Synthesis of [13C]- and [14C]-labeled phenolic humus and lignin monomers

Natural phenolic monomers are ubiquitous in the environment and are involved in the stabilization of atmospheric carbon and the transformation of xenobiotics. Investigations on the stabilization of phenolic carbons and their environmental fate are hampered by the unavailability of commercial [13C]- and [14C]-labeled phenols. Here we report the complete chemical synthesis of the lignin and humus structural monomers p-coumaric, ferulic, and caffeic acids, p-hydroxybenzaldehyde, protocatechualdehyde, vanillin, catechol, and guaiacol, uniformly [13C]- or [14C]-labeled in the aromatic ring, starting from commercially available [U-ring-13C]- or [U-ring-14C]-labeled phenol. The synthesis of these compounds involved selective ortho-hydroxylation of the aromatic ring, Friedel-Crafts alkylation, and Knoevenagel condensation. [U-ring-13C]- or [U-ring-14C]-p-coumaric acid was synthesized via p-hydroxybenzaldehyde with a 75% yield with respect to phenol. Synthesis of [U-ring-13C]- or [U-ring-14C]-ferulic acid, consisting of six single steps via guaiacol and vanillin, had an overall yield of up to 45%. Uniformly ring-labeled caffeic acid was synthesized either via catechol and protocatechualdehyde in five single steps, yielding [U-ring-14C]-caffeic acid with a 37% yield, or via guaiacol, vanillin, and ferulic acid in seven steps, yielding [U-ring-13C]-caffeic acid with an 18% yield. Ferulic acid, [14C]-labeled at beta-C of the propenoic side chain, was synthesized from [2-14C]-malonic acid under Knoevenagel conditions with a 67% yield with respect to malonic acid. Demethylation of the [beta-14C]-ferulic acid with BBr3 in CH3CN resulted in [beta-14C]-caffeic acid with a 62% yield. All [U-ring-13C]-labeled phenolic products were analyzed by 13C nuclear magnetic resonance (13C-NMR) spectroscopy and gas chromatography-mass spectrometry (GC-MS).     

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.     

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.     

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.     

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.     

Formation, characterization and release of non-extractable residues of [14C] -labeled organic xenobiotics in soils

The amount of non-extractable residues (NER) of organic xenobiotics in the soil can considerably exceed the amount of extractable residues which are accessible to normal residue analysis. The NER therefore present a burden to the soil, the toxicological and ecotoxicological potential of which is largely unknown. For the characterization of bound residues and their binding type, special solubilization methods such as supercritical fluid extraction are applied and experiments with radiolabeled model polymers are performed. Mineralization experiments with [¹⁴C] labeled xenobiotics in natural soil show that a total degradation is still also possible in the environment when in a bound form. Ecotoxicological effects of non-extractable residues may be recorded when their concentration is high, when the parent compound exhibits a high ecotoxicity and the applied detection method is sufficiently sensitive.     

Comment on “Analysis of groundwater contamination using concentration-time series recorded during an integral pumping test: Bias introduced by strong concentration gradients within the plume” by Allelign Zeru and Gerhard Schäfer

We consider the results of a recent paper in this journal [Zeru, A. and Schäfer, G., 2005. Analysis of groundwater contamination using concentration–time series recorded during an integral pumping test: Bias introduced by strong concentration gradients within the plume. Journal of Contaminant Hydrology 81 (2005) 106–124], which addresses the field-scale characterisation of contaminant plumes in groundwater. There, it is concluded that contaminant concentration gradients can bias Integral Pumping Test (IPT) interpretations considerably, in particular if IPTs are conducted in advective fronts of contaminant plumes. We discuss implications of this setting and also argue that the longitudinal and transverse dispersivities used in the examples of Zeru and Schäfer (2005) of up to 30 m and 3 m, respectively, are generally very high for the here relevant capture zone scale (< 20 m). However, regardless of both longitudinal and transverse concentration gradients, we further show through a counter-example that IPT results are unbiased as long as the concentration attenuation along the flow direction is linear over the capture zone extent.