Discussion of Chicgoua Noubactep on “Removal of thiobencarb in aqueous solution by zero valent iron” by Md. Nurul Amin et al. [Chemosphere 70 (3) (2008) 511–515]

The following comments are proposed to clarify some related issues on the use of zero valent iron micrometric particles for the treatment of a thiobencarb pesticide solution published in a recent article by Nurul Amin et al., [Nurul Amin Md., Kaneco, S., Kato, T., Katsumata, H., Susuki, T., Otha, K., 2008. Removal of thiobencarb in aqueous solution by zero valent iron. Chemosphere 70 (3), 511–515], and discussed later by Chicgoua Noubactep.     

Air ventilation impacts of the “wall effect” resulting from the alignment of high-rise buildings

The objective of this study is to investigate the air ventilation impacts of the so called “wall effect” caused by the alignment of high-rise buildings in complex building clusters. The research method employs the numerical algorithm of computational fluid dynamics (CFD – FLUENT) to simulate the steady-state wind field in a typical Hong Kong urban setting and investigate pollutant dispersion inside the street canyon utilizing a pollutant transport model. The model settings of validation study were accomplished by comparing the simulation wind field around a single building block to wind tunnel data. The results revealed that our model simulation is fairly close to the wind tunnel measurements. In this paper, a typical dense building distribution in Hong Kong with 2 incident wind directions (0° and 22.5°) is studied. Two performance indicators are used to quantify the air ventilation impacts, namely the velocity ratio (VR) and the retention time (T_r) of pollutants at the street level. The results indicated that the velocity ratio at 2 m above ground was reduced 40% and retention time of pollutants increased 80% inside the street canyon when high-rise buildings with 4 times height of the street canyon were aligned as a “wall” upstream. While this reduction of air ventilation was anticipated, the magnitude is significant and this result clearly has important implications for building and urban planning.     

Increasing the efficiency of solute leaching: impacts of flow interruption with drainage of the “preferential flow paths”

Most soils contain preferential flow paths that can impact on solute mobility. Solutes can move rapidly down the preferential flow paths with high pore-water velocities, but can be held in the less permeable region of the soil matrix with low pore-water velocities, thereby reducing the efficiency of leaching. In this study, we conducted leaching experiments with interruption of the flow and drainage of the main flow paths to assess the efficiency of this type of leaching. We compared our experimental results to a simple analytical model, which predicts the influence of the variations in concentration gradients within a single spherical aggregate (SSA) surrounded by preferential flow paths on leaching. We used large (length: 300 mm, diameter: 216 mm) undisturbed field soil cores from two contrasting soil types. To carry out intermittent leaching experiments, the field soil cores were first saturated with tracer solution (CaBr₂), and background solution (CaCl₂) was applied to mimic a leaching event. The cores were then drained at 25- to 30-cm suction to empty the main flow paths to mimic a dry period during which solutes could redistribute within the undrained region. We also conducted continuous leaching experiments to assess the impact of the dry periods on the efficiency of leaching. The flow interruptions with drainage enhanced leaching by 10–20% for our soils, which was consistent with the model's prediction, given an optimised “equivalent aggregate radius” for each soil. This parameter quantifies the time scales that characterise diffusion within the undrained region of the soil, and allows us to calculate the duration of the leaching events and interruption periods that would lead to more efficient leaching. Application of these methodologies will aid development of strategies for improving management of chemicals in soils, needed in managing salts in soils, in improving fertiliser efficiency, and in reclaiming contaminated soils.     

Dioxin removal in “energy from waste plants” - comparison of air pollution control methods

The graph below shows the emitted dioxin - equivalents (Eadon) in grams per year in flue gas from municipal solid waste incinerators with various air pollution control methods for plants of capacity of 200 000 ton municipal solid waste (MSW) per year.

Full-size image (15K)

With optimized combustion and an effective air pollution control system the emissions of dioxins can be kept very low (concentrations below 0.1 ng/m³n).

With a very effective air pollution control system the total emission from all Swedish MSW-incinerators burning approximately 1.5 Mton/year will by 1990 be below 2 g/year - a drastic reduction from approximately 15 g today. As the total dioxin - equivalent emission to the environment in Sweden in the year 1987 was almost 500 g we see that municipal waste incineration really is on the way to solve their dioxin problem.     

Micro-scale bromination procedure for synthesis of “2,3,7,8-substituted” brominated dibenzo-p-dioxins and dibenzofurans from [C]-labeled precursors

Brominated dibenzo-p-dioxin and dibenzofuran (BDD/BDF) isomers, specifically having from one to three halogens located in the 2,3,7,8-substituent positions, that are [¹³C]-labeled for use as analytical internal standards in mass spectrometric methods are not yet commercially available. Based upon the current availability of [¹³C]-labeled dibenzo-p-dioxin and dibenzofuran (DD/DF) precursors, we have developed a simple and efficient synthetic procedure which produces brominated congeners that are predominantly substituted in the 2,3,7, and 8-positions. The gas/solid reaction of vaporized precursor and surface-supported iron (III) bromide occurs rapidly (seconds) at temperatures ≥ 240°C and can provide total product yields in the range of 30 to 50 mole % for initial precursor amounts between 1 μg and 10 mg. In this paper we shall describe the utility of this approach to produce 5 μg quantities of [¹³C₁₂]-2,7-dibromodibenzo-p-dioxin (27-DBDD) and [¹³C₁₂]-2,8-dibromodibenzo-p-dioxin (28-DBDD).     

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 .