Abstract. MBTCA (3-methyl-1,2,3-butanetricarboxylic acid), a low-volatile, highly oxidized, secondary-generation product of monoterpenes, is one of the most relevant tracer compounds for biogenic secondary organic aerosols (SOAs). In this study, laboratory-generated, micrometer-sized, pure-MBTCA, mono-/di-/trisodium MBTCA salts and MBTCA–NaCl mixture aerosol particles of four mixing ratios (molar ratios = 1 : 1, 1 : 2, 1 : 3, and 2 : 1) were examined systematically to observe their hygroscopic behavior by varying the relative humidity (RH) using in situ Raman microspectrometry (RMS) assembled with either a see-through impactor, where the particles were deposited on a Si wafer, or a levitation system. The pure MBTCA droplets effloresced at RH = ∼ 30 %–57.8 % and did not deliquesce until RH > 95 %. The mono- and disodium MBTCA salt aerosols did not show clear efflorescence RH (ERH) and deliquescence RH (DRH). In contrast, the trisodium MBTCA salt exhibited ERH = ∼ 44.4 %–46.8 % and DRH = ∼ 53.1 % during the hygroscopic experiment cycle. The mixture aerosols generated from solutions of MBTCA : NaCl = 1 : 1 and 2 : 1 showed no visible ERH and DRH in the see-through impactor because of the partial and total consumption of NaCl, respectively, through chemical reactions during the dehydration process. The mixture particles with a 1 : 1 molar ratio in the levitation system exhibited a clear DRH at ∼ 71 % and ERH at ∼ 50 %. This suggests less reaction between the mixtures and a larger portion of NaCl remaining in the levitation system. The other mixtures of MBTCA : NaCl = 1 : 2 and 1 : 3 displayed single-stage efflorescence and deliquescence at ERH = ∼ 45 %–50 % and DRH = ∼ 74 %, respectively, because of the considerable amount of NaCl present in the mixture aerosols in both systems. Observations and Raman analyses indicated that only monosodium MBTCA salt aerosols could be formed through a reaction between MBTCA and NaCl. The reaction occurred more rapidly with a more elevated concentration of either MBTCA or NaCl, and the controlling factor for the reactivity of the mixtures depended mostly on the availability of H+ dissociated from the MBTCA tricarboxylic acid. The lower degree of reaction of the mixture particles in the levitation system might be caused by the relatively airtight circumstance inside, i.e., less release of HCl. The study revealed that the interactions between the MBTCA and NaCl could modify the properties of the organic acid in the atmosphere, leading to enhanced capability of the probable heterogeneous chemistry in the aqueous aerosols.

Abstract. Secondary organic aerosols (SOAs), which are formed and transformed through complex physicochemical processes in the atmosphere, have attracted considerable attention over the past decades because of their impacts on both climate change and human health. Recently, 3-methyl-1,2,3-butanetricarboxylic acid (MBTCA), a low volatile, highly oxidized, secondary generation product of monoterpenes, is one of the most relevant tracer compounds for biogenic SOAs. Therefore, MBTCA was selected to understand its hygroscopic properties better. In addition, interactions between the organic acid and inorganic components have been reported, which may alter their hygroscopic properties mutually. In this study, laboratory-generated, micrometer-sized, pure MBTCA, mono-/di-/tri-sodium MBTCA salts, and MBTCA-NaCl mixture aerosol particles of four mixing ratios (molar ratios = 1 : 1, 1 : 2, 1 : 3, and 2 : 1) were examined systematically to observe their hygroscopic behavior by varying the relative humidity (RH) from RH = ~95 % to ~1 % through a dehydration process, followed by a humidification process from RH = ~1 % to ~95 %, using in-situ Raman microspectrometry (RMS) assembled with a see-through impactor where the particles were deposited on a Si wafer. The hygroscopic behavior of pure MBTCA and MBTCA-NaCl mixture aerosol particles of three mixing ratios (molar ratios = 1 : 1, 1 : 2, and 1 : 3) were also examined using a levitation system mounted on in-situ RMS through a humidification process from RH = ~10 % to ~80 % after a quenching process from droplets, followed by dehydration from RH = ~80 % to ~10 %. The pure MBTCA droplets effloresced at RH = ~30–57.8 % and did not dissolve until RH > 95 %. The mono- and di-sodium MBTCA salt aerosols did not show clear efflorescence RH (ERH) and deliquescence RH (DRH). In contrast, the tri-sodium MBTCA salt exhibited ERH = ~44.4–46.8 % and DRH = ~53.1 %, during the hygroscopic experiment cycle. The mixture aerosols generated from solutions of MBTCA : NaCl = 1 : 1 and 2 : 1 showed no visible ERH and DRH in the see-through impactor because of the partial and total consumption of NaCl, respectively, through chemical reactions during the dehydration process. The mixture particles with a 1 : 1 molar ratio in the levitation system exhibited a clear DRH at ~71 % and ERH at ~50 %. This suggests less reaction between the mixtures and a larger portion of NaCl remaining in the levitation system. The other mixtures of MBTCA : NaCl = 1 : 2 and 1 : 3 displayed single-stage efflorescence and deliquescence at ERH = ~45–50 % and DRH = ~74 %, respectively, because of the considerable amount of NaCl present in the mixture aerosols in both systems. Observations and Raman analyses indicated that only monosodium MBTCA salt aerosols could be formed through a reaction between MBTCA and NaCl. The reaction occurred more rapidly with a more elevated concentration of either MBTCA or NaCl, and the controlling factor for the reactivity of the mixtures depended mostly on the availability of H+ dissociated from the MBTCA tricarboxylic acid. The lower degree of reaction of the mixture particles in the levitation system might be caused by the relatively airtight circumstance inside, i.e., the less release of HCl. In addition, the quenching process, i.e., the starting point of the hygroscopicity experiments, induced the solidification of MBTCA, and further, a slow reaction between MBTCA and NaCl. The study revealed that the interactions between the MBTCA and NaCl could modify the properties of the organic acid in the atmosphere, leading to enhanced capability of the probable heterogeneous chemistry in the aqueous aerosols.