New metallothionein assay in Scrobicularia plana: heating effect and correlation with other biomarkers

Metallothionein (MT) and other biomarker levels were measured in Scrobicularia plana clams to assess pollution of the Guadalquivir Estuary possibly affected by metals released from Aznalcóllar pyrite mine in 1998. After optimizing reagent concentrations for monobromobimane derivatization, MT levels were quantified by reversed-phase high-performance liquid chromatography coupled to fluorescence detection (RP-HPLC-FD) in heated or unheated digestive gland extracts and compared to those obtained by differential pulse polarography (DPP). MT content assayed by RP-HPLC-FD in unheated samples was higher than that obtained by DPP and correlated better with metals and anti-oxidant activities. MT assay by RP-HPLC-FD in unheated extracts would be preferable for assessing metal pollution, due to its greater sensitivity and specificity. In addition to MT induction, glyoxalase II inhibition was well correlated with metal contents. Our results suggest that metals at the estuary do not originate from Aznalcóllar spill, but from those carried along by the river and deposited at its concave bank.     

Semiconductor-assisted photocatalytic degradation of reactive dyes in aqueous solution

This work reports the semiconductor-assisted photochemical degradation of reactive dyes. In an oxygenated-UV-ZnO system almost total decolorization of Remazol Brilliant Blue R, Remazol Black B, Reactive Blue 221 and Reactive Blue 222 was observed in reaction times of about 60 min. Extending the photochemical treatment up to 120 min, mineralization higher than 80% for all the dyes was observed. During the same period, the residual acute toxicity was significantly reduced only for Remazol Black B. A systematic optimization study carried out by factorial design showed that for the reactive dyes tested, the ZnO semiconductor exhibits a better efficiency than that observed with anatase TiO2. A synergistic effect in the coupled TiO2-ZnO system was not observed.     

Homogenous catalyzed ozonation of simazine. Effect of Mn(II) and Fe(II).

Simazine, [2-chloro, 4,6-bis(ethylamino)-1,3,5-s-triazine], a common herbicide typically found in surface and ground water was ozonised by using catalytic amounts of Mn(II) and Fe(II). An optimum value for metal concentration was found in the process. Some inhibition of the simazine degradation rate was observed when these metals were added above the optimum concentration. The pH of the reaction media played a significant role in the simazine oxidation rate. Thus, an increase in simazine conversion was observed when the pH was raised from 5 to 9. However, the catalytic effect of added manganese was negligible at the highest pH used in this study (pH 9). The beneficial influence of Fe(II) was also observed when utilising the combination of ozone and hydrogen peroxide. Contrarily, Mn(II) presented a negative influence on simazine conversion when using this oxidation technology.     

First assessment of dioxin emissions from coal-fired power stations in Spain

In this work, the findings of the first assessment of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) in emissions releases to the atmosphere from coal-fired power plants are given. A total of five plants were selected for the study located at different provinces in Spain. In all the cases, the results revealed very low levels, in the range of 0.41 pg I-TEQ/Nm(3). The profile indicated in the majority of the cases predominance of highly chlorinated congeners being OCDD the most important contributor. The findings were also used to estimate contribution of PCDDs/PCDFs emitted from coal-fired power plants in Spain. Individual plant results revealed values below 0.02 g I-TEQ per year and plant. Nevertheless, considering the total coal consumption in Spain in 1997, the values are comparable to those reported in other countries in the range of 0.6-0.7 g I-TEQ per year. Moreover, emission factors were determined considering operating conditions of evaluated plants. In general, large variability was observed and values below 1-5 pg I-TEQ/kg coal were early reached.     

Four years of continuous monitoring of the Meirama end-pit lake and its impact in the definition of future uses

Following the technical closure of the brown lignite Meirama mine (NW Spain) in April 2008, the reclamation of the mined area is being accomplished with the controlled flooding of its large pit. During the first 7 months of flooding, the sequential arrest of the ground water dewatering system led to the growth of an acidic water body of about 2 hm³. Since October 2008, the surface waters from some local streams have been diverted towards the pit so that these have become the major water input in the flooding process. Surface water has promoted a major change in the chemical composition of the lake water so that, at present, its surface has a circum neutral pH, net alkalinity, and low conductivity. At present, the lake has slightly more than one half of its final volume, and it is expected the overflow in 3 to 3.5 years. The lake is meromictic, with a sharp chemocline separating the acidic monimolimnion (pH?≈?3.2, acidity?≈?150 mg CaCO₃/L, κ ₂₅?≈?2.4 mS/cm) from the main water body (pH?≈?6.5, alkalinity?≈?15 mg CaCO₃/L, κ ₂₅?≈?0.3 mS/cm). Oxygen is being depleted at the bottom of the lake so that the monimolimnion became anoxic in January 2011. Above the chemocline, the composition of the lake is similar, but not identical, to that of the flooding stream waters. Close to the surface, some constituents (pH, metals) show strong seasonal variations in coincidence with the phytoplankton growing periods. Those parameters whose limits are legally prescribed comply with the corresponding water quality standards, and they are also consistent with the forecasting results obtained in early modeling. At present, a project considering the construction of an uptake tunnel to exploit the lake is being developed for the emergency water supply of the metropolitan area of A Coruña.     

Photo-Fenton-assisted ozonation of p-Coumaric acid in aqueous solution

The degradation of p-Coumaric acid present in olive oil mill wastewater was investigated as a pretreatment stage to obtain more easily biodegradable molecules, with lower toxicity that facilitates subsequent anaerobic digestion. Thus, photo-Fenton-assisted ozonation has been studied and compared with ozonation at alkaline pH and conventional single ultraviolet (UV) and acid ozonation treatments. In the combined process, the overall kinetic rate constant was split into various components: direct oxidation by UV light, direct oxidation by ozone and oxidation by hydroxyl radicals. Molecular and/or radical ozone reaction was studied by conducting the reaction in the presence and absence of tert-butylalcohol at pHs 2, 7 and 9. Ozone oxidation rate increases with pH or by the addition of Fenton reagent and/or UV radiation due to generation of hydroxyl radicals, *OH. Hydrogen peroxide and ferrous ion play a double role during oxidation since at low concentrations they act as initiators of hydroxyl radicals but at high concentrations they act as radical scavengers. Finally, the additional levels of degradation by formation of hydroxyl radicals have been quantified in comparison to the conventional single processes and an equation is proposed for the reaction rate as a function of studied operating variables.     

Efficient use of Fe metal as an electron transfer agent in a heterogeneous Fenton system based on Fe0/Fe3O4 composites

In this work a novel heterogeneous Fenton system based on Fe(0)/Fe3O4 composites is described. The composites with several Fe(0)/Fe3O4 ratios were prepared by two different methods, i.e. mechanical alloying of Fe(0) and Fe3O4 powders and controlled reduction of Fe3O4 with H2. Reaction studies and detailed Conversion Electron M?ssbauer surface characterization of the composites Fe(0)/Fe3O4, Fe(0), Fe3O4, alpha-Fe2O3 and gamma-Fe2O3 suggested that Fe2+surf species are essential to produce an active Fenton system. Kinetic studies for the oxidation of the dye methylene blue, used as an organic model molecule, and for the peroxide decomposition suggest that the reactions proceed via HO* radicals generated from Fe2+surf species and H2O2 in a Fenton like mechanism. The increase in activity caused by the addition of Fe(0) is discussed in terms of a creation of Fe2+surf species during the preparation of the composite and by an electron transfer mechanism from Fe(0) to Fe3+surf during the Fenton reaction to regenerate the Fe2+surf active species.     

Residues of organochlorinated pesticides in soils from the Czech Republic

National POPs inventories carried out currently in many countries as a part of the implementation of Stockholm Convention revealed the need for detailed information about a distribution of pollutants in various regions. Screening for the residues of selected organochlorinated pesticides (chlordane, heptachlor, dieldrin, aldrin, endrin, isodrin, endosulfan I, endosulfan II, methoxychlor, mirex) in soil and biotic samples from the Czech Republic was performed. Although these pesticides have never been used in large quantities in this region, results indicate that their residues still persist in the top layer soils more than 20 years after they have been banned. The fact that their soil concentrations in the mountains are generally higher than those in agricultural areas, and detection of the traces of pesticides that have never been used in this region suggest on their occurrence in soils due to the atmospheric redistribution rather than as a result of direct application.     

Photocatalytic reduction of carbon dioxide over Cu/TiO<Subscript>2</Subscript> photocatalysts

The photocatalytic reduction of CO₂ with H₂O was investigated using Cu/TiO₂ photocatalysts in aqueous solution. For this purpose, Cu/TiO₂ photocatalysts (with 0.2, 0.9, 2, 4, and 6 wt.% of Cu) have been synthesized via sol-gel method. The photocatalysts were extensively characterized by means of inductively coupled plasma optical emission spectrometry (ICP-OES), N₂ physisorption (BET), XRD, UV-vis DRS, FT-IR, Raman spectroscopy, TEM-EDX, and photoelectrochemical measurements. The as-prepared photocatalysts contain anatase as a major crystalline phase with a crystallite size around 13 nm. By increasing the amount of Cu, specific surface area and band gap energy decreased in addition to the formation of large agglomeration of CuO. Results revealed that the photocatalytic reduction of CO₂ decreased in the presence of Cu/TiO₂ in comparison to pure TiO₂, which might be associated to the formation of CuO phase acting as a recombination center of generated electron-hole pair. Decreasing of photoactivity can also be connected with a very low position of conduction band of photocatalysts with high Cu content, which makes H₂ production necessary for CO₂ reduction more difficult.