Abstract. The accumulation of secondary acids and ammonium on individual mineral dust particles during ACEAsia has been measured with an online single-particle mass spectrometer, the ATOFMS. Changes in the amounts of sulphate, nitrate, and chloride mixed with dust particles correlate with air masses from different source regions. The uptake of secondary acids depended on the individual dust particle mineralogy; high amounts of nitrate accumulated on calcium-rich dust while high amounts of sulphate accumulated on aluminosilicate-rich dust. Oxidation of S(IV) to S(VI) by iron in the aluminosilicate dust is a possible explanation for this enrichment of sulphate, which has important consequences for the fertilization of remote oceans by soluble iron. This study shows the segregation of sulphate from nitrate and chloride in individual aged dust particles for the first time. A transport and aging timeline provides an explanation for the observed segregation. Our data suggests that sulphate became mixed with the dust first. This implies that the transport pathway is more important than the reaction kinetics in determining which species accumulate on mineral dust. Early in the study, dust particles in volcanically influenced air masses were mixed predominately with sulphate. Dust mixed with chloride then dominated over sulphate and nitrate when a major dust front reached the R. V. Ronald Brown. We hypothesize that the rapid increase in chloride on dust was due to mixing with HCl(g) released from acidified sea salt particles induced by heterogeneous reaction with volcanic SO 2 (g), prior to the arrival of the dust front. The amount of ammonium mixed with dust correlated strongly with the total amount of secondary acid reaction products in the dust. Submicron dust and ammonium sulphate were internally mixed, contrary to frequent reports that they exist as external mixtures. The size distribution of the mixing Correspondence to: K. Prather (kprather@ucsd.edu) state of dust with these secondary species validates previous mechanisms of the atmospheric processing of dust and generally agrees with simulated aerosol chemistry from the STEM-2K3 model. This series of novel results has important implications for improving the treatment of dust in global chemistry models and highlights a number of key processes that merit further investigation through laboratory and field studies.

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Abstract. The accumulation of secondary acid products and ammonium on individual mineral dust particles during ACE-Asia has been measured in real-time using ATOFMS. Changes in the amounts of sulphate, nitrate, and chloride mixed with dust particles corresponded to different air mass source regions. During volcanically influenced periods, dust mixed with sulphate dominated. This rapidly switched to dust predominantly mixed with chloride when the first Asian dust front reached the R/V Ronald Brown. We hypothesise that the high degree of mixing of dust with chloride was caused by the prior reaction of NOy(g) and volcanic SO2(g) with sea salt particles, reducing the availability of nitrate and sulphate precursors while releasing HCl(g), which then reacted with the incoming dust front. The segregation of sulphate from nitrate and chloride in individual dust particles is demonstrated for the first time. This is likely caused by the dust plume encountering elevated SO2(g) in the Chinese interior before reaching coastal urban areas polluted by both SO2(g) and NOx(g). This caused the fractions of dust mixed with nitrate and/or chloride to be strongly dependent on the total dust loadings, whereas dust mixed with sulphate did not show this same dust concentration dependence. Ammonium was also significantly mixed with dust and the amount correlated strongly with the total amount of secondary acid reaction products in the dust. Submicron dust and ammonium sulphate were internally mixed, contrary to frequent statements that they exist as an external mixture. The size distribution of the mixing state of dust with these secondary species validates previous models and mechanisms of the atmospheric processing of dust. The uptake of secondary acids was also dependent on the individual dust particle mineralogy; nitrate accumulated on calcium-rich dust while sulphate accumulated on aluminosilicate-rich dust. Oxidation of S(IV) to S(VI) by iron in the aluminosilicate-rich dust is a probable explanation for this result, with important consequences for dust as a vector for the fertilization of remote oceans by soluble iron. This series of novel results has important implications for improving the treatment of dust in global chemistry models and highlights several key processes requiring further investigation through laboratory and field studies.

Vertical and horizontal profiles of atmospheric aerosols are necessary for understanding the impact of air pollution on regional and global climate. To gain further insight into the size-resolved chemistry of individual atmospheric particles, a smaller aerosol time-of-flight mass spectrometer (ATOFMS) with increased data acquisition capabilities was developed for aircraft-based studies. Compared to previous ATOFMS systems, the new instrument has a faster data acquisition rate with improved ion transmission and mass resolution, as well as reduced physical size and power consumption, all required advances for use in aircraft studies. In addition, real-time source apportionment software allows the immediate identification and classification of individual particles to guide sampling decisions while in the field. The aircraft (A)-ATOFMS was field-tested on the ground during the Study of Organic Aerosols in Riverside, CA (SOAR) and aboard an aircraft during the Ice in Clouds Experiment-Layer Clouds (ICE-L). Initial results from ICE-L represent the first reported aircraft-based single-particle dual-polarity mass spectrometry measurements and provide an increased understanding of particle mixing state as a function of altitude. Improved ion transmission allows for the first single-particle detection of species out to approximately m/z 2000, an important mass range for the detection of biological aerosols and oligomeric species. In addition, high time resolution measurements of single-particle mixing state are demonstrated and shown to be important for airborne studies where particle concentrations and chemistry vary rapidly.