Self-attenuation artifacts and correction factors of light element measurements by X-ray analysis: Implication for mineral dust composition studies

On a global scale, mineral dust is one of the major components of atmospheric aerosols and has important effects on the radiative budget of the atmosphere and thus on climate forcing. An accurate measurement of the concentration of crustal elements, namely Na, Mg, Al, Si, K, Ca, Ti, and Fe, is mandatory for the study of desert aerosols. The concentration of light elements, when measured by X-ray emission techniques such as X-ray fluorescence (XRF) and particle-induced X-ray emission (PIXE), can be underestimated owing to self-absorption of the emitted soft X-rays inside aerosol particles. In this work, we analyzed dust samples collected in field campaigns and samples produced in the laboratory using dust of known composition. Measurements have been conducted with PIXE and energy-dispersive XRF (ED-XRF), together with an attenuation-free technique such as particle-induced gamma-ray emission (PIGE) and attenuation corrected wavelength-dispersive XRF (WD-XRF) by internal standard calibration. We focus on the determination of Al and present results of a PIXE versus PIGE intercomparison. Aluminum concentration was measured with both techniques in dust samples collected by aircraft sampling over western Africa during winter 2006 and summer 2007. An underestimation of the Al concentration determined by PIXE was observed (up to 40%), and it was compared with the results of a simple calculation using basic physics and the size distribution of the collected aerosol. Similar attenuation was observed for Mg, Al, and Si in the laboratory samples analyzed by ED-XRF and WD-XRF. In order to use concentration ratios involving light elements as tracers of the region of emission of the sampled dust, these artifacts (i.e., underestimation of the concentration of light elements) induced by self-attenuation should be properly considered and corrected.