairs alone and that the presence of helpers has a beneficial effect on overall reproductive success.Communicated by J. Dickinson     

Delineation of Environmental Units by Multivariate Techniques in the Duero River Watershed,Michoacán,Mexico

Environmental or hydrological landscape units can integrate various environmental characteristics to support proper management of natural resources. To delineate these units, quantitative methods such as ordination, clustering, and classification of abiotic factor information are used. In the present work, environmental units were delineated in the Duero River watershed of Michoacán, Mexico. This will enhance understanding of the hydrologic landscape, which is a fundamental to natural resource management. A digital elevation model was used to generate sub-basins. Climatic data were obtained from 16 meteorological stations. Sixty-nine soil and 150 water samples were collected and analyzed in the laboratory. Geostatistical methods for spatial prediction of the environmental variables were used. Mean data for each sub-basin were obtained from the environmental variable grids, generating an abiotic factor data matrix. A multivariate analysis was conducted. Exponential, linear, spherical, and Gaussian models were fit to an empirical variogram. Spatial prediction of the environmental data was done via universal and ordinary kriging. Based on principal component analysis, abiotic factors evaporation, total nitrogen, soil pH, and sodium absorption ratio of water were selected for cluster analysis. Five environmental units were delineated in the Duero watershed. One environmental unit (number 4) provided greater than 50 % of the payment for ecosystem services. The general trend is an increase of urban area. The urban surface in 1983 and 2014 was 1724 and 4750 ha, respectively, an increase of 275 %. Environmental unit 1 showed the greatest urban area growth (1336 ha) during the latter period.     

Gasification of the char derived from distillation of granulated scrap tyres

This work reports the effect of pressure on the steam/oxygen gasification at 1000 °C of the char derived from low temperature-pressure distillation of granulated scrap tyres (GST). The study was based on the analysis of gas production, carbon conversion, cold gas efficiency and the high heating value (HHV) of the product. For comparison, similar analyses were carried out for the gasification of coals with different rank.In spite of the relatively high ash (≈12 wt.%) and sulphur (≈3 wt.%) contents, the char produced in GST distillation can be regarded as a reasonable solid fuel with a calorific value of 34 MJ kg⁻¹. The combustion properties of the char (E_A ≈ 50 kJ mol⁻¹), its temperature of self-heating (≈264 °C), ignition temperature (≈459 °C) and burn-out temperature (≈676 °C) were found to be similar to those of a semi-anthracite.It is observed that the yield, H₂ and CO contents and HHV of the syngas produced from char gasification increase with pressure. At 0.1 MPa, 4.6 Nm³ kg_char⁻¹ of syngas was produced, containing 28% v/v of H₂ and CO and with a HHV around 3.7 MJ Nm⁻³. At 1.5 MPa, the syngas yield achieved 4.9 Nm³ kg_char⁻¹ with 30% v/v of H₂-CO and HHV of 4.1 MJ Nm⁻³. Carbon conversion significantly increased from 87% at 0.1 MPa to 98% at 1.5 MPa.It is shown that the char derived from distillation of granulated scrap tyres can be further gasified to render a gas of considerable heating value, especially when gasification proceeds at high pressure.     

Characterisation of agroindustrial solid residues as biofuels and potential application in thermochemical processes

In the present work, selected agroindustrial solid residues from Brazil – biosolids from meat processing wastewater treatment and mixture of sawdust with these biosolids; residues from apple and orange juice industries; sugarcane bagasse; açaí kernels (Euterpe oleracea) and rice husk – were characterised as solid fuels and an evaluation of their properties, including proximate and ultimate composition, energy content, thermal behaviour, composition and fusibility of the ashes was performed. The lower heating value of the biomasses ranged from 14.31 MJ kg^?1 to 29.14 MJ kg^?1, on a dry and ash free basis (daf), all presenting high volatile matter content, varying between 70.57 wt.% and 85.36 wt.% (daf) what improves the thermochemical conversion of the solids. The fouling and slagging tendency of the ashes was predicted based on the fuel ash composition and on the ash fusibility correlations proposed in the literature, which is important to the project and operation of biomass conversion systems. The potential for application of the Brazilian agroindustrial solid residues studied as alternative energy sources in thermochemical processes has been identified, especially concerning direct combustion for steam generation.     

Effect of MgO and CaO/SiO2 on the immobilization of chromium in synthetic slags

This work investigated the chemical and mineralogical properties of CaO–SiO₂–Cr₂O₃–CaF₂–MgO slags. Synthetic slags were prepared and the effect of the slag basicity (mass ratio CaO/SiO₂) and MgO contents on the stability of the mineralogical species formed was analyzed. The morphology and composition of the slags were analyzed by X-ray powder diffraction (XRD) and scanning electron microscope-energy dispersive spectroscopy (SEM–EDS), whilst their chemical stability was evaluated by leaching with an aqueous acetic acid solution. It was found that in slags with CaO/SiO₂?=?1, the main Cr-compound was MgCr₂O₄ spinel, which forms octahedron crystals. Small amounts of CaCr₂O₄ and CaCrO₄ were also observed. It was found that with increasing the slag basicity from 1 to 2 the compounds MgCr₂O₄ and CaCr₂O₄ were formed together with the Cr(V)-containing compound complex Ca₅(CrO₄)₃F which forms hexagonal crystals. The results showed that the highest Cr concentration levels in the leaching liquors corresponded to slags with CaO/SiO₂?=?2, probably owing to the formation of CaCrO₄ and Ca₅(CrO₄)₃F, whilst the lowest chromium concentration levels corresponded to MgO-based slags owing to the stable binding of chromium in spinel with MgO. Additionally, potential–pH diagrams for the Ca–Cr–H₂O and Mg–Cr–H₂O systems at 25?°C were calculated.