Journal cover Journal topic
Atmospheric Chemistry and Physics An interactive open-access journal of the European Geosciences Union
Journal topic

Journal metrics

Journal metrics

  • IF value: 5.668 IF 5.668
  • IF 5-year value: 6.201 IF 5-year
    6.201
  • CiteScore value: 6.13 CiteScore
    6.13
  • SNIP value: 1.633 SNIP 1.633
  • IPP value: 5.91 IPP 5.91
  • SJR value: 2.938 SJR 2.938
  • Scimago H <br class='hide-on-tablet hide-on-mobile'>index value: 174 Scimago H
    index 174
  • h5-index value: 87 h5-index 87
Volume 15, issue 19
Atmos. Chem. Phys., 15, 11273–11290, 2015
https://doi.org/10.5194/acp-15-11273-2015
© Author(s) 2015. This work is distributed under
the Creative Commons Attribution 3.0 License.
Atmos. Chem. Phys., 15, 11273–11290, 2015
https://doi.org/10.5194/acp-15-11273-2015
© Author(s) 2015. This work is distributed under
the Creative Commons Attribution 3.0 License.

Research article 12 Oct 2015

Research article | 12 Oct 2015

Hygroscopic behavior of NaCl–MgCl2 mixture particles as nascent sea-spray aerosol surrogates and observation of efflorescence during humidification

D. Gupta, H.-J. Eom, H.-R. Cho, and C.-U. Ro D. Gupta et al.
  • Department of Chemistry, Inha University, Incheon, 402-751, South Korea

Abstract. As Na+, Mg2+, and Cl are major ionic constituents of seawater, NaCl–MgCl2 mixture particles might represent sea-spray aerosols (SSAs) better than pure NaCl. However, there have been very few hygroscopic studies of pure MgCl2 and NaCl–MgCl2 mixture aerosol particles despite the MgCl2 moiety playing a major role in the hygroscopic behavior of nascent SSAs. Laboratory-generated pure MgCl2 and NaCl–MgCl2 mixture aerosol particles with 12 mixing ratios (0.01 ≤ mole fraction of NaCl (XNaCl) ≤ 0.9) were examined systematically by optical microscopy (OM), in situ Raman micro-spectrometry (RMS), and scanning electron microscopy/energy dispersive X-ray spectrometry (SEM/EDX) elemental X-ray mapping to observe their hygroscopic behavior, derive the experimental phase diagrams, and obtain the chemical micro-structures. Dry-deposited MgCl2 ⋅ 6H2O particles exhibited a deliquescence relative humidity (DRH) of ~ 33.0 % and an efflorescence RH (ERH) of 10.8–9.1 %, whereas the nebulized pure MgCl2 and MgCl2-dominant particles of XNaCl = 0.026 (eutonic) and 0.01 showed single-stage transitions at DRH of ~ 15.9 % and ERH of 10.1–3.2 %. The characteristic OH-stretching Raman signatures indicated the crystallization of MgCl2 ⋅ 4H2O at low relative humidities (RHs), suggesting that the kinetic barrier to MgCl2 ⋅ 6H2O crystallization is not overcome in the timescale of the dehydration measurements. The NaCl–MgCl2 mixture particles of 0.05 ≤ XNaCl ≤ 0.9 generally showed two-stage deliquescence: first at the mutual DRH (MDRH) of ~ 15.9 %; and second with the complete dissolution of NaCl at the second DRHs depending on the mixing ratios, resulting in a phase diagram composed of three distinct phases. During dehydration, most particles of 0.05 ≤ XNaCl ≤ 0.9 exhibited two-stage efflorescence: first, by the homogeneous nucleation of NaCl; and second, at mutual ERH (MERH) of ~ 10.4–2.9 %, by the crystallization of the MgCl2 ⋅ 4H2O moiety, also resulting in three distinct phases. Interestingly, particles of XNaCl = 0.1 and 0.2 frequently showed three different types of mutual deliquescence behaviors. The first type exhibited an MDRH at ~ 15.9 %. The second exhibited the first MDRH at ~ 15.9 %, efflorescence to MgCl2 ⋅ 6H2O (confirmed by in situ RMS) at RH of ~ 16.1–25.0 %, and a second MDRH at ~ 33.0 %. The third showed an MDRH at ~ 33.0 %. Some particles of XNaCl = 0.1 and 0.2 also exhibited higher MERHs = 15.2–11.9 % and 23.7–15.3 %, respectively, forming MgCl2 ⋅ 6H2O. These observations suggest that the presence of sufficient condensed water and optimally sized crystalline NaCl (XNaCl = 0.1 and 0.2) acting as heterogeneous nucleation seeds helps overcome the kinetic barrier, leading to the structural growth and crystallization of MgCl2 ⋅ 6H2O. SEM/EDX elemental X-ray mapping showed that the effloresced NaCl-rich particles contain homogeneously crystallized NaCl in the center, surrounded by MgCl2 ⋅ 4H2O. The observation of an aqueous phase over a wider RH range for NaCl–MgCl2 mixture particles indicates their more probable heterogeneous chemistry compared to pure NaCl particles as a nascent SSA surrogate.

Please read the corrigendum first before accessing the article.
Publications Copernicus
Download
Notice on corrigendum

The requested paper has a corresponding corrigendum published. Please read the corrigendum first before downloading the article.

Short summary
Pure MgCl2 particles and NaCl-MgCl2 mixed particles are systematically investigated to observe their hygroscopic behavior, derive experimental phase diagrams, and obtain chemical micro-structures. This work provides new interesting revelations regarding the efflorescence of MgCl2 hydrates during dehydration and also humidification. The observation of an aqueous phase over a wider RH range for NaCl-MgCl2 mixture particles indicates their more probable heterogeneous chemistry than NaCl particles.
Pure MgCl2 particles and NaCl-MgCl2 mixed particles are systematically investigated to observe...
Citation