Halogen production from aqueous tropospheric particles

Box model studies have been performed to study the role of aqueous phase chemistry with regard to halogen activation for marine and urban clouds and the marine aerosol as well. Different chemical pathways leading to halogen activation in diluted cloud droplets and highly concentrated sea salt aerosol particles are investigated. The concentration of halides in cloud droplets is significantly smaller than in sea-salt particles, and hence different reaction sequences control the overall chemical conversions. In diluted droplets radical chemistry involving OH, NO(3), Cl/Cl(2)(-)/ClOH(-), and Br/Br(2)(-)/BrOH(-) gains in importance and pH independent pathways lead to the release of halogens from the particle phase whereas the chemistry in aerosol particles with high electrolyte concentrations is controlled by non-radical reactions at high ionic strengths and relatively low pH values.For the simulation of halogen activation in tropospheric clouds and aqueous aerosol particles in different environments a halogen module was developed including both gas and aqueous phase processes of halogen containing species. This module is coupled to a base mechanism consisting of RACM (Regional Atmospheric Chemistry Mechanism) and the Chemical Aqueous Phase Radical Mechanism CAPRAM 2.4 (MODAC-mechanism). Phase exchange is described by the resistance model by Chemistry of Multiphase Atmospheric Systems, NATO ASI Series, 1986.It can be shown that under cloud conditions the bromine atom is mainly produced by OH initiated reactions, i.e. its concentration maximum is reached at noon. In contrast, the concentration level of chlorine atoms is linked to NO(3) radical chemistry leading to a smaller amplitude between day and night time concentrations.The contribution of radical processes to halogen atom formation in the particle phase is evident, e.g. by halogen atoms which undergo direct phase transfer. Furthermore, the application of the multiphase model for initial concentrations for sea-salt aerosols shows that the particle phase can act as a main source of halogen containing molecules (Cl(2), BrCl, Br(2)) which are photolysed in the gas phase to yield halogen atoms (about 70% of all Cl sources and more than 99% for Br).     

Arsenic(III) and iron(II) co-oxidation by oxygen and hydrogen peroxide: Divergent reactions in the presence of organic ligands

Iron-catalyzed oxidation of As(III) to As(V) can be highly effective for toxic arsenic removal via Fenton reaction and Fe(II) oxygenation. However, the contribution of ubiquitous organic ligands is poorly understood, despite its significant role in redox chemistry of arsenic in natural and engineered systems. In this work, selected naturally occurring organic ligands and synthetic ligands in co-oxidation of Fe(II) and As(III) were examined as a function of pH, Fe(II), H₂O₂, and radical scavengers (methanol and 2-propanol) concentration. As(III) was not measurably oxidised in the presence of excess ethylenediaminetetraacetic acid (EDTA) (i.e. Fe(II):EDTA < 1:1), contrasting with the rapid oxidation of Fe(II) by O₂ and H₂O₂ at neutral pH under the same conditions. However, partial oxidation of As(III) was observed at a 2:1 ratio of Fe(II):EDTA. Rapid Fe(II) oxidation in the presence of organic ligands did not necessarily result in the coupled As(III) oxidation. Organic ligands act as both iron speciation regulators and radicals scavengers. Further quenching experiments suggested both hydroxyl radicals and high-valent Fe species contributed to As(III) oxidation. The present findings are significant for the better understanding of aquatic redox chemistry of iron and arsenic in the environment and for optimization of iron-catalyzed arsenic remediation technology.     

Selective redox degradation of chlorinated aliphatic compounds by Fenton reaction in pyrite suspension

Selective redox degradation of chlorinated aliphatics by Fenton reaction in pyrite suspension was investigated in a closed system. Carbon tetrachloride (CT) was used as a representative target of perchlorinated alkanes and trichloroethylene (TCE) was used as one of highly chlorinated alkenes. Degradation of CT in Fenton reaction was significantly enhanced by pyrite used as an iron source instead of soluble Fe. Pyrite Fenton showed 93% of CT removal in 140 min, while Fenton reaction with soluble Fe(II) showed 52% and that with Fe(III) 15%. Addition of 2-propanol to the pyrite Fenton system significantly inhibited degradation of TCE (99% to 44% of TCE removal), while degradation of CT was slightly improved by the 2-propanol addition (80-91% of CT removal). The result suggests that, unlike oxidative degradation of TCE by hydroxyl radical in pyrite Fenton system, an oxidation by the hydroxyl radical is not a main degradation mechanism for the degradation of CT in pyrite Fenton system but a reductive dechlorination by superoxide can rather be the one for the CT degradation. The degradation kinetics of CT in the pyrite Fenton system was decelerated (0.13-0.03 min⁻¹), as initial suspension pH decreased from 3 to 2. The formation of superoxide during the CT degradation in the pyrite Fenton system was observed by electron spin resonance spectroscopy. The formation at initial pH 3 was greater than that at initial pH 2, which supported that superoxide was a main reductant for degradation of CT in the pyrite Fenton system.     

Decolorization and degradation of dyes with mediated fenton reaction.

A mediated Fenton system has been evaluated for decolorization of several types of dyes. The result shows that the Fenton system with a dihydroxybenzoic acid (DHBA) chelator-mediator effectively reduced the color of a diluted solution of Carta Yellow RW liquid, Carta Yellow G liquid, and Cartasol Red 2GF liquid dye to a colorless level after 90 minutes of treatment with 100 microM iron II (Fe[II]), 100 microM DHBA, and 10 mM hydrogen peroxide (H2O2) at room temperature. Our results show that compared to a neat Fenton process, the mediated Fenton decolorization process increased the production, and therefore the effective longevity, of hydroxyl radical (OH) species to increase the decolorization efficiency. Our results suggest that application of this system would also result in an increase in dissolved oxygen (DO) in solution, which in turn would result in reduction of chemical oxygen demand (COD), biochemical oxygen demand (BOD), and total organic carbon (TOC).     

Hydroxyl radical concentration profile in photo-Fenton oxidation process: generation and consumption of hydroxyl radicals during the discoloration of azo-dye Orange II

Dynamic behaviors of hydroxyl (OH) radical generation and consumption in photo-Fenton oxidation process were investigated by measuring OH radical concentration during the discoloration of azo-dye Orange II. The effects of operating parameters for photo-Fenton discoloration, i.e. dosages of H₂O₂ and Fe, initial dye concentration, solution pH and UV irradiation, on the generation and consumption of OH radicals playing the main role in advanced oxidation processes were extensively studied. The scavenger probe or trapping technique in which coumarin is scavenger of OH radical was applied to estimate OH radical concentration in the photoreactor during the photo-Fenton discoloration process. The OH radical generation was enhanced with increasing the dosages of Fenton regents, H₂O₂ and Fe. At the initial stage of photo-Fenton discoloration of Orange II, the OH radical concentration rapidly increased (Phase-I) and the OH radical concentration decreased after reaching of OH radical concentration at maximum value (Phase-II). The decrease in OH radical concentration started when the complete discoloration of Orange II was nearly achieved and the H₂O₂ concentration became rather low. The dynamic behavior of OH radical concentration during the discoloration of Orange II was found to be strongly linked with the change in H₂O₂ concentration. The generation of OH radical was maximum at solution pH of 3.0 and decreased with an increase of solution pH. The OH radical generation rate in the Fenton Process was rather slower than that in the photo-Fenton process.     

2-Chlorophenol induced hydroxyl radical production in mitochondria in Carassius auratus and oxidative stress--an electron paramagnetic resonance study

In our previous study, electron paramagnetic resonance (EPR) evidence of reactive oxygen species (ROS) production in Carassius auratus following 2-chlorophenol (2-CP) administration was provided. To further investigate the potential pathway of ROS production, liver mitochondria of C. auratus was isolated and incubated with 2-CP for 30 min. An EPR analysis indicated ROS was produced, and intensities of ROS increased with increasing concentrations of 2-CP. The ROS was then assigned OH by comparing with Fenton reaction. Either catalase or superoxide dismutase, extinguished OH completely in the mitochondria mixture. These facts suggested that O2(.-) and H2O2 contributed to the formation of OH in mitochondria in C. auratus stressed by 2-CP. Combining previous references and our own data, it is reasonable to suggest that 2-CP is first oxidized by H2O2 present in vivo to form phenoxyl radical under the catalytic action of cellular peroxidase (1); phenoxyl radical oxidizes mitochondria NADH to NAD in the presence of NADH (2); NAD reacts with oxygen in vivo to produce O2(.-) (3); O2(.-) is spontaneously dismutated by SOD to form H2O2 and O2, which creates a renewable supply of H2O2 as the initiators of the chain reactions until NADH is consumed (4); simultaneously with reaction (4), O2(.-) reacts with H2O2 to form OH radical via the Haber-Weiss reaction (5). A strong negative correlation (r=-0.9278, p<0.01) between glutathione (GSH) pool and OH production was observed after fish were i.p. injected with 2-CP (250 mg kg(-1)), indicating the depletion of GSH caused by OH.     

A new model of tropospheric hydroxyl radical concentrations

A chemistry model of the global troposphere is presented which focuses on the hydroxyl radical, OH. Global distributions of OH are calculated based on known chemical reaction pathways, experimentally measured values of precursor species O3, H2O, NOx (defined as NO+NO2), CO, CH4, and actinic flux (which includes the effects of cloud cover and O3 column absorption). Model grid resolution is 1 km in altitude by 10 degrees latitude, and zonally divided into land or ocean. Species are calculated as seasonal averages. Global annual mean OH in the troposphere (up to 14 km altitude) is calculated to be 9.2 x 10(5) molcm(-3) with averages of 9.8 x 10(5) in the northern hemisphere, and 8.5 x 10(5) in the southern hemisphere. Global CO and CH(4) oxidation rates by OH are calculated to be 1840 Tgyear(-1) and 580 Tgyear(-1), respectively. OH is found to be most sensitive to O3 and H2O concentrations, as well as to the photolysis rate of O3 to O1D. Sensitivity of CO and CH4 oxidation rates to cloud presence shows an inverse relationship to cloud amount and optical depth. Model results are shown to be consistent with results from two other published models.     

Effect of ethylenediamine-N,N′-disuccinic acid on Fenton and photo-Fenton processes using goethite as an iron source: optimization of parameters for bisphenol A degradation

The main disadvantage of using iron mineral in Fenton-like reactions is that the decomposition rate of organic contaminants is slower than in classic Fenton reaction using ferrous ions at acidic pH. In order to overcome these drawbacks of the Fenton process, chelating agents have been used in the investigation of Fenton heterogeneous reaction with some Fe-bearing minerals. In this work, the effect of new iron complexing agent, ethylenediamine-N,N'-disuccinic acid (EDDS), on heterogeneous Fenton and photo-Fenton system using goethite as an iron source was tested at circumneutral pH. Batch experiments including adsorption of EDDS and bisphenol A (BPA) on goethite, H₂O₂ decomposition, dissolved iron measurement, and BPA degradation were conducted. The effects of pH, H₂O₂ concentration, EDDS concentration, and goethite dose were studied, and the production of hydroxyl radical (^?OH) was detected. The addition of EDDS inhibited the heterogeneous Fenton degradation of BPA but also the formation of ^?OH. The presence of EDDS decreases the reactivity of goethite toward H₂O₂ because EDDS adsorbs strongly onto the goethite surface and alters catalytic sites. However, the addition of EDDS can improve the heterogeneous photo-Fenton degradation of BPA through the propagation into homogeneous reaction and formation of photochemically efficient Fe-EDDS complex. The overall effect of EDDS is dependent on the H₂O₂ and EDDS concentrations and pH value. The high performance observed at pH 6.2 could be explained by the ability of O ₂ ^?? to generate Fe(II) species from Fe(III) reduction. Low concentrations of H₂O₂ (0.1 mM) and EDDS (0.1 mM) were required as optimal conditions for complete BPA removal. These findings regarding the capability of EDDS/goethite system to promote heterogeneous photo-Fenton oxidation have important practical implications for water treatment technologies.     

Mercury and photochemistry in the marine boundary layer-modelling studies suggest the in situ production of reactive gas phase mercury

Following a modelling investigation of the role of the ambient aerosol in the cycling—that is the transport, transformation and deposition—of mercury in the atmosphere, the precise part played by the sea salt component of the marine aerosol in the remote marine boundary layer has been studied using a combination of models to describe the photolytic, gas phase and aqueous phase and heterogeneous chemistry of the marine boundary layer, in conjunction with inter phase mass transport and mercury chemistry. The role of the ocean in the emission of elemental mercury is, as yet, not entirely understood, but certainly the speciation of mercury deposited to the ocean surface is important as regards its re-emission. Models of mercury chemistry to date have tended to focus on cloud chemistry, and with good reason, as precipitation accounts for a large part of the global mercury deposition pattern; however, the composition of the marine aerosol is entirely different from that of cloud or fog droplets and the modelling studies here show that it plays a more local role being partially responsible for the gas phase speciation of mercury. The role of photochemical processes is investigated and particular attention is paid to halogen chemistry, as the chloride ion has been shown previously to have a notable effect on the concentration of oxidised mercury associated with particles, or better, solution droplets. The role of the sea salt component of the marine aerosol in the production of gas phase oxidised mercury species is described qualitatively and quantitatively.     

Light-induced formation of hydroxyl radicals in fog waters determined by an authentic fog constituent,hydroxymethanesulfonate

The determination of the photo-production rate of hydroxyl radical (OH) in atmospheric liquids is of fundamental importance to an understanding of atmospheric aquatic chemistry. Recently, several studies have been performed to examine the photo-chemical formation rate of OH in cloud and fog waters using a free radical quenching technique with addition of a relatively large concentration of organic compounds as an OH scavenger. The addition of free-radical scavenger chemicals may significantly alter the nature of the sample water and its OH production rate. In this paper, an authentic constituent, hydroxymethanesulfonate, is proposed as a free radical probe for the measurement of photo-chemical generation rate of OH in fog water. At 313 nm, an apparent quantum yield for the production of OH in a fog water was found to be 0.012+/-0.001, indicating that aqueous-phase photo-chemical processes could represent a significant and may be a dominant source of OH in atmospheric liquids.     

A model for tropospheric multiphase chemistry: application to one cloudy event during the CIME experiment

A multiphase box model for a remote environment of the troposphere has been developed with an explicit chemistry for both gas and aqueous phase. The model applied to a set of measurements performed by Voisin et al. (2000) during the European CIME experiment for a cloud event on 13th December 1997 at the top of the Puy de Dôme (France). The results of the simulation are compared to the measurements in order to follow the evolution of the ambient chemical composition as a function of the pH and of the varying water content. After verifying that the model retrieves the main features observed in the behavior of species in the cloud droplets, a detailed analysis of the simulated chemical regime is performed. It essentially discusses the sources and sinks of radical in aqueous phase, the relative importance of the oxidation pathways of volatile organic compounds by the main radicals and the conversion of S(IV) into S(VI) which seems to be influenced by the presence of peroxonitric acid, HNO₄, in aqueous phase in the environmental conditions that are considered with low H₂O₂. These numerical results are then compared with the theoretical study from Herrmann et al. (2000), who proposed a slightly different mechanism, including C2 chemistry and transition metal chemistry whereas they neglect some reaction pathways, such as the one involving OHCH₂O₂ radical. This double confrontation between model results and both real experimental data and numerical results from Herrmann et al. (1999c) underlines limitations of such modeling approach that does not include any dynamical or microphysical coupling but also demonstrates its capability to identify the main oxidants or reactants in aqueous phase in real environmental conditions more realistic than a purely theoretical approach. The originality of this study resides in the explicit and exhaustive ways the chemical reactions are treated in aqueous phase and in a first attempt to compare such a detailed chemical scheme to real environmental conditions.     

Degradation of Acid Orange 7 in aqueous solution by dioxygen activation in a pyrite/H2O/O2 system

Increasing attention has been paid to pyrite due to its ability to generate hydroxyl radicals in air-saturated solutions. In this study, the mineral pyrite was studied as a catalyst to activate molecular oxygen to degrade Acid Orange 7 (AO7) in aqueous solution. A complete set of control experiments were conducted to optimize the reaction conditions, including the dosage of pyrite, the AO7 concentration, as well as the initial pH value. The role of reactive oxygen species (ROS) generated by pyrite in the process was elucidated by free radical quenching reactions. Furthermore, the concentrations of Fe(II) and total Fe formed were also measured. The mechanism for the production of ROS in the pyrite/H₂O/O₂ system was that H₂O₂ was formed by hydrogen ion and superoxide anion (O₂ ^·?) which was produced by the reaction of pyrite activating O₂ and then reacted with Fe(II) dissolved from pyrite to produce ^·OH through Fenton reaction. The findings suggest that pyrite/H₂O/O₂ system is potentially practical in pollution treatment. Moreover, the results provide a new insight into the understanding of the mechanism for degradation of organic pollutants by pyrite.     

Formation of estrogenic products from environmental phthalate esters under light exposure

Phthalate esters (PEs) have been suspected to be environmental endocrine disruptors and the detailed mechanism remains unclear. The activities of these chemicals can be enhanced through chemical modification under the environmental conditions. We demonstrate that PEs acquire unequivocal estrogenic activity by light exposure. Through UV exposure of an aqueous PE solution, one active photoproduct, identified as 4-hydroxyPE (PE-4OH) based on its characteristic UV and mass spectra, was detected in an estrogen receptor alpha-dependent transactivation assay. PE-4OH was effectively generated by UV 290 nm. The PE-4OH production accompanied H2O2 generation in a UV dose-dependent manner. Both PE and UV irradiation were indispensable in the generation of H2O2. Addition of H2O2 to the PE solution increased PE-4OH production under UV irradiation. The PE-4OH production was also observed in the PE reaction with the Fenton reagent generating hydroxyl radical without UV irradiation. The proposed mechanism for PE-4OH production based on these results is such that by PE-mediated photosensitization H2O2 is generated from O2 and H+ and decomposed to hydroxyl radical, thus oxidizing the PE benzene ring. The PEs-4OH are remarkably active estrogenic products of PEs and would be involved in ER-mediated endocrine disruption.     

Optimizing electron spin resonance detection of hydroxyl radical in water

The parameters affecting the electron spin resonance (ESR) detection of hydroxyl free radical in water are studied and optimized. The hydroxyl radical is generated by the Fenton reaction with iron (II) ammonium sulfate and hydrogen peroxide reacting in a phosphate buffer using N-tert-butyl-alpha-phenylnitron as the spin trap. The concentrations of Fe²⁺, H₂O₂, and phosphate buffer are the parameters studied. The Taguchi method and the orthogonal experiment design were used to evaluate the effects of these parameters on the ESR signal intensity. By the analysis of the signal-to-noise ratio and the analysis of variance, the order of importance of the various parameters on the hydroxyl radical formation is determined for optimal ESR detection of hydroxyl radical. The results will help the development of water purification technologies using hydroxyl free radical as a green oxidant.     

Organosulfates from glycolaldehyde in aqueous aerosols and clouds: Laboratory studies

Secondary organic aerosol (SOA) formation is enhanced on acidic seed particles; SOA also forms during cloud processing reactions where acidic sulfate is prevalent. Recently several studies have focused on the identification of organosulfates in atmospheric aerosols or smog chamber experiments, and upon the mechanism of formation for these products. We identify several organosulfate products formed during the laboratory OH radical oxidation of dilute aqueous glycolaldehyde in the presence of sulfuric acid. We propose a radical–radical reaction mechanism as being consistent with formation of these products under our experimental conditions. Using a kinetics model we estimate that organosulfates account for less than 1% of organic matter formed from these precursors during cloud processing. However, in wet acidic aerosols, where precursors are highly concentrated and acidic sulfate makes up close to half of the aerosol mass, this radical–radical reaction could account for significant organosulfate production.     

The chemistry of atmospheric mercury: a review

The atmosphere is an important transient reservoir of mercury. In addition to its great capacity, the chemical processes transforming mercury between the elemental and divalent states strongly influence the transport characteristics and deposition rate of this toxic metal back to the ground. Modeling efforts to assess global cycling of mercury require an in-depth knowledge of atmospheric mercury chemistry. This review article provides selected physical and chemical properties of atmospheric mercury, and discusses the identified mercury transformation pathways mediated by ozone, S(IV), hydroperoxyl radical, hydroxyl radical, chlorine, nitrate radical and photolysis of Hg(II) complexes. Special attention is paid to the kinetics and mechanisms of the reactions interconverting mercury between elemental and divalent states. The significance and implications of each transformation pathway under atmospheric conditions are addressed. Future research areas that must be pursued to better understand the fate and transformation of mercury in the atmosphere are also projected.     

Phenol nitration upon oxidation of nitrite by Mn(III,IV) (hydr)oxides

An interesting aspect of the chemistry of nitrite is the possibility for this compound to interact with other environmental factors and many oxidising species, which results in the oxidation of nitrite to nitrogen dioxide. This is a potentially interesting process that can lead to the formation of nitroaromatic compounds in the environment. In previous papers we have shown that nitrite can interact with dissolved Fe(III) and nitrate under irradiation, Fenton and heterogeneous photo-Fenton reagents, and semiconductor oxides such as TiO2, alpha-Fe2O3, and beta-FeOOH under irradiation. This paper reports on the interaction between nitrite/nitrous acid and the Mn(III,IV) (hydr)oxides beta-MnO2 and gamma-MnOOH, both in neutral solution under irradiation and in acidic conditions in the dark. beta-MnO2 and gamma-MnOOH originate from the oxidation of Mn(II) and play a key role in the redox cycling of manganese in the environment. These Mn(III,IV) (hydr)oxides show some photocatalytic activity, and they can act as thermal oxidants at acidic pH. The photoinduced oxidation of nitrite and the thermal oxidation of nitrous acid by Mn(III,IV) (hydr)oxides yield nitrogen dioxide and lead to the formation of nitrophenols in the presence of phenol. These processes can take place at the water-sediment or water-colloid interface in natural waters and on the surface of atmospheric particulate. Furthermore, the phenol/gamma-MnOOH/HNO2 system in dark acidic solution is an interesting model due to the formation of phenoxyl radical upon phenol monoelectronic oxidation by gamma-MnOOH. The kinetics of nitrophenol generation under such conditions indicates that phenol nitration is unlikely to take place upon reaction between phenoxyl and *NO2 and suggests a solution to a literature debate on the subject.     

Formation of oxidized products from the reaction of gaseous phenanthrene with the OH radical in a reaction chamber

The reaction of gas phase phenanthrene (Phen) with the OH radical in the presence of NO_x was studied in a reaction chamber. A number of oxidation products were identified by two dimensional gas chromatography–time of flight mass spectrometry (GC × GC–TOFMS). Identified products included 9-fluorenone, 1,2-naphthalic anhydride, 2,2′-diformylbiphenyl, dibenzopyranone, 1, 2, 3, 4 and 9-phenanthrols, 2, 3, 4 and 9-nitrophenanthrenes, 1,4-phenanthrenequinone, 9,10-phenanthrenequinone, and 2- and 4-nitrodibenzopyranones. This is the first study to identify 1,2-naphthalic anhydride and 1,4-phenanthrenequinone as products of the gas phase reaction of Phen with the OH radical. Eight more products were tentatively identified by their mass spectral fragmentation patterns and based on the typical OH radical initiated photochemical reaction mechanisms of simple aromatic compounds and naphthalene. In the reaction chamber, particle formation of products as a function of irradiation time was measured. Phenanthrenequinones, phenanthrol, nitrophenanthrene and nitrobenzopyranone were observed predominantly in the particle phase. This implies that these oxidized products formed from the reaction of Phen with the OH radical in the chamber would be associated with particles in the atmosphere and may, therefore, have an impact on human health. Possible pathways for the formation of these products are suggested and discussed.     

A new detailed chemical model for indoor air pollution

A detailed chemical box model has been constructed based on a comprehensive chemical mechanism (the Master Chemical Mechanism) to investigate indoor air chemistry in a typical urban residence in the UK. Unlike previous modelling studies of indoor air chemistry, the mechanism adopted contains no simplifications such as lumping or the use of surrogate species, allowing more insight into indoor air chemistry than previously possible. The chemical mechanism, which has been modified to include the degradation reactions of key indoor air pollutants, contains around 15,400 reactions and 4700 species. The results show a predicted indoor OH radical concentration up to 4.0×10⁵ molecule cm⁻³, only a factor of 10–20 less than typically observed outdoors and sufficient for significant chemical cycling to take place. Concentrations of PAN-type species and organic nitrates are found to be important indoors, reaching concentrations of a few ppb. Sensitivity tests highlight that the most crucial parameters for modelling the concentration of OH are the light-intensity levels and the air exchange rate. Outdoor concentrations of O₃ and NO_X are also important in determining radical concentrations indoors. The reactions of ozone with alkenes and monoterpenes play a major role in producing new radicals, unlike outdoors where photolysis reactions are pivotal radical initiators. In terms of radical propagation, the reaction of HO₂ with NO has the most profound influence on OH concentrations indoors. Cycling between OH and RO₂ is dominated by reaction with the monoterpene species, whilst alcohols play a major role in converting OH to HO₂. Surprisingly, the absolute reaction rates are similar to those observed outdoors in a suburban environment in the UK during the summer. The results from this study highlight the importance of tailoring a model for its particular location and the need for future indoor air measurements of radical species, nitrated species such as PANs and organic nitrates, photolysis rates of key species over the range of wavelengths observed indoors and concurrent measurements of outdoor air pollutant concentrations.     

The role of ferrous ion in Fenton and photo-Fenton processes for the degradation of phenol

The efficiency of different Fenton-related oxidative processes such as Fenton, solar-Fenton and UV-Fenton were examined using phenol as a model compound in simulated and industrial wastewater. A batch study was conducted to optimize parameters like pH, hydrogen peroxide concentration and ferrous ion concentration governing the Fenton process. At optimum conditions, different Fenton-related processes were compared for the degradation of phenol. Increased degradation and mineralisation efficiency were observed in photo-Fenton processes as compared to conventional Fenton process. The maximum mineralising efficiency for phenol with Fenton, solar and UV-Fenton processes were 41%, 96% and 97% respectively. In Fenton process, carboxylic acids like acetic acid and oxalic acid were formed as end products during the degradation of phenol while in photo-Fenton processes, both these ions were identified during the early stages of phenol degradation and were oxidized almost completely at 120 min of the reaction time. In photo-Fenton processes (solar and UV light) complete degradation were observed with 0.4 mM of Fe2+ catalyst as compared to 0.8 mM of Fe2+ in conventional Fenton process. In Fenton and solar-Fenton processes, an iron reusability study was performed to minimize the amount of iron used in treatment process. The efficacy of Fenton and solar-Fenton processes was applied to effluent from phenol resin-manufacturing unit for the removal and mineralisation of phenol.