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Crystalline Organic Compounds as Effective Nuclei in Contact Efflorescence of Ammonium Sulfate

Journal Article · · Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory
Contact nucleation is believed to play a role in liquid-to-solid phase transitions in the atmosphere including ice nucleation and salt efflorescence. Here, for this work, contact efflorescence of optically levitated ammonium sulfate droplets by collisions with organic particles is probed using a long working-distance optical trap. Two highly viscous water-soluble organic compounds (d-(+)-raffinose and citric acid), and two insoluble highly surface-active organic compounds (stearic acid and cis-pinonic acid) were probed for their ability to induce efflorescence upon contact. While three of the organics showed minimal effectiveness as contact nuclei, cis-pinonic acid showed a remarkable ability to initiate contact efflorescence of ammonium sulfate, occurring near ammonium sulfate’s deliquescence relative humidity. Further analysis of cis-pinonic acid using bright-field microscopy in an electrodynamic balance provided evidence that the cis-pinonic acid particles are crystalline under the laboratory conditions. We suggest that the close lattice match between crystalline ammonium sulfate and crystalline cis-pinonic acid may account for the observed effectiveness in initiating contact efflorescence of ammonium sulfate. In contrast, tests of contact nucleation between cis-pinonic acid and sodium chloride, a pair with a poor lattice match, did not result in efflorescence. These findings suggest that crystalline organic compounds in the atmosphere could act as effective nuclei for contact efflorescence of atmospherically relevant salts, provided they share a compatible lattice structure.
Research Organization:
Sandia National Laboratories (SNL-NM), Albuquerque, NM (United States)
Sponsoring Organization:
USDOE Laboratory Directed Research and Development (LDRD) Program; USDOE National Nuclear Security Administration (NNSA)
Grant/Contract Number:
NA0003525
OSTI ID:
2530822
Report Number(s):
SAND--2025-02782J
Journal Information:
Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory, Journal Name: Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory Journal Issue: 9 Vol. 129; ISSN 1089-5639
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English

References (82)

A microphysical parameterization of aqSOA and sulfate formation in clouds journal July 2017
Studies of moisture exchange between stearic acid, calcium stearate, and magnesium stearate journal June 2010
Stability and occurrence of polymorphic modifications of the stearic acid in polar and nonpolar solutions journal March 1984
Heterogeneous chemistry and tropospheric ozone journal January 2000
Surface tension of aqueous solutions of water-soluble organic and inorganic compounds journal September 2007
Aerosol Optical Tweezers Elucidate the Chemistry, Acidity, Phase Separations, and Morphology of Atmospheric Microdroplets journal October 2020
Long Working-Distance Optical Trap for in Situ Analysis of Contact-Induced Phase Transformations journal May 2015
Dual-Balance Electrodynamic Trap as a Microanalytical Tool for Identifying Gel Transitions and Viscous Properties of Levitated Aerosol Particles journal January 2020
Seeded Crystal Growth of Internally Mixed Organic–Inorganic Aerosols: Impact of Organic Phase State journal September 2021
Role of Organic Hydrocarbons in Atmospheric Ice Formation via Contact Freezing journal December 2016
Immersion and Contact Efflorescence Induced by Mineral Dust Particles journal January 2018
Physicochemical Properties of Pinic, Pinonic, Norpinic, and Norpinonic Acids as Relevant α-Pinene Oxidation Products journal August 2019
Multivalent Surface Cations Enhance Heterogeneous Freezing of Water on Muscovite Mica journal September 2020
Contact Freezing of Water by Salts journal August 2015
Probing Heterogeneous Efflorescence of Mars-Relevant Salts with an Optical Levitator journal September 2020
Metal Oxide Particles as Atmospheric Nuclei: Exploring the Role of Metal Speciation in Heterogeneous Efflorescence and Ice Nucleation journal March 2023
Kinetically Driven Crystallization of a Pure Polymorphic Phase of Stearic Acid from CO2-Expanded Solutions journal February 2010
The Influence of Organic Films at the Air−Aqueous Boundary on Atmospheric Processes journal April 2006
Phase Transitions of Aqueous Atmospheric Particles journal September 2000
Impact of Organic Coating on Optical Growth of Ammonium Sulfate Particles journal November 2013
Deliquescence and Hygroscopic Growth of Mixed Inorganic−Organic Atmospheric Aerosol journal October 2000
Vibrational spectroscopic study on the occurrence of stearic acid B and E forms: heterogeneous nucleation of the B form on the surface of E crystals and the topotactic phase transition from E to B journal December 1992
A New Mechanism for Nucleation beneath Monolayer Films? journal February 1998
Ice Nucleation Efficiency of Hydroxylated Organic Surfaces Is Controlled by Their Structural Fluctuations and Mismatch to Ice journal February 2017
Surface Tensions and Densities of Oxalic, Malonic, Succinic, Maleic, Malic, and cis-Pinonic Acids journal December 2005
The Solubilities of the Normal Saturated Fatty Acids journal November 1942
Heterogeneous Ice Nucleation on Simulated Sea-Spray Aerosol Using Raman Microscopy journal August 2014
Surface-Active cis-Pinonic Acid in Atmospheric Droplets: A Molecular Dynamics Study journal February 2010
Heterogeneous nucleation of the efflorescence of (NH4)2SO4 particles internally mixed with Al2O3, TiO2, and ZrO2 journal February 1999
Nighttime removal of NO x in the summer marine boundary layer : NIGHTTIME NO journal April 2004
Hygroscopic and optical properties of organic sea salt aerosol and consequences for climate forcing journal January 2004
Heterogeneous freezing of ammonium sulfate and sodium chloride solutions by long chain alcohols journal January 2006
Global distribution of solid and aqueous sulfate aerosols: Effect of the hysteresis of particle phase transitions journal January 2008
The deposition ice nucleation and immersion freezing potential of amorphous secondary organic aerosol: Pathways for ice and mixed-phase cloud formation: ICE NUCLEATION BY AMORPHOUS SOA journal August 2012
Aerosol Mixing State: Measurements, Modeling, and Impacts journal May 2019
Dissolution behavior and surface tension effects of organic compounds in nucleating cloud droplets journal February 1996
Thermodynamic and optical properties of mixed-salt aerosols of atmospheric importance journal January 1997
Organic films on atmospheric aerosol particles, fog droplets, cloud droplets, raindrops, and snowflakes journal May 1983
Global distribution of particle phase state in atmospheric secondary organic aerosols journal April 2017
Heterogeneous nucleation of ice particles on glassy aerosols under cirrus conditions journal March 2010
The viscosity of atmospherically relevant organic particles journal March 2018
Predicting heterogeneous ice nucleation with a data-driven approach journal September 2020
Significant underestimation of radiative forcing by aerosol–cloud interactions derived from satellite-based methods journal June 2021
Uptake of N2O5 by aqueous aerosol unveiled using chemically accurate many-body potentials journal March 2022
Emerging investigator series: determination of biphasic core–shell droplet properties using aerosol optical tweezers journal January 2018
Exploring the hygroscopicity, water diffusivity, and viscosity of organic–inorganic aerosols – a case study on internally-mixed citric acid and ammonium sulfate particles journal January 2023
Spontaneous fission of atmospheric aerosol particles journal November 2001
Polymorphism of even saturated carboxylic acids from n-decanoic to n-eicosanoic acid journal January 2007
Glass transition and phase state of organic compounds: dependency on molecular properties and implications for secondary organic aerosols in the atmosphere journal January 2011
Crystal structure of the C form of stearic acid journal January 1971
The Nucleation of Ice Formation by Silver Iodide journal July 1947
Neutron-Diffraction Study of the Structures of Ferroelectric and Paraelectric Ammonium Sulfate journal June 1966
Towards understanding ice nucleation by long chain alcohols journal February 2006
Viscosity of  -pinene secondary organic material and implications for particle growth and reactivity journal April 2013
Improving our fundamental understanding of the role of aerosol−cloud interactions in the climate system journal May 2016
Contact efflorescence as a pathway for crystallization of atmospherically relevant particles journal December 2015
Optical deformation of single aerosol particles journal September 2019
Solid organic-coated ammonium sulfate particles at high relative humidity in the summertime Arctic atmosphere journal March 2022
Effect of aerosol radiative forcing uncertainty on projected exceedance year of a 1.5 °C global temperature rise journal September 2020
Structure of (±)-cis-pinonic acid journal December 1986
Structure of stearic acid E form journal August 1990
Double-layered polytypic structure of the E form of octadecanoic acid, C18H36O2 journal February 1994
Double-layered polytypic structure of the B form of octadecanoic acid, C18H36O2 journal February 1994
(+)-cis-Pinonic acid: catemeric hydrogen bonding in a non-racemic ∊-keto acid journal November 1999
Crystal nucleation initiated by transient ion-surface interactions at aerosol interfaces journal July 2017
A Possible Mechanism for Contact Nucleation journal October 1974
A Study of the Mechanism of Contact Ice Nucleation journal August 1975
The Crystal Structure of the B-form of Stearic Acid journal September 1978
Accurate and efficient determination of the radius, refractive index, and dispersion of weakly absorbing spherical particle using whispering gallery modes journal January 2013
Stimulated Raman scattering from individual water and ethanol droplets at morphology-dependent resonances journal January 1985
Halite-sylvite thermoelasticity journal January 2004
Is Contact Nucleation Caused by Pressure Perturbation? journal December 2019
Secondary organic aerosol formation in cloud droplets and aqueous particles (aqSOA): a review of laboratory, field and model studies journal January 2011
Glassy aerosols with a range of compositions nucleate ice heterogeneously at cirrus temperatures journal January 2012
State transformations and ice nucleation in amorphous (semi-)solid organic aerosol journal January 2013
Ice nucleation efficiency of AgI: review and new insights journal January 2016
Diffusivity measurements of volatile organics in levitated viscous aerosol particles journal January 2017
A parameterization of the heterogeneous hydrolysis of N2O5 for mass-based aerosol models: improvement of particulate nitrate prediction journal January 2018
Surface tensions of multi-component mixed inorganic/organic aqueous systems of atmospheric significance: measurements, model predictions and importance for cloud activation predictions journal January 2007
Do atmospheric aerosols form glasses? journal January 2008
Inhibition of ice crystallisation in highly viscous aqueous organic acid droplets journal January 2008
A new experimental approach to study the hygroscopic and optical properties of aerosols: application to ammonium sulfate particles journal January 2014