CaltechTHESIS
  A Caltech Library Service

Investigation of Fundamental Processes Governing Secondary Organic Aerosol Formation in Laboratory Chambers

Citation

Zhang, Xuan (2015) Investigation of Fundamental Processes Governing Secondary Organic Aerosol Formation in Laboratory Chambers. Dissertation (Ph.D.), California Institute of Technology. doi:10.7907/Z9QZ27WP. http://resolver.caltech.edu/CaltechTHESIS:05282015-214235298

Abstract

Our understanding of the processes and mechanisms by which secondary organic aerosol (SOA) is formed is derived from laboratory chamber studies. In the atmosphere, SOA formation is primarily driven by progressive photooxidation of SOA precursors, coupled with their gas-particle partitioning. In the chamber environment, SOA-forming vapors undergo multiple chemical and physical processes that involve production and removal via gas-phase reactions; partitioning onto suspended particles vs. particles deposited on the chamber wall; and direct deposition on the chamber wall. The main focus of this dissertation is to characterize the interactions of organic vapors with suspended particles and the chamber wall and explore how these intertwined processes in laboratory chambers govern SOA formation and evolution.

A Functional Group Oxidation Model (FGOM) that represents SOA formation and evolution in terms of the competition between functionalization and fragmentation, the extent of oxygen atom addition, and the change of volatility, is developed. The FGOM contains a set of parameters that are to be determined by fitting of the model to laboratory chamber data. The sensitivity of the model prediction to variation of the adjustable parameters allows one to assess the relative importance of various pathways involved in SOA formation.

A critical aspect of the environmental chamber is the presence of the wall, which can induce deposition of SOA-forming vapors and promote heterogeneous reactions. An experimental protocol and model framework are first developed to constrain the vapor-wall interactions. By optimal fitting the model predictions to the observed wall-induced decay profiles of 25 oxidized organic compounds, the dominant parameter governing the extent of wall deposition of a compound is identified, i.e., wall accommodation coefficient. By correlating this parameter with the molecular properties of a compound via its volatility, the wall-induced deposition rate of an organic compound can be predicted based on its carbon and oxygen numbers in the molecule.

Heterogeneous transformation of δ-hydroxycarbonyl, a major first-generation product from long-chain alkane photochemistry, is observed on the surface of particles and walls. The uniqueness of this reaction scheme is the production of substituted dihydrofuran, which is highly reactive towards ozone, OH, and NO3, thereby opening a reaction pathway that is not usually accessible to alkanes. A spectrum of highly-oxygenated products with carboxylic acid, ester, and ether functional groups is produced from the substituted dihydrofuran chemistry, thereby affecting the average oxidation state of the alkane-derived SOA.

The vapor wall loss correction is applied to several chamber-derived SOA systems generated from both anthropogenic and biogenic sources. Experimental and modeling approaches are employed to constrain the partitioning behavior of SOA-forming vapors onto suspended particles vs. chamber walls. It is demonstrated that deposition of SOA-forming vapors to the chamber wall during photooxidation experiments can lead to substantial and systematic underestimation of SOA. Therefore, it is likely that a lack of proper accounting for vapor wall losses that suppress chamber-derived SOA yields contribute substantially to the underprediction of ambient SOA concentrations in atmospheric models.

Item Type:Thesis (Dissertation (Ph.D.))
Subject Keywords:Secondary Organic Aerosol; Environmental Chamber; Vapor Wall Loss
Degree Grantor:California Institute of Technology
Division:Engineering and Applied Science
Major Option:Environmental Science and Engineering
Thesis Availability:Public (worldwide access)
Research Advisor(s):
  • Seinfeld, John H.
Thesis Committee:
  • Wennberg, Paul O. (chair)
  • Seinfeld, John H.
  • Flagan, Richard C.
  • Hoffmann, Michael R.
Defense Date:12 May 2015
Record Number:CaltechTHESIS:05282015-214235298
Persistent URL:http://resolver.caltech.edu/CaltechTHESIS:05282015-214235298
DOI:10.7907/Z9QZ27WP
Related URLs:
URLURL TypeDescription
http://www.atmos-chem-phys.net/13/5907/2013/acp-13-5907-2013.htmlPublisherArticle adapted for ch. 2
http://www.atmos-chem-phys.net/14/1733/2014/acp-14-1733-2014.htmlPublisherArticle adapted for ch. 3
http://www.pnas.org/content/111/16/5802.shortPublisherArticle adapted for ch. 4
http://www.atmos-chem-phys.net/15/4197/2015/acp-15-4197-2015.htmlPublisherArticle adapted for ch. 4
Default Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:8911
Collection:CaltechTHESIS
Deposited By: Xuan Zhang
Deposited On:01 Jun 2015 18:44
Last Modified:12 Apr 2016 21:57

Thesis Files

[img]
Preview
PDF - Final Version
See Usage Policy.

27Mb

Repository Staff Only: item control page