Biochemical modifications in Pinus pinaster Ait. as a result of environmental pollution

Exposure to chemical pollution can cause significant damage to plants by imposing conditions of oxidative stress. Plants combat oxidative stress by inducing antioxidant metabolites, enzymatic scavengers of activated oxygen and heat shock proteins. The accumulation of these proteins, in particular heat shock protein 70 and heme oxygenase, is correlated with the acquisition of thermal and chemical adaptations and protection against oxidative stress. In this study, we used Pinus pinaster Ait. collected in the areas of Priolo and Aci Castello representing sites with elevated pollution and reference conditions, respectively. The presence of heavy metals and the levels of markers of oxidative stress (lipid hydroperoxide levels, thiol groups, superoxide dismutase activity and expression of heat shock protein 70, heme oxygenase and superoxide dismutase) were evaluated, and we measured in field-collected needles the response to environmental pollution. P. pinaster Ait. collected from a site characterized by industrial pollution including heavy metals had elevated stress response as indicated by significantly elevated lipid hydroperoxide levels and decreased thiol groups. In particular, we observed that following a chronic chemical exposure, P. pinaster Ait. showed significantly increased expression of heat shock protein 70, heme oxygenase and superoxide dismutase. This increased expression may have protective effects against oxidative stress and represents an adaptative cellular defence mechanism. These results suggest that evaluation of heme oxygenase, heat shock protein 70 and superoxide dismutase expression in P. pinaster Ait. could represent a useful tool for monitoring environmental contamination of a region and to better understand mechanisms involved in plant defence and stress tolerance.     

Cellulose and Nanocellulose from Maize Straw: An Insight on the Crystal Properties

In this work cellulose was extracted from corn/maize straw (Zea mays) by means of an environmental-friendly multistep procedure involving alkaline treatment and a totally chlorine-free bleaching. This multistep procedure efficiently removed lignin and hemicelluloses. The pulp resulting from each step was characterized by attenuated total reflectance fourier transform infrared spectroscopy (ATR-FTIR). The optimum pulping time (time of alkaline treatment) was determined by means of thermogravimetric analysis. The extracted cellulose is highly crystalline as verified by X-ray diffraction. The partial acid hydrolysis with sulfuric acid led to the isolation of cellulose whiskers in aqueous suspension as confirmed by light scattering and transmission electron microscopy. The depolarization ratio value of these nanocrystals is the same as that determined for cotton whiskers, showing that this ratio does not depend on the cellulose source. The maize whiskers are arranged laterally in bundles with average thickness around five times that of the crystallite.     

Electro-Fenton degradation of the antibiotic sulfanilamide with Pt/carbon-felt and BDD/carbon-felt cells. Kinetics,reaction intermediates,and toxicity assessment

The degradation of 230 mL of a 0.6-mM sulfanilamide solution in 0.05 M Na₂SO₄ of pH 3.0 has been studied by electro-Fenton process. The electrolytic cell contained either a Pt or boron-doped diamond (BDD) anode and a carbon-felt cathode. Under these conditions, organics are oxidized by hydroxyl radicals formed at the anode surface from water oxidation and in the bulk from Fenton’s reaction between initially added (and then electrochemically regenerated) Fe²⁺ and cathodically generated H₂O₂. From the decay of sulfanilamide concentration determined by reversed-phase liquid chromatography, an optimum Fe²⁺ concentration of 0.20 mM in both cells was found. The drug disappeared more rapidly using BDD than Pt, and, in both cases, it was more quickly removed with raising applied current. Almost total mineralization was achieved using the BDD/carbon-felt cell, whereas the alternative use of Pt anode led to a slightly lower mineralization degree. In both cells, the degradation rate was accelerated at higher current but with the concomitant fall of mineralization current efficiency due to the greater increase in rate of the parasitic reactions of hydroxyl radicals. Reversed-phase liquid chromatography allowed the identification of catechol, resorcinol, hydroquinone, p-benzoquinone, and 1,2,4-trihydroxybenzene as aromatic intermediates, whereas ion exclusion chromatography revealed the formation of malic, maleic, fumaric, acetic, oxalic, formic, and oxamic acids. NH₄ ⁺, NO₃ ^?, and SO₄ ^2? ions were released during the electro-Fenton process. A plausible reaction sequence for sulfanilamide mineralization involving all detected intermediates has been proposed. The toxicity of the solution was assessed from the Vibrio fischeri bacteria luminescence inhibition. Although it acquired its maximum value at short electrolysis time, the solution was completely detoxified at the end of the electro-Fenton treatment, regardless of the anode used.     

Assessment of a composting process for the treatment of beef cattle manure

The intensive breeding of beef cattle in Juncosa de les Garrigues (Catalonia, Spain) leads to the production of a large volume of manure that needs appropriate management. Land application in the area at agronomic rates is not enough to ensure good management practices, making necessary extended on-farm storage and the export of part of the production to long distances. In this context, the implementation of a collective treatment based on composting could help in enhancing the handling of manure. We assessed a full-scale composting process based on turned windrows (W), and involving treatment of beef cattle manure (CM) alone (two typologies were considered according to carbon-to-nitrogen ratios of ~25 (CM1, W1) and ~14 (CM2, W2)), or mixed with bulking agent (CM2/BA, W3) and dewatered digested sewage sludge (CM2/BA/DDSS, W4). Composting significantly improved the transportability of nutrients (final volumes were 40–54% of the initial volume). Temperature >55°C was reached in all the treatments but following different time patterns. Under the applied conditions of turning and rewetting, 14 weeks of processing did not ensure the production of stable, and mature, compost. Thus, only compost from W1 attained the maximum degree of stability as well as concentration of ammonium–N < 0.01% (with ammonium–N/nitrate–N ratio of 0.2) and low phytotoxicity. However, high pH, salinity, and heavy metal contents (Cu and Zn) may limit its final use. Addition of BA was advised to be kept to minimum, whereas use of DDSS as a co-substrate was not recommended in agreement to the higher loss of N and levels of heavy metals in the final compost.     

Microbial and physicochemical parameters associated with Legionella contamination in hot water recirculation systems

Hot water recirculation systems (HWRS) in hotels and nursing homes, which are common in countries such as Spain, have been related to outbreaks of legionellosis. To establish the relationships of microbial and physicochemical parameters, especially protozoa, with the occurrence of Legionella in HWRS, 231 samples from hotels and nursing homes were analysed for Legionella, protozoa, heterotrophic plate counts (HPC) at 22 and 37 °C, Pseudomonas, metals, temperature and others. Legionella pneumophila was the dominant species isolated, and 22 % were sg. 1. The sampling method became particularly important in order to define which factors were involved on the occurrence of Legionella. Results showed that the bacteria and the accompanying microbiota were more abundant in the first flush water whose temperature was lower. The bacteria occurred in those samples with high HPC and were inversely correlated with high temperatures. Multivariate regression showed that a concentration above 1?×?10⁵?CFU/100 mL of HPC at 37 °C, Fe above 0.095 ppm and the presence of protozoa increased significantly the risk of Legionella colonization, while univariant regression showed that the presence of Cu above 0.76 ppm and temperature above 55 °C diminished it. Therefore, to reduce the risk associated with Legionella occurrence in HWRS these parameters should be taken into consideration.     

Degradation of clofibric acid in acidic aqueous medium by electro-Fenton and photoelectro-Fenton

Acidic aqueous solutions of clofibric acid (2-(4-chlorophenoxy)-2-methylpropionic acid), the bioactive metabolite of various lipid-regulating drugs, have been degraded by indirect electrooxidation methods such as electro-Fenton and photoelectro-Fenton with Fe(2+) as catalyst using an undivided electrolytic cell with a Pt anode and an O(2)-diffusion cathode able to electrogenerate H(2)O(2). At pH 3.0 about 80% of mineralization is achieved with the electro-Fenton method due to the efficient production of oxidant hydroxyl radical from Fenton's reaction between Fe(2+) and H(2)O(2), but stable Fe(3+) complexes are formed. The photoelectro-Fenton method favors the photodecomposition of these species under UVA irradiation, reaching more than 96% of decontamination. The mineralization current efficiency increases with rising metabolite concentration up to saturation and with decreasing current density. The photoelectro-Fenton method is then viable for treating acidic wastewaters containing this pollutant. Comparative degradation by anodic oxidation (without Fe(2+)) yields poor decontamination. Chloride ion is released during all degradation processes. The decay kinetics of clofibric acid always follows a pseudo-first-order reaction, with a similar rate constant in electro-Fenton and photoelectro-Fenton that increases with rising current density, but decreases at greater metabolite concentration. 4-Chlorophenol, 4-chlorocatechol, 4-chlororesorcinol, hydroquinone, p-benzoquinone and 1,2,4-benzenetriol, along with carboxylic acids such as 2-hydroxyisobutyric, tartronic, maleic, fumaric, formic and oxalic, are detected as intermediates. The ultimate product is oxalic acid, which forms very stable Fe(3+)-oxalato complexes under electro-Fenton conditions. These complexes are efficiently photodecarboxylated in photoelectro-Fenton under the action of UVA light.     

Degradation of the herbicide 2,4-DP by anodic oxidation, electro-Fenton and photoelectro-Fenton using platinum and boron-doped diamond anodes

This paper reports the degradation of 2,4-DP (2-(2,4-dichlorophenoxy)-propionic acid) solutions of pH 3.0 by environmentally friendly electrochemical methods such as anodic oxidation, electro-Fenton and photoelectro-Fenton with a Pt or boron-doped diamond (BDD) anode. In the two latter techniques an O(2)-diffusion cathode was used and 1.0mM Fe(2+) was added to the solution to give hydroxyl radical (*OH) from Fenton's reaction between Fe(2+) and H(2)O(2) generated at the cathode. All treatments with BDD are viable to decontaminate acidic wastewaters containing 2,4-DP since they give complete mineralization, with loss of chloride ion, at high current due to the great production of oxidant *OH at the BDD surface favoring the destruction of final carboxylic acids. *OH formed from Fenton's reaction destroys more rapidly aromatic products, making the electro-Fenton and photoelectro-Fenton processes much more efficient than anodic oxidation. UVA light in photoelectro-Fenton with BDD has little effect on the degradation rate of pollutants. The comparative procedures with Pt lead to slower decontamination because of the lower oxidizing power of this anode. The effect of current on the degradation rate and efficiency of all methods is studied. The 2,4-DP decay always follows a pseudo-first-order kinetics. Chlorohydroquinone, chloro-p-benzoquinone and maleic, fumaric, malic, lactic, pyruvic, acetic, formic and oxalic acids are detected as products by chromatographic techniques. A general sequence accounting for by the reaction of all these intermediates with the different oxidizing agents is proposed.     

Concomitant Zn-Cd and Pb retention in a carbonated fluvio-glacial deposit under both static and dynamic conditions

The chemical and physical processes involved in the retention of 10(-2)M Zn, Pb and Cd in a calcareous medium were studied under saturated dynamic (column) and static (batch) conditions. Retention in columns decreased in order: Pb>Cd approximately Zn. In the batch experiments, the same order was observed for a contact time of less than 40h and over, Pb>Cd>Zn. Stronger Pb retention is in accordance with the lower solubility of Pb carbonates. However, the equality of retained Zn and Cd does not fit the solubility constants of carbonated solids. SEM analysis revealed that heavy metals and calcareous particles are associated. Pb precipitated as individualized Zn-Cd-Ca- free carbonated crystallites. All the heavy metals were also found to be associated with calcareous particles, without any change in their porosity, pointing to a surface/lattice diffusion-controlled substitution process. Zn and Cd were always found in concomitancy, though Pb fixed separately at the particle circumferences. The Phreeqc 2.12 interactive code was used to model experimental data on the following basis: flow fractionation in the columns, precipitation of Pb as cerrusite linked to kinetically controlled calcite dissolution, and heavy metal sorption onto proton exchanging sites (presumably surface complexation onto a calcite surface). This model simulates exchanges of metals with surface protons, pH buffering and the prevention of early Zn and Cd precipitation. Both modeling and SEM analysis show a probable significant decrease of calcite dissolution along with its contamination with metals.     

Proposal for an Integral Quality Index for Urban and Urbanized Beaches

A composite index, based on function analysis and including thirteen sub-indices, was developed to assess the overall quality of urban and urbanized beaches in the Mediterranean area. The aggregation of components and sub-indices was based on two questionnaires completed by beach users and experts. Applying the new Beach Quality Index (BQI) demonstrated that the quality of beaches could be improved. In general, the strongest aspects of the beaches assessed were those related to short-term user demand, and the weakest were those related to the consequences of human pressure on the area, in particular, erosion problems. The composite index is intended to be used together with Environmental Management Beach Systems (EMBs) as a hierarchical management scorecard and in monitoring programs. This new tool could also make planning more proactive by synthesizing the state of the most important beach processes.     

Characterization of Atrazine-Loaded Biodegradable Poly(Hydroxybutyrate-Co-Hydroxyvalerate) Microspheres

Polyhydroxybutyrate-co-hydroxyvalerate microspheres (PHBV-MS) were prepared as a delivery system for the herbicide atrazine (ATZ). Characterization of the system included investigation of in vitro release properties and genotoxicity. ATZ − PHBV-MS particle diameters showed a size distribution range of 1–13 μm. Differential scanning calorimetry analyses indicated that ATZ was associated with the PHBV microparticles. The release profiles showed a different release behavior for the pure herbicide in solution, as compared with that containing ATZ-loaded PHBV-MS. Korsmeyer–Peppas model analyses showed that atrazine release from the microparticles occurred by a combination of diffusion through the matrix and partial diffusion through water-filled pores of the PHBV microparticles. A Lactuca sativa test result showed that the genotoxicity of ATZ-loaded PHBV-MP was decreased in relation to ATZ alone. The results demonstrate a viable biodegradable herbicide release system using atrazine for agrochemical purposes.