Removal of the herbicide amitrole from water by anodic oxidation and electro-Fenton

Here we demonstrate that an aqueous solution of the herbicide amitrole can be completely depolluted at pH 3.0 by anodic oxidation and electro-Fenton process. Anodic oxidation gives faster degradation with a boron-doped diamond anode than with a Pt anode. Electro-Fenton with a Pt anode and 1 mmol l ^–1 Fe²⁺ as catalyst yields the quickest depollution. Amitrole decay always follows a pseudo first-order reaction. NO₃^– and NH₄⁺ are accumulated in the medium during mineralization, although volatile N-products are also formed. These environmentally friendly electrochemical treatments could be applied to the remediation of wastewaters containing amitrole.     

Abatement of spinosad and indoxacarb residues in pure water by photocatalytic treatment using binary and ternary oxides of Zn and Ti

The photodegradation of indoxacarb, a broad spectrum foliar insecticide and spinosad, a natural insecticide containing two active ingredients, spinosyn A (major component) and spinosyn D (minor component), was studied in aqueous suspensions of binary (ZnO and TiO₂) and ternary (Zn₂TiO₄ and ZnTiO₃) oxides under artificial light (300–460 nm) irradiation. As expected, the influence of the semiconductor materials on the degradation of both was very significant in all cases. Photocatalytic experiments showed that the addition of semiconductors in tandem with Na₂S₂O₈ as electron acceptor strongly improved the removal of indoxacarb and spinosad in water compared with the photolytic tests. The reaction rates significantly increased, especially for the ZnO/Na₂S₂O₈ and TiO₂/Na₂S₂O₈ systems. The first-order equation (monophasic model) satisfactorily explained the disappearance process, although it offered no explanation for the small concentrations remaining in the process.     

Toxicity of lindane (γ-hexachloroxiclohexane) in Sparus aurata,Crassostrea angulata and Scrobicularia plana

The purpose of the present study was to research the sublethal and/or lethal effects produced by the exposure of fish and shellfish to the γ isomer of lindane, γ-hexachlorocyclohexane (γ-HCH). The teleostean fish Sparus aurata and the shellfish Crassostrea angulata and Scrobicularia plana, were exposed to 16 μ g/L of lindane for 15 days. Samples of different fish (liver, kidney and gills) and shellfish (gills, gut, digestive gland and mantle) tissues were extracted and processed for histopathological observations. Although mortality was not detected during the bioassay, sublethal effects (histopathological alterations) were observed. Vacuolization in the liver cells and lamellar fusion in gills from exposed fish were observed. Disorganization of normal gill structure, epithelial desquamation with the disappearance of apical ciliature in intestine, and inflammatory response in mantle from exposed shellfish were also observed. Thus, it can be concluded that the lindane concentration employed in the present research did not produce lethal effects in the exposed organisms but it caused sublethal effects. Lindane has time-dependent multiple toxic effects in S. aurata, C. angulata and S. plana, which were more severe at the end of the experimental time. The toxicological implications arising from these results are subjects for further multiconcentration tests dealing with lethal responses (mortality) or with sublethal responses (cellular/molecular biomarkers) of the aforementioned species.     

Host-guest complexes of phenoxy alkyl acid herbicides and cyclodextrins. MCPA and β-cyclodextrin

The chlorophenoxy herbicide MCPA (4-chloro-2-methylphenoxyacetic acid), widely used for the control of broad-leaf weeds primarily in cereal and grass seed crops, still remains one of the most often used herbicides in Portugal. As the formation of inclusion complexes with cyclodextrins can improve its solubility properties, the interaction between the herbicide MCPA and β-cyclodextrin was investigated. The stability constants describing the extent of formation of the complexes have been determined by phase-solubility studies. Different analytical techniques [ultraviolet-visible spectroscopy (UV-Vis), differential scanning calorimetry (DSC), Fourier transform infrared spectroscopy (FTIR), proton nuclear magnetic resonance spectroscopy (¹H NMR)] were employed for a thorough investigation of the structural characteristics of the obtained complexes, which exhibited distinct features and properties from both “guest” and “host” molecules. FTIR and ¹H NMR data obtained for the MCPA/β-CD complexes gave information about the interaction between MCPA and the nonpolar cyclodextrin cavity. The dramatic change observed in band frequency and proton displacements of OCH₂ group and H6 aromatic proton confirmed the inclusion of MCPA in β-CD.

The formation of an inclusion complex between MCPA and β-CD increased the aqueous solubility of this herbicide which could be a particularly advantageous property for some specific applications, namely to improve commercial formulation and for environmental protection.     

Behaviour of alpha-, beta-, gamma-, and delta-hexachlorocyclohexane in the soil-plant system of a contaminated site

The behaviour of the organochlorine pesticide hexachlorocyclohexane (HCH) is investigated. The concentrations of alpha-, beta-, gamma-, and delta-HCH isomers were measured in soils, rhizosphere and vegetation in a contaminated area in Galicia (NW Spain). The total concentration of HCH in soils reached values close to 20,000 mgkg(-1). The plants analysed (Avena sativa L., Chenopodium spp., Solanum nigrum L., Cytisus striatus (Hill) Roth, and Vicia sativa L.) accumulated HCH, especially the beta-HCH isomer, in their tissues. The most likely mechanisms of HCH accumulation in plants were sorption of soil HCH on roots and sorption of volatilized HCH on aerial plant tissues. The concentrations of HCH obtained from the bulk and rhizosphere soils of selected plant species suggest that roots tend to reduce levels of the HCH isomers in the rhizosphere. The results reflect the importance of vegetation in the distribution of organochlorine compounds in the soil-plant system.     

Nitrate and phosphate leaching in a Phaeozem soil treated with biosolids,composted biosolids and inorganic fertilizers

The use of organic wastes in agriculture may increase the production of crops by incorporating organic matter and nutrients into the soil, and by improving its physical characteristics; however, this use may cause environmental problems such as the leaching of certain ions. The objective of this study was to establish possible nitrogen and phosphorus leaching under real field conditions in Phaeozem soils. The experimental work was performed in a corn (Zea mays L.) field where three plots were conditioned with inorganic fertilizer, three plots with 4.5 Mg ha^?1 of biosolids on dry basis, and three plots with the same amount of composted biosolids. The quality of biosolids and composted biosolids complied with the Mexican Official Standards. Soil water samples were collected with suction cups during two agricultural cycles and were analysed. Soil samples were also taken and analysed.The N–NO₃ concentrations in soil water fluctuated between 0.9 and 98 mg L^?1 in the composted biosolid treatment, between 0.7 and 64 mg L^?1 in the biosolid treatment, and between 1 and 61 mg L^?1 in the inorganic fertilizer treatment. The maximum concentration of N–NO₂ and N–NH₃ in soil water was 1.02 and 2.65 mg L^?1, respectively. The greatest percentage of nitrogen leached is produced when inorganic fertilizer is used (37.4% and 24.0% N leached in the first and second years, respectively), followed by composted biosolids (17.1% and 13.5% N leached in the first and second years, respectively) and last by biosolids (11% for both years). This difference could be related to the form in which nitrogen is present in the fertilizers, while commercial fertilizer is as inorganic nitrogen, organic wastes are basically presented as organic nitrogen. The maximum ${\text{PO}}_4^{3-}$ concentration in soil water was 1.9 mg L^?1 in the composted biosolid treatment, 1.7 mg L^?1 in the biosolid treatment and 0.9 mg L^?1 in the inorganic fertilizer treatment. The estimated percentage of leached phosphorus was less than 1% for all treatments. The minimum leaching that occurred seemed to be due to a sorption–precipitation process.     

Mineralization of paracetamol in aqueous medium by anodic oxidation with a boron-doped diamond electrode

The degradation of 100ml of solutions with paracetamol (N-(4-hydroxyphenyl)acetamide) up to 1 g l(-1) in the pH range 2.0-12.0 has been studied by anodic oxidation in a cell with a boron-doped diamond (BDD) anode and a graphite cathode, both of 3-cm2 area, by applying a current of 100, 300 and 450 mA between 25 and 45 degrees C. Complete mineralization is always achieved due to the great concentration of hydroxyl radical (*OH) generated at the BDD surface, with release of NH4+ and NO3- ions. The mineralization rate is pH-independent, increases with increasing applied current and temperature, but decreases when drug concentration raises from 315 mg l(-1). Reversed-phase chromatography revealed a similar complex paracetamol decay in acid and alkaline media. Ion-exclusion chromatography allowed the detection of oxalic and oxamic acids as ultimate carboxylic acids. When the same solutions have been comparatively treated with a Pt anode, a quite poor mineralization is found because of the production of much lower *OH concentration. Under these conditions, the degradation rate is enhanced in alkaline medium and polymerization of intermediates is favored in concentrated solutions. Paracetamol can be completely destroyed with Pt and its kinetics follows a pseudo-first-order reaction with a constant rate independent of pH.     

Changes in the sorption, desorption, distribution, and availability of copper, induced by application of sewage sludge on Chilean soils contaminated by mine tailings

The effect of mine tailings and sewage sludge was evaluated on sorption, desorption, availability and distribution of copper in two soils, one high (sandy soil) and one low in copper (clay soil). In both soils contaminated by mine tailings the copper sorption capacity and the affinity of the substrate for the metal decreased substantially compared to the uncontaminated soils, however, the sorption remained always high in the clay soil substrates. In the substrates with sandy soil, the high Cu content and lower clay content were determining factors in the lower magnitude of the sorption. Similarly, metal desorption was closely related to these two parameters, and it was higher in clay soil with lower pH. In general, the application of sewage sludge favored the sorption of Cu in soils contaminated and uncontaminated with mine tailings, and in all cases desorption decreased, an effect that remained for at least 30 days. Simple extraction of Cu with CaCl2 and diethylenetriaminepentaacetic acid gave contradictory results, so a careful choice of the procedure is required, depending on the level of metal in the soil and on the acting principle of the extracting agent. In that relation, more complete information on the changes in the metal forms was obtained by application of the sequential extraction procedure proposed by the European Community Bureau of Reference.