Autoxidation of N(III), S(IV), and other Species in Frozen Solution – A Possible Pathway for Enhanced Chemical Transformation in Freezing Systems

The chemistry of glycolaldehyde (hydroxyacetaldehyde) relevant to the troposphere has been investigated using UV absorption spectrometry and FTIR absorption spectrometry in an environmental chamber. Quantitative UV absorption spectra have been obtained for the first time. The UV spectrum peaks at 277 nm with a maximum cross section of (5.5± 0.7)×10^–20 cm² molecule^–1. Studies of the ultraviolet photolysis of glycolaldehyde ( = 285 ± 25 nm) indicated that the overall quantum yield is > 0.5 in one bar of air, with the major products being CH₂OH and HCO radicals. Rate coefficients for the reactions of Cl atoms and OH radicals with glycolaldehyde have been determined to be (7.6± 1.5)×10^–11 and (1.1± 0.3)×10^–11 cm³ molecule^–1 s^–1, respectively, in good agreement with the only previous study. The lifetime of glycolaldehyde in the atmosphere is about 1.0 day for reaction with OH, and > 2.5 days for photolysis, although both wet and dry deposition should also be considered in future modeling studies.     

Paleolimnological assessment of human impacts on an urban South African lake

North End Lake is a polluted and eutrophic freshwater system located in Port Elizabeth, South Africa. Since the lake is expected to be used for recreational/tourist purposes by 2010, a rehabilitation program will have to be designed. For this reason, we retrieved a sediment core from the central region of the lake to decipher the effect of historical human impacts on the water body. Pre-disturbance paleolimnological inferences indicate that the lake was likely mesotrophic. After ∼1831, when sheep farming activities were undertaken in the catchment, increases in trophic state and changes in sediment composition were observed. After ∼1937, increases in trace metal levels, organic matter, spheroidal carbonaceous particles (SCP) and changes in sediment composition were recorded. The system became eutrophic as indicated by the dominance of the diatom Actinocyclus normanii, a cosmopolitan species often observed in systems where water quality has been dramatically degraded. The conditions worsened after 1986 because of the construction of a storm-water retention system, which intentionally channeled storm-water runoff into the lake. Because of this, extremely high values of fecal coliforms (i.e. 2 × 10⁶ every 100 ml) have been measured in the water column. The paleolimnological information identified the sharp increase in organic content in the uppermost section of the core, and this could be correlated to the operation of the storm-water retention system. Therefore, as an immediate management measure, we suggest that the storm-water retention system should either no longer be utilized, or the storm-water runoff should be treated before disposal into the lake. In addition, an effective sewage system has to be constructed.     

Zoning in garnets—Diffusion models

When reference frames and diffusing components are properly selected, the flux equations for diffusion of the major components in natural garnets may often be approximated by: J DC. In such cases it is shown that, for reasonable diffusion coefficients and boundary conditions, observed zoning profiles in natural garnets may be explained with pure diffusion models. These models allow for original inhomogeneities in the host rock and may be used to explain why single hand specimens may show such a variety of zoning profiles within a single mineral species.     

The sorption of silver by poorly crystallized manganese oxides

The sorption of silver by poorly crystallized manganese oxides was studied using synthesized samples of three members of the manganous manganite (birnessite) group, of different chemical composition and crystallinity, and a poorly organized γ-MnO₂. All four oxides sorbed significant quantities of silver. The manganous manganites showed the greatest sorption (up to 0.5 moles silver/mole MnO_x at pH 7) while the γ-MnO₂ showed the least (0.3 moles silver/ mole MnO_x at pH 7). Sorption of silver was adequately described by the Langmuir equation over a considerable concentration range. The relationship failed at low pH values and high equilibrium silver concentrations. The sorption capacity showed a direct relationship with pH. However, the rate of increase of sorption capacity decreased at the higher pH values.Silver sorption maxima. were not directly related to surface area but appeared to vary with the amount of occluded sodium and potassium present in the manganese oxide. The important processes involved in the uptake of silver by the four poorly crystallized manganese oxides ara considered to be surface exchange for manganese, potassium and sodium as well as exchange for structural manganese, potassium and sodium.