Aromatic contamination

Among the spectroscopic methods applicable to polysaccharides, u.v. spectrophotometry is of little value for characterizing heparin, whose main, electronic chromophore (the C02 group) displays a band at 220 nm, that is, in a region where all glycosaminoglycans absorb (also through their N-acetyl chromophores), and where minor proportions of unsaturated or aromatic contaminants cause serious interference.77 With pure heparin preparations, the carboxylate chromophore is most useful for chiroptical measurements, and a semi-quantitative evaluation of the extent of N-acetylation of 2-amino-2-deoxy-D-glucose residues is also possible.78... 

There are several chemical compounds found in the waste waters of a wide variety of industries that must be removed because of the danger they represent to human health. Among the major classes of contaminants, several aromatic molecules, including phenols and aromatic amines, have been reported. Enzymatic treatment has been proposed by many researchers as an alternative to conventional methods. In this respect, PX has the ability to coprecipitate certain difficult-to-remove contaminants by inducing the formation of mixed polymers that behave similarly to the polymeric products of easily removable contaminants. Thus, several types of PX, including HRP C, LiP, and a number of other PXs from different sources, have been used for treatment of aqueous aromatic contaminants and decolorization of dyes. Thus, LiP was shown to mineralize a variety of recalcitrant aromatic compounds and to oxidize a number of polycyclic aromatic and phenolic compounds. Furthermore, MnP and a microbial PX from Coprinus macrorhizus have also been observed to catalyze the oxidation of several monoaromatic phenols and aromatic dyes (Hamid and Khalil-ur-Rehman 2009). 

Lovley DR, Beadecker M, Lonergan D, et al. 1989. Oxidation of aromatic contaminants coupled to microbial iron reduction. Nature 339 297-9. 

The photocatalyzed oxidation of gas-phase contaminants in air has been demonstrated for a wide variety of organic compounds, including common aromatics like benzene, toluene, and xylenes. For gas-phase aromatic concentrations in the sub-lOO-ppm range, typical of common air contaminants in enclosed spaces (office buildings, factories, aircraft, and automobiles), photocatalytic treatment leads typically to complete oxidation to CO2 and H2O. This generality of total destruction of aromatic contaminants at ambient temperatures is attractive as a potential air purification and remediation technology. 

Chlorinated aromatics are primarily of interest in the liquid, rather than gas, phase and will not be covered in detail. However, chlorinated aromatic contaminants, particularly various chlorophenols, represent a significant class of water contaminants, and considerable research into the photocatalytic degradation of these materials has been conducted in recent years [29-35]. Many chlorinated aromatics are resistant to biological degradation, allowing them to accumulate in the environment and persist for long periods of time. Some are known to have significant. 

A. Dark Adsorption of Aromatic Contaminants onto TiO2... 

The quantity of aromatic contaminants that adsorb onto TiO2 surfaces is also relatively low. d Hennezel and Ollis [47] measured the dark adsorption of the BTEX compounds at a gas-phase concentration of 50 mg/m . Benzene displays the lowest dark adsorption, followed by ethylbenzene. Higher dark adsorption was observed for toluene and xylenes. At 50 mg/m, the dark adsorption of m-xylene was nearly 10 times that of benzene (Table 1). 

Dark adsorption measurements made for a variety of compounds by d Hen-nezel and Ollis [47] displayed a considerable range in the amount of material adsorbed onto TiO2 catalyst surfaces. For gas-phase contaminant concentrations of 50 mg/m and a relative humidity of 7%, dark adsorption measurements for aldehydes and alcohols show approximately 10 times more material adsorbing than do aromatic contaminants (Table 1). Similarly, adsorption isotlierms gener-... 

In all four cases, tlie initial reaction rates at the start of illumination in the continuous-feed photoreactor were higher than the pseudo-steady-state reaction rates the reaction rates declined over time until pseudo-steady-state operation was achieved. Tliis apparent deactivation phenomenon, often observed with aromatic contaminants, is discussed in Sec. III.E. In a transient reaction system, the time required to reach pseudo-steady-state operation also appears to increase in the same order as the reaction rates. For example, for the continuous photocatalytic oxidation of aromatic contaminants at 50 mg/m in a powder-layer photoreactor, the time required for pseudo-steady-state operation to be achieved was reported to be approximately 90 min for benzene, 120 min for toluene, and as long as 6 hr for wz-xylene [50,51]. Under such conditions, the difference in reaction rates between the aromatic contaminants is magnified by the fact that the more reactive aromatics retain their higher transient reaction rates for longer periods (Fig. 7). 

Most photocatalytic studies conducted at low aromatic concentrations report no detectable concentrations of gas-phase intermediates [12,17,18]. Traces of intermediates may be present in the gas phase, but at levels below the detection limits of the analytical instruments employed in these studies. There is evidence, however, for either reaction intermediates or reaction by-products on the catalyst surface, even at these low concentrations. Catalyst discoloration, typically a yellowish or brownish color, is often reported following the photocatalytic oxidation of aromatic contaminants at low to moderate gas-phase concentrations [3,4,7,17,52]. These intermediates or reaction by-products may be largely trapped on the catalyst surface by the higher affinity of oxygenated species, like alcohols and aldehydes, for TiO, surfaces when compared to the aromatic parent compounds. 

As the feed concentrations of aromatic contaminants are increased, low concentrations of gas-phase intermediate products are occasionally reported. During the photocatalytic oxidation of aromatic contaminants in the 25-500-ppm range, some researchers have observed up to several ppm of gas-phase intermediate products. For example, Ibusuki and Takeuchi [8] detected 1-2 ppm of benzaldehyde in the gas phase following photocatalytic oxidation of 80 ppm of toluene in a batch-reactor system. Even at moderate aromatic feed concentrations, gas-phase intermediate concentrations may be too low to be detected reliably. 

Humidity has a significant influence on the photocatalytic oxidation of aromatic contaminants in the gas phase. This is of particular interest, because commercial photocatalytic systems will be required to operate under a broad range of relative-humidity levels. The specific influence of relative humidity on the photocatalytic reaction has generally proved rather difficult to quantify because water has a dual role It may compete with contaminants for surface adsorption sites (a negative influence) and it plays a role in the regeneration of surface hydroxyl groups during photocatalysis (a positive influence). 

The presence of gas-phase water is generally beneficial to the photocatalytic oxidation of aromatic contaminants. In continuous photoreactors, humidity appears to prolong catalyst activity and delay or prevent catalyst deactivation. The effects of humidity on reaction rates, however, appear to vary, depending on the aromatic contaminant concentration and the humidity level. For example. Petal and Ollis [18] examined the continuous photocatalytic oxidation of m-xylene in a powder-layer photoreactor at several different relative humidity levels. The m-xylene photo-oxidation reaction rate was observed to increase for gas-phase water concentrations up to 1000 mg/m (—7% relative humidity). Increasing the humidity level further (up to 5500 mg/m ) produced a gradual decrease in the observed reaction rate, possibly due to increased adsorption-site competition between xylene and water. The reported xylene removal rate for a water concentration of 5500 mg/m was approximately half that seen at 1000 mg/m. ... 

The possible accumulation of intermediates during the photocatalytic oxidation of aromatic contaminants has been studied with a variety of techniques, including temperature-progranuned desorption (TPD), oxidation (TPO), and hydrogenation (TPH), Fourier transform infrared analysis (FTIR), and extraction of adsorbed species with a variety of solvents. 

Neither Larson and Falconer [43] nor Blount and Falconer [54] definitely identified the compound or compounds responsible for the observed drop in catalyst activity during the photocatalytic oxidation of aromatic contaminants. Some possible intermediates, including benzaldehyde and benzoic acid, were considered, but were ruled out as being die species responsible for the apparent deactivation of the photocatalysts. 

Mendez-Roman and Cardona-Martinez [55] examined titanium dioxide catalysts with FTIR spectroscopy during the photocatalytic oxidation of toluene. Reaction intermediates, believed to be benzaldehyde and benzoic acid, were reported to accumulate on catalyst samples. This accumulation of intermediates was found to be reduced in the presence of gas-phase water. Mendez-Roman and Cardona-Martinez concluded that toluene appeared to be converted to benzaldehyde, which was then oxidized further to form benzoic acid. They suggested that the accumulation of benzoic acid led to the observed apparent catalyst deactivation. Other researchers, however, have argued that benzoic acid is unlikely to be the compound responsible for apparent deactivation in the photocatalytic oxidation of aromatics. For example, Larson and Falconer [43] concluded, based on higher CO2 evolution rates for benzoic acid relative to toluene during photooxidation, that benzoic acid was not sufficiently recalcitrant to be responsible for the deactivation seen with aromatic contaminants. 

Lewandowski and Ollis have proposed a simple kinetic model describing the transient photocatalytic oxidation of aromatic contaminants [50]. The model considered three chemical species an aromatic contaminant, preadsorbed onto the catalyst in the dark and refreshed continuously from the gas phase a strongly bound, recalcitrant reaction intermediate and final reaction products (CO or CO2), assumed for simplicity to be strictly gas-phase species. The model also assumed that two types of catalyst site were present on the photocatalyst surface, with the first suitable for the adsorption of aromatic contaminants, as well as reaction intermediates, and the second type considered to be more polar in nature, suitable only for adsorption of partially oxidized reaction intermediates. 

The presence of chlorine radical chain reactions in a photocatalytic reaction system may significantly increase reaction rates and photocatalytic efficiencies. These enhancements would appear to have the potential to overcome the shortcomings typically associated with the photocatalytic oxidation of aromatic contaminants if a chlorine radical chain reaction could be initiated in conjunction with an aromatic photocatalytic reaction and if the chlorine radicals were capable of reacting with (and thus accelerating the conversion of) the aromatic contaminant of interest. Two potential configurations for combining chlorine radical promotion with the photocatalytic oxidation of aromatic contaminants have been examined in some detail mixed contaminant feeds and prechlorinated catalysts. 

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