Anthropogenic Influence on the Fate of Secondary Organic Aerosol

Anthropogenic Influence on the Fate of Secondary Organic Aerosol
Author: Dongyu Wang
Publisher:
Total Pages: 0
Release: 2018
Genre:
ISBN:

Oxidation of volatile organic compounds (VOC) in the atmosphere leads to the formation of secondary organic aerosol (SOA), which can have extensive impacts on air quality, health, and climate. Existing air quality models used to describe the fate of ambient organic aerosol tend to underpredict the aerosol oxidation state. In addition, modeled concentrations of nitrogen oxides (NO [subscript x]) and other reactive nitrogen compounds (NO [subscript y]), including alkyl nitrates, often deviate from field observations. Certain SOA formation pathways, SOA ageing mechanisms, and alkyl nitrate decay mechanisms may be missing. Recent field studies show that NO [subscript x]-mediated heterogeneous production of nitryl chloride, ClNO2, could provide a ubiquitous source for chlorine atoms. Little is known about the role of chlorine atoms in SOA formation and ageing, or their interaction with other anthropogenic emissions found in polluted environments, where alkane oxidation chemistry is important. Environmental chamber experiments are carried out to address knowledge gaps in atmospheric chlorine and alkane oxidation chemistry. Results show that chlorine-initiated oxidation of isoprene leads to SOA formation, organic chloride formation, and possibly secondary HO [subscript x] chemistry. Alkane-derived alkyl nitrate compounds are found not to hydrolyze appreciably in humid environments or in the presence of acidic aerosol. Uptake of inorganic nitrate and inorganic chloride are observed in the presence of deliquescent particles. Chlorine-initiated oxidation of linear alkanes is shown to result in prompt SOA formation and delayed organic chloride formation, which is enabled by the addition of chlorine radical to dihydrofuran, a heterogeneously produced multi-generational oxidation product. Improvements are made for the detection of organic chloride using aerosol mass spectrometry, and for aerosol volatility measurements using temperature programmed thermal desorption techniques. A two-dimensional thermogram framework is developed to visualize aerosol composition, aerosol volatility, and thermal fragmentation simultaneously

Insights Into Predicting Secondary Organic Aerosol Formation from Anthropogenic Volatile Organic Compounds

Insights Into Predicting Secondary Organic Aerosol Formation from Anthropogenic Volatile Organic Compounds
Author: Lijie Li
Publisher:
Total Pages: 274
Release: 2016
Genre: Air
ISBN: 9781369092509

Understanding secondary organic aerosol (SOA) formation is of critical importance to public health and global climate. SOA formation from anthropogenic volatile organic compounds (VOCs) is influenced by NO, precursor molecular structure, oxidation conditions and other factors. This dissertation explores the impact of NO effect and molecular structure for two categories of VOCs at urban atmosphere relevant conditions by utilizing the state of art 90 m3 UCR/CE-CERT chamber facilities.

Environmental Simulation Chambers: Application to Atmospheric Chemical Processes

Environmental Simulation Chambers: Application to Atmospheric Chemical Processes
Author: Ian Barnes
Publisher: Springer Science & Business Media
Total Pages: 492
Release: 2006-01-13
Genre: Nature
ISBN: 9781402042317

The book gives in the first instance descriptions of different types of so-called environment chambers or photoreactors used mainly for the simulation and/or investigation of important chemical processes occurring in the atmosphere. The types of reactor described include outdoor and indoor chambers, temperature regulated chambers and glass and Teflon foil chambers The practical use of chambers is demonstrated in contributions by leading scientists in the field of atmospheric chemistry using, in many cases, current results. The types of atmospherically relevant investigations described include the measurement of reactivities, the measurement of radicals, the measurement of photolysis frequencies and products, kinetic and product studies on the oxidation of different types of hydrocarbons by important oxidant species (OH, N03, 03), formation of secondary organic aerosol from hydrocarbon oxidation etc. A special section includes contributions from eastern European countries which highlight some of the environmental research being performed in these countries. An abridged version of a specially commissioned review by the JRC Ispra on the status of environmental research in eastern European countries is also included in this section.

Establishing Chemical Mechanisms and Estimating Phase State of Secondary Organic Aerosol From Atmospherically Relevant Organic Precursors

Establishing Chemical Mechanisms and Estimating Phase State of Secondary Organic Aerosol From Atmospherically Relevant Organic Precursors
Author: Shashank Jain
Publisher:
Total Pages: 352
Release: 2016
Genre:
ISBN:

Organic aerosol (OA) is a ubiquitous component of atmospheric particulate that influences both human health and global climate. A large fraction of OA is secondary in nature (SOA), being produced by oxidation of volatile organic compounds (VOCs) emitted by biogenic and anthropogenic sources. Despite the integral role of SOA in atmospheric processes, there remains a limited scientific understanding of the chemical and physical changes induced in SOA as it ages in the atmosphere. This thesis describes work done to increase the knowledge of processes and properties of atmospherically relevant SOA. In the work presented in this thesis, I have worked on improving an existing innovative, soft ionization aerosol mass spectrometer and utilized it to establish chemical mechanisms for oxidation of atmospherically relevant organic precursors (i.e., Green Leaf Volatiles). I discovered that SOA formation from cis-3-hexen-1-ol is dominated by oligomer and higher molecular weight products, whereas the acetate functionality in cis-3-hexenylacetate inhibited oligomer formation, resulting in SOA that is dominated by low molecular weight products. One of the most important factors contributing to uncertainties in our estimations of SOA mass in the atmosphere, remains our basic assumption that atmospheric SOA is liquid-like, which we have found to be untrue. Hence, I developed a methodology to estimate the phase state of SOA and identified new parameters that can have significant influence on the phase state of atmospheric aerosol. This simplified method eliminates the need for a Scanning Mobility Particle Sizer (SMPS) and directly measures Bounce Factor (BF) of polydisperse SOA using only one multi-stage cascade Electrostatic Low Pressure Impactor (ELPI). The novel method allows for the real time determination of SOA phase state, permitting studies of the relationship between SOA phase, oxidative formation and chemical aging in the atmosphere. I demonstrated that SOA mass loading (CSOA) influences the phase state significantly. Results show that under nominally identical conditions, the maximum BF decreases by approximately 30% at higher CSOA and suggests that extrapolation of experiments not conducted at atmospherically relevant SOA levels to simulate the chemical properties may not yield results that are relevant to our natural environment. My work has provided a better understanding of the mechanisms of aerosol formation at atmospheric concentrations, which is necessary to understand its physical properties. This improved understanding is fundamental to accurately model aerosol formation in the atmosphere, and subsequently evaluate their large-scale effect on human health and environment.

Characterizing the Formation of Secondary Organic Aerosols

Characterizing the Formation of Secondary Organic Aerosols
Author:
Publisher:
Total Pages: 34
Release: 2004
Genre:
ISBN:

Organic aerosol is an important fraction of the fine particulate matter present in the atmosphere. This organic aerosol comes from a variety of sources; primary organic aerosol emitted directly from combustion process, and secondary aerosol formed in the atmosphere from condensable vapors. This secondary organic aerosol (SOA) can result from both anthropogenic and biogenic sources. In rural areas of the United States, organic aerosols can be a significant part of the aerosol load in the atmosphere. However, the extent to which gas-phase biogenic emissions contribute to this organic load is poorly understood. Such an understanding is crucial to properly apportion the effect of anthropogenic emissions in these rural areas that are sometimes dominated by biogenic sources. To help gain insight on the effect of biogenic emissions on particle concentrations in rural areas, we have been conducting a field measurement program at the University of California Blodgett Forest Research Facility. The field location includes has been used to acquire an extensive suite of measurements resulting in a rich data set, containing a combination of aerosol, organic, and nitrogenous species concentration and meteorological data with a long time record. The field location was established in 1997 by Allen Goldstein, a professor in the Department of Environmental Science, Policy and Management at the University of California at Berkeley to study interactions between the biosphere and the atmosphere. The Goldstein group focuses on measurements of concentrations and whole ecosystem biosphere-atmosphere fluxes for volatile organic compounds (VOC's), oxygenated volatile organic compounds (OVOC's), ozone, carbon dioxide, water vapor, and energy. Another important collaborator at the Blodgett field location is Ronald Cohen, a professor in the Chemistry Department at the University of California at Berkeley. At the Blodgett field location, his group his group performs measurements of the concentrations of important gas phase nitrogen compounds. Experiments have been ongoing at the Blodgett field site since the fall of 2000, and have included portions of the summer and fall of 2001, 2002, and 2003. Analysis of both the gas and particle phase data from the year 2000 show that the particle loading at the site correlates with both biogenic precursors emitted in the forest and anthropogenic precursors advected to the site from Sacramento and the Central Valley of California. Thus the particles at the site are affected by biogenic processing of anthropogenic emissions. Size distribution measurements show that the aerosol at the site has a geometric median diameter of approximately 100 nm. On many days, in the early afternoon, growth of nuclei mode particles (

Composition and Photochemistry of Anthropogenic and Biogenic Organic Aerosols

Composition and Photochemistry of Anthropogenic and Biogenic Organic Aerosols
Author: Sandra Louise Blair
Publisher:
Total Pages: 228
Release: 2016
Genre:
ISBN: 9781339820262

Aerosols can substantially impact human health, atmospheric chemistry, and climate. The composition and photochemistry of a variety of anthropogenic and biogenic primary and secondary organic aerosols (POA and SOA) have yet to be fully characterized. The composition of organic aerosols is extremely complex - they contain a variety of highly oxidized, multifunctional, low vapor pressure organic compounds. The primary focus of this thesis is on the molecular characterization of organic aerosols that are not well understood or have not been studied before, such as primary emissions from electronic cigarettes, iron (III) mediated SOA, and photooxidized biodiesel and diesel fuel SOA. Another focus of this dissertation is the effect of direct photochemical aging on the composition of organic aerosol. Direct photolysis experiments were first applied to a system that is known to have a photolabile composition, alpha-pinene ozonolysis SOA, such that characterization of a photochemical effect would be possible to quantify. Photolysis of more complex SOA that have not been studied before, photooxidized biodiesel and diesel fuel SOA, were also investigated in this thesis. Advanced high resolution mass spectrometry techniques were used in the molecular characterization of organic aerosols, including nano-Desorption Electrospray Ionization Mass Spectrometry (nano-DESI) and Fourier Transform Ion Cyclotron Resonance Mass Spectrometry (FTICR). An additional suite of online instrumentation was used to measure gas-phase composition, particle-phase composition, particle size and concentration, and absorption properties: Proton Transfer Reaction Time-of-Flight Mass Spectrometry (PTR-ToF-MS), Aerosol Mass Spectrometry (ToF-AMS), Scanning Mobility Particle Sizing (SMPS), and UV-vis spectroscopy. The molecular analysis of these aerosols provides valuable insight to the formation and photochemical behavior of unexpected, polymeric, light absorbing, and unique organosulfur species.

Fundamentals of Chemical Reaction Engineering

Fundamentals of Chemical Reaction Engineering
Author: Mark E. Davis
Publisher: Courier Corporation
Total Pages: 385
Release: 2013-05-27
Genre: Technology & Engineering
ISBN: 0486291316

Appropriate for a one-semester undergraduate or first-year graduate course, this text introduces the quantitative treatment of chemical reaction engineering. It covers both homogeneous and heterogeneous reacting systems and examines chemical reaction engineering as well as chemical reactor engineering. Each chapter contains numerous worked-out problems and real-world vignettes involving commercial applications, a feature widely praised by reviewers and teachers. 2003 edition.

Atmospheric Aerosols

Atmospheric Aerosols
Author: Rekha Kale
Publisher: Scitus Academics LLC
Total Pages: 0
Release: 2015-03
Genre: Aerosols
ISBN: 9781681171326

Atmospheric Aerosols is a vital problem in current environmental research due to its importance in atmospheric optics, energetics, radiative transfer studies, chemistry, climate, biology and public health. Aerosols can influence the energy balance of the terrestrial atmosphere, the hydrological cycle, atmospheric dynamics and monsoon circulations. Because of the heterogeneous aerosol field with large spatial and temporal variability and reduction in uncertainties in aerosol quantification is a challenging task in atmospheric sciences. Keeping this in view the present study aims to assess the impact of aerosols on coastal Indian station Visakhapatnam and the adjoining Bay of Bengal. An aerosol is a colloid of fine solid particles or liquid droplets, in air or another gas. Aerosols can be natural or not. Examples of natural aerosols are fog, forest exudates and geyser steam.