Degradation of acetic acid with sulfate radical generated by persulfate ions photolysis

The photolysis of was studied for the removal of acetic acid in aqueous solution and compared with the H₂O₂/UV system. The radicals generated from the UV irradiation of ions yield a greater mineralization of acetic acid than the OH radicals. Acetic acid is oxidized by radicals without significant formation of intermediate by-products. Increasing system pH results in the formation of OH radicals from radicals. Maximum acetic acid degradation occurred at pH 5. The results suggest that above this pH, competitive reactions with the carbon mineralized inhibit the reaction of the solute with and also OH radicals. Scavenging effects of two naturally occurring ions were tested; in contrast to ions, the presence of Cl⁻ ions enhances the efficiency of the /UV process towards the acetate removal. It is attributed to the formation of the Cl radical and its great reactivity towards acetate.     

Removal of toxic ions (chromate, arsenate, and perchlorate) using reverse osmosis, nanofiltration, and ultrafiltration membranes

Rejection characteristics of chromate, arsenate, and perchlorate were examined for one reverse osmosis (RO, LFC-1), two nanofiltration (NF, ESNA, and MX07), and one ultrafiltration (UF and GM) membranes that are commercially available. A bench-scale cross-flow flat-sheet filtration system was employed to determine the toxic ion rejection and the membrane flux. Both model and natural waters were used to prepare chromate, arsenate, and perchlorate solutions (approximately 100 μg L⁻¹ for each anion) in mixtures in the presence of other salts (KCl, K₂SO₄, and CaCl₂); and at varying pH conditions (4, 6, 8, and 10) and solution conductivities (30, 60, and 115 mS m⁻¹). The rejection of target ions by the membranes increases with increasing solution pH due to the increasingly negative membrane charge with synthetic model waters. Cr(VI), As(V), and rejection follows the order LFC-1 (>90%) > MX07 (25–95%)  ESNA (30–90%) > GM (3–47%) at all pH conditions. In contrast, the rejection of target ions by the membranes decreases with increasing solution conductivity due to the decreasingly negative membrane charge. Cr(VI), As(V), and rejection follows the order CaCl₂ < KCl  K₂SO₄ at constant pH and conductivity conditions for the NF and UF membranes tested. For natural waters the LFC-1 RO membrane with a small pore size (0.34 nm) had a significantly greater rejection for those target anions (>90%) excluding (71–74%) than the ESNA NF membrane (11–56%) with a relatively large pore size (0.44 nm), indicating that size exclusion is at least partially responsible for the rejection. The ratio of solute radius (r_i,s) to effective membrane pore radius (r_p) was employed to compare ion rejection. For all of the ions, the rejection is higher than 70% when the r_i,s/r_p ratio is greater than 0.4 for the LFC-1 membrane, while for di-valent ions (, , and ) the rejection (38–56%) is fairly proportional to the r_i,s/r_p ratio (0.32–0.62) for the ESNA membrane.     

Important role of reaction field in photodegradation of deca-bromodiphenyl ether: Theoretical and experimental investigations of solvent effects

Photolysis of deca-bromodiphenyl ether (BDE-209) was investigated in tetrahydrofuran, dichloromethane, isopropanol, acetone, ethanol, methanol, acetonitrile and dimethylsulfoxide. Noticeable differences of the photolytic rates and quantum yields were found in the diverse solvents. Different to the previous deductions, hydrogen donating efficiency and electron donating efficiency of solvents were not the decisive factors for the photolytic rate in this study, which was proved by the fast photolysis of BDE-209 in CCl₄, a solvent without hydrogen and difficult to donate electrons. Besides hydrogen addition process, intermolecular polymerization might occur during the photolysis. Density functional theory (DFT) calculation was performed to understand the molecular properties of BDE-209 in different solvents. The lowest singlet vertical excitation energy (E_ex) and the average formal charge on Br () of BDE-209, reflecting the difficulty for the excitation of BDE-209 and for the departing of Br atom, respectively, were changed by the reaction fields formed by the different solvents. E_ex and linearly correlated with the photolytic activity (log k). This study is helpful to better understand the photolytic behavior of BDE-209 in different media.     

Correlations between physicochemical properties of PAHs and their distribution in soil, moss and reindeer dung at Ny-Ålesund of the Arctic

Concentrations of 16 polycyclic aromatic hydrocarbons (PAHs) in soil, moss and reindeer dung collected at Ny-Ålesund of the Arctic were measured to investigate their accumulation trends and distribution in the three compartments. Compared with the other regions, the proportions of 2 + 3 ring PAHs to the total PAHs were higher, whereas the proportions of 5 + 6 ring PAHs were lower in the three compartments at Ny-Ålesund. Significant log/log-linear relationship was observed between the sub-cooled liquid vapor pressure and the soil/moss quotient (Q_SM). The relation was similar to the relationship between the gas/particle partition coefficient (K_P) and of PAHs, implying Q_SM would be a “mirror image” of K_P. Excellent log/log-linear relationships were observed between Q_SM and K_OA as well as between the moss/dung quotient (Q_MD) and K_OW. The results presented here indicate the physicochemical properties are suitable for characterizing the distribution of PAHs in soil, moss and reindeer dung.     

A new approach to quantify the degradation kinetics of linuron with UV, ozonation and UV/O3 processes

The degradation of linuron, one of phenylurea herbicides, was investigated for its reaction kinetics by different treatment processes including ultraviolet irradiation (UV), ozonation (O₃), and UV/O₃. The decay rate of linuron by UV/O₃ process was found to be around 3.5 times and 2.5 times faster than sole-UV and ozone-alone, respectively. Experimental results also indicate overall rate constants increased exponentially with pH above 9.0 while the increase of rate constants with pH below 9 is insignificant in O₃ system. All dominant parameters involved in the three processes were determined in the assistant of proposed linear models in this study. The approach was found useful in predicting the process performances through the quantification of quantum yield (rate constant for the formation of free radical HOO⁻ from ozone decomposition at high pH), rate constant of linuron with ozone (k_O3,LNR), rate constant of linuron with hydroxyl radical (k_OH,LNR), and α (the ratio of the production rate of OH and the decay rate of ozone in UV/O₃ system).     

Formation and growth of indoor air aerosol particles as a result of d-limonene oxidation

Oxidation of d-limonene, which is a common monoterpene, can lead to new aerosol particle formation in indoor environments. Thus, products containing d-limonene, such as citrus fruits, air refresheners, household cleaning agents, and waxes, can act as indoor air aerosol particle sources. We released d-limonene into the room air by peeling oranges and measured the concentration of aerosol particles of three different size ranges. In addition, we measured the concentration of d-limonene, the oxidant, and the concentration of ozone, the oxidizing gas. Based on the measurements we calculated the growth rate of the small aerosol particles, which were 3–10 nm in diameter, to be about , and the losses of the aerosol particles that were due to the coagulation and condensation processes. From these, we further approximated the concentration of the condensable vapour and its source rate and then calculated the formation rate of the small aerosol particles. For the final result, we calculated the nucleation rate and the maximum number of molecules in a critical cluster. The nucleation rate was in the order of and the number of molecules in a critical-sized cluster became 1.2. The results were in agreement with the activation theory.     

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 .     

Nitric oxide and nitrous oxide emission from Hungarian forest soils; linked with atmospheric N-deposition

Studies of forest nitrogen (N) budgets generally measure inputs from the atmosphere in wet and dry deposition and outputs via hydrologic export. Although denitrification has been shown to be important in many wetland ecosystems, emission of N oxides from forest soils is an important, and often overlooked, component of an ecosystem N budget. During 1 year (2002–03), emissions of nitric oxide (NO) and nitrous oxide (N₂O) were measured from Sessile oak and Norway spruce forest soils in northeast Hungary. Accumulation in small static chambers followed by gas chromatography-mass spectrometry detection was used for the estimation of N₂O emission flux. Because there are rapid chemical reactions of NO and ozone, small dynamic chambers were used for in situ NO flux measurements. Average soil emissions of NO were 1.2 and 2.1 μg N m⁻² h⁻¹, and for N₂O were 15 and 20 μg N m⁻² h⁻¹, for spruce and oak soils, respectively. Due to the relatively high soil water content, and low C/N ratio in soil, denitrification processes dominate, resulting in an order of magnitude greater N₂O emission rate compared to NO. The previously determined N balance between the atmosphere and the forest ecosystem was re-calculated using these soil emission figures. The total (dry+wet) atmospheric N-deposition to the soil was 1.42 and 1.59 g N m⁻² yr⁻¹ for spruce and oak, respectively, while the soil emissions are 0.14 and 0.20 g N m⁻² yr⁻¹. Thus, about 10–13% of N compounds deposited to the soil, mostly as and , were transformed in the soil and emitted back to the atmosphere, mostly as greenhouse gas (N₂O).