Analysis of small volume liquid samples using cavity enhanced absorption spectroscopies

Cavity enhanced absorption spectroscopies have earned themselves a place as one of the methods of choice for sensitive absorption measurements on gas-phase samples, but their application to liquid samples has so far been more limited. Sensitive short pathlength analysis of liquid samples is required for online analysis of microfluidic samples, which are processed in channels with dimensions of tens to hundreds of micrometres. Microfluidics is important for a range of applications including drug discovery and environmental sensing. This thesis explores the application of cavity enhanced absorption spectroscopies to short pathlength (0.010 mm to 2 mm) analysis of sub-microlitre volumes of liquids.
Three experimental set-ups have been been examined. Firstly, a single-wavelength cavity ringdown (CRD) spectrometer operating at 532 nm was assembled using two 99.8% reflectivity mirrors. High optical quality flow cells with short pathlengths ranging from 0.1 mm to 2 mm were inserted into this cavity at Brewster’s angle. The detection limit of the set-up with each inserted flow cell was established using a concentration series of aqueous potassium permanganate (KMnO₄) solutions. For the 1 mm flow cell, a detection limit of 29 nM KMnO₄ or 1.4 x 10⁻⁴ cm⁻¹ was established. Several different types of microfluidic devices were also inserted into the cavity, and it was found that the losses arising from the inserted chip were highly dependent on the method of chip manufacture. The CRD set-up with inserted 1 mm flow cell was applied to the detection of two important species, nitrite and iron(II), via analyte-specific colourimetric reactions. Detection limits of 1.9 nM nitrite and 3.8 nM iron(II) were established.
The second experimental set-up utilised broadband, supercontinuum light generated in a 20 m length of nonlinear photonic crystal fibre. Broadband mirrors with around 99% reflectivity over the wavelength range from 400 to 800 nm were used to form the cavity, and a miniature spectrometer was used to wavelength-resolve the time-integrated cavity output. Flow cells and microfluidic chips were inserted into the cavity either at normal incidence or at Brewster’s angle. This set-up was employed for reaction analysis of an iron complexation reaction with bathophenanthroline, and for a model organic reaction, the Diels-Alder reaction between anthracene and 4-phenyl-1,2,4-triazoline-3,5-dione. The same broadband set-up was also used for pH measurements using bromocresol green indicator solution. Using dual-wavelength CRD spectroscopy, the pH sensitivity was established to be around a few milli pH units.
Finally, an alternative type of cavity, formed from a loop of optical fibre has been investigated. A novel light-coupler was designed and fabricated in 365 μm core diameter multimode optical fibre. Sample designs employing both direct and evanescent wave absorption were investigated in small-core and large-core optical fibres, and the lowest detection limit of 0.11 cm⁻¹ was determined in direct absorption measurements, with a pathlength of 180 μm, using our novel light coupler in 365 μm core diameter optical fibre.

Keywords: microfluidics
absorption spectroscopy
cavity enhancement
Advisor: Vallance, C