Deliquescence and Crystallization of Ammonium Sulfate Particles Internally Mixed with Water-Soluble Organic Compounds

Parsons, Matthew T.; Knopf, Daniel A.; Bertram, Allan K.

doi:10.1021/jp0462862

Cited by 119 publications

(158 citation statements)

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“…However, no complete crystallization was observed in particle 2 down to 1% RH. The observations generally agreed with the results by Braban et al (2004) and Parsons et al (2004) who detected no crystallization of submicron particles and observed CRHs between 0 and 20% RH. It is clear that MA could significantly suppress or even inhibit the crystallization of AS in this system.…”

Section: Partial Phase Transitions Of As-organic Mixedsupporting

confidence: 92%

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Water Content and Phase Transitions in Particles of Inorganic and Organic Species and their Mixtures Using Micro-Raman Spectroscopy

Yeung

Chan

2010

Aerosol Science and Technology

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Hygroscopicity and phase transitions were measured with deposited particles of ammonium sulfate (AS), ammonium nitrate (AN), malonic acid (MA), glutaric acid (GA), glyoxylic acid (GlyA), as well as two mixed particle systems AS-MA and AS-GA using micro-Raman spectroscopy. Hygroscopicity was presented in terms of water-to-solute mass ratios, which were obtained from the integrated area ratios of the Raman water band to a distinct solute peak. Deliquescence and crystallization were confirmed by abrupt changes in the Raman peak positions and the full-widthhalf-heights of distinct solute peaks. The results for AS, AN, MA, and GA agreed well with literature reports and model predictions. For GlyA, we detected the Raman water band at near 0% RH, indicating that the spectral technique is sensitive for hygroscopic measurements at very low RH. Additional spectral feature at ∼0% RH was also observed. In the case of more complicated ASdicarboxylic acid mixed systems, the partial phase transitions of the organic components were identified using the intensity ratios of aqueous to solid C=O peaks. AS-MA particles did not completely crystallize and gradual water uptake with increasing RH from 3% was observed. Moreover, it was found that AS-GA particles showed step-wise crystallization in which the AS fraction crystallized prior to the GA fraction. The measured water content and complete DRH of both mixed systems were consistent with the published values. The results show the utility of micro-Raman spectroscopic analysis in studying hygroscopicity and phase characterizations of the chemical species in mixed particles.

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Section: Partial Phase Transitions Of As-organic Mixedsupporting

confidence: 92%

“…The further increase in fwhh at 74% suggests that the AS fraction completely deliquesced at this RH. The complete DRH found in this study also agreed well with the 73.4% RH reported by Parsons et al (2004).…”

Section: Partial Phase Transitions Of As-organic Mixedsupporting

confidence: 91%

Water Content and Phase Transitions in Particles of Inorganic and Organic Species and their Mixtures Using Micro-Raman Spectroscopy

Yeung

Chan

2010

Aerosol Science and Technology

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“…Meanwhile, the crystallization of AS is also influenced due to the presence of OA. A similar phenomenon was also observed for malonic acid / AS mixtures with minor organic content (Braban and Abbatt, 2004;Parsons et al, 2004). Braban and Abbatt (2004) found that the ERH of malonic acid / AS mixed particles was considerably decreased compared to that of pure AS for mass fractions of malonic acid less than 0.3.…”

Section: Hygroscopic Growth Of Pure and Mixed Componentssupporting

confidence: 72%

Hygroscopic behavior and chemical composition evolution of internally mixed aerosols composed of oxalic acid and ammonium sulfate

et al. 2017

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Abstract. Although water uptake of aerosol particles plays an important role in the atmospheric environment, the effects of interactions between components on chemical composition and hygroscopicity of particles are still not well constrained. The hygroscopic properties and phase transformation of oxalic acid (OA) and mixed particles composed of ammonium sulfate (AS) and OA with different organic to inorganic molar ratios (OIRs) have been investigated by using confocal Raman spectroscopy. It is found that OA droplets first crystallize to form OA dihydrate at 71 % relative humidity (RH), and further lose crystalline water to convert into anhydrous OA around 5 % RH during the dehydration process. The deliquescence and efflorescence point for AS is determined to be 80.1 ± 1.5 % RH and 44.3 ± 2.5 % RH, respectively. The observed efflorescence relative humidity (ERH) for mixed OA / AS droplets with OIRs of 1 : 3, 1 : 1 and 3 : 1 is 34.4 ± 2.0, 44.3 ± 2.5 and 64.4 ± 3.0 % RH, respectively, indicating the elevated OA content appears to favor the crystallization of mixed systems at higher RH. However, the deliquescence relative humidity (DRH) of AS in mixed OA / AS particles with OIRs of 1 : 3 and 1 : 1 is observed to occur at 81.1 ± 1.5 and 77 ± 1.0 % RH, respectively. The Raman spectra of mixed OA / AS droplets indicate the formation of ammonium hydrogen oxalate (NH 4 HC 2 O 4 ) and ammonium hydrogen sulfate (NH 4 HSO 4 ) from interactions between OA and AS in aerosols during the dehydration process on the time scale of hours, which considerably influence the subsequent deliquescence behavior of internally mixed particles with different OIRs. The mixed OA / AS particles with an OIR of 3 : 1 exhibit no deliquescence transition over the RH range studied due to the considerable transformation of (NH 4 ) 2 SO 4 into NH 4 HC 2 O 4 with a high DRH. Although the hygroscopic growth of mixed OA / AS droplets is comparable to that of AS or OA at high RH during the dehydration process, Raman growth factors of mixed particles after deliquescence are substantially lower than those of mixed OA / AS droplets during the efflorescence process and further decrease with elevated OA content. The discrepancies for Raman growth factors of mixed OA / AS particles between the dehydration and hydration process at high RH can be attributed to the significant formation of NH 4 HC 2 O 4 and residual OA, which remain solid at high RH and thus result in less water uptake of mixed particles. These findings improve the understanding of the role of reactions between dicarboxylic acid and inorganic salt in the chemical and physical properties of aerosol particles, and might have important implications for atmospheric chemistry.

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“…Using this simplified approach, it was determined that atmospheric aerosol in the Po valley in Italy exhibits a seasonal profile, with mono-and dicarboxylic acids dominating in the summer and polycarboxylic acids in spring, winter and autumn (Decesari et al, 2001). NMR profiles of the atmospheric aerosol were found to be similar to those obtained from terrestrial fulvic acids, for example Suwannee River fulvic acid (SRFA, Cappiello et al, 2003), which has been used as a surrogate for ambient aerosol in studies of physico-chemical properties (Parsons et al, 2004;Topping et al, 2005b;Dinar et al, 2006b). This technique has been used in numerous studies, including source identification and a recent improvement involves the derivatization of the carboxylic group with diazomethane to allow a direct determination of carboxylic acids in WSOC .…”

Section: Off-line High Complexity Soa Measurementsmentioning

confidence: 98%

The formation, properties and impact of secondary organic aerosol: current and emerging issues

et al. 2009

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Abstract. Secondary organic aerosol (SOA) accounts for a significant fraction of ambient tropospheric aerosol and a detailed knowledge of the formation, properties and transformation of SOA is therefore required to evaluate its impact on atmospheric processes, climate and human health. The chemical and physical processes associated with SOA formation are complex and varied, and, despite considerable progress in recent years, a quantitative and predictive understanding of SOA formation does not exist and therefore represents a major research challenge in atmospheric science. This review begins with an update on the current state of knowledge on the global SOA budget and is followed by an overview of the atmospheric degradation mechanisms for SOA precursors, gas-particle partitioning theory and the analytical techniques used to determine the chemical composition of SOA. A survey of recent laboratory, field and modeling studies is also presented. The following topical and emerging issues are highlighted and discussed in detail: molecular characterization of biogenic SOA constituents, condensed phase reactions and oligomerization, the interaction of atmospheric organic components with sulfuric acid, the chemical and photochemical processing of organics in the atmospheric aqueous phase, aerosol formation from real plant emissions, interaction of atmospheric organic components with water, thermodynamics and mixtures in atmospheric models. Finally, the major challenges ahead in laboratory, field and modeling studies of SOA are discussed and recommendations for future research directions are proposed.

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Deliquescence and Crystallization of Ammonium Sulfate Particles Internally Mixed with Water-Soluble Organic Compounds

Cited by 119 publications

References 56 publications

Water Content and Phase Transitions in Particles of Inorganic and Organic Species and their Mixtures Using Micro-Raman Spectroscopy

Water Content and Phase Transitions in Particles of Inorganic and Organic Species and their Mixtures Using Micro-Raman Spectroscopy

Hygroscopic behavior and chemical composition evolution of internally mixed aerosols composed of oxalic acid and ammonium sulfate

The formation, properties and impact of secondary organic aerosol: current and emerging issues

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