Oxidative regeneration of toluene-saturated natural zeolite by gaseous ozone: the influence of zeolite chemical surface characteristics.

In this study, the effect of zeolite chemical surface characteristics on the oxidative regeneration of toluene saturated-zeolite samples is investigated. A Chilean natural zeolite (53% clinoptilolite, 40% mordenite and 7% quartz) was chemically modified by acid treatment with hydrochloric acid and by ion-exchange with ammonium sulphate. Thermal pre-treatments at 623 and 823K were applied and six zeolite samples with different chemical surface characteristics were generated. Chemical modification of natural zeolite followed by thermal out-gassing allows distinguishing the role of acidic surface sites on the regeneration of exhausted zeolites. An increase in Brønsted acid sites on zeolite surface is observed as a result of ammonium-exchange treatment followed by thermal treatment at 623K, thus increasing the adsorption capacity toward toluene. High ozone consumption could be associated to a high content of Lewis acid sites, since these could decompose ozone into atomic active oxygen species. Then, surface oxidation reactions could take part among adsorbed toluene at Brønsted acid sites and surface atomic oxygen species, reducing the amount of adsorbed toluene after the regenerative oxidation with ozone. Experimental results show that the presence of adsorbed oxidation by-products has a negative impact on the recovery of zeolite adsorption capacity.

Natural zeolite reactivity towards ozone: the role of compensating cations.

Among indoor pollutants, ozone is recognised to pose a threat to human health. Recently, low cost natural zeolites have been applied as alternative materials for ozone abatement. In this work, the effect of compensating cation content of natural zeolite on ozone removal is studied. A Chilean natural zeolite is used here as starting material. The amount of compensating cations in the zeolite framework was modified by ion exchange using an ammonium sulphate solution (0.1 mol L(-1)). Characterisation of natural and modified zeolites were performed by X-ray powder diffraction (XRD), nitrogen adsorption at 77K, elemental analysis, X-ray fluorescence (XRF), thermogravimetric analysis coupled with mass spectroscopy (TGA-MS), and temperature-programmed desorption of ammonia (NH(3)-TPD). Ozone adsorption and/or decomposition on natural and modified zeolites were studied by diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS). Results show that the zeolite compensating cation content affects ozone interaction with zeolite active sites. Ammonium ion-exchange treatments followed by thermal out-gassing at 823 K, reduces ozone diffusion resistance inside the zeolite framework, increasing ozone abatement on zeolite surface active sites. Weak and strong Lewis acid sites of zeolite surface are identified here as the main active sites responsible of ozone removal.

Catalytic ozone aqueous decomposition promoted by natural zeolite and volcanic sand.

Chemical oxidation using ozone in the presence of appropriate catalysts offers an attractive option for removing poorly biodegradable pollutants. However, the effect of such catalysts on ozone aqueous decomposition is not well documented. This study compares experimental results on ozone aqueous decomposition promoted by zeolite and volcanic sand. These are two low costs natural materials identified as suitable catalysts for heterogeneous ozonation. The effects of pH (2-8) and free radical scavengers (acetic acid) on the dissolved ozone decay rate are evaluated at laboratory scale. Results show that the ozone decay rate increases in the presence of natural materials tested here. Under alkaline conditions, the effect of free radical scavengers on ozone self-decomposition is significantly reduced when such materials were present, particularly in the case of volcanic sand. Results suggest that ozone aqueous decomposition in the presence of zeolite and volcanic sand take place mainly on the natural material surface. The presence of metal oxides in zeolite and volcanic sand might catalyse ozone decomposition into more active radicals, thus enhancing the oxidation of organic pollutant.

Heterogeneous and homogeneous catalytic ozonation of benzothiazole promoted by activated carbon: kinetic approach.

Ozone oxidation combined with activated carbon adsorption (O(3)/AC) has recently started to be developed as a single process for water and wastewater treatment. While a number of aspects of aqueous ozone decomposition are well understood, the importance and relationship between aqueous ozone decomposition and organic contaminant degradation in the presence of activated carbon is still not clear. This study focuses on determining the contribution of homogeneous and heterogeneous reactions to organic contaminants removal in O(3)/AC system. Benzothiazole (BT) was selected as a target organic pollutant due to its environmental concern. A reactor system based on a differential circular flow reactor composed by a 19 cm(3) activated carbon fixed bed column and 1 dm(3) storage tank was used. Ozone was produced from pure and dry oxygen using an Ozocav ozone generator rated at 5 g O(3)h(-1). Experimental results show that BT removal rate was proportional to activated carbon dosage. Activated carbon surface contribution to BT oxidation reactions with ozone, increased with pH in absence of radical scavengers. The radical reaction contribution within the pH range 2-11 accounted for 67-83% for BT removal in O(3)/AC simultaneous treatment. Results suggest that at pH higher than the pH of the point of zero charge of the activated carbon dissociated acid groups such as carboxylic acid anhydrides and carboxylic acids present on activated carbon surface could be responsible for the observed increase in the ozone decomposition reaction rate. A simplified mechanism and a kinetic scheme representing the contribution of homogeneous and heterogeneous reactions on BT ozonation in the presence of activated carbon is proposed.

Analysis of aerosol particles and coarse particulate matter concentrations in Chillán, Chile, 2001-2003.

Daily particle samples were collected in Chillán, Chile, at six urban locations from September 1, 2001, through September 30, 2003. Aerosol samples were collected using monitors equipped with a Sierra Andersen 246-b cyclone inlet on Teflon filters. Average concentrations of coarse particulate matter (PM10) for the 2001-2003 period ranged from 43.4 microg/m3 to 81.8 microg/m3 across the six sites. Annual PM10 concentration levels exceeded the European Union concentration limits. Mean PM10 levels during the cold season (April through September) were more than twice as high as those observed in the warm season (October through March). Average contributions to PM10 from organic matter, soil dust, nitrate (NO3-), elemental carbon, ammonium (NH4+), and sulfate (SO4(2-)) were 31%, 27%, 11%, 8%, 7%, and 5%, respectively. The chemical analyses indicated that carbonaceous substances were the most abundant components of PM10 in cold months, whereas crustal material was the most abundant component of PM10 during warm months. Higher concentration levels were observed in the downtown area suggesting a clear anthropogenic origin, whereas in the rural sites the source was mainly natural, such as resuspended soil dust associated with traffic on unpaved roads and agricultural activities.

A study of the particulate matter PM10 composition in the atmosphere of Chillán, Chile.

Inhalable particulate matter (PM10) concentrations were measured over 24-h intervals at six different urban sites in the city of Chillán from September 2001 to April 2003. Sampling locations were selected to represent central city, commercial, residential, and industrial portions of the city. Chemical composition of PM10 was performed to samples of 47 mm diameter Teflon membranes within the city of Chillán. The spatial and temporal variability of the chemical composition of PM10 was evaluated taking into account additional data from meteorology and further air pollutants. The majority of PM mass was comprised of carbon, nitrate, sulfate, ammonium, and crustal components but in different proportion on different days and at different sites. The chemical analyses showed that carbonaceous substances and crustal material were the most abundant component of PM10 during the winter and summer, respectively. The concentrations of PM10 were higher during the cold season than during the warm season. The PM10 concentrations were higher in the downtown area of the city of Chillán, where also the chemical composition was more variable due to urban traffic and other anthropogenic sources.