Diffusive sampling of a mixture of 42 volatile organic compounds (VOCs) in humidified, purified air onto the solid adsorbent Carbopack X was evaluated under controlled laboratory conditions. The evaluation included variations in sample air temperature, relative humidity and ozone concentration. Linearity of samples with loading was examined both for a constant concentration with time varied up to 24 h and for different concentrations over 24 h. Reverse diffusion and its increase with accumulation of sample were determined for all compounds. Tubes were examined for blank levels, change of blanks with storage time, and variability of blanks. Method detection limits were determined based on seven replicate samples. Based on this evaluation, 27 VOCs were selected for quantitative monitoring in the concentration range from approximately 0.1 to 4 ppbv. Comparison results of active and diffusive samples taken over 24 h and under the same simulated ambient conditions at a constant 2 ppbv were interpreted to estimate the effective diffusive sampling rates (ml min(-1)) and their uncertainties and to calculate the corresponding diffusive uptake rates (ng ppmv(-1) min(-1)).

This study evaluates performance of nitrogen dioxide (NO2) and volatile organic compound (VOC) passive samplers with corresponding reference monitors at two sites in the Detroit, Michigan area during the summer of 2005. Ogawa passive NO2 samplers and custom-made, re-useable Perkin-Elmer (PE) tubes with Carbopack X sorbent for VOCs were deployed under week-long sampling periods for six weeks. Precise results (5% relative standard deviation, RSD) were found for NO2 measurements from collocated Ogawa samplers. Reproducibility was also good for duplicate PE tubes for benzene, toluene, ethylbenzene, and xylene isomers (BTEX species, all < or = 6% RSD). As seen in previous studies, comparison of Ogawa NO2 samplers with reference chemiluminescence measurements suggested good agreement. Generally good agreement was also found between the PE tubes and reference methods for BTEX species.

Analytical results obtained by thermal desorption GC/MS for 24 h diffusive sampling of 11 volatile organic compounds (VOCs) are compared with results of time-averaged active sampling at a known constant flow rate. Air samples were collected with co-located duplicate diffusive sampling tubes and one passivated canister. A total of eight multiple-component sampling events took place at fixed positions inside and outside three private homes. Subsequently, a known amount of sample air was transferred from the canister to an adsorbent tube for analysis by thermal desorption GC/MS. Results for the 11 most prevalent compounds--Freon 11, 1,3-butadiene, benzene, toluene, tetrachloroethene, ethylbenzene, m,p-xylene, o-xylene, 4-ethyltoluene, 1,3,5-trimethylbenzene, and p-dichlorobenzene--show that the ratio of average study values (diffusive sampling to active sampling) is 0.92 with 0.70 and 1.14 extreme ratios. Absolute percent difference for duplicate samples using diffusive sampling was <10% for the four most prevalent compounds. Agreement between the two sampling approaches indicates that the prediction of approximately constant diffusive sampling rates based on previous laboratory studies is valid under the field conditions.

Ambient air spiked with 1-10 ppbv concentrations of 41 toxic volatile organic compounds (VOCs) listed in US Environmental Protection Agency (EPA) Compendium Method TO-14A was monitored using solid sorbents for sample collection and a Varian Saturn 2000 ion trap mass spectrometer for analysis. The adsorbent was a combination of graphitic carbon and a Carboxen-type carbon molecular sieve. The method detection limits (MDLs) for 11 samples were typically 0.5 parts per billion by volume (ppbv) and lower except for bromomethane and chloromethane, both of which exhibited breakthrough. Thirty-day sample storage on the sorbents resulted in less than a 20% change for most compounds, and water management was required for humid samples to avoid major anomalous decreases in response during analyses. The adsorbent-based system, a system using canister-based monitoring, and a semi-continuous automated GC/MS (autoGC) monitoring system with a Tenax GR/Carbotrap B/Carbosieve S-III adsorbent preconcentrator were compared using spiked ozone concentrations as a variable. In this comparison, the target compounds included a number of n-aldehydes as well as those listed in TO-14A. The effects of ozone on the TO-14A compounds were relatively minor with the exception of negative artifacts noted for styrene and 1,1,2,2-tetrachloroethane. However, a small, systematic decrease in response was evident for a number of aromatic VOCs and 1,1,2,2-tetrachloroethane when ozone was increased from 50 to 300 ppbv. Method averages for multiple runs under the same conditions were typically within +0.25 ppbv of their mean for most compounds. For n-aldehydes, strong positive artifacts using the autoGC preconcentrator and strong negative artifacts for the canister-based and carbon sorbent approaches caused major disagreement among methods. These artifacts were mostly eliminated by using MnO2 ozone scrubbers, although loss of the n-aldehydes for all methods occurred after a single sample collection of 1 h duration, apparently due to the interaction of the n-aldehydes and products of the O3, MnO2 reaction on the scrubber.