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This paper describes the optimization and validation of a new simple method for the quantitative determination of water in atmospheric particulate matter (PM). The analyses are performed by using a coulometric Karl-Fisher system equipped with a controlled heating device; different water contributions are separated by the application of an optimized thermal ramp (three heating steps: 50-120 degrees C, 120-180 degrees C, 180-250 degrees C).

The analytical performance of the method was verified by using standard materials containing 5.55% and 1% by weight of water. The recovery was greater than 95 %; the detection limit was about 20 mu g. The method was then applied to NIST Reference Materials (NIST1649a, urban particulate matter) and to real PM10 samples collected in different geographical areas. In all cases the repeatability was satisfactory (10-15 %).

When analyzing the Reference Material, the separation of four different types of water was obtained. In real PM10 samples the amount of water and its thermal profile differed as a function of the chemical composition of the dust. Mass percentages of 3-4% of water were obtained in most samples, but values up to about 15% were reached in areas where the chemical composition of PM is dominated by secondary inorganic ions and organic matter. High percentages of water were also observed in areas where PM is characterized by the presence of desert dust.

A possible identification of the quality of water released from the samples was tried by applying the method to some hygroscopic compounds that are likely contained in PM (pure SiO2, Al2O3, ammonium salts, carbohydrates and dicarboxylic acids) and by comparing the results with those obtained from field samples.