Applications of fluorescence spectroscopy to environmental chemistry
type: CreativeWork
description: The work presented in this thesis consists of three parts. The first is a photophysical study of the mechanism of fluorescence quenching by stable nitroxyl radicals, which are becoming an important analytical tool for the study of reactive transients in surface waters (1, 2). In part two, quenching of dissolved organic matter (DOM) fluorescence by nitroxides is employed to investigate the electrostatic propertie~ of DOM in aqueous solution, with the goal of elucidating the apparent ionic strength and pH dependence of metal-fulvic acid binding constants. In part three, the intrinsic optical properties (absorbance, fluorescence, and fluorescence efficiency) of DOM are examined in a coastal region to understand how these properties vary with source. age and sunlight exposure time. Nitroxide-fluorophore adducts were employed to investigate the mechanism by which nitroxyl radicals quench fluorescence (3). Fluorescence quantum yields and lifetimes were measured for a series of adducts, and quenching rates were shown to be quite high (kq≈108-1010 s-1), even at distances of ≈12 Å. Forster or Dexter energy transfer mechanisms are unable to account for the observed rates and lack of solvent dependence in quenching. An excellent correlation is observed between kq and the non-radiative relaxation rate. These results confirm that nitroxyl radicals are very non-selective in their quenching abilities, and suggest that the best analytical probe adducts will include a fluorophore with an appreciable non-radiative relaxation rate. Diffusional quenching by charged and neutral nitroxides was employed to explore the electrostatic properties of fulvic (FA) and humic (HA) acids. Cationic nitroxides were found to be up to 16 times more effective than neutral analogues in quenching the fluorescence of humic materials. This result is attributed to the enhanced coulombic attraction of cations to the anionic FA or HA surface, and is interpreted as an estimate of surface electrostatic potential…
abstract: The work presented in this thesis consists of three parts. The first is a photophysical study of the mechanism of fluorescence quenching by stable nitroxyl radicals, which are becoming an important analytical tool for the study of reactive transients in surface waters (1, 2). In part two, quenching of dissolved organic matter (DOM) fluorescence by nitroxides is employed to investigate the electrostatic propertie~ of DOM in aqueous solution, with the goal of elucidating the apparent ionic strength and pH dependence of metal-fulvic acid binding constants. In part three, the intrinsic optical properties (absorbance, fluorescence, and fluorescence efficiency) of DOM are examined in a coastal region to understand how these properties vary with source. age and sunlight exposure time. Nitroxide-fluorophore adducts were employed to investigate the mechanism by which nitroxyl radicals quench fluorescence (3). Fluorescence quantum yields and lifetimes were measured for a series of adducts, and quenching rates were shown to be quite high (kq≈108-1010 s-1), even at distances of ≈12 Å. Forster or Dexter energy transfer mechanisms are unable to account for the observed rates and lack of solvent dependence in quenching. An excellent correlation is observed between kq and the non-radiative relaxation rate. These results confirm that nitroxyl radicals are very non-selective in their quenching abilities, and suggest that the best analytical probe adducts will include a fluorophore with an appreciable non-radiative relaxation rate. Diffusional quenching by charged and neutral nitroxides was employed to explore the electrostatic properties of fulvic (FA) and humic (HA) acids. Cationic nitroxides were found to be up to 16 times more effective than neutral analogues in quenching the fluorescence of humic materials. This result is attributed to the enhanced coulombic attraction of cations to the anionic FA or HA surface, and is interpreted as an estimate of surface electrostatic potential…
author: Green, Sarah A.
language: en_US
keywords: Fluorescence spectroscopy, Chemical oceanography, Optical oceanography, Columbus Iselin (Ship) Cruise, Knorr (Ship : 1970-) Cruise KN134-12
date published: 1992-02
date modified: 2026-07-27T22:05:02Z
provider: Woods Hole Oceanographic Institute
publisher: Networked Digital Library of Theses and Dissertations
type: WebPage
source organization: Massachusetts Institute of Technology and Woods Hole Oceanographic Institution

PropertyValue
property ID: Handle
value: https://hdl.handle.net/1912/5491

PropertyValue
property ID: DOI
value: 10.1575/1912/5491