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Fiber-loop ring-down spectroscopy (FLRDS) is a recently developed absorption spectroscopic technique suitable for very small liquid samples. It is based on measurements of the optical decay constant of laser intensity in a loop made of optical waveguide material. This decay constant changes as small liquid samples containing absorbing species are introduced into the loop. In this report, it is demonstrated that one can also obtain the optical decay constant using a continuous wave laser beam that is intensity modulated and then coupled into an optical fiber loop. The inherent exponential decay in the fiber loop introduces a phase shift of the light emitted from the loop with respect to the pumping beam. By measuring rids phase shift, one can readily determine the concentration of the analyte introduced between the two fiber ends and a model is established to describe the relationship. It is demonstrated that this technique, dubbed phase-shift fiber-loop ring-down spectroscopy (PS-FLRDS), is well suited as an absorption detector for any flow system in which the optical absorption path is limited by the instrument architecture. By measuring the phase angle as a function of concentration of 1, 1'-diethyl-4,4'-dicarbocyanine iodide in dimethyl sulfoxide, the detection limit was determined as ~6 [micro]M for a 30-40-[micro]m absorption path. A temporal resolution of ~100 ms was demonstrated by a rapid displacement of the solutions between the two fiber ends. Proof-of-principle use of the PS-FLRDS detection in capillary flow systems using a commercial four-way microcross established that the alignment of the fiber and the capillary can be made simple and effective, while retaining both a low detection limit and a fast response.

Cavity ring-down (CRD) spectrometers used for analytical applications frequently have design requirements different from spectrometers used for gas-phase spectroscopic applications. A formalism that allows for maximization of the relative sensitivity by adapting the cavity length and absorption path through the sample is presented. These experimental configurations may not reduce the detection limit but do allow for a high sensitivity of the ring-down time measurement in the concentration range of interest. The formalism is applied to two common CRDS experimental configurations and to a fiber-loop ring-down experiment. Key words: cavity ring-down (CRD), absorption, detector, fiber-loop, sensitivity, detection limit.

Pulsed, visible and near-infrared laser light is coupled into an optical fiber, which is wound into a loop using a fiber splice connector. The light pulses traveling through the fiber-loop are detected using a photomultiplier detector. It is found that once the light is coupled into the fiber it experiences very little loss and the light pulses do a large number of round trips before their intensity is below the detection threshold. Measurements of the loss-per-pass and of the ring-down time allow for characterization of the different loss mechanisms of the light pulses in the fiber and splice connector. This method resembles "cavity ring-down absorption spectroscopy" and is well suited to characterize low-loss processes in fiber optic transmission independent from power fluctuations of the light source. It is demonstrated that by measuring the ring-down times one can accurately determine the absolute transmission of an optical fiber and of the fiber connector. In addition it is demonstrated that the technique is useful as an absorption spectroscopic technique of very small sample volumes. A solution of an organic dye was placed between the fiber ends instead of the usual index matching fluid, and an absorption spectrum of 7 × 10[sup -15] mol of the dye 1,1'-diethyl4,4'-dicarbocyanine iodide in 7 × 10[sup -12] L of dimethylsulfoxide was recorded. [ABSTRACT FROM AUTHOR]