Thesis (Ph.D.)--Massachusetts Institute of Technology, Dept. of Meteorology and Physical Oceanography, 1982. / Microfiche copy available in Archives and Science / Bibliography: leaves 194-201. / by Amram Golombek. / Ph.D.

This dissertation is a collection of works that investigates issues related to environmental chemistry. The first portion of this research explores the role of water vapor on the kinetics of important atmospheric reactions. Work is presented on the self-reaction of β-hydroxyethyl peroxy radical (β-HEP) and the catalytic increase in reaction rate by water vapor. β-HEP serves as a model system for investigating the possible role of water vapor in perturbing the kinetics and product branching ratio of atmospheric reactions of other alkyl peroxy radicals. The self-reaction rate coefficient of β-HEP was investigated between 276-296 K with 1.0 × 10^15 to 2.5 × 10^17 molecules cm^-3 of water vapor at 200 Torr total pressure by slow-flow laser flash photolysis coupled with UV time-resolved spectroscopy and long-path, wavelength-modulated, diode-laser spectroscopy. The overall disproportionation rate constant is expressed as the product of temperature-dependent and water vapor-dependent terms giving k(T,H2O) = 7.8 × 10^-14 (e^8.2 ^(±2.5) ^kJ/RT)(1 + 1.4 × 10^-34 × e^92 ^(±11) ^kJ/RT[H2O]). The results suggest that formation of a β--HEP-H2O complex is responsible for the observed water vapor enhancement of the self-reaction rate coefficient. Complex formation is supported with computational results identifying three local energy minima for the β--HEP-H2O complex. Both the temperature range and water vapor concentrations used were chosen because of their significance to conditions in the troposphere. As the troposphere continues to get warmer and wetter, more complexes with water will form, which in turn may perturb the kinetics and product branching ratios of atmospheric reactions. Future studies are proposed for the reaction of β-HEP + NO leading to NO2 formation. A laser-induced fluorescence cell was designed, built, and tested in preparation for studies of NO2 formation. Additionally Harriott-cell optics were manufactured and tested to detect HO2 using two-tone frequency-modulated diode-laser spectroscopy. In a related work, the breakdown of the environmental contaminants polychlorinated biphenyls (PCB's) was investigated using a new method. A new method for analyzing anaerobic digestion is also presented. The degradation rate and efficiency of digestion processes are typically measured by introducing a substrate or pollutant into a digester and then monitoring the effluents for the pollutant or substrate, a costly and slow process. A new method for rapid measurement of the rates and efficiencies of anaerobic degradation of pollutants and lignocellulose substrates from various pretreatments is described. The method uses micro-reactors (10-30 mL) containing a mixed culture of anaerobic bacteria obtained from a working anaerobic digester. The rates of degradation and metabolism of pollutants are measured in parallel sets of micro-reactors. Measurements of metabolic rate and pollutant degradation simultaneously is an effective means of rapidly examining pollutant degradation on a micro-scale. Calorimetric measurements alone allow rapid, relative evaluation of various substrate pretreatment methods. Finally calorimetric and electrophoretic methods were used to further knowledge in analytical techniques applied to important problems. In the last section of this dissertation the thermal and photolytic breakdown of promethazine hydrochloride is reported. Promethazine hydrochloride is a mediation that is commonly used as an antihistamine, a sedative, and an antiemetic, and to treat motion sickness. Perivascular extravasation, unintentional intra-arterial injection and intraneuronal or perineuronal infiltration may lead to irreversible tissue damage if the drug is not properly diluted or is administered too quickly. Data on the stability of promethazine hydrochloride diluted in sodium chloride 0.9% are lacking. This study evaluates the thermal and photolytic degradation of promethazine hydrochloride concentrations of 250 µg/mL and 125 µg/mL diluted in sodium chloride 0.9% over a period of 9 days. Degradation rates of promethazine hydrochloride were determined under UV-light, fluorescent light, and no light at various temperatures and concentrations to determine medication stability. The shelf-life (<10% degradation) at 25°C under normal fluorescent lights is 4.9 days, at 25°C protected from light, 6.6 days, and at 7°C in the dark, 8.1 days. These results may increase patient safety by improving current protocols for intravenous promethazine administration

This dissertation is a collection of works that investigate non-prototypical sources leading to new particle formation in the atmosphere. Particles play a major role in atmospheric chemistry. For example, particles are a component of smog and are commonly found in high concentrations under conditions of atmospheric inversions. In order to reconcile the difference between measured and modeled particle concentrations new mechanisms from non-prototypical sources for particle formation need to be determined. Formation of particles has frequently been modeled using classical nucleation theory (CNT). The first step in CNT is the nucleation step where molecular clusters form. In a second step, these clusters grow into particles through coagulation or condensation. First, this research aims to improve the modeling of equilibrium constants for the formation of peroxy radical-water complexes. Failure of the harmonic approximation in the partition function for describing the low frequency vibrational modes of the complexes was explored. Instead the dissociative hydrogen bond mode using a Lennard-Jones 6-3 potential and the other low frequency vibrational modes using one- and two-fold hindered rotors was modeled. It was determined that the contribution of the two-fold hindered rotors is more important than the long-range dipole-dipole potentials and of vibration-rotation coupling. In related work, the hydroperoxy radical was investigated as a non-prototypical source of particles using high level ab initio calculations. The results indicate that the addition of an amine to the dimer increased the overall stability of complex through the increased number and strength of the hydrogen bonds. When compared to prototypical systems, sulfuric acid and methane sulfonic acid, the strength of the complex was found to be similar to the peroxy radical system. Finally, carboxylic acids, formic acid and acetic acid, were investigated as a source for new particle formation using computational and experimental techniques. Using a slow flow reactor cell particle formation was enhanced by the addition of trimethylamine. High level ab initio calculations indicate like the peroxy radicals, carboxylic acids may act as a molecular cluster in particle formation

<p>  </p> <p>Secondary organic aerosols (SOA) play an important role in the Earth’s radiative budget due to their potential to either warm or cool the atmosphere through light absorption or light scattering, respectively, and to cool or warm the lower atmosphere by acting as cloud condensation nuclei. SOA are air-suspended liquid and semi-solid droplets that form through multiphase chemical processes. Atmospheric photochemical oxidation of volatile organic compounds (VOCs) in the presence of air pollutants, such as NO_x (NO + NO₂) and the OH radical, promote formation of low volatility organic products that eventually condense to form SOA. To better understand the sources and sinks, formation, and fate of SOA, laboratory studies investigating oxidation of a biogenic VOC as well as anthropogenic emissions of SOA precursors were conducted. The first study (<em>Chapter 3</em>) investigated the OH-initiated oxidation of β-ocimene, a biogenic volatile organic compound (BVOC) released from vegetation, including forests, agricultural landscapes, and grasslands emitted during the daytime. The oxidation of BVOCs in the presence of NO_x leads to the formation of functionalized organic nitrate (RONO₂) compounds and isomers that easily condense to form SOA. To understand their atmospheric fate, the RONO₂ hydrolysis rate constants were quantified and found to be highly pH dependent. The findings of this study provide key insights into the formation and fate of organic nitrates and NO_x cycling in forested environments from daytime monoterpenes that were not previously included in atmospheric models. </p> <p>The second study (<em>Chapters 4 and 5</em>) investigated condensed waste emissions generated during Cured-In-Place-Pipe (CIPP) installations. This installation process is the most popular, least expensive, and most frequently used technology that cures leaking sanitary and stormwater sewers. Waste plumes discharged during pipe manufacture are complex multi-phase mixtures of volatile and semi-volatile organic compounds (VOC and SVOC, respectively), primary organic aerosols and SOA, fine debris of partially cured resin, and direct emission of nanoplastic particles that are all blown into the atmospheric environment at significant concentrations at worksites. This work unveiled a direct emission source of airborne nanoplastic particles as well as substantial concentrations of hazardous compounds and SOA precursors that were previously unrecognized. </p>

Indoor air quality (IAQ) has a direct impact on our health, as more than half the air we inhale throughout our lifetimes is indoor air. With an increasing trend in dampness in modern buildings due to urban expansion into wetland environments and increased use of gypsum board in construction, hydrolysis in indoor surface films has been suggested to be an important chemical process in the indoor environment. Several synthetic esters (SEs) found in building materials, electronics, and consumer products may undergo hydrolysis to produce harmful volatile organic compounds (VOCs) to which building occupants may be exposed. In this dissertation, the impact of hydrolysis on indoor air quality is explored by experiments on alkaline hydrolysis kinetics and ventilation, followed by simulations of VOC production from hydrolysis. Alkaline hydrolysis kinetics of four SEs, 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate (TMPD-MIB), butylparaben (BP), bis (2-ethylhexyl) adipate (DEHA), and butyl benzyl phthalate (BBzP), in bulk solutions are investigated in chapter 2. With concentration decay profiles following pseudo first-order kinetics, the second order-rate constants were determined from measured pH values. The determined rate constants of the aforementioned SEs are compared with those of respective ester categories (e.g., parabens, phthalates), and the steric/polar effects of the ester substituents are discussed in detail. The results of this study contributed to the completion of the indoor chemistry box model GAMMA-CIE which was used for simulation studies in chapter 4. Room-level ventilation measurements in educational spaces across different US regions (e.g., Northeastern, Southeastern, Western) are presented in chapter 3. In the wake of COVID-19 pandemic, ventilation data on a room-by-room basis were critical in planning a safe reopening in schools and universities. Three major approaches to ventilation measurements are outlined in this chapter: direct flow measurement, controlled release, and passive/in-situ monitoring. The application of these approaches is presented in case studies across various educational institutions, showcasing their advantages and disadvantages. The frequently observed range of 0.5-5.5 ACH in this study is taken into account in simulation conditions in chapter 4. The predicted indoor generation of VOCs from alkaline hydrolysis of SEs occurring in surface aqueous films is discussed in chapter 4. Simulations were performed using GAMMA-CIE, which considers aqueous hydrolysis kinetics, interphase mass transport, and loss by ventilation. Three different scenarios were studied: (1) installation of PVC flooring on concrete; (2) coating of latex paint on concrete; and (3) uptake of airborne SEs by surface aqueous films. The simulation results suggested that: (1) the rate of hydrolysis of DEHA and DEHP from PVC flooring is not fast enough to generate high concentrations of 2-ethylhexanol observed during episodes of sick building syndrome (SBS); (2) fresh application of latex paint may cause acute exposure to 2,2,4-trimethyl-1,3-pentanediol (TMPD); and (3) hydrolysis of SEs diffused from indoor air is unlikely to produce significant amounts of alcohols associated with SBS.

No description available.

No description available.

Dust is a critical component of the Earth System. The central and western Sahara (CWS) is the dustiest place on Earth during the northern hemisphere summer. Understanding patterns and causes of spatial and temporal variability of dust presence here is essential for its reliable simulation in numerical models of weather and climate. Four papers in this thesis contribute to that objective, utilising a combination of high temporal resolution satellite data and global atmospheric reanalyses for June – August 2004 – 2010 inclusive. The first paper develops an objective dust detection scheme for the CWS using data from the Spinning Enhanced Visible and Infrared Imager (SEVIRI), which are available every 15 minutes around the clock. These data have shed valuable insight on CWS dust processes, but their subjective application has to date limited their range of applications. The SEVIRI dust flag (SDF) developed here is evaluated against other widely used surface and satellite derived indicators of dustiness and it is found to reliably detect the presence of moderate-heavy dust loadings. The distribution of dust each summer is presented, revealing a high degree of interannual variability in overall dust coverage. The second paper utilises SDF to create an objective, high spatial resolution dust source map, based on the automated tracking of individual dust plumes. The most active sources are associated predominantly with palaeo-lakes and outwash plains, typically around the Saharan mountains. There is a clear intraseasonal progression of active source areas, controlled by regional climatology. The tracking scheme describes the transport trajectory of dust events following their initiation and the spatial association with deep convection at this time, revealing a clear regional divide in the relative importance of known meteorological mechanisms that drive dust emission from the dominant sources. The third paper uses an unsupervised clustering algorithm to classify maps of daily dust presence frequency and identify patterns of intraseasonal variability in CWS dust coverage. The resulting idealised dust states vary according to frequency of dust occurrence and its location, demonstrating a clear progression in preferred dust location from June – August and preferred state transitions from one day to the next. High daily dust occurrence frequency corresponds to an advanced West African Monsoon flow and low daily dust occurrence frequency corresponds to a Harmattan-dominated CWS. The overall location of the dust is linked to the location of the Sahara Heat Low, which changes as the summer progresses. The final paper addresses interannual variability in summertime dust presence frequency by comparing the 2 years with highest (2005) and lowest (2008) dust presence. The key difference is the occurrence of 3 multi-day periods in 2005 characterised by anomalously high dust presence. Case study comparison with the 3 periods of highest dust presence in 2008 identifies the anticyclonic circulation of the midtroposphere as a key control on dust duration over the CWS, dictating whether emitted dust is efficiently transported away from the CWS or whether it remains in suspension over the region for prolonged periods of time, up to several days in the anomalously dusty periods of 2005.

Clusters/nanoparticles are aggregates of a “small” number of building blocks, atoms or molecules, ranging from two up to millions of atoms. Two main groups of clusters have been studied using photoelectron spectroscopy based on synchrotron radiation. They are dry/wet alkali-halide clusters, including pure water clusters, and metal-based nanoparticles. For the dry alkali halide clusters, analysis of the data and theoretical modeling has allowed us insights into the local electronic properties at nanoscale: a change of polarizability of ions in the alkali-halide clusters due to the varying environment has been suggested. The study of the wet salt clusters shows that the alkali-halides are already solvated at the nanoscale reached by water clusters doped with salt vapor. The photoelectron angular distribution of water cluster shows lower anisotropy parameters as compared to the separate monomers. A model based on intracluster scattering has been built to partly explain the reduction. In the last part of the thesis, metal-based multi-component nanoparticles have been produced by self-assembly processes using reactive magnetron sputtering. Depending on the specific metal element, oxidation processes have been applied before or after the aggregation. Clearly radial distributions such as core-shell and “sandwich-like” structures have unambiguously determined by photoelectron spectroscopy.

This thesis presents the study of a selection of gas phase chemical processes using time-resolved Fourier transform infrared (FTIR) emission spectroscopy. Such processes include molecular energy transfer, chemical reaction and photodissociation. The major focus of this thesis was the investigation of collisional energy transfer from the electronically excited states of NO and OH, with particular attention paid to the fate of the electronic energy. NO A²&Sigma;⁺(v = 0) is prepared by laser excitation, pumping the overlapped Q₁ and P₂₁ band heads of the NO A-X (0,0) transition at 226.257 nm. The quenching of this state by O₂ and CO₂ was studied. Experiments were performed to investigate what channels contribute to the quenching process, the branching ratio of these different channels and the partitioning of energy among the various products. Quenching by O₂ was found to proceed mostly through non-reactive channels. High vibrational excitation of NO X ²&Pi; was observed, with population detected in v = 22, representing 79% of the available energy. The O₂ product was found to be formed in more than one electronic state: the ground state, X ³&Sigma;^-<sub style='position: relative; left: -.3em;'>g</sub>, and a high-lying electronically excited state, such as the A ³&Sigma;⁺<sub style='position: relative; left: -.5em;'>u</sub>, A' ³&Delta;_u or c ¹&Sigma;^-<sub style='position: relative; left: -.5em;'>u</sub> states. A reactive channel producing vibrationally excited NO₂ was observed, but was found to be a minor process with an upper limit of 18% for the branching ratio. In contrast the quenching of NO A ²&Sigma;⁺(v = 0) by CO₂ was found to proceed predominately by reaction, with a branching ratio of 76 %. While emission from NO₂ was observed, it was weak, and therefore it was concluded that the main reaction products were CO, O(³P) and NO X ²&Pi;(v = 0). The nascent strong CO₂ v3 emission band from the non-reactive channel exhibited a large red-shift from its fundamental position. This indicates that the CO₂ vibrational distribution is significantly hotter than statistical. Investigations were then performed studying the quenching of NO A ²&Sigma;⁺(v = 1) by NO and CO₂, with both systems exhibiting similar characteristics to the quenching of the ground vibrational level of NO A ²&Sigma;⁺. From comparison of the emission intensity of the CO fundamental and CO₂ v3 mode following quenching of the v = 0 and 1 levels of the NO A ²&Sigma;⁺ state, it was concluded that the branching ratio for reactive quenching was larger in the latter case. Secondly, experiments were performed to measure the rate constants for the quenching of NO A ²&Sigma;⁺(v = 0) by the noble gases. The noble gases are inefficient quenchers of electronically excited NO and therefore careful experimental design was required to minimise the influence of impurities on the results. All the rate constants were found to be of the order of 10^-14 cm³ molecule^-1 s^-1. The value for Xe was 50 times smaller than reported previously in the literature. In light of this new measurement, a re-analysis of experiments, performed previously in the group, on the electronic quenching of NO A ²&Sigma;⁺(v = 0) by Xe was performed. A very hot vibrational distribution of NO X ²&Pi; was obtained. Next, the collisional quenching of OH A ²&Sigma;⁺(v = 0) by H₂ was investigated. OH radicals were generated in situ by the photolysis of HNO₃ at 193 nm, which were excited to the A ²&Sigma;⁺(v = 0) state on the overlapped Q₁(1) and P₂₁(1) rotational lines at 307.935 nm. Reactive quenching was found to be the major pathway, in agreement with the literature. Copious emission from vibrationally excited water was observed. Comparison of this emission with theoretical calculations revealed a hotter distribution than predicted. It was concluded that the energy channelled into the vibrational modes of H₂O is in excess of 60% of the available energy. Experiments performed with D₂ allowed the non-reactive channel to be studied; a cold vibrational distribution of the OH X ²&Pi; was observed. Finally the reaction between CN radicals and cyclohexane was studied. CN was generated by the photolysis of ICN at 266 nm. Prompt emission from HCN in the C-H stretching region was observed meaning the new bond was formed in a vibrationally excited state. Analysis of the emission revealed HCN was populated up to v3 = 2. Excellent agreement with the results of a theoretical study of the system was found.