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Samples of fine atmospheric particulate matter (APM) were collected in Londrina/PR and Assis/SP and analysed in order to investigate the correlation between soluble ionic species from anthropogenic sources (nitrate and sulphate). Secondary ions such as chloride, nitrate and sulfate were measured using ion chromatography. Diagnostic ratios (DR) were calculated indicating the signature of current vehicular emissions as well as stationary sources. The data obtained at the open sites in Londrina and Assis showed that chloride, nitrate and sulphate may have distinct formation or removal mechanisms depending on the size fraction of the MPA. RD can be applied to infer on sources of atmospheric contaminants.