Analysis of Crystalline Silica Aerosol Using Portable Raman Spectrometry: Feasibility of Near Real-time Measurement.

A Raman spectroscopy based method has been developed for measurement of trace airborne concentrations of respirable crystalline silica (RCS) using various aerosol sampling and analysis techniques. Three aerosol microconcentration techniques were investigated for effective coupling of collected particulate samples with micro-Raman spectroscopy: (i) direct analysis on a particulate filter after focused aerosol collection using a converging nozzle; (ii) analysis of dried particulate deposit on a filter obtained directly from the aerosol phase using the Spotsampler device; and (iii) analysis of a dried spot (similar to 1-3 mm diameter) obtained by redepositing the particulate sample, after low temperature plasma ashing of the filter sample. The deposition characteristics (i.e., spot diameter, shape, and deposit uniformity) of each technique were investigated. Calibration curves were constructed and detection limits were estimated for a-quartz using the A(1) Raman Si-O-Si stretching bending phonon mode at 465 The measurement sensitivity could be substantially improved by increasing the signal integration time and by reducing the particle deposition area. Detection limits in the range of 8-55 ng could be achieved by microconcentrating the aerosol sample over a spot measuring 400-1000 mu m in diameter. These detection limits were two to three orders of magnitude lower compared to those attainable using current standardized X-ray diffraction and infrared spectroscopy methods. The low detection limits suggest that near real-time measurements of RCS could be achieved with limits of quantification ranging from 2 to 18.5 mu g/m(3) (at 10 min collection time and 1.2 L/min sampling flow rate), depending on microconcentration technique used. The method was successfully extended to the measurement of alpha-quartz air concentration in representative workplace aerosol samples. This study demonstrates the potential of portable micro-Raman spectroscopy for near-real time measurement of trace RCS in air.