On-line differentiation of mineral phase in aerosol particles by ion formation mechanism using a LAAP-ToF single particle mass spectrometer

Abstract. Mineralogy of silicate mineral dust has a strong influence on climate and eco-systems due to variation in physicochemical properties that result from differences in composition and crystal structure (mineral phase). Traditional off-line methods of analysing mineral phase are labour intensive and the temporal resolution of the data is much longer than many atmospheric processes. Single particle mass spectrometry (SPMS) is an established technique for the on-line size resolved measurement of particle composition by laser desorption ionisation (LDI) followed by time-of-flight mass spectrometry (TOF-MS). Although non-quantitative, the technique is able to identify the presence of silicate minerals in airborne dust particles from markers of alkali metals and silicate molecular ions in the mass spectra. However, the differentiation of mineral phase in silicate particles by traditional mass spectral peak area measurements is not possible. This is because instrument function and matrix effects in the ionisation process result in variations in instrument response that are greater than the differences in composition between common mineral phases. In this study, a novel technique is introduced that enables the differentiation of mineral phase in silicate mineral particles by ion formation mechanism measured from subtle changes in ion arrival times at the TOF-MS detector. Using a combination of peak area and peak centroid measurements, we show that the arrangement of the interstitial alkali metals in the crystal structure, an important property in silicate mineralogy, influences the ion arrival times of elemental and molecular ion species in the negative ion mass spectra. A classification scheme is presented that allows for the differentiation of illite/smectite, kaolinite and feldspar minerals on a single particle basis. On-line analysis of mineral dust aerosol generated from clay mineral standards produced mineral fractions that are in agreement with bulk measurements reported by traditional XRD analysis.