Why ozonolysis may not increase the hydrophilicity of particles

It is commonly assumed that atmospheric oxidation of hydrocarbon particles or hydrocarbon coatings on particles leads to polar products and increased water uptake, altering atmospheric visibility and increasing the likelihood they will act as cloud condensation nuclei (CCN). We show here through laboratory experiments that increased water uptake depends on the 3-dimensional structure of the particles. Laboratory studies of particles formed during ozonolysis of surface-bound alkenes, present as terminally unsaturated self-assembled monolayers (C8= SAM) on a silica substrate, were carried out at room temperature and 1 atm pressure. SAMs were exposed to ～10¹³ O₃ molecules cm^?3 for 40 min and resultant particles were analyzed using single particle Fourier transform infrared micro-spectroscopy (micro-FTIR) and secondary ion mass spectroscopy (SIMS). Spectroscopy results show that –COOH and other polar groups are formed but are buried inside a hydrophobic shell, consistent with earlier observations (McIntire et al., 2005, Moussa et al., 2009) that water uptake does not increase after reaction of the terminal alkene with O₃. These insights into the 3-D structure of particles formed on oxidation have important implications for the ability of secondary organic aerosols to act as CCN. In addition, the nature of the surface of the particles is expected to determine their uptake into biological systems such as the surface of the lungs.     

Comparison between measured and predicted CCN concentrations at Egbert,Ontario: Focus on the organic aerosol fraction at a semi-rural site

Aerosol–cloud condensation nuclei (CCN) closure was studied in a semi-rural location 80 km north of Toronto, Canada at the Centre for Atmospheric Research Experiments outside of Egbert, Ontario during the fall of 2005. This site is subject to both polluted air from southern Ontario and clean air from the north. The purpose of the investigation was to evaluate the degree to which closure is attained at a supersaturation of 0.32% when size-resolved aerosol compositions from an Aerodyne Quadrupole Aerosol Mass Spectrometer are made alongside measurements of CCN number density and aerosol size distribution. Attention was given to assessing the sensitivity of closure to assumptions made concerning the water solubility and surface tension of the organic fraction of the aerosol in the Köhler analysis. By assuming that the organics are insoluble and that the growing droplet has the surface tension of water, a good overall degree of closure is attained throughout the analysis time period, with the predicted numbers of CCN within 15% of the modelled numbers, which is within our estimated systematic uncertainties. However, for the specific periods during which the organic content of the aerosol is high, the degree of closure is significantly lower. Sensitivity analyses indicate that some degree of organic water solubility and/or surface tension reduction is necessary to achieve the best agreement and least variance between the modelled and measured numbers of CCN. A general conclusion is that significant uncertainties arise in predicting CCN levels only when the level of soluble inorganic species is below approximately 25% by mass.     

Kinetics of OH-initiated oxidation of oxygenated organic compounds in the aqueous phase: new rate constants, structure–activity relationships and atmospheric implications

The kinetics of OH oxidation of several organic compounds of atmospheric relevance were measured in the aqueous phase. Relative kinetics were performed using various organic references and OH sources. After validation of the protocol, temperature-dependent rate constants for the reactions of OH radical with ethyl ter-butyl ether (, E_a/R=580 (±560) K), n-butyl acetate ( (±0.4)×10⁹ M⁻¹ s⁻¹, E_a/R=1000 (±200) K), acetone ( (±0.05)×10⁹ M⁻¹ s⁻¹, E_a/R=1400 (±500) K), methyl ethyl ketone (, E_a/R=1200 (±200) K), methyl iso-butyl ketone (, E_a/R=1200 (±300) K) and methylglyoxal (, E_a/R=1100 (±300) K) were determined. A non-Arrhenius behavior was found for phenol, in good agreement with the contribution of an OH addition to the mechanism, which also includes H-abstraction by OH radicals. Global rate constants of acetaldehyde, propionaldehyde, butyraldehyde and valeraldehyde were studied at 298 K only, as these compounds partly hydrate in the aqueous phase. All the obtained data (except those of phenol) complemented by literature data were used to investigate three methods to estimate rate constants for H-abstraction reactions of OH radicals in aqueous solutions when measured data were not available: Evans-Polanyi-type correlations, comparisons with gas-phase data, structure activity relationships (SAR). The results show that the SAR method is promising; however, the data set is currently too small to extend this method to temperatures other than 298 K. The atmospheric impact of aqueous phase OH oxidation of water-soluble organic compounds is discussed with the determination of their global atmospheric lifetimes, taking into account both gas- and aqueous-phase reactivities. The results show that atmospheric droplets can act as powerful photoreactors to eliminate soluble organic compounds from the atmosphere.     

Do aerosols act as catalysts in the OH radical initiated atmospheric oxidation of volatile organic compounds?

Smog chamber/FTIR techniques were used to study the relative reactivity of OH radicals with methanol, ethanol, phenol, C₂H₄, C₂H₂, and p-xylene in 750 Torr of air diluent at 296±2 K. Experiments were performed with, and without, 500–8000 μg m⁻³ (4000–50 000 μm² cm⁻³ surface area per volume) of NaCl, (NH₄)₂SO₄ or NH₄NO₃ aerosol. In contrast to the recent findings of Oh and Andino (Atmospheric Environment 34 (2000) 2901, 36 (2002) 149; International Journal of Chemical Kinetics 33 (2001) 422) there was no discernable effect of aerosol on the rate of loss of the organic compounds via reaction with OH radicals. Gas kinetic theory arguments cast doubt upon the findings of Oh and Andino. The available data suggest that the answer to the title question is “No”. As part of this work the rate constants for reactions of OH radicals with methanol, ethanol, and phenol in 750 Torr of air at 296 K were determined to be: k_OH+CH3OH=(8.12±0.54)×10⁻¹³, k_OH+C2H5OH=(3.47±0.32)×10⁻¹² and k_OH+phenol=(3.27±0.31)×10⁻¹¹ cm³ molecule⁻¹ s⁻¹.     

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.     

Preparation of a titanium dioxide photocatalyst codoped with cerium and iodine and its performance in the degradation of oxalic acid

A novel class of visible light-activated photocatalysts was prepared by codoping TiO(2) with cerium and iodine (Ce-I-TiO(2)). The particles were characterized using the Brunauer-Emmett-Teller method, X-ray diffraction, scanning electron microscopy, X-ray photoelectron spectroscopy and UV-Visible light absorption. Particles of Ce-I-TiO(2) had greater photoabsorption in the 400-800 nm wavelength range than iodine-doped TiO(2) (I-TiO(2)). The effects on the photocatalytic degradation of oxalic acid under visible light or UV-Visible light irradiation were investigated. The photocatalytic activity of Ce-I-TiO(2) calcined at 673 K was significantly higher than that of Ce-I-TiO(2) calcined at 773 K and I-TiO(2) calcined at 673 K in aqueous oxalic acid solution under visible light or UV-Visible light irradiation. Under visible light irradiation, oxalic acid was first adsorbed on the surface of the catalysts rather than reacted with free radicals in the bulk solution, and then oxidized by (·)OH(ads) to CO(2), which was verified by studying the effects of nitrogen purging and scavengers, as well as by gas chromatography/mass spectrometry.     

Gas-phase terpene oxidation products: a review

Terpenes are emitted in large quantities from vegetation into the troposphere, where they react readily with ozone, OH and NO₃ radicals leading to a number of oxidation products. The current knowledge about gas-phase terpene oxidation products is reviewed. Their formation and decomposition pathways, their products and their relevance for the troposphere, and their chemical analysis are discussed. Data on oxidation kinetics, and product yields is presented for 23 terpenes and 65 oxidation products. A total of 84 references are quoted.     

Solar driven nitrous acid formation on building material surfaces containing titanium dioxide: A concern for air quality in urban areas?

The photoenhanced uptake of nitrogen dioxide (NO₂) to the surface of commercially available self-cleaning window glass has been studied under controlled laboratory conditions. This material is one of an array of modern building products which incorporate titanium dioxide (TiO₂) nanoparticles and are finding increasing use in populated urban areas. Amongst the principal drivers for the use of these materials is that they are thought to facilitate the irreversible removal of pollutants such as NO₂ and organic molecules from the atmosphere and thus act to remediate air quality. While it appears that TiO₂ materials do indeed remove organic molecules from built environments, in this study we show that the photoenhanced uptake of NO₂ to one example material, self-cleaning window glass, is in fact accompanied by the substantial formation (50–70%) of gaseous nitrous acid (HONO). This finding has direct and serious implications for the use of these materials in urban areas. Not only is HONO a harmful respiratory irritant, it is also readily photolysed by solar radiation leading to the formation of hydroxyl radicals (OH) together with the re-release of NO_x as NO. The net effect of subsequent OH initiated chemistry can then be the further degradation of air quality through the formation of secondary pollutants such as ozone and VOC oxidation products. In summary, we suggest that a scientifically conceived technical strategy for air quality remediation based on this technology, while widely perceived as universally beneficial, could in fact have effects precisely opposite to those intended.     

Photochemical formation of hydroxyl radicals catalyzed by montmorillonite

In this work, the photooxidation of benzene and the formation of phenol in aqueous suspensions of the iron-rich montmorillonite under irradiation of a 250W metal halide lamp (lambda> or = 365nm) were investigated. We confirmed that hydroxyl radicals (()OH) were produced by illuminating montmorillonite and was responsible for the photooxidation of benzene in aqueous suspensions of montmorillonite. Low pH value facilitated the formation of hydroxyl radicals in the pH range of 2.0-10.0. The ()OH concentration increased with increasing the concentration of montmorillonite in aqueous solutions in the range of 0-20.0gl(-1). Higher concentration like 25.0gl(-1) montmorillonite inhibited the ()OH production. Iron, predominantly free iron in the clays, is believed to be one of the most important factors determining ()OH formation. Structural irons in montmorillonite have contributions to ()OH formation, especially in the presence of carboxylate ions. The formation of ()OH from montmorillonite under irradiation of near UV and visible light indicates that clays might play important role not only in transfer through adsorption but also in transformation through oxidation of organic compounds on the surface of clay particles in air, water, soil or even top sediments.     

Tetracycline removal enhancement with Fe-saturated nanoporous montmorillonite in a tripartite adsorption/desorption/photo-Fenton degradation process

The adsorption and photo-Fenton degradation of tetracycline (TC) over Fe-saturated nanoporous montmorillonite was analyzed. The synthesized samples were characterized using XRD, FTIR, SEM, and XRF analysis, and the adsorption and desorption of TC onto these samples, as well as the antimicrobial activity of TC during these processes, were analyzed at different pH. Initially, a set of adsorption/desorption experiments was conducted, and surprisingly, up to 50% of TC adsorbed was released from Mt structure. Moreover, the desorbed TC had strong antibacterial activity. Then, an acid treatment (for the creation of nanoporous layers) and Fe saturation of the montmorillonite were applied to improve its adsorption and photocatalytic degradation properties over TC. Surprisingly, the desorption of TC from modified montmorillonite was still high up to 40% of adsorbed TC. However, simultaneous adsorption and photodegradation of TC were detected and almost no antimicrobial activity was detected after 180 min of visible light irradiation, which could be due to the photo-Fenton degradation of TC on the modified montmorillonite surface. In the porous structures of modified montmorillonite high, ˙OH radicals were created in the photo-Fenton reaction and were measured using the Coumarin technique. The ˙OH radicals help the degradation of TC as proposed in an oxidation process. Surprisingly, more than 90% of antimicrobial activity of the TC decreased under visible light (after 180 min) when desorbed from nanoporous Fe-saturated montmorillonite compared to natural montmorillonite. To the best of our knowledge, this is the first time that such a high TC desorption rate from an adsorbent with the least residual antimicrobial activity is reported which makes nanoporous Fe-saturated montmorillonite a perfect separation substance of TC from the environment.

     

Gas-phase ozonolysis of the monoterpenoids (S)-(+)-carvone, (R)-(−)-carvone, (−)-carveol, geraniol and citral

Biogenic emissions of volatile organic compounds (VOCs) play a fundamental role in atmospheric chemistry. Vegetation is the most abundant natural source of VOCs, while terpenoids, as limonene, α and β pinene and mircene, top the plants emission list. Much interest has been demonstrated in oxidation and photooxidation reactions of VOCs, particularly of monoterpenoids, owing to their diversity and to uncertainties regarding their mechanism of reaction. Quantification of primary carbonylic compounds, as well as of biradical reaction components, is highly relevant to the understanding of the major reactions. In this context, taking into account both structural factors and the fact that these compounds are found in the essential oils of plants typically found in Brazil and that they may be present in the atmosphere from emission by the plants, the monoterpenoids (S)-(+)-carvone, (R)-(−)-carvone, (−)-carveol, geraniol and citral (a mixture of the isomers geranial and neral) were selected for this study.The ozonolysis reactions of the monoterpenoids were carried out under dark conditions for all experiments, due to their photochemical reactivity. The analysis of the results lets us propose a mechanism by which these reactions occur. The observed results of the ozonolysis of S and R carvone suggest that the stereochemistry of asymmetric carbon does not affect either in the yields of both formaldehyde and of OH radicals produced in the reaction, or in the reactivity of these compounds, for which the rate constants were in the scale of 10⁻⁶ s⁻¹.We found that, in the (−)-carveol's cis and trans mixture, even though the hydroxyl in the axial position—in the case of trans-(C) and cis-(D′) isomers—favors the attack by the ozone molecule on the external double bond, thus increasing the mixture's reactivity , it affects the average production of formaldehyde. The presence of geraniol and citral led to the production of formaldehyde, propanone, glyoxal, methyl–glyoxal and cyclohexanone (OH radicals) as reaction products. The influence of an electron attractor group bonded to the carbon of the double bond, on the reactivity of the double bond, could not be observed in the case of citral, due to strong interference occurring in the instrument in all experiments with this monoterpenoid. For this reason, only the kinetics of geraniol was monitored .     

Degradation of tris(1-chloro-2-propanyl) phosphate by the synergistic effect of persulfate and zero-valent iron during a mechanochemical process

This study revealed a dual pathway for the degradation of tris(1-chloro-2-propanyl) phosphate (TCPP) by zero-valent iron (ZVI) and persulfate as co-milling agents in a mechanochemical (MC) process. Persulfate was activated with ZVI to degrade TCPP in a planetary ball mill. After milling for 2 h, 96.5% of the TCPP was degraded with the release of 63.16, 50.39, and 42.01% of the Cl^?, SO₄^2?, and PO₄^3?, respectively. In the first degradation pathway, persulfate was activated with ZVI to produce hydroxyl (·OH) radicals, and ZVI is oxidized to Fe(II) and Fe(III). A substitution reaction occurred as a result of the attack of ·OH on the P–O–C bonds, leading to the successive breakage of the three P–O–C bonds in TCPP to produce PO₄^3?. In the second pathway, a C–Cl bond in part of the TCPP molecule was oxidized by SO₄·^? to carbonyl and carboxyl groups. The P–O–C bonds continued to react with ·OH to produce PO₄^3?. Finally, the intermediate organochloride products were further reductively dechlorinated by ZVI. However, the synergistic effect of the oxidation (·OH and SO₄·^?) and the reduction reaction (ZVI) did not completely degrade TCPP to CO₂, resulting in a low mineralization rate (35.87%). Moreover, the intermediate products still showed the toxicities in LD₅₀ and developmental toxicant. In addition, the method was applied for the degradation of TCPP in soil, and high degradations (>?83.83%) were achieved in different types of soils.

     

Kinetics of the reactions of soot surface-bound polycyclic aromatic hydrocarbons with the OH radicals

The kinetics of the heterogeneous reaction of OH radicals with 15 polycyclic aromatic hydrocarbons (PAHs) present in laboratory generated simulated kerosene combustion soot was studied at T = 290 K in a low pressure discharge-flow reactor combined with an electron-impact mass spectrometer. The kinetics of soot-bound PAH consumption in reaction with OH were monitored using off-line HPLC measurements of their concentrations in soot samples as a function of time of exposure to OH. Concentration of OH radicals in the gas phase was measured by mass spectrometry. The first-order rate constants measured for the individual PAH at T = 290 K ranged from 0.02 to 0.04 s^?1 and were found to be independent of the OH concentration ([OH] = (0.34–2.5) × 10¹² molecule cm^?3) and of the molecular structure of the PAH. In addition, the uptake coefficient of OH on soot surface and the diffusion coefficient of OH in He were measured to be 0.19 ± 0.03 (calculated with geometric surface area) and (615 ± 80) Torr cm² s^?1, respectively. Comparison of the results on the PAH + OH reaction to those from previous studies carried out on different carbonaceous substrates, indicates probable dependence of the heterogeneous reactivity of PAH toward OH on the substrate nature. Rapid reaction with OH can be an important potential pathway of the atmospheric degradation of non-volatile PAH present mainly in the particulate phase in the atmosphere.     

Heterogeneous reactions of suspended parathion, malathion, and fenthion particles with NO(3) radicals

Organophosphorus pesticides (OPPs) emit into the atmosphere in both gas and particulate phases via spray drift from treatments and post-application emission, but most of their degradations in the atmosphere are not well known. In this study, the heterogeneous reactions of nitrate (NO₃) radicals with three typical OPPs (parathion, malathion, and fenthion) absorbed on azelaic acid particles are investigated using an online vacuum ultraviolet photoionization aerosol time-of-flight mass spectrometer (VUV-ATOFMS). The reaction products observed with the VUV-ATOFMS are identified on the basis of GC/MS analysis of the products in the reaction between NO₃ radicals and the coating of the pesticide. Paraoxon is identified as the only product of parathion; malaoxon and bis(1,2-bis-ethoxycarbonylethyl)disulfide as the products of malathion; fenoxon, fenoxon sulfoxide, fenthion sulfoxide, fenoxon sulfone, and fenthion sulfone as the products of fenthion. The degradation rates of parathion, malathion, and fenthion under the experimental conditions are 5.5 × 10⁻³, 5.6 × 10⁻², and 3.3 × 10⁻² s⁻¹, respectively. The pathways of the heterogeneous reactions between the three OPPs and NO₃ radicals are proposed. The experimental results reveal the possible transformations of these OPPs through the oxidation of NO₃ radicals in the atmosphere.     

The ratio between nitrogen oxides and carbon monoxide total emissions as precursors of tropospheric hydroxyl content evolution

The Main Geophysical Observatory 2D channel photochemical model is used to study the behavior of tropospheric OH within the 30–60°N zonal belt in relation to changing NO_X and CO emissions. The changes of tropospheric OH as a function of the contributions by NO_X and CO emissions during the period 1850–2050 are calculated. Our estimations show that the largest annual increment of total tropospheric OH within the belt considered occurs in the 1985–1995 period, about 0.27% yr⁻¹. Based on scenarios of tropospheric pollution emissions in the first half of 21st century, the total tropospheric OH content will increase more slowly, by 0.12–0.15% yr⁻¹. The maximum growth of OH concentration occurs close to air pollution locations—in the lower troposphere during 1850–1995 but in the upper troposphere in the 21st century when the NO_X source from subsonic aircraft increases faster than the surface source.     

Investigation on the photoreactions of nitrate and nitrite ions with selected azaarenes in water

The photoreactions of selected azaarenes with nitrate and nitrite ions were investigated under irradiation at lambda = 313 nm. The excitation of both anions leads to several photochemical reactions forming mainly hydroxyl radicals and nitrogen oxides. The purification capability of natural waters i.e. the oxidation of inorganic and organic substances results from the formation of hydroxyl radicals. Nitrated isomers of azaarenes were found among the main products of the investigated photoreactions. The nitrogen oxides were responsible for the production of nitrated derivatives which possess a high toxic potential. Their formation was explained by the parallel occurance of two mechanism, a molecular and a radical one. The molecular mechanism became more important with increasing ionisation potentials of the azaarenes. The spectrum of oxidized products corresponded to the one got in the photoreactions of azaarenes with hydrogen peroxide. The formation of several oxidation and nitration products of the pyridine ring with its low electron density was explained by the reaction of excited states of azaarenes. The photoreactions with nitrite ions only led to the formation of oxidized and nitrated products. Nitroso products were not formed. The reactivity of nitrogen monoxide is too low for its reaction with the azaarenes.     

高锰酸钾缓释剂的制备及其性能研究

利用油相相分离法微胶囊技术,以硬脂酸为壳物质,制备高锰酸钾缓释剂,通过条件优化实验,确定最佳工艺条件为:壳核比值为3∶1、搅拌速度450 r/min以及超声时间为10 min。所制的高锰酸钾缓释剂包覆率为163.3%,在水中缓释行为符合Q=0.00518×t0.611(R2=0.9951)动力学方程,理论缓释期为229.4 d,具有较好的缓释效果。对高锰酸钾缓释剂进行红外光谱和环境电镜扫描分析,结果表明,成膜前后硬脂酸的结构发生改变,硬脂酸对高锰酸钾的微胶囊化不是简单的物理吸附,而是通过化学键合包覆在高锰酸钾表面。     

Measurement of total OH reactivity by laser-induced pump and probe technique—comprehensive observations in the urban atmosphere of Tokyo

Total OH reactivity was observed by use of the laser-induced pump and probe technique, and the urban air quality in Tokyo was diagnosed comprehensively. The concentrations of NO_x, CO, O₃, non-methane hydrocarbons (NMHCs) and oxygenated volatile organic compounds (OVOCs) were observed simultaneously. The observations were conducted in July and August 2003, and in January, February, May, and November 2004. Generally, the observed OH reactivity was higher than the calculated values derived using the observed concentrations of the trace species. The differences between the observed and calculated values in summer, spring, and autumn were approximately 30%. However, the difference in winter was smaller than those in the other seasons. In addition, while the differences observed in summer, spring, and autumn correlated with the total reactivity of the OVOCs (Σ_i k_OVOCi[OVOC_i](s⁻¹), k_i is rate constant of its compounds with OH), the correlations were not confirmed in the case of winter because atmospheric oxidation was less active and OVOCs levels were low in winter. These results suggest that the secondary products of the photochemical reactions in the atmosphere would be a missing sink for the OH loss process in the urban area.