Ageing of chromium(III)-bearing slag and its relation to the atmospheric oxidation of solid chromium(III)-oxide in the presence of calcium oxide

Slag arising in ferrochromium and stainless steel production is known to contain residual levels of trivalent chromium. As the chromium is normally bound in the slag matrix in various silicate or spinel phases, and hence not easily mobilised, utilisation or controlled disposal of such slag is generally considered unproblematic. Experimental test work with a number of slag materials indicates, however, that very gradual oxidation of trivalent to hexavalent chromium does occur when the slag is exposed to atmospheric oxygen, rendering a quantifiable but small portion of chromium in this much more mobile and toxic form. Mechanisms and rates of the oxidation reaction were investigated in a number of long-term studies using both original slag materials and artificial mixes of chromium and calcium oxides. Powders of these materials, some of them rolled into balls, were left to age under different conditions for periods of up to 12 months. In the slag samples, which contained between 1 and 3 wt.% chromium, 1000–10 000 μg Cr(VI) were found per gram of chromium within 6–9 months of exposure to an ambient atmosphere. The rate of the oxidation reaction decreased exponentially, and the reaction could generally be said to have ceased within 12 months. In mixtures of calcium and chromium oxides the oxidation reaction is presumed to occur at the boundaries between chromium oxide and calcium oxide phases through diffusion of oxygen along the grain boundaries and of Cr³⁺ across the boundaries, resulting in the formation of calcium chromate. In the slags, where calcium and chromium oxide can form a solid solution, the oxidation is likely to occur at the exposed surface of grains containing this solution.     

Sequentielle Schwermetallextraktion aus Staubniederschlägen und Straßensedimenten

For the application of sequential extraction of heavy metals from samples that can only be obtained in amounts of a few milligrams (micro samples, e.g. airborne dust fallout), the method afterZeien &Brümmer (1989) was progressed. A down scale to 1∶100 was carried out and the accuracy of this method with variable sample amounts of about 20 mg and an extraction volume of 500 μl was proofed with standard soil samples. The influence of variable extraction ratios (ratio of sample amount and volume of extraction solvent) and the influence of intensive treatment of dust sampled by the Bergerhoff-method (VDI 2119/2, 1972) prior sequential extraction, was within the precision of measurement of our method. Thus, we showed that sequential extraction can be applied for the investigation of heavy metal mobilization in micro samples with variable sample amounts. A first application of our method for microsamples was carried out to investigate airborne dust fallout and street sediments at two urban sites where different heavy metal immission rates due to traffic influence occur. These investigations will be presented in part 2 (“Sequential extraction of heavy metals from urban dust”).     

Aerosol particle number concentration measurements in five European cities using TSI-3022 condensation particle counter over a three-year period during health effects of air pollution on susceptible subpopulations

In this study, long-term aerosol particle total number concentration measurements in five metropolitan areas across Europe are presented. The measurements have been carried out in Augsburg, Barcelona, Helsinki, Rome, and Stockholm using the same instrument, a condensation particle counter (TSI model 3022). The results show that in all of the studied cities, the winter concentrations are higher than the summer concentrations. In Helsinki and in Stockholm, winter concentrations are higher by a factor of two and in Augsburg almost by a factor of three compared with summer months. The winter maximum of the monthly average concentrations in these cities is between 10,000 cm(-3) and 20,000 cm(-3), whereas the summer min is approximately 5000-6000 cm(-3). In Rome and in Barcelona, the winters are more polluted compared with summers by as much as a factor of 4-10. The winter maximum in both Rome and Barcelona is close to 100,000 cm(-3), whereas the summer minimum is > 10,000 cm(-3). During the weekdays the maximum of the hourly average concentrations in all of the cities is detected during the morning hours between 7 and 10 a.m. The evening maxima were present in Barcelona, Rome, and Augsburg, but these were not as pronounced as the morning ones. The daily maxima in Helsinki and Stockholm are close or even lower than the daily minima in the more polluted cities. The concentrations between these two groups of cities are different with a factor of about five during the whole day. The study pointed out the influence of the selection of the measurement site and the configuration of the sampling line on the observed concentrations.