Cavity ring-down spectroscopy has been used over the last twenty years as a highly sensitive absorption spectroscopic technique to measure light attenuation in gases, liquids, and solid samples. An optical cavity is used as a multi-pass cell, and the decay time of the light intensity in the cavity is measured, thereby rendering the techniques insensitive to light intensity fluctuations. Optical waveguides are used to build the optical cavities presented in this work. The geometries of such waveguides permit the use of very small liquid sample volumes while retaining the advantages of cavity ring-down spectroscopy. In this thesis cavity ring-down measurements are conducted, both, in the time domain and by measuring phase-shifts of sinusoidally modulated light, and the two methods are theoretically connected using a simple mathematical model, which is then experimentally confirmed. A new laser driver, that is compatible with high powered diode lasers, has to be designed to be able to switch from time domain to frequency domain measurements. A sample path length enhancement within the optical cavity is explored with the use of liquid core waveguides. The setup was optimised with respect to the matrix liquid, the geometrical matching of waveguide geometries, and the shape of liquid core waveguide ends. Additionally, a new technique of producing concave lenses at fibre ends has been developed and the output of a general fibre lens is simulated. Finally, liquid core waveguides are incorporated into a fibre-loop ring-down spectroscopy setup to measure the attenuation of two model dyes in a sample volume of <1 µL. The setup is characterized by measuring concentrations of Allura Red AC and Congo Red from 1 µM to a limit of detection of 5 nM. The performance of the setup is compared to other absorption techniques measuring liquid samples. / Thesis (Ph.D, Chemistry) -- Queen's University, 2013-04-23 14:08:16.33