Photodegradation of atrazine and ametryn with visible light using water soluble porphyrins as sensitizers

The photodegradation of the herbicides atrazine and ametryn with visible light in aerated neutral aqueous solutions and 5, 10, 15, 20-tetrakis (2,6-dichloro-3-sulfophenyl) porphyrin or 5, 10, 15, 20-tetrakis (4-sulfophenyl) porphyrin as sensitizers are reported for the first time. Our findings show that the degradation percentage reached 30% for atrazine and 63% for ametryn. The final photoproducts were characterized as dealkylated s-triazines. Photolysis of the pesticides in the presence of a singlet oxygen quencher showed only a minor contribution of this type of mechanism, while a bimolecular quenching reaction between the triplet state of the sensitizer and the pesticides is excluded by flash photolysis studies. It is proposed that the mechanism may involve the formation of a superoxide radical anion from the triplet state of the sensitizer and molecular oxygen, followed by a radical decomposition pathway. Selected article from 1st International Meeting on Photochemistry, Photocatalysis and Environmental Applications, Agadir, 2006, organised by Prof. Dr. Ait Ichou, University Ibn Zohr, Agadir, Morocco     

Partitioning studies of coal-tar constituents in a two-phase contaminated ground-water system

Organic compounds derived from coal-tar wastes in a contaminated aquifer in St. Louis Park, Minnesota, were identified, and their partition coefficients between the tar phase and aqueous phase were determined and compared with the corresponding n-octanol/water partition coefficients. Coal tar contains numerous polycyclic aromatic compounds, many of which are suspected carcinogens or mutagens. Groundwater contamination by these toxic compounds may pose an environmental health hazard in nearby public water-supply wells. Fluid samples from this aquifer developed two phases upon settling: an upper aqueous phase, and a lower oily-tar phase. After separating the phases, polycyclic aromatic compounds in each phase were isolated using complexation with N-methyl-2-pyrrolidone and identified by fused-silica capillary gas chromatography/mass spectrometry. Thirty-one of the polycyclic aromatic compounds were chosen for further study from four different classes: 12 polycyclic aromatic hydrocarbons, 10 nitrogen heterocycles, 5 sulfur heterocycles, and 4 oxygen heterocycles. Within each compound class, the tar/water partition coefficients of these compounds were reasonably comparable with the respective n-octanol/water partition coefficient.     

Ground-level ozone mapping in large urban areas using multivariate statistical analysis: application to the São Paulo Metropolitan Area

A statistical study on the behavior of ground-level O3 concentration in different regions of a large urban area was carried out, with emphasis on pollutant gas concentrations and meteorological variables. The study was based on data generated by a network of measuring stations distributed throughout the S?o Paulo Metropolitan Area, in regions with different characteristics of traffic and economic activities. The combined application of principal component analysis and clustering techniques to data collected from 1997 until 2000 has led to the identification of implicit relationships between variables that have been associated with dominant processes related to O3 formation in different locations. Similarities between different regions of the city have also been detected and associated with local characteristics. The results indicate that the application of such statistical techniques to data collected in large urban areas enables the grouping of different regions according to their behavior in terms of O3 levels, as well as the identification of dominant processes in each group. These techniques are thus important in the planning of air pollution policies, especially in the case of O3, a pollutant that is not directly related to pollution levels alone.     

Gas-phase ozonolysis of the monoterpenoids (S)-(+)-carvone, (R)-(−)-carvone, (−)-carveol, geraniol and citral

Biogenic emissions of volatile organic compounds (VOCs) play a fundamental role in atmospheric chemistry. Vegetation is the most abundant natural source of VOCs, while terpenoids, as limonene, α and β pinene and mircene, top the plants emission list. Much interest has been demonstrated in oxidation and photooxidation reactions of VOCs, particularly of monoterpenoids, owing to their diversity and to uncertainties regarding their mechanism of reaction. Quantification of primary carbonylic compounds, as well as of biradical reaction components, is highly relevant to the understanding of the major reactions. In this context, taking into account both structural factors and the fact that these compounds are found in the essential oils of plants typically found in Brazil and that they may be present in the atmosphere from emission by the plants, the monoterpenoids (S)-(+)-carvone, (R)-(−)-carvone, (−)-carveol, geraniol and citral (a mixture of the isomers geranial and neral) were selected for this study.The ozonolysis reactions of the monoterpenoids were carried out under dark conditions for all experiments, due to their photochemical reactivity. The analysis of the results lets us propose a mechanism by which these reactions occur. The observed results of the ozonolysis of S and R carvone suggest that the stereochemistry of asymmetric carbon does not affect either in the yields of both formaldehyde and of OH radicals produced in the reaction, or in the reactivity of these compounds, for which the rate constants were in the scale of 10⁻⁶ s⁻¹.We found that, in the (−)-carveol's cis and trans mixture, even though the hydroxyl in the axial position—in the case of trans-(C) and cis-(D′) isomers—favors the attack by the ozone molecule on the external double bond, thus increasing the mixture's reactivity , it affects the average production of formaldehyde. The presence of geraniol and citral led to the production of formaldehyde, propanone, glyoxal, methyl–glyoxal and cyclohexanone (OH radicals) as reaction products. The influence of an electron attractor group bonded to the carbon of the double bond, on the reactivity of the double bond, could not be observed in the case of citral, due to strong interference occurring in the instrument in all experiments with this monoterpenoid. For this reason, only the kinetics of geraniol was monitored .     

Causal chain analysis and root causes: the GIWA approach

The Global International Waters Assessment (GIWA) was created to help develop a priority setting mechanism for actions in international waters. Apart from assessing the severity of environmental problems in ecosystems, the GIWA's task is to analyze potential policy actions that could solve or mitigate these problems. Given the complex nature of the problems, understanding their root causes is essential to develop effective solutions. The GIWA provides a framework to analyze these causes, which is based on identifying the factors that shape human behavior in relation to the use (direct or indirect) of aquatic resources. Two sets of factors are analyzed. The first one consists of social coordination mechanisms (institutions). Faults in these mechanisms lead to wasteful use of resources. The second consists of factors that do not cause wasteful use of resources per se (poverty, trade, demographic growth, technology), but expose and magnify the faults of the first group of factors. The picture that comes out is that diagnosing simple generic causes, e.g. poverty or trade, without analyzing the case specific ways in which the root causes act and interact to degrade the environment, will likely ignore important links that may put the effectiveness of the recommended policies at risk. A summary of the causal chain analysis for the Colorado River Delta is provided as an example.     

Sardine (Sardina pilchardus) stress reactions to purse seine fishing

Observations from the purse seine fishery off northern Portugal are used to describe the early dynamics of sardine (Sardina pilchardus) stress reactions and identify likely stressors during the commercial fishing operation. Sardine blood and muscle were sampled from the onset of fishing (school identification and encircling) to the end of fish transfer onboard (90–120 min later). The evolution of haematocrit, haemoglobin, cortisol, glucose, ionic concentrations, ATP and its catabolites were modelled using linear mixed models as a function of time spent in the net, biological (sex, reproductive state and condition) and operational variables (catch, light level and phase of fishing operation). Significant linear trends with time were detected for most stress variables and mean concentrations after 2 h in the net were similar to literature values corresponding to acute stress reactions for teleosts. Biological variables were rarely significant and explained a small proportion of variation, while operational variables were never significant. For each stress variable, levels varied considerably between trips but the temporal evolution was common across trips. Random trip effects were uncorrelated among most biochemical variables, suggesting that distinct factors affected each stress variable during the sampled trips. However, the linear trend with time spent in the net observed for most stress variables indicates that the duration of the fishing operation is an important stressor in purse seine fishing due to the progressive water volume restriction, crowding and manipulation associated to the fishing method.     

A simple voltammetric procedure for speciation and evaluation of As removal from water

Here, we show a fast and sensitive method for the determination of inorganic arsenic in natural waters using differential pulse cathodic stripping voltammetry. All the arsenite determinations were done in 2.0 mol L⁻¹ HCl + 3.15 × 10⁻⁴ mol L⁻¹ Cu(II) supporting electrolyte. 1 × 10⁻³ mol L⁻¹ sodium thiosulphate was used as As(V) reducing agent. The detection limit was 0.5 μg L⁻¹ for both species. The method has been applied to water samples collected in an arsenic-contaminated region of Brazil, in particular, to verify the efficiency of the solar oxidation and removal of arsenic process applied to these waters.     

Growth and development of nauplii and copepodites of the estuarine copepod Acartia tonsa from southern Europe (Ria de Aveiro, Portugal) under saturating food conditions

A temperature-dependent growth model is presented for nauplii and copepodites of the estuarine calanoid copepod Acartia tonsa from southern Europe (Portugal). Development was followed from egg to adult in the laboratory at four temperatures (10, 15, 18 and 22°C) and under saturating food conditions (>1,000 μg C l⁻¹). Development times versus incubation temperature were fitted to a Belehradek’s function, showing that development times decreased with increasing incubation temperature: at 10°C, A. tonsa need 40.3 days to reach adult stage, decreasing to 8.9 days when reared at 22°C. ANCOVA (homogeneity of slopes) showed that temperature (P<0.001) and growth phase (P<0.01) had a significant effect on the growth rate. Over the range of temperatures tested in this study, highest weight-specific growth rates were found during naupliar development (NI–NVI) and varied from 0.185 day⁻¹ (10°C) to 0.880 day⁻¹ (22°C) with a Q ₁₀ equal to 3.66. During copepodite growth (CI–CV), the weight-specific growth rates ranged from 0.125 day⁻¹ (10°C) to 0.488 day⁻¹ (22°C) with a Q ₁₀ equal to 3.12. The weight-specific growth rates (g) followed temperature (T) by a linear relationship and described as ln g=−2.962+0.130 T (r ²=0.99, P<0.001) for naupliar stages and ln g=−3.134+0.114T (r ²=0.97, P<0.001) for copepodite stages. By comparing in situ growth rates (juvenile growth and fecundity) for A. tonsa taken from the literature with the temperature-dependent growth model defined here we suggest that the adult females of A. tonsa are more frequently food limited than juveniles.