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ACCEPTED MANUSCRIPT ACCEPTED MANUSCRIPT2 This review synthesizes the existing knowledge on the characteristics of PM 2.5 at sites under the direct influence of industrial emissions, with a specific focus on their morphology, size distributions and chemical composition. Results from on-line and off-line analytical techniques indicate a high temporal and spatial variability of mass size distribution and chemical composition depending on the type of industrial processes, the sampling distances and frequencies, and the meteorological conditions. Tracers of specific activities have been identified in a number of studies and may help to provide estimates of the relative contribution of pollutant sources from heavily industrialized areas.

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.

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