Chemical speciation of chlorine in atmospheric aerosol samples by high-resolution proton induced X-ray emission spectroscopy

Chlorine is a main elemental component of atmospheric particulate matter (APM). The knowledge of the chemical form of chlorine is of primary importance for source apportionment and for estimation of health effects of APM. In this work the applicability of high-resolution wavelength dispersive proton induced X-ray emission (PIXE) spectroscopy for chemical speciation of chlorine in fine fraction atmospheric aerosols is studied. A Johansson-type crystal spectrometer with energy resolution below the natural linewidth of Cl K lines was used to record the high-resolution Kα and Kβ proton induced spectra of several reference Cl compounds and two atmospheric aerosol samples, which were collected for conventional PIXE analysis. The Kα spectra which refers to the oxidation state, showed very minor differences due to the high electronegativity of Cl. However, the Kβ spectra exhibited pronounced chemical effects which were significant enough to perform chemical speciation. The major chlorine component in two fine fraction aerosol samples collected during a 2010 winter campaign in Budapest was clearly identified as NaCl by comparing the high-resolution Cl Kβ spectra from the aerosol samples with the corresponding reference spectra. This work demonstrates the feasibility of high-resolution PIXE method for chemical speciation of Cl in aerosols.