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

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.

Site-Specific Isotopes in Small Organic Molecules

Stable isotope geochemistry is a valuable toolkit for addressing a broad range of problems in the geosciences. Recent technical advances provide information that was previously unattainable or provide unprecedented precision and accuracy. Two such techniques are site-specific stable isotope mass spectrometry and clumped isotope thermometry. In this thesis, I use site-specific isotope and clumped isotope data to explore natural gas development and carbonate reaction kinetics. In the first chapter, I develop an equilibrium thermodynamics model to calculate equilibrium constants for isotope exchange reactions in small organic molecules. This equilibrium data provides a framework for interpreting the more complex data in the later chapters. In the second chapter, I demonstrate a method for measuring site-specific carbon isotopes in propane using high-resolution gas source mass spectrometry. This method relies on the characteristic fragments created during electron ionization, in which I measure the relative isotopic enrichment of separate parts of the molecule. My technique will be applied to a range of organic compounds in the future. For the third chapter, I use this technique to explore diffusion, mixing, and other natural processes in natural gas basins. As time progresses and the mixture matures, different components like kerogen and oil contribute to the propane in a natural gas sample. Each component imparts a distinct fingerprint on the site-specific isotope distribution within propane that I can observe to understand the source composition and maturation of the basin. Finally, in Chapter Four, I study the reaction kinetics of clumped isotopes in aragonite. Despite its frequent use as a clumped isotope thermometer, the aragonite blocking temperature is not known. Using laboratory heating experiments, I determine that the aragonite clumped isotope thermometer has a blocking temperature of 50-100°C. I compare this result to natural samples from the San Juan Islands that exhibit a maximum clumped isotope temperature that matches this blocking temperature. This thesis presents a framework for measuring site-specific carbon isotopes in organic molecules and new constraints on aragonite reaction kinetics. This study represents the foundation of a future generation of geochemical tools for the study of complex geologic systems.

Field and Laboratory Studies of Atmospheric Organic Aerosol

This thesis is the culmination of field and laboratory studies aimed at assessing processes that affect the composition and distribution of atmospheric organic aerosol. An emphasis is placed on measurements conducted using compact and high-resolution Aerodyne Aerosol Mass Spectrometers (AMS). The first three chapters summarize results from aircraft campaigns designed to evaluate anthropogenic and biogenic impacts on marine aerosol and clouds off the coast of California. Subsequent chapters describe laboratory studies intended to evaluate gas and particle-phase mechanisms of organic aerosol oxidation.

The 2013 Nucleation in California Experiment (NiCE) was a campaign designed to study environments impacted by nucleated and/or freshly formed aerosol particles. Terrestrial biogenic aerosol with > 85% organic mass was observed to reside in the free troposphere above marine stratocumulus. This biogenic organic aerosol (BOA) originated from the Northwestern United States and was transported to the marine atmosphere during periodic cloud-clearing events. Spectra recorded by a cloud condensation nuclei counter demonstrated that BOA is CCN active. BOA enhancements at latitudes north of San Francisco, CA coincided with enhanced cloud water concentrations of organic species such as acetate and formate.

Airborne measurements conducted during the 2011 Eastern Pacific Emitted Aerosol Cloud Experiment (E-PEACE) were aimed at evaluating the contribution of ship emissions to the properties of marine aerosol and clouds off the coast of central California. In one study, analysis of organic aerosol mass spectra during periods of enhanced shipping activity yielded unique tracers indicative of cloud-processed ship emissions (m/z 42 and 99). The variation of their organic fraction (f₄₂ and f₉₉) was found to coincide with periods of heavy (f₄₂ > 0.15; f₉₉ > 0.04), moderate (0.05 < f₄₂ < 0.15; 0.01 < f₉₉ < 0.04), and negligible (f₄₂ < 0.05; f₉₉ < 0.01) ship influence. Application of these conditions to all measurements conducted during E-PEACE demonstrated that a large fraction of cloud droplet (72%) and dry aerosol mass (12%) sampled in the California coastal study region was heavily or moderately influenced by ship emissions. Another study investigated the chemical and physical evolution of a controlled organic plume emitted from the R/V Point Sur. Under sunny conditions, nucleated particles composed of oxidized organic compounds contributed nearly an order of magnitude more cloud condensation nuclei (CCN) than less oxidized particles formed under cloudy conditions. The processing time necessary for particles to become CCN active was short ( < 1 hr) compared to the time needed for particles to become hygroscopic at sub-saturated humidity ( > 4 hr).

Laboratory chamber experiments were also conducted to evaluate particle-phase processes influencing aerosol phase and composition. In one study, ammonium sulfate seed was coated with a layer of secondary organic aerosol (SOA) from toluene oxidation followed by a layer of SOA from α-pinene oxidation. The system exhibited different evaporative properties than ammonium sulfate seed initially coated with α-pinene SOA followed by a layer of toluene SOA. This behavior is consistent with a shell-and-core model and suggests limited mixing among different SOA types. Another study investigated the reactive uptake of isoprene epoxy diols (IEPOX) onto non-acidified aerosol. It was demonstrated that particle acidity has limited influence on organic aerosol formation onto ammonium sulfate seed, and that the chemical system is limited by the availability of nucleophiles such as sulfate.

Flow tube experiments were conducted to examine the role of iron in the reactive uptake and chemical oxidation of glycolaldehyde. Aerosol particles doped with iron and hydrogen peroxide were mixed with gas-phase glycolaldehyde and photochemically aged in a custom-built flow reactor. Compared to particles free of iron, iron-doped aerosols significantly enhanced the oxygen to carbon (O/C) ratio of accumulated organic mass. The primary oxidation mechanism is suggested to be a combination of Fenton and photo-Fenton reactions which enhance particle-phase OH radical concentrations.

Hydrothermal Synthesis and Study of Inorganic-Organic Hybrid Vanadate of Nickel(II) Coordination Complex with Pyrazine, Ni3(C4H4N2)3(V8O23)

Artículo científico: postprint

Cadmium leachability and microbial population dynamics in a stabilized and bioaugmented model contaminated soil

This article presents a laboratory study on the consequences of the application of combined soil stabilization and bioaugmentation in the remediation of a model contaminated soil. Stabilization and bioaugmentation are two techniques commonly applied independently for the remediation of heavy metal and organic contamination respectively. However, for a cocktail of contaminants combined treatments are currently being considered. The model soil was contaminated with a cocktail of organics and heavy metals based on the soil and contaminant conditions in a real contaminated site. The soil stabilization treatment was applied using either zeolite or green waste compost as additives and a commercially available hydrocarbon degrading microbial consortium was used for the bioaugmentation treatment. The effects of stabilization with or without bioaugmentation on the leachability of cadmium and copper was observed using an EU batch leaching test procedure and a flow-through column leaching test, both using deionized water at a pH of 5.6. In addition, the population of hydrocarbon degrading microorganisms was monitored using a modified plate count procedure in cases where bioaugmentation was applied. It was found that while the stabilization treatment reduced the metal leachability by up to 60%, the bioaugmentation treatment increased it by up to 100% Microbial survival was also higher in the stabilized soil samples.

Biomimetic calcium carbonate-gelatin composites as a model system for eggshell mineralization

The composite nature of mineralized natural materials is achieved through both the microstructural inclusion of an organic component and an overall microstructure that is controlled by templating onto organic macromolecules. A modification of an existing laboratory technique is developed for the codeposition of a CaCO3-gelatin composite with a controllable organic content. First, calibration curves are developed to determine the organic content of a CaCO3-gelatin composite from infrared spectra. Second, a CaCO3-gelatin composite is deposited on either glass coverslips or demineralized eggshell membranes using an automated alternating soaking process. Electron microscopy images and use of the infrared spectra calibration curves show that by altering the amount of gelatin in the ionic growth solutions, the final organic component of the mineral can be regulated over the range of 1-10%, similar to that of natural eggshell. © 2012 Materials Research Societ.

Stable isotope variations in particulate organic matter and a planktivorous fish in the Yangtze River

Temporal and spatial changes in delta(13) C and delta 15 N of particulate organic matter (POM) and Hemiculter leucisculus were studied in the Yangtze River of China. Isotopic signatures of POM showed seasonal variations, which was assumed to be associated with allochthonous organic input and autochthonous phytoplankton growth. delta C-13 of H. leucisculus was 1.1 % higher than that of POM, which suggested that the food source of H. leucisculus was mostly from the POM. A mass balance model indicated the trophic position of H. leucisculus in the food web of Yangtze River was estimated to be 2.0 - 2.1, indicating that this fish mainly feeds on planktonic organic matter, which agreed with previous gut content analysis.

In situ intercalation dynamics in inorganic-organic layered perovskite thin films.

The properties of layered inorganic semiconductors can be manipulated by the insertion of foreign molecular species via a process known as intercalation. In the present study, we investigate the phenomenon of organic moiety (R-NH3I) intercalation in layered metal-halide (PbI2)-based inorganic semiconductors, leading to the formation of inorganic-organic (IO) perovskites [(R-NH3)2PbI4]. During this intercalation strong resonant exciton optical transitions are created, enabling study of the dynamics of this process. Simultaneous in situ photoluminescence (PL) and transmission measurements are used to track the structural and exciton evolution. On the basis of the experimental observations, a model is proposed which explains the process of IO perovskite formation during intercalation of the organic moiety through the inorganic semiconductor layers. The interplay between precursor film thickness and organic solution concentration/solvent highlights the role of van der Waals interactions between the layers, as well as the need for maintaining stoichiometry during intercalation. Nucleation and growth occurring during intercalation matches a Johnson-Mehl-Avrami-Kolmogorov model, with results fitting both ideal and nonideal cases.

Photoluminescence properties of tensile-strained GaAsP/GaInP single quantum wells grown by metal organic chemical vapor deposition

Tensile-strained GaAsP/GaInP single quantum well (QW) laser diode (I-D) structures have been grown by low-pressure metal organic chemical vapor deposition (LP-MOCVD) and related photoluminescence (PL) properties have been investigated in detail. The samples have the same well thickness of 16 nm but different P compositions in a GaAsP QW. Two peaks in room temperature (RT) PL spectra are observed for samples with a composition larger than 0.10. Temperature and excitation-power-dependent PL spectra have been measured for a sample with it P composition of 0.15. It is found that the two peaks have a 35 meV energy separation independent of temperature and only the low-energy peak exists below 85 K. Additionally, both peak intensities exhibit a monotonous increase as excitation power increases. Analyses indicate that the two peaks arise from the intrinsic-exciton recombination mechanisms of electron-heavy hole (e-hh) and electron-light hole (e-hh). A theoretical calculation based oil model-solid theory, taking, into account the spin-orbit splitting energy, shows good agreement with our experimental results. The temperature dependence of PL intensity ratio is well explained using the spontaneous emission theory for e-hh and e-hh transitions. front which the ratio can be characterized mainly by the energy separation between the fill and Ill states.

Well-Aligned Zn-Doped InN Nanorods Grown by Metal-Organic Chemical Vapor Deposition and the Dopant Distribution

We report the synthesis and characterization of Zn-doped InN nanorods by metal-organic chemical vapor deposition. Electron microscopy images show that the InN nanorods are single-crystalline structures and vertically well-aligned. Energy-dispersive X-ray spectroscopy analyses suggest that Zn ions are distributed nonhomogenously in InN nanorods. Simulations based on diffusion model show that the doping concentration along the radial direction of InN nanorod is bowl-like from the exterior to the interior, the doping concentration decreases, and Such dopant distribution result in a bimodal EDXS spectrum of Zn across the nanorod. The study of the mechanism of doping effect is useful for the design of InN-based nanometer devices. Also, high-quality Zn-doped InN nanorods will be very attractive as building blocks for nano-optoelectronic devices.'

Scanning electron microscope studies of cubic AlxGa1-xN films grown on GaAs(100) by metal organic vapor phase epitaxy (MOVPE)

Cubic AlGaN films were grown on GaAs(100) substrates by MOVPE. Scanning electron microscope and photoluminescence were used to analyze the surface morphology and the crystalline quality of the epitaxial layers. We found that both NH, and TEGa fluxes have a strong effect on the surface morphology of AlGaN films. A model for the lateral growth mechanism is presented to qualitatively explain this effect. The content of hexagonal AlGaN in the cubic AlGaN films was also related to the NH3 flux. (C) 1999 Elsevier Science B.V. All rights reserved.

Using HPLC retention parameters to estimate fish bioconcentration factors of organic compounds

Reversed-phase high performance liquid chromatography (RP-HPLC) was employed to develop predictive models for fish bioconcentration factors (BCF) of organic compounds. Estimation of BCF from RP-HPLC retention parameters on octadecyl-bonded silica gel (ODS), cyanopropyl-bonded silica gel (CN), and phenyl-bonded silica gel (Ph) columns were investigated. The results show that, for a set of compounds belonging to different chemical classes, the CN stationary phase is the best one among the three columns and better than n-octanol/water model for BCF estimation. A multi-column RP-HPLC model, using the retention parameters on the CN and Ph columns as the variables of multiple linear regression equations, was further evaluated to estimate BCF of organic compounds belonging to different chemical classes, and the results show that the multi-column RP-HPLC model is better than that of any single RP-HPLC column for BCF estimation.

A model study on carbon cycle and phytoplankton dynamical processes in the Bohai Sea

The carbon cycle of lower trophic level in the Bohai Sea is studied with a three-dimension-al biological and physical coupled model. The influences of the processes (including horizontal advection,river nutrient load, active transport etc. ) on the phytoplankton biomass and its evolution are estimated.The Bohai Sea is a weak sink of the CO2 in the atmosphere. During the cycle, 13.7% of the gross pro-duction of the phytoplankton enter the higher trophic level and 76.8 % of it are consumed by the respira-tion itself. The nutrient reproduction comes mainly from the internal biogeochemical loop and the rem-ineralization is an important mechanism of the nutrient transfer from organic form to inorganic. Horizon-tal advection decreases the total biomass and the eutrophication in some sea areas. Change in the nutrientload of a river can only adjust the local system near its estuary. Controlling the input of the nutrient,which limits the alga growth, can be very useful in lessening the phytoplankton biomass.

Modeling the effect of ozone loss on photobleaching of chromophoric dissolved organic matter in the St. Lawrence estuary

Temporal trends in total ozone for the St. Lawrence estuary were estimated from ground-based measurements at the NOAA/CMDL station in Caribou, Maine. Linear regression analysis showed that from 1979 to 1999 total ozone has decreased by about 3.3% per decade on an annual basis and ≤6.2% per decade on a monthly basis relative to unperturbed (pre-CFC) levels. The influence of increased ultraviolet-B (280–320 nm) radiation associated with ozone depletion on water column photochemical processes was evaluated by modeling the photobleaching of chromophoric dissolved organic material (CDOM). Linear regression analysis showed small (<0.5% per decade), but statistically significant upward trends in maximum noontime photobleaching rates. Most notably, positive trends in relative rates for May, June, and July, when maximum absolute rates are expected, were predicted. A global model based on TOMS ozone data revealed increases in photobleaching of ≤3% per decade at high latitudes in the Southern Hemisphere. Radiation amplification factors for increases in photochemically weighted UV (280–400 nm) in response to ozone depletion were estimated at 0.1 and 0.08 for photobleaching of CDOM absorbance at 300 and 350 nm, respectively. Application of the laboratory-based model to conditions that more closely resembled those in situ were variable with both overestimation and underestimation of measured rates. The differences between modeled rates and observed rates under quasi-natural conditions were as large or larger than the predicted increases due to ozone depletion. These comparisons suggest that biological activity and mixing play an important, but as yet ill-defined, role in modifying photochemical processes.

New Organic Sensitizer for Stable Dye-Sensitized Solar Cells with Solvent-Free Ionic Liquid Electrolytes

We report a high molar extinction coefficient metal-free sensitizer composed of a triarylamine donor in combination with the 2-(2,2'-bithiophen-5-yl)acrylonitrile conjugation unit and cyanoacrylic acid as an acceptor. In conjugation with a volatile acetonitrile-based electrolyte or a solvent-free ionic liquid electrolyte, we have fabricated efficient dye-sensitized solar cells showing a corresponding 7.5% or 6.1% efficiency measured under the air mass 1.5 global sunlight. The ionic liquid cell exhibits excellent stability during a 1000 h accelerated test under the light-soaking and thermal dual stress. Intensity-modulated photocurrent and photovolatge spectroscopies were employed along with the transient photoelectrical decay measurements to detail the electron transport in the mesoporous titania films filled with these two electrolytes.