The real-time detection of trace species is key to a wide range of applications such as on-line chemical process analysis, medical diagnostics, identification of environmentally toxic species and atmospheric pollutant sensing. There is a growing demand for suitable techniques that are not only sensitive, but also simple to operate, fast and versatile. Most currently available techniques, such as spectrophotometry, are neither sensitive enough nor fast enough for kinetic studies, whilst other techniques are too complex to be operated by the non-specialist. This thesis presents two techniques that have been developed for and applied to liquid-phase analysis, with supercontinuum (SC) radiation used for liquid-phase absorption for the first time. Firstly, supercontinuum cavity enhanced absorption spectroscopy (SC-CEAS) was used for the kinetic measurement of chemical species in the liquid phase using a linear optical cavity. This technique is simple to implement, robust and achieves a sensitivity of 9.1 × 10−7 cm−1 Hz−1/2 at a wavelength of 550nm for dye species dissolved in water. SC-CEAS is not calibration-free and for this purpose a second technique, a time-resolved variant called broadband cavity ring-down spectroscopy (BB-CRDS), was successfully developed. Use of a novel single-photon avalanche diode (SPAD) array enabled the simultaneous detection of ring-down events at multiple spectral positions for BB-CRDS measurements. The performance of both techniques is demonstrated through a number of applications that included the monitoring of an oscillating (Belousov-Zhabotinsky) reaction, detection of commercially important photoluminescent metal complexes (europium(III)) at trace level concentration, and the analysis of biomedical species (whole and lysed blood) and proteins (amyloids). Absorption spectra covering the entire visible wavelength range can be acquired in fractions of a second using sample volumes measuring only 1.0mL. Most alternative devices capable of achieving similar sensitivity have, up until now, been restricted to single wavelength measurements. This has limited speed and number of species that can be measured at once. The work presented here exemplifies the potential of these techniques as analytical tools for research scientists, healthcare practitioners and process engineers alike.

Cavity enhanced spectroscopies (CES) are currently amongst the most sensitive spectroscopic techniques available for probing gas-phase samples, however their application to the liquid-phase has been more limited. Sensitive analysis of submicrolitre liquid samples is highly desirable, as miniaturisation allows for the reaction and analysis of scarce or expensive reagents, produces less waste, and can increase the speed of separations and reactions, whilst having a small footprint and high throughput. Absorption spectroscopy is a particularly desirable technique due to its universal, label-free nature, however its application to small volume liquid samples is hampered by the associated short absorption pathlengths, which limit sensitivity. CES improve sensitivity by trapping light within a confined region, increasing the effective pathlength through the sample. Three distinct types of optical cavity were constructed and evaluated for the purposes of making optical absorption measurements on liquid samples. The first incorporated a high optical quality flow cell into a "macrocavity" formed from two dielectric mirrors separated by 51.3 cm. Cavity losses were minimised by positioning the flow cell at Brewster's angle to the optical axis, and the setup was used to perform a single-wavelength cavity ringdown spectroscopy experiment to detect and quantify nitrite within aqueous samples. The detection limit was determined to be 8.83 nM nitrite in an illuminated volume of only 74.6 nL. Scattering and reflective losses from the flow cell surfaces were found to be the largest barrier to increased sensitivity, leading us to focus on the integration of cavity mirrors within a microfluidic flow system in the work that followed. In the second set of experiments, cavity enhanced absorption spectroscopy (CEAS) measurements were performed on Thymol Blue using custom-made microfluidic chips with integrated cavity mirrors. Unfortunately, due to the plane-parallel configuration of the mirrors and the corresponding difficulty in sustaining stable cavity modes, the results were underwhelming, with a maximum cavity enhancement factor (CEF) of only 2.68. At this point, attention was focussed toward a more well-defined cavity geometry: open-access plano-concave microcavities. The microcavities consist of an array of micron-scale concave mirrors opposed by a planar mirror, with a pathlength that is tunable to sub-nanometer precision using piezoelectric actuators. In contrast to the other experimental setups described, themicrocavities allow for optical measurements to be performed in which we monitor the change of wavelength and/or amplitude of a single well-defined cavity mode in response to a liquid sample introduced between the mirrors. In the first microcavity experiment, we used 10 μm diameter mirrors with cavity lengths from 2.238 μm to 10.318 μm to demonstrate refractive index sensing in glucose solutions with a limit of detection of 3.5 x 10^-4 RIU. The total volume of detection in our setup was 54 fL. Thus, at the limit of detection, the setup can detect the change of refractive index that results from the introduction of 900 zeptomoles (500,000 molecules) of glucose into the device. The microcavity sensor was then adapted to enable broadband absorption measurements of methylene blue via CEAS. By recording data simultaneously from multiple cavities of differing lengths, absorption data is obtained at a number of wavelengths. Using 10 μm diameter mirrors with cavity pathlengths from 476 nm to 728 nm, a limit of detection, expressed as minimum detectable absorption per unit pathlength, of 1.71 cm^-1 was achieved within a volume of 580 attolitres, corresponding to less than 2000 molecules within the mode volume of the cavity. Finally, a new prototype was developed with improved cavity finesse, a much more intense and stable light source, and improved flow design. Using a single plano-concave microcavity within the array with a cavity pathlength of 839.7 nm, and 4 μm radius of curvature mirror, absorption measurements were performed on Methylene Blue. Analysis of this data indicated a CEF of around 9270, and a limit of detection based on the measured signal-to-noise ratio of 0.0146 cm^-1. This corresponds to a minimum detectable concentration of 104 nM Methylene Blue, which given the mode volume of 219 aL, suggests a theoretical minimum detectable number of molecules of 14.

Novel applications of optical analytical techniques have been demonstrated in three general areas, namely application of broadband cavity enhanced absorption spectroscopy (BBCEAS) to the detection of liquid phase analytes, the use of total luminescence spectroscopy to discriminate between different type of teas and the development of an optical sensor to detect ammonia gas, based on the fluorescence quenching of a dye immobilised in a sol gel matrix. A simple BBCEAS setup has been developed with a view to perform sensitive visible wavelength measurements on liquid phase solutions. In the present work a simple low-cost experimental setup has been demonstrated for the measurement of the visible spectra of representative liquid-phase analytes in a 2 mm quartz cuvette placed at normal incidence to the cavity mirrors. Measurements on Ho3+ and sudan black with a white LED and the R ≥ 0.99 mirrors covered a broad wavelength range (~250 nm) and represents the largest wavelength range covered to date in a single BBCEAS experiment. The sensitivity of the technique as determined by the best αmin value was 5.1 x 10-5 cm-1 and was obtained using the R ≥ 0.99 mirrors. The best limit of detection (LOD) for the strong absorber brilliant blue-R, was approximately 620 pM. The optical setup was then optimised for the application of BBCEAS detection to an HPLC system. A 1 cm pathlength HPLC cell with a nominal volume of 70 ml was used in this study. The cavity was formed by two R ≥ 0.99 plano-concave mirrors with a bandwidth of ~ 420 – 670 nm. Two analytes rhodamine 6G and rhodamine B were chosen for separation by HPLC, as they were chemically similar species with distinctive visible spectra and would co-elute in an isocratic separation. The lowest value of amin obtained was 1.9 x 10-5 cm-1. The most significant advantage of the HPLC-BBCEAS study over previous studies arose from the recording of the absorption spectrum over a range of wavelengths. It was demonstrated that the spectral data collected could be represented as a contour plot which was useful in visualising analytes which nearly co-eluted. The LOD values for the two analytes studied indicated that the developed HPLC-BBCEAS setup was between 54 and 77 times more sensitive than a commercial HPLC system. For improved sensitivity and lower detection limits the low cost BBCEAS setup was used with a significantly longer 20 cm pathlength cell where the mirrors were in direct contact with the liquid phase analyte. This also reduced interface losses. The experiments were carried out using both R ³ 0.99 and R ³ 0.999 mirrors. The lowest αmin value obtained in this study was 2.8 x 10-7 cm-1 which is the lowest reported value to date for a liquid phase measurement, making this study the most sensitive liquid phase absorption measurement reported. The lowest LOD recorded was 4.6 pM, and was obtained for methylene blue with the R ³ 0.999 mirrors. A novel application of total luminescence spectroscopy to discriminate between different types of teas objectively was also investigated. A pattern recognition technique based on principal component analysis (PCA) was applied to the data collected and resulted in discrimination between both geographically similar and dissimilar teas. This work has shown the potential of fluorescence spectroscopy to distinguish between seven types of teas from Africa, India, Sri Lanka and Japan. Geographically similar black teas from 15 different plantation estates in Sri Lanka were also studied. The visualisation technique allowed the separation of all 11 types of teas when the first two principal components were utilised. The final part of the thesis describes the development of an optical sensor for the detection of ammonia gas. The operation of the sensor depended on the fluorescence quenching of the dye 9 amino acridine hydrochloride (9 AAH) immobilised in a sol gel matrix. It was also shown that the sensor response was not affected by the presence of acidic gases such as HCl and SO2. The final version of the sensor made use of dual channel monitoring to improve the sensitivity of the sensor. Measurements using diluted mixtures of ammonia gas in the range 5 -70 ppm showed that the response of the sensor was nonlinear, with the sensitivity increasing at lower concentrations. The measurement of the baseline noise allowed the LOD to be estimated at ~400 ppb.

Diode lasers are a convenient and economical source of near-infrared radiation, which may usefully be applied to a host of different sensitive detection methods; this thesis presents novel extensions of these methods, making use of the favourable characteristics of this type of light source. The first part of this thesis details the development of an optical feedback cavity-enhanced absorption spectroscopy (OF-CEAS) apparatus, including the development of the optical system, the sample handling, and the electronics for feedback phase control. A preliminary demonstration of the system is reported, presenting the detection of atmospheric water absorptions close to 1596 nm. Optimisation and application of the OF-CEAS spectrometer are then demonstrated, after which the spectrometer is applied to the sensitive detection of carbon dioxide absorptions suitable as a diagnostic aid in identifying Heliobacter pylori infection. A time-normalised α-min value of 5.8 × 10⁻⁹ cm⁻¹s^1/2 was measured for these spectra. Further optimisation of the system leads to an ultimate detection sensitivity of 1.42 × 10⁻⁹ cm⁻¹s^1/2, measured on absorption transitions in acetylene close to 1532 nm. In order further to characterise the performance of the OF-CEAS system, analogous experiments are presented using the OF-CEAS setup and a standard diode-laser cavity-enhanced absorption spectroscopy (CEAS) apparatus. Detection is carried out on the P(6) line of the ν₁ + ν₃ vibrational band of the mixed isotopologue of acetylene, ¹²-C¹³-CH₂. Direct comparison is made between the sensitivities of the two methods, and in light of this the suitability of each technique for detection in different environments is considered. The well-characterised and consistent frequency scale which is inherent to the OF-CEAS technique is then applied to a line shape analysis for the presented absorption spectra. Pressure-broadening coefficients are determined for selected absorptions in the ν₁ + ν₃ band of acetylene. In spite of the low resolution associated with this technique, this accurate frequency scaling allows observation of subtle line shape effects such as Dicke collisional narrowing using the data presented in Chapter 3 for the R(60) line in the 3ν₁ + ν₃ vibrational band of CO₂. These effects are quantified through use of a Galatry fit to each absorption spectrum. The statistical significance associated with the use of such a model, and the physical meaning of the results, are examined and discussed. An alternative strategy for increasing the sensitivity of a diode-laser-based gas monitoring technique lies in moving detection to the mid-infrared region, where the absorption cross-sections are generally larger. With this motivation, difference frequency generation is presented, to produce radiation close to 3.5 µm which is then applied to a series of different enhanced spectroscopy techniques. The optimal sensitivity, of 32 ppb NO2 at 45 Torr total sample pressure, was achieved using wavelength modulation spectroscopy. The different techniques are compared and possible improvements to them are put forward. Finally, proof-of-principle work is presented seeking to combine the enhanced circulating power associated with the optical-feedback-locked techniques and non-linear optical techniques to move detection to a more favourable spectral region. Light close to 429 nm is generated by second harmonic generation in a crystal of potassium niobate, with resonance-enhancement afforded by a feedback V-cavity of the sort employed in OF-CEAS. The potential of such a system for diode-laser-based generation of blue and ultraviolet light is demonstrated and discussed, along with improvements that might be implemented to increase the efficiency of the system.

Cavity ring-down spectroscopy (CRDS) and cavity enhanced absorption spectroscopy (CEAS) are two well-established absorption spectroscopic techniques originally developed for gas-phase samples. Condensed-phase applications of these techniques still remain rare, complicated as they are by additional background losses induced by condensed-phase samples as well as the intracavity components in which the sample is constrained. This thesis is concerned with the development and application of optical-cavity-based techniques in the condensed phase. Polarization-dependent evanescent wave CRDS (EW-CRDS) has been used to study the molecular orientation at the solid/air and solid/liquid interfaces. An increase in average orientation angle with respect to the surface normal has been observed for both methylene blue and coumarin molecules as a function of coverage at the fused silica/air interface. An orientation-angle-dependent photobleaching of pyridin molecules at the fused silica/methanol interface have also been observed. EW-CRDS has also been used to monitor slow in situ photobleaching of thin dye films deposited on the prism surface. The photobleaching dynamics is interpreted as a combination of first- and second-order processes. A significant fraction of this thesis has been devoted to studying magnetic field effects (MFEs) on the kinetics of the radical pair (RP) reactions in solution, in an effort to understand the ability of animals to sense the geomagnetic field. Two novel optical-cavity-based techniques – broadband CEAS (BBCEAS) and CRDS have been developed for this purpose. BBCEAS uses a supercontinuum (SC) source as the cavity light source and a CCD camera as photodetector, enabling simultaneous acquisition of absorption spectrum across the whole visible region (400 – 800 nm). In CRDS, a tunable optical parametric oscillator has been used as the cavity light source. Combined with the switching of external magnetic field (SEMF) method, this technique allows the decay kinetics of the geminate RPs to be monitored, with nanosecond resolution. Both BBCEAS and CRDS provide sensitivity superior to single-pass transient absorption (TA), a technique traditionally used in the MFE studies. A series of photochemical systems have been studied by BBCEAS and CRDS, respectively, among which, the MFEs of drosophila melanogaster cryptochrome has been observed. Importantly, this is the first time an MFE has been observed in an animal cryptochrome, and provides key supporting evidence for the cryptochrome hypothesis of magnetoreception in animals. Besides the optical-cavity-based techniques, a novel fluorescence detection method of MFEs has also been demonstrated. This technique proved ultrahigh sensitivity when applicable.

Species must interact with air—aqueous interfaces in order to transport between either phase, however organic coated water surfaces are ubiquitous in the environment, and the physical and chemical processes that occur at organic coated aqueous surfaces are often different than those at pure air—water interfaces. Three studies were performed investigating the transport of species across air—aqueous interfaces with organic coatings in an effort to gain further insight into these processes. Gas and solution phase absorption spectroscopy were used to study the effect of octanol coatings on the formation of molecular iodine (I2) by the heterogeneous ozonation of iodide and its partitioning between phases. Compared to uncoated solutions, the presence of octanol monolayers had a minor effect on the total amount of I2 produced, however, it did significantly enhance the gas to solution partitioning of I2. Incoherent broadband cavity-enhanced absorption spectroscopy (IBBC-EAS) was used to measure the gas-phase nitrogen dioxide (NO2) evolved via photolysis of aqueous nitrate solutions either uncoated or containing octanol, octanoic acid and stearic acid monolayers. Both octanol and stearic acid reduced the rate of gaseous NO2 evolution, and octanol also decreased the steady-state amount of gaseous NO2. Alternatively, octanoic acid enhanced the rate of gaseous NO2 evolution. Finally, the loss of aqueous carbon dioxide (CO2) from aqueous solutions saturated with CO2 was measured using a CO2 electrode in the absence and presence of stearic acid monolayers and octanol coatings, and a greenhouse gas analyzer was used to measure the evolution of gaseous CO2 from solutios with octanol monolayers. Enhanced losses of aqueous and evolved gaseous CO2 were observed with organic coated solutions compared to those uncoated. The results of these studies suggest that organic coatings influence the transport of I2, NO2 and CO2 via one, or a combination of: barrier effects, surface tension effects, chemistry effects and aqueous – surface – gas partitioning effects. These results, particularly the enhanced partitioning of these species to octanol coated aqueous surfaces, have important implications for species transport at air—aqueous interfaces, and may provide useful insight for future studies and parameters for atmospheric models of these species.

Species must interact with air—aqueous interfaces in order to transport between either phase, however organic coated water surfaces are ubiquitous in the environment, and the physical and chemical processes that occur at organic coated aqueous surfaces are often different than those at pure air—water interfaces. Three studies were performed investigating the transport of species across air—aqueous interfaces with organic coatings in an effort to gain further insight into these processes. Gas and solution phase absorption spectroscopy were used to study the effect of octanol coatings on the formation of molecular iodine (I2) by the heterogeneous ozonation of iodide and its partitioning between phases. Compared to uncoated solutions, the presence of octanol monolayers had a minor effect on the total amount of I2 produced, however, it did significantly enhance the gas to solution partitioning of I2. Incoherent broadband cavity-enhanced absorption spectroscopy (IBBC-EAS) was used to measure the gas-phase nitrogen dioxide (NO2) evolved via photolysis of aqueous nitrate solutions either uncoated or containing octanol, octanoic acid and stearic acid monolayers. Both octanol and stearic acid reduced the rate of gaseous NO2 evolution, and octanol also decreased the steady-state amount of gaseous NO2. Alternatively, octanoic acid enhanced the rate of gaseous NO2 evolution. Finally, the loss of aqueous carbon dioxide (CO2) from aqueous solutions saturated with CO2 was measured using a CO2 electrode in the absence and presence of stearic acid monolayers and octanol coatings, and a greenhouse gas analyzer was used to measure the evolution of gaseous CO2 from solutios with octanol monolayers. Enhanced losses of aqueous and evolved gaseous CO2 were observed with organic coated solutions compared to those uncoated. The results of these studies suggest that organic coatings influence the transport of I2, NO2 and CO2 via one, or a combination of: barrier effects, surface tension effects, chemistry effects and aqueous – surface – gas partitioning effects. These results, particularly the enhanced partitioning of these species to octanol coated aqueous surfaces, have important implications for species transport at air—aqueous interfaces, and may provide useful insight for future studies and parameters for atmospheric models of these species.

This dissertation is a collection of studies that investigates the issue of air pollution in the field of environmental chemistry. My thesis consists of research works done to measure the concentration of particulate matter (PM) and gas-phase species in ambient air. High concentrations of PM is a significant problem in Utah and in other regions of the world. Particles having an aerodynamic diameter of 2.5 micrometers and smaller play a crucial role in air pollution and pose serious health risks when inhaled. PM is composed of both organic and inorganic components. The organic fraction in PM ranges from 10-90% of the total particle mass. Several methods have been employed to measure the organic fraction of PM, but these techniques require extensive laboratory analysis, expensive bench top equipment, and do a poor job of capturing diurnal variations of the concentrations of ambient organic compounds. The Hansen Lab has developed a new instrument called the Organic Aerosol Monitor (OAM) which is based on gas chromatography followed by mass spectrometry detection platform for measuring the carbonaceous component of PM2.5 on an hourly averaged basis. Organic marker data collected in 2016 using the OAM was used in a Positive Matrix Factorization (PMF) analysis to identify the sources of PM in West Valley City, Utah. Additionally, data was collected in Richfield and Vernal, UT in 2017 - 2018 to quantitatively monitor the composition of organic markers of PM2.5. Some previously unidentified organic compounds in PM were successfully identified during this study, including terpenes, polycyclic aromatic hydrocarbons (PAHs), diethyl phthalate, some herbicides, and pesticides. Gas-phase species play a significant role in driving the formation of air pollutants in Earth's atmosphere. Traditional gas detection methods do not provide high temporally and spatially resolved data; therefore, it becomes important to detect and measure gas-phase species both qualitatively and quantitatively to better understand the sources of air pollution. An incoherent broadband cavity enhanced absorption spectrometer (IBBCEAS) combines a broadband incoherent light source, a stable optical cavity formed by two highly reflective mirrors and a charged-coupled device (CCD) detector to quantitatively measure the gas-phase compounds present in the atmosphere. The concentrations of formaldehyde (HCHO) were measured using IBBCEAS to investigate the sources of this hydrocarbon in Bountiful, Utah during 2019. Another important species is OH radical. It is one of the most predominant oxidizing species present in the atmosphere. It is found in low concentrations, 0.1 ppt. Detecting concentrations this low is challenging. A new IBBCEAS instrument has been designed and elements of this instrument were tested by measuring the OH overtones in a variety of short chained alcohols. A set of experiments were conducted to measure the absorption cross-sections for the 5th and 6th OH vibrational overtones in a series of short chained alcohols by IBBCEAS. Because OH radical's lowest energy electronic state occurs in the same wavelength region (i.e., 308 nm) that SO2 absorbs (300-310 nm), a study was conducted in which the concentrations of SO2 were measured using an IBBCEAS and compared with a commercially available SO2 monitor.

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