Polycyclic aromatic hydrocarbons sorption on soils: some anomalous isotherms.

The sorption of four polycyclic aromatic hydrocarbons (PAHs), namely acenaphthene (Ac), phenanthrene (Ph), anthracene (An), and fluoranthene (Fl), on soil has been investigated. The kinetics of the sorption is characterised by the presence of two distinct periods. A fast initial stage followed by a second slower sorption process. Various kinetic models (i.e., Elvoich, Lagergren, second order and double exponential models) have been used to fit experimental data. The sorption equilibrium of individual PAHs has been assessed in the 298-333 K temperature range. Unlike Ac, Ph at 333 K and An and Fl at any temperature showed anomalous isotherms. The reason seems to rely on the "trapping" of dissolved PAHs by soil organic matter (SOM) released to water. This abnormal trend was not experienced when the isotherms were obtained for four PAHs mixture. Apparently, the most soluble Ac was capable of binding all the released material so no effect was thereafter observed.

Kinetic modelling of aqueous atrazine ozonation processes in a continuous flow bubble contactor.

The ozonation of atrazine in different waters (ultrapure and surface waters) has been studied in continuous bubble contactors with kinetic modelling purposes. Three ozonation processes have been considered: ozonation alone and combined with hydrogen peroxide or UV radiation. The kinetic models are based on a molecular and free radical mechanism of reactions, reaction rate and mass transfer data and non-ideal flow analysis models for gas and water phases through the contactors (the tanks in series model and the dispersion model). The models predict well the experimental concentrations of atrazine, dissolved ozone and hydrogen peroxide both at non-steady state and steady state regimes. From both experimental and calculated results, atrazine conversions are observed to be highly dependent on the nature of water where ozonation is carried out. As far as removal of atrazine and oxidation intermediates are concerned, ozone combined with UV radiation resulted in the most effective ozonation process among the three studied.

Chemical and photochemical degradation of acenaphthylene. Intermediate identification.

Removal of acenaphthylene from water has been carried out by means of different treatments combining UV radiation, ozone and hydrogen peroxide. Ozonation alone or in conjunction with hydrogen peroxide (10(-3) M) resulted in the highest elimination rates. Thus, conversions as high as 95-100% were obtained in less than 3 min with an ozone dose of 4.1x10(-3) mol O(3) h(-1) (flow rate 2x10(-2) m(3) h(-1)). Slightly lower efficiencies were experienced when using systems containing UV radiation. By considering the kinetics of the direct photolysis of acenaphthylene and the UV/H(2)O(2) system the photochemical reaction quantum yield φ(A) (4.0+/-0.1x10(-3) mol/photon) and the rate constant of the reaction of acenaphthylene with the hydroxyl radical k(OH,A) (8.0+/-0.5x10(9) M(-1) s(-1)) were calculated. Intermediates identified by GC/MS were in many cases similar regardless of the oxidation treatment used. Most of these by-products constituted oxygenated species of the parent compound (mainly ketones, aldehydes and carboxylic acids) that further degraded to low molecular, harmless end products.

Atrazine removal by ozonation processes in surface waters.

Atrazine (6-chloro-N-ethyl-N'-isopropyl-1,3,5-triazinedyl-2,4-diamine) was treated with ozone alone and in combination with hydrogen peroxide or UV radiation in three surface waters. Experiments were carried out in two bubble reactors operated continuously. Variables investigated were the ozone partial pressure, temperature, pH, mass flow ratio of oxidants fed: hydrogen peroxide and ozone and the type of oxidation including UV radiation alone. Residence time for the aqueous phase was kept at 10 min. Concentrations of some intermediates, including deethylatrazine, deisopropylatrazine and deethyldeisopropylatrazine, were also followed. The nature of water, specifically the alkalinity and pH were found to be important variables that affected atrazine (ATZ) removal. Surface waters with low alkalinity and high pH allowed the highest removal of ATZ to be reached. There was an optimum hydrogen peroxide to ozone mass flow ratio that resulted in the highest ATZ removal in each surface water treated. This optimum was above the theoretical stoichiometry of the process. Therefore, to reach the maximum removal of ATZ in a O3/H2O2 process, more hydrogen peroxide was needed in the surface waters treated than in ultrapure water under similar experimental conditions. In some cases, UV radiation alone resulted in the removal of ATZ higher than ozonation alone. This was likely due to the alkalinity of the surface water. Ozonation and UV radiation processes yield different amounts of hydrogen peroxide. Combined ozonations (O3/H2O2 and O3/UV) lead to ATZ removals higher than single ozonation or UV radiation but the formation of intermediates was higher.