Environmental effects of ozone depletion and its interactions with climate change: progress report, 2004.
The complexity of the linkages between ozone depletion, UV-B radiation and climate change has become more apparent.
Biomedical subjects
Publications and source records attributed to Barbara Sulzberger.
The complexity of the linkages between ozone depletion, UV-B radiation and climate change has become more apparent.
Cu(II) is a key species with respect to the bioavailability and hence toxicity of copper. Therefore, it is important to elucidate the factors that control Cu(I) steady-state concentrations in natural waters. In this study, a solid-phase-extraction-based method was developed that allows Cu(I) measurements at ambient concentrations. Cu(I) is selectively enriched as a bathocuproine complex on a hydrophobic polymer column, whereas Cu(II), bound to ethylenediamine, is not retained on the column. After elution with acidic methanol, Cu is analyzed with graphite-furnace atomic absorption spectroscopy. The detection limit of the whole analytical procedure is below 1 x 10(-9) M, and the mean recovery of Cu(I) is approximately 70%. We then applied this method to determine Cu(I) in water samples collected from the River Scheldt estuary and the North Sea. Upon irradiation of these filtered water samples in the laboratory (with approximately 5 kW m(-2)), Cu(I) steady-state concentrations ([Cu(I)]ss) were established within a few minutes, and [Cu(I)]ss ranged from 5% to 80% of total dissolved copper, depending on the origin of the water samples. Measured [Cu(I)]ss can be interpreted by considering light-induced reduction of Cu(II) and stabilization of Cu(I) by chloride at high salinity, thermal reduction of Cu(II) by sulfide-containing compounds at low salinity, and fast reoxidation of Cu(I) due to stabilization of Cu(II) by strong organic ligands present at intermediate salinity.
The photochemical reduction of Cr(VI) by iron and aquatic dissolved organic matter (DOM) was investigated. DOM sampled from a number of surface waters (a eutrophic wetland, a blackwater stream, and river water from a mix-use watershed) was used in this study. Moreover, a fulvic acid from Lake Fryxell, Antarctica, was also used to represent a DOM derived from a strictly autochthonous source. Cr(VI) reduction to Cr(III) at pH 5.5 was observed for all target DOMs used in this study, but rates varied widely. In general, photoreduction rates increased with increasing iron concentrations, but the type of DOM appeared to influence the kinetics to a larger degree. The rate of reduction was significantly greater for DOM derived from terrestrial systems than from predominantly autochthonous materials even if additional iron was added to the later. A positive correlation was observed between rates of Cr(VI) photoreduction and properties of the isolated DOM samples whereby faster reduction was observed for larger more aromatic substrates. On the basis of the fast rates reported for the dark reduction of Cr(VI) to Cr(III) by Fe(II)-organic ligands, we hypothesize that the rate-limiting step in these reactions is the photoreduction of Fe(III) to Fe(II) by a ligand-to-metal charge-transfer pathway after absorption of light by Fe(III)-DOM complexes or by reduction of Fe(III) by superoxide or other intermediates formed after light absorption by DOM. Thus, the rate of Cr(VI) photoreduction to Cr(III) in natural sunlit waters is dependent upon both the amount of iron present and the nature of the dissolved organic matter substrate.
In this study we used multidimensional solution-state NMR to elucidate the differences in the chemical composition of solid phase extracted and ultrafiltered DOM isolates. DOM was isolated from water sampled from an oligotrophic river, the River Tagliamento (Italy). The recovery of total DOM was up to 42% with both isolation techniques. In addition to 1- and 2-D solution-state NMR, we also applied 1-D solid-state 13C NMR spectroscopy for DOM characterization. 13C NMR spectroscopy only produced broad overlapping resonances, thus allowing a bulk characterization of DOM composition. However, it demonstrated that the bulk chemical composition of the two DOM fractions exhibited minor spatial-temporal changes. The 2-D experiments (TOCSY, HMQC) showed that the solid phase extracted hydrophobic DOM contained predominantly aliphatic esters, ethers, and hydroxyl groups, whereas the ultrafiltered DOM was comprised partially of peptides/protein, with further evidence for a small amount of aliphatic/fatty acid material. Sugars were present in both DOM fractions. The results show the two isolation techniques selected for different suites of compounds within the bulk DOM pool.