Chemical degradation of chlorophenols with Fenton's reagent (Fe + H2O2)

Aqueous solutions of Fenton's reagent (Fe²⁺ + H₂O₂) have been used to effect the total decomposition of the chlorophenols: 2-chlorophenol, 3-chlorophenol, 4-chlorophenol, 3,4-dichlorophenol and 2,4,5-trichlorophenol. The mineralization of these chlorinated aromatic substrates to CO₂ and free Cl⁻ has been studied as a function of [Fe²⁺] and [HClO₄]. Increasing the concentration of Fe²⁺ enhances the decomposition process, while an increase in the concentration of HClO₄, inhibits the reaction. The presence of Fe³⁺ alone (without any Fe²⁺) with H₂O₂ has no effect on the degradation of the chlorophenols. In all cases, the stoichiometric quantity of free Cl⁻ was obtained at the completion of the decomposition reaction; but the rates of disappaearance of the chlorophenol and of the formation of the Cl⁻ are not similar. This suggests that some chlorinated aliphatic species may be formed as possible intemediates.     

Testing the extended biotic index in Slovakia: consistency, advantages, and limitations versus the saprobic assessment method of water quality.

The European Union Water Framework Directive requires the achievement of environmental objectives for the ecological quality of water bodies. A comparable implementation of the Directive throughout member countries of the European Union is necessary to verify equal protection of surface waters. The Directive specifies that member states determine ecological quality by means of biological indices. To improve comparability of water quality assessment, this research carried out an intercalibration trial between the Slovak Saprobic Index and the Italian protocol of the Extended Biotic Index, as part of a cooperative program between Italy and the Slovak Republic. When assessing streams with no or low pollution, statistics showed similar results for both methods. In contrast, the comparison of indices was not accurate in the case of severely affected waters. Reliable conversion formulas are feasible to transform the Italian Extended Biotic Index into the Slovak Saprobic Index, and not vice versa.     

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.     

Nitration and hydroxylation of benzene in the presence of nitrite/nitrous acid in aqueous solution

This paper studies the nitration and hydroxylation of benzene in the presence of nitrite/nitrous acid in aqueous solution, both in the dark upon addition of hydrogen peroxide and under 360 nm irradiation. In both cases the detected transformation intermediates were phenol (P), nitrobenzene (NB), 2-nitrophenol (2NP) and 4-nitrophenol (4NP). P and NB directly form from benzene, and the initial formation rate of P is at least an order of magnitude higher than that of NB. In our experiments nitrophenols arise from P nitration, as can be inferred by their time evolution and isomer ratio (2NP:4NP=60:40, 3NP below detection limit). Nitrophenols may also form upon hydroxylation of NB, but in a different ratio (2NP:3NP:4NP=45:30:25). The detection of 3NP is thus a marker for the hydroxylation of NB, since this isomer is not formed in P nitration processes. The formation rates of P and NB increase with decreasing pH, both in the presence of HNO₂ + H₂O₂ in the dark (which produce HOONO) and in the presence of NO₂⁻/HNO₂ under irradiation. In the former case the pH dependence reflects the formation rate of HOONO. In the case of the irradiation experiments the pH effect can be accounted for by the higher molar absorbivity and photolysis quantum yield of nitrous acid when compared with nitrite. Interestingly, benzene does not react with HNO₂ alone in the dark. An important feature of benzene nitration in the presence of NO₂⁻/HNO₂ under irradiation is that the process is not inhibited by the addition of hydroxyl scavengers, differently from the case of phenol nitration. This finding indicates that nitrite irradiation might lead to the nitration of certain aromatic compounds in natural waters even in the presence of natural hydroxyl scavenging agents, which are usually thought to limit the environmental role of many photochemical processes.     

Comparison of different probe molecules for the quantification of hydroxyl radicals in aqueous solution

We show that the transformation of benzene into phenol is a more selective probe for the hydroxyl radical than the transformation of nitrobenzene or the generation of 4-hydroxybenzoic acid from benzoic acid. The benzene to phenol system showed adequate performance as a probe upon irradiation of lake water samples and humic acids. We show that the use of nitrobenzene and benzoic acid as hydroxyl probes should be avoided because of poor selectivity. Moreover, all the tested probe molecules underwent important interference by irradiated antraquinone-2-sulphonate, and considerably overestimated the formation of the hydroxyl radicals.     

Adsorption and desorption variability of four herbicides used in paddy rice production

This investigation was performed to determine the effect of physicochemical soil properties on penoxsulam, molinate, bentazon, and MCPA adsorption–desorption processes. Four soils from Melozal (35° 43′ S; 71° 41′ W), Parral (36° 08′ S; 71° 52′ W), San Carlos (36° 24′ S; 71° 57′ W), and Panimavida (35° 44′ S; 71° 24′ W) were utilized. Herbicide adsorption reached equilibrium after 4 h in all soils. The Freundlich L-type isotherm described the adsorption process, which showed a high affinity between herbicides and sorption sites mainly because of hydrophobic and H-bonds interaction. Penoxsulam showed the highest adsorption coefficients (4.23 ± 0.72 to 10.69 ± 1.58 mL g^?1) and were related to soil pH. Molinate showed K_d values between 1.72 ± 0.01 and 2.3 ± 0.01 mL g^?1and were related to soil pH and organic matter, specifically to the amount of humic substances. Bentazon had a high relationship with pH and humic substances and its K_d values were the lowest, ranging from 0.11 ± 0.01 to 0.42 ± 0.01 mL g^?1. MCPA K_d ranged from 0.14 ± 0.02 to 2.72 ± 0.01 mL g^?1, however its adsorption was related to humic acids and clay content. According to these results, the soil factors that could explain the sorption process of the studied herbicides under paddy rice soil conditions, were principally humic substances and soil pH. Considering the sorption variability observed in this study and the potential risk for groundwater contamination, it is necessary to develop weed rice management strategies that limit use of herbicides that exhibit low soil adsorption in areas with predisposing conditions to soil leaching.     

Neuro-fuzzy and neural network systems for air quality control

In order to define efficient air quality plans, Regional Authorities need suitable tools to evaluate both the impact of emission reduction strategies on pollution indexes and the costs of such emission reductions. The air quality control can be formalized as a two-objective nonlinear mathematical problem, integrating source–receptor models and the estimate of emission reduction costs. Both aspects present several complex elements. In particular the source–receptor models cannot be implemented through deterministic modelling systems, that would bring to a computationally unfeasible mathematical problem. In this paper we suggest to identify source–receptor statistical models (neural network and neuro-fuzzy) processing the simulations of a deterministic multi-phase modelling system (GAMES). The methodology has been applied to ozone and PM10 concentrations in Northern Italy. The results show that, despite a large advantage in terms of computational costs, the selected source–receptor models are able to accurately reproduce the simulation of the 3D modelling system.     

Assessing the transformation kinetics of 2- and 4-nitrophenol in the atmospheric aqueous phase. Implications for the distribution of both nitroisomers in the atmosphere

Different transformation processes for nitrophenols in the atmospheric aqueous phase were considered to assess their relative importance, and their ability to account for the higher occurrence of 4-nitrophenol (4NP) compared to 2-nitrophenol (2NP) in the atmosphere. The importance of the different processes was in the order ^?OH > ^?NO₃ > direct photolysis > nitration to 2,4-dinitrophenol. 2NP is more reactive than 4NP with the hydroxyl radical, but the difference is low. Accordingly, such a process could account for the higher atmospheric occurrence of 4NP only if the observed atmospheric nitrophenols were what was left of an almost complete degradation by ^?OH. This would imply the unlikely scenario that the known nitrophenol sources to the atmosphere were only a limited fraction of the actual ones. A more likely, tentative possibility would be connected with the higher occurrence of 4NP on particles. If the reactivity order of nitrophenols in the atmospheric compartments was water droplets > gas phase > particles, particulate matter could act as a reservoir of 4NP. 2NP would undergo degradation in gas phase or solution at a higher rate than 4NP on particles, which could decrease the atmospheric levels of 2NP below those of 4NP.     

Low to negligible photoactivity of lake-water matter in the size range from 0.1 to 5 μm

We found that the photochemical generation of reactive transients such as singlet oxygen and triplet states upon irradiation of different lake water samples is mostly accounted for by components smaller than 0.10 μm. Larger components often showed a much lower absorption and/or scattering of radiation compared with the smaller ones, with one exception where the minor to negligible photochemical activity of larger species was associated with significant radiation absorption/scattering. It is also shown that filtration of the lake water samples at 0.10 μm was able to effectively remove the suspended particles, differently from the usually suggested filtration at 0.45 μm.     

Enhancement by anthraquinone-2-sulphonate of the photonitration of phenol by nitrite: implication for the photoproduction of nitrogen dioxide by coloured dissolved organic matter in surface waters

Anthraquinone-2-sulphonate (AQ2S) under UVA irradiation is able to oxidise nitrite to (·)NO(2) and to induce the nitration of phenol. The process involves the very fast reactions of the excited triplet state (3)AQ2S(*) and its 520-nm absorbing exciplex with water, at different time scales (ns and μs, respectively). Quinones are ubiquitous components of coloured dissolved organic matter (CDOM) in surface waters and AQ2S was adopted here as a proxy of CDOM. Using a recently developed model of surface-water photochemistry, we found that the oxidation of nitrite to (·)NO(2) by (3)CDOM(*) could be an important (·)NO(2) source in water bodies with high [NO(2)(-)] to [NO(3)(-)] ratio, for elevated values of column depth and NPOC.