Fe and Mn oxidation states by TEM-EELS in fine-particle emissions from a Fe-Mn alloy making plant.

Fine particles were sampled both inside the chimneys and in the near-field of an Fe-Mn-alloy manufacturing plant. The transfer from one point to another point in the environment, as well as the bioavailability and toxicity of these two metals, depend above all on their speciation. The oxidation states of iron and manganese in the collected particles were determined by using transmission electron microscopy coupled with electron energy-loss spectroscopy (TEM-EELS). The mineralogical identity of these metal-rich particles was determined by selected area electron diffraction (SAED) coupled with energy-dispersive X-ray spectroscopy (EDX). This study shows that both iron and manganese in metallic particles are prone to oxidation reactions via gas/particle conversion mechanisms, which take place in the flue gases within the smoke stacks. This phenomenon is more pronounced for the smallest Fe-rich particles. However, no further change of oxidation state of the two elements was observed in the near-field of the plant, after emission into the atmosphere (within <2000 m of the smoke stacks). The oxidation states of iron and manganese remain mainly between +II and +III, which is probably due to short residence time of these particles in the pollution plume.

Investigation on the near-field evolution of industrial plumes from metalworking activities.

In a context where a significant fraction of the population lives near industrial areas, the main objectives of this study are to provide (a) new data on PM2.5 chemical compositions, heavy-metal concentrations and trace gases released by metalworking activities and (b) new information on the near-field evolution (up to about a thousand meters) of such industrial plumes in terms of particle chemical composition and size distribution. For that purpose, a one-month field campaign was performed in an industrial area near the city of Dunkirk (Northern France), combining measurements of atmospheric dynamics and physico-chemical characterization of air masses. Comparisons between several elemental ratios (mainly Mn/Fe), particle size distributions and volatile organic compound (VOC) concentrations at the stacks and at a near-field site suggest that plumes of a ferromanganese alloy plant were quickly mixed with pollutants emitted by other sources (mainly other industries, possibly traffic and sea spray), in particular a neighboring steelworks, before reaching the sampling site. This led to the emergence of secondary particles related to condensation and/or aggregation phenomena inside the plumes. Metalworking emissions were also identified as a source of new particle formation, formed through the emission of gaseous precursors and their fast transformation and condensation, over a timescale of minutes before reaching the near-field site 800 m downwind. Ultrafine particles emitted at the stacks also quickly agglomerated to form larger particles before reaching the near-field site. These results show that, even over short distances, the chemical composition and size distribution of metalworking plumes may evolve rapidly and the characteristics of particles at the boundary of an industrial area (especially in contiguous urban areas) may differ from those emitted directly at the stacks.

Fast changes in chemical composition and size distribution of fine particles during the near-field transport of industrial plumes.

Aerosol sampling was performed inside the chimneys and in the close environment of a FeMn alloys manufacturing plant. The number size distributions show a higher abundance of ultrafine aerosols (10-100 nm) inside the plume than upwind of the plant, indicating the emissions of nanoparticles by the industrial process. Individual analysis of particles collected inside the plume shows a high proportion of metal bearing particles (Mn-/Fe-) consisting essentially of internally mixed aluminosilicate and metallic compounds. These particles evolve rapidly (in a few minutes) after emission by adsorption of VOC gas and sulfuric acid emitted by the plant but also by agglomeration with pre-existing particles. At the moment, municipalities require a monitoring of industrial emissions inside the chimneys from manufacturers. However those measures are insufficient to report such rapid changes in chemical composition and thus to evaluate the real impact of industrial plumes in the close environment of plants (when those particles leave the industrial site). Consequently, environmental authorities will have to consider such fast evolutions and then to adapt future regulations on air pollution sources.