Simple system for part-per-billion-level volatile organic compound analysis in groundwater and urban air

A simple device is described, capable of measuring reliably and reproducibly low levels (0.1 ppbv with a total analysis time of approximately 40 min) of volatile organic compounds (VOCs) in urban air and in the headspace of groundwater. The VOCs were pre-concentrated onto a small bed of Tenax TA(R), and subsequently released by temperature-programmed thermal desorption (TPD). TPD profiles were recorded by a solid-state sensor array. The success of the method was based on a well defined TPD peak shape if the absorbent bed was sufficiently thin, linearity and additivity of appropriately transformed sensor signals, the use of a very stable sensor array utilizing chromium-titanium oxide as the sensor material and devices with different electrode gaps and the use of dry air as the carrier gas. Successful analysis of groundwater headspace was achieved by diluting the sample stream 1:4 with dry air (which prevented saturation of the adsorbent surface by water) and by introducing a dry air purge of the bed at room temperature before desorption (which removed excess water from the bed and hence stabilized the sensor baseline before the desorption). Principal components analysis and spectral decomposition (SD) methods were used successfully for identification of VOCs and quantification in simple mixtures. The SD method expressed the measured desorption trace on the elements of the sensor array as the sum of a small number of sensor array spectra. The individual desorption traces for each characteristic sensor spectrum thus derived could be further resolved by a peak fitting procedure because the TPD trace had a well defined form, in which both peak temperature and peak width in TPD correlated with the boiling temperature of the VOCs, and peak width varied according to functional type: phenols > aliphatics > alkyl-substituted benzenes.