A new method to quantify particulate sodium and potassium salts (nitrate, chloride, and sulfate) by thermal desorption aerosol mass spectrometry

<jats:p>Abstract. The reaction of sea salt (or biomass burning) particles with sulfuric acid and nitric acid leads to the displacement of chloride relative to sodium (or potassium). We have developed a new particle mass spectrometer to quantify non-refractory and refractory sulfate aerosols (referred to as refractory aerosol thermal desorption mass spectrometer: rTDMS). The combination of a graphite particle collector and a carbon dioxide laser enables high desorption temperature (blackbody equivalent radiation temperature of up to 930 ∘C). Ion signals originating from evolved gas molecules are detected by a quadrupole mass spectrometer. Here we propose a new method to quantify the mass concentrations of sodium nitrate (NaNO3: SN), sodium chloride (NaCl: SC), sodium sulfate (Na2SO4: SS), potassium nitrate (KNO3: PN), potassium chloride (KCl: PC), and potassium sulfate (K2SO4: PS) particles by using the rTDMS. Laboratory experiments were performed to test the sensitivities of the rTDMS to various types of particles. We measured ion signals originating from single-component particles for each compound and found a good linearity (r2>0.8) between the major ion signals and mass loadings. We also measured ion signals originating from internally mixed SN + SC + SS (or PN + PC + PS) particles and found that the temporal profiles of ion signals at m/z 23 (Na+) (or 39; K+) were characterized by three sequential peaks associated with the evolution of the desorption temperature. We tested potential interferences in the quantification of sea salt particles under real-world conditions by artificially generating “modified” sea salt particles from a mixture of diluted seawater and SN (or SS) solution. The SS/SC ratios estimated from the ion signals at m/z 23, 36 (H35Cl+), and 48 (SO+) agreed well with those predicted from the solution concentrations to within ∼10 %. The SN/SC ratios estimated from the ion signals at m/z 30 (NO+) and 36 also agreed with those predicted from the solution concentrations to within ∼15 %, whereas the SN/SC ratios estimated from m/z 23 were significantly lower than the predicted values. Based on these experimental results, the applicability of the rTDMS to ambient measurements of sea salt particles is discussed. </jats:p>