The effects of high energy processes on atmospheric species: Investigations of isotope effects in the photoionization of N2 and CO2 and in the corona discharge formation of N2O and light-scattering from photochemically-generated aerosols

In the research reported in this dissertation, experiments were designed and performed to investigate the interactions of atmospheric gases with high-energy photons and/or electrons, which can produce highly reactive ions and radicals via ionization and dissociation, and which in turn may result in previously unexplored isotope effects or in formation of aerosols with optical properties that are difficult to predict and measure. Knowledge of both isotope effects and the optical properties of aerosols formed by UV photolysis of precursor gases are highly relevant for interpreting observations of and understanding chemical and physical processes occurring in a wide variety of planetary atmospheres. Here, photoionization efficiency spectra of isotopologues of N2 (14N2, 15N14N, and 15N2) and CO2 (12C16O2, 13C16O2, 12C16O18O, 13C16O18O, 12C18O2, and 13C18O2) using synchrotron radiation at the Advanced Light Source were measured, the polarization and intensity of laser light scattered by photochemically-generated aerosols suspended in the gas phase as a function of scattering angle were investigated in situ using a newly designed and built computer-controlled custom polarimeter, and the isotopic composition of N2O produced in a newly designed and constructed corona discharge apparatus was measured./nIsotope effects in the photoionization of N2 and CO2 may be important in determining the isotopic composition in planetary atmospheres, such as those on Earth and Titan in the case of N2 and on Mars and Venus in the case of CO2, and provide new data to address uncertainties in spectral peak assignments in the photoionization spectra, and yet have not been previously measured. For example, for N2, the measured differences in photoinization efficiencies between 14N2 and 15N14N, may help resolve differences in the isotopic composition of N2 versus that for HCN observed on Titan. In addition, the spectral assignment for the feature at 15.677 eV in the 14N2 photoionization spectrum has remained controversial despite decades of research. The measured isotope shifts for this peak are compared with isotope shifts predicted using Herzberg equations for the isotopic differences in harmonic oscillator energy levels plus the first anharmonic correction for the three proposed assignments. The measured isotope shifts for this peak relative to 14N2 are 0.015 +/- 0.001 eV for 15N2 and 0.008 +/- 0.001 eV for 15N14N (reported here for the first time), which match most closely with the isotope shifts predicted for transitions to the (A 2-Pi-u v=2)4-s-sigma-g 1-Pi-u state of 0.0143 eV for 15N2 and 0.0071 eV for 15N14N, and thus assignment to this transition is favored. For CO2, the measured isotope effects in photoionization yield ratios of photoionization rate coefficients, J (i.e., photoionization cross-sections convolved with the solar spectrum and integrated over all photoionization energies), that are less than 1: J(13C16O2)/J(12C16O2) = 0.97 +/- 0.02, J(12C16O18O)/J(12C16O2) = 0.97 +/- 0.02, J(13C16O18O)/J(12C16O2) = 0.97 +/- 0.02, J(12C18O2)/J(12C16O2) = 0.99 +/- 0.02, and J(13C18O2)/J(12C16O2) = 0.98 +/- 0.02. These isotope effects in photoionization rate coefficients are likely large enough to contribute to (if not dominate) enrichments in 13C in CO2 in the martian atmosphere, which have largely been attributed to atmospheric escape over billions of years, and may also be important in the atmospheres of Venus and Earth, thus warranting inclusion in models of the isotopic composition of CO2 in planetary atmospheres./nAerosols generated by UV photolysis of precursor gases are present in a number of planetary atmospheres, including Titan, and most likely, early Earth and early Mars, and are expected to have a profound effect on atmospheric radiative transfer, yet the number of investigations of aerosol optical properties suspended in the gas phase is extremely limited. In order to measure the intensity and polarization state of light scattered by photochemically-generated aerosols as a function of scattering angle, a custom polarimeter consisting of a quarter-wave plate mounted in a computer-controlled rotating stage and a linear polarizer was designed and built. The polarimeter was placed into the 13 L reaction chamber to measure the intensity and polarization of light scattered by photochemically-generated aerosol in situ, and the parameters of the Stokes vector were calculated at a number of scattering angles. The results demonstrate that this technique can be used to measure the polarization and angular dependence (phase function) of light scattered by aerosol particles in situ while still suspended in the gas phase, with the ultimate goal of using these measurements to attain the size distribution and index of refraction of the aerosol particles for applications to radiative transfer in planetary atmospheres, such as early Earth and Titan./nMeasurements of the isotopic composition of N2O can be used to infer its sources and sinks, and understanding the isotopic composition of N2O formed by corona discharge in air (a process which can occur, for example, in thunderstorms) may be important for understanding atmospheric observations of N2O if the isotope effects in N2O formation are large. To measure the isotopic composition of N2O formed by corona discharge, a new apparatus was designed and built to produce N2O by corona discharge and isolate and collect the N2O cryogenically for subsequent analysis by continuous flow isotope ratio mass spectrometry. Results from the first measurements of isotopic composition (reported as delta-15 N, delta-18O, and the "site-specific" delta-15N values, delta-15N-alpha and delta-15N-beta) indicate that, under some conditions, the isotopic composition of N2O formed by corona discharge is significantly different from the reactant N2 and O2 and from background tropospheric N2O, although none of the measurements reported here show fractionations larger than 4% (i.e., 40 per mil) relative to the starting N2 or O2 or tropospheric N2O. Additional testing under other experimental conditions (e.g., pressure, discharge residence time, discharge current) is warranted to assess whether fractionations might be large enough to include in atmospheric models.

Advisor: Boering, Kristie A