Oxidation polyaromatic hydrocarbons

Parallel reactions involving selectivity are important in most chemical processes, where they typically control the formation of minor products or pollutants. In combustion, pollutants such as nitrogen oxides, polyaromatic hydrocarbons, and soot are formed by reactions that compete with parallel steps, leading to less harmful products. 

Wang Y, Vazquez-Duhalt R, Pickard MA (2003) Manganese-lignin peroxidase hybrid from Bjerkandera adusta oxidizes polyaromatic hydrocarbons more actively in the absence of manganese. Can J Microbiol 49 675-682... 

Fig. 2. Overall schematic of solid fuel combustion (1). Reaction sequence is A, heating and drying B, solid particle pyrolysis C, oxidation and D, post-combustion. In the oxidation sequence, left and center comprise the gas-phase region, tight is the gas—solids region. Noncondensible volatiles include CO, CO2, CH4, NH, H2O condensible volatiles are C-6—C-20 compounds oxidation products are CO2, H2O, O2, N2, NO, gaseous organic compounds are CO, hydrocarbons, and polyaromatic hydrocarbons (PAHs) and particulates are inerts, condensation products, and solid carbon products.

In densely populated areas, traffic is responsible for massive exhausts of nitrous oxides, soot, polyaromatic hydrocarbons, and carbon monoxide. Traffic emissions also markedly contribute to the formation of ozone in the lower parts of the atmosphere. In large cities, fine particle exposure causes excess mortality which varies between one and five percent in the general population. Contamination of the ground water reservoirs with organic solvents has caused concern in many countries due to the persistent nature of the pollution. A total exposure assessment that takes into consideration all exposures via all routes is a relatively new concept, the significance of which is rapidly increasing. 

Although the ECL phenomenon is associated with many compounds, only four major chemical systems have so far been used for analytical purposes [9, 10], i.e., (1) the ECL of polyaromatic hydrocarbons in aqueous and nonaqueous media (2) methods based on the luminol reaction in an alkaline solution where the luminol can be electrochemically produced in the presence of the other ingredients of the CL reaction (3) methods based on the ECL reactions of rutheni-um(II) tra(2,2 -bipyridinc) complex, which is used as an ECL label for other non-ECL compounds such as tertiary amines or for the quantitation of persulfates and oxalate (this is the most interesting type of chemical system of the four) and (4) systems based on analytical properties of cathodic luminescence at an oxide-coated aluminum electrode. 

Much of the study of ECL reactions has centered on two areas electron transfer reactions between certain transition metal complexes, and radical ion-annihilation reactions between polyaromatic hydrocarbons. ECL also encompasses the electrochemical generation of conventional chemiluminescence (CL) reactions, such as the electrochemical oxidation of luminol. Cathodic luminescence from oxide-covered valve metal electrodes is also termed ECL in the literature, and has found applications in analytical chemistry. Hence this type of ECL will also be covered here. 

Haapakka and Kankare have studied this phenomenon and used it to determine various analytes that are active at the electrode surface [44-46], Some metal ions have been shown to catalyze ECL at oxide-covered aluminum electrodes during the reduction of hydrogen peroxide in particular. These include mercu-ry(I), mercury(II), copper(II), silver , and thallium , the latter determined to a detection limit of <10 10 M. The emission is enhanced by organic compounds that are themselves fluorescent or that form fluorescent chelates with the aluminum ion. Both salicylic acid and micelle solubilized polyaromatic hydrocarbons have been determined in this way to a limit of detection in the order of 10 8M. 

Abbreviations PAH = polyaromatic hydrocarbon, TCDD = Tetrachlorodibenzo-p-dioxin, PCB = polychlorinated biphenyl, PBB = polybrominated biphenyl, TBTO = tributyltin oxide, DBTO = dibutyltin oxide, TPT = triphenyltin. 

Hawthorne et al. [53] compared supercritical extraction with chlorodifluoromethane, nitrous oxide and carbon dioxide for the extraction of polychlorobiphenyls and polyaromatic hydrocarbons from soil. Chlorodifluoromethane provided the highest recoveries while methanol modified carbon dioxide gave a 90% recovery of polychlorobiphenyls from soil. 

Site-specific risk analysis of oxidation by-product emissions, including dioxins and nitrated polyaromatic hydrocarbons. 

The marine environment acts as a sink for a large proportion of polyaromatic hydrocarbons (PAH) and these compounds have become a major area of interest in aquatic toxicology. Mixed function oxidases (MFO) are a class of microsomal enzymes involved in oxidative transformation, the primary biochemical process in hydrocarbon detoxification as well as mutagen-carcinogen activation (1,2). The reactions carried out by these enzymes are mediated by multiple forms of cytochrome P-450 which controls the substrate specificity of the system (3). One class of MFO, the aromatic hydrocarbon hydroxylases (AHH), has received considerable attention in relation to their role in hydrocarbon hydroxylation. AHH are found in various species of fish (4) and although limited data is available it appears that these enzymes may be present in a variety of aquatic animals (5,6,7,8). 

Metabolic degradation of polyaromatic hydrocarbons is believed to involve oxidation with an activated oxygen species by an enzyme in aU aerobic organisms and also in... 

Because of the extensive reuse of combustion air in the process at Calaveras facility, the fabric filter exhaust is the only point of emissions for the kiln, clinker cooler, and raw mill. Exhaust gases from the fabric filter are monitored continuously for carbon monoxide, nitrogen oxides, and hydrocarbons. Calaveras has tested toxic pollutants while burning 20 percent TDF. Table 4-5 summarizes these test results, giving emission factors for metals, hazardous air pollutants, polyaromatic hydrocarbons, dioxins and... 

In an attempt to minimize overoxidation we explored the oxidation system m-chloroperbenzoic acid/NaHCC /CE C (34) with three thiophenes and three polyaromatic hydrocarbons. The results are summarized in Table II, where it is seen that the thiophenes are converted to their sulfones after only 30 minutes reaction time and the polyaromatic hydrocarbons are either unaffected by the oxidation or are oxidized much more slowly. The sulfones of the thiophenes listed in Table II are not oxidized further under these conditions. The thiophene content of Syncrude maltene was found to be 6.4% by the present method while the recovery was only 4.2% using the method of Willey et al. (25). Increasing the time of the oxidation reaction in the present procedure from 20 to 60 minutes had only a minor ( 10%) effect on the yield of isolated thiophenes. 

Oxidation of phenols, dyes, and polycyclic aromatic hydrocarbons [48,49], decolorization of Kraft bleaching effluents, binding of phenols and aromatic amines with humus [47] Transformation of phenols, aromatic amines, polyaromatic hydrocarbons, and other aromatic compounds, decolorization of Kraft bleaching effluents, treatment of dioxins, pyrene [86-89,114] Improved sludge dewatering [59]... 

Paalme L., Irha N., Urbas E., Tsyban A., and Kirso U. (1990) Model studies of photochemical oxidation of carcinogenic polyaromatic hydrocarbons. Mar. Chem. 30, 105-111. 

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