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.     

Modeling the Entrepe?as Reservoir.

The Entrepe?as Reservoir is a monomictic reservoir located in River Tagus (Spain). The aim of this work is to establish a feasible model to predict the depth of the thermocline that is developed in the reservoir during the period of natural thermal stratification. Entrainment, eddy diffusion, inflow of external energy, and other factors are considered to calibrate the parameters of the model. The methodology involves the measure of actual temperature and electrical conductivity profiles, use of meteorological data and reservoir parameters, and selection and application of several models from the literature. The calculations and predictions are integrated to a software packet that is able to predict thermocline depth and water temperature profile during a 1-year period on a day-by-day basis. In the thermocline depth, the prediction error, on the basis of real data, is less than 6% and, in the water temperature, it is 2 degrees C.     

Application of the Microtox test and pollution indices to the study of water toxicity in the Albufera Natural Park (Valencia, Spain)

The toxic effects of waters collected from irrigation channels in a Mediterranean wetland (Albufera Natural Park, Valencia, Spain) were tested with the Microtox assay and compared with six pollution indices (PIs) defined from analytical parameters. Chemical oxygen demand (COD), biological oxygen demand (BOD), nutrients, heavy metals and pesticides were measured. The bioassay result (concentrations of the water sample (% V/V) that reduced light emission to 10%, 20% and 50%, EC10, EC20 and EC50, respectively (ECs)) was compared with the PIs. This comparison has demonstrated a general agreement between ECs and PIs, except in the case of irrigation channels affected by herbicides used in rice farming (molinate and thiobencarb). No pronounced inhibition was detected in the bioluminescence in relation to the eutrophic parameters in the irrigation waters for EC50 values, indicating that this parameter does not suffice to detect eutrophic waters. Data derived from irrigation water pollution and bioassay were assembled by multivariate statistical techniques (principal component analysis). These components were associated with various contamination sources.     

Heavy metal extractable forms in sludge from wastewater treatment plants

The analysis of heavy metals is a very important task to assess the potential environmental and health risk associated with the sludge coming from wastewater treatment plants (WWTPs). However, it is widely accepted that the determination of total elements does not give an accurate estimation of the potential environmental impact. So, it is necessary to apply sequential extraction techniques to obtain a suitable information about their bioavailability or toxicity. In this paper, a sequential extraction scheme according to the BCR's guidelines was applied to sludge samples collected from each sludge treatment step of five municipal activated sludge plants. Al. Cd, Co, Cu, Cr, Fe, Mn, Hg, Mo, Ni, Pb, Ti and Zn were determined in the sludge extracts by inductively coupled plasma atomic emission spectrometry. In relation to current international legislation for the use of sludge for agricultural purposes none of metal concentrations exceeded maximum permitted levels. In most of the metal elements under considerations, results showed a clear rise along the sludge treatment in the proportion of two less-available fractions (oxidizable metal and residual metal).     

Bioaccumulation and elimination of 14C-lindane by Enchytraeus albidus in artificial (OECD) and a natural soil

Bioaccumulation and elimination of 14C-lindane in Enchytraeus albidus was studied in artificial OECD soil and a silty loam from an agricultural field in Central West Portugal. Results showed that enchytraeids were able to bioaccumulate the chemical with a kinetic pattern similar to that of earthworms: fast uptake within a few days and a biphasic elimination pattern. A 10 day period to study uptake was sufficient, but a few more days were probably necessary for elimination. Bioaccumulation was influenced by soil type. The authors suggest that higher organic matter (OM) content and also the higher content on sand particles in the OECD soil may have led to a faster elimination: hydrophobic chemicals tend to adsorb to OM being in this way less bioavailable and therefore less bioaccumulated having bioaccumulation factor value around 6 while in natural soil is 10; the sand could act as abrasive particles (helpers) in the elimination process leading to an elimination of 90% of the chemical in two days while in natural soil 67% was eliminated in the same period of time.     

Pesticides in precipitation in the Gdańsk region (Poland)

Selected organonitrogen, organophosphorus and organochlorine pesticides have been determined in precipitation samples collected at 10 sites in the Gdańsk region (northern Poland) over a period of one year (1998). Compounds which were detected most often included simazine (0.11-5.80 ng/l), fenitrothion (0.1-2.10 ng/l), chlorfenvinfos (0.1-1.30 ng/l), gamma-HCH (0.012-5.06 ng/l), heptachlor epoxide (0.05-3.28 ng/l) and aldrin (0.02-3.28 ng/l). The pesticide concentrations in precipitation samples revealed seasonal fluctuations, with higher concentrations observed during the application periods (June and July). The concentrations observed were also affected by the inflow of polluted air masses from the southwest. The total pesticide concentration in the precipitation samples was strongly related to the abundance of green areas in the vicinity of the sampling sites. A weak correlation was also found between the total concentration of organonitrogen and organophosphorus pesticides, and the total concentration of organochlorine pesticides in the samples collected.     

H2O2 formation from photocatalytic processes at the ZnO/water interface

The paper focuses on the production of H2O2 by photocatalysis over ZnO in an aerated aqueous phase. The presence of different reductants that increase the H2O2 production in the aqueous phase is analysed; particular attention is paid to nitrite, which has been shown to be the reductant that produces the most significant increments in the H2O2 production. The photocatalytic anodic decomposition of ZnO in the presence of the different reductants is also investigated. From the results obtained, the relevance of the ZnO photocatalysis in the formation of environmental hydrogen peroxide is estimated.     

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.     

Kinetics of simazine advanced oxidation in water

Comparison of the effects and kinetics of UV photolysis and four advanced oxidation systems (ozone, ozone/hydrogen peroxide, ozone/UV radiation and UV radiation/hydrogen peroxide) for the removal of simazine from water has been investigated. At the conditions applied, the order of reactivity was ozone < ozone/hydrogen peroxide < UV radiation < ozone/UV radiation and UV radiation/hydrogen peroxide. Rate constants of the reactions between ozone and simazine and hydroxyl radical and simazine were found to be 8.7 M-1s-1 and 2.1 x 10(9) M-1s-1, respectively. Also, a quantum yield of 0.06 mol.photon-1 was found for simazine at 254 nm UV radiation. The high value of the quantum yield corroborated the importance of the direct photolysis process. Percentage contributions of direct reaction with ozone, reaction with hydroxyl radicals and direct photolysis were also quantified.     

Occupational exposure

Concentrations of polychlorinated biphenyls (PCB), polychlorinated naphthalenes (PCN), polychlorinated dibenzo-p-dioxins (PCDD), polychlorinated dibenzofurans (PCDF), hexachlorobenzene and methylsulphonyl metabolites of PCB were determined in blood plasma from potentially exposed workers and controls. Three of the potentially exposed subjects had worked with cable incineration and two were electricians. Extraction of the organochlorine compounds and lipids were performed using the lipophilic gel Lipidex. Different adsorbents and gel permeation chromatography were applied for further purification of the samples and separation of analytes. Determinations of the chlorinated compounds were made by using gas chromatography with electron-capture detection and gas chromatography-mass spectrometry. Only small differences in the concentrations of organochlorine compounds were found in the plasma from the three subject groups. Thus, specific exposure of the workers could not be confirmed.