Positive and negative artifacts in particulate organic carbon measurements with denuded and undenuded sampler configurations

Abstract

Measurement of ambient particulate organic carbon (POC) with quartz filters is prone to positive and negative sampling artifacts. One approach for estimating these artifacts is to sample with a backup quartz filter placed behind either the main quartz filter or a Teflon filter in a parallel line. Another approach is to use a denuder to reduce the positive artifact in combination with a highly adsorbent backup filter to capture any negative artifact. Results obtained using both of these approaches in parallel for over one year in Pittsburgh, PA are presented in this article. A sampler using an activated carbon monolith denuder has been developed and tested extensively. Transmission losses were found to be negligible, and the denuder is on average 94% efficient at removing gas-phase organics. Denuder breakthrough is corrected for each run using a dynamic blank in parallel with the sample line. Comparisons with the dynamic blank indicate that the denuder almost eliminates the positive artifact on the quartz filter. Negative artifact from the denuded quartz filter is quantified using a carbon-impregnated glass fiber (CIG) backup filter and was found to be small, typically less than 10% of the ambient POC. Compared to the denuded sampler POC, 24 h bare quartz samples showed an almost constant positive artifact of 0.5 μg-C/m3 for samples taken throughout the year-long study period. Sampling for shorter durations (4-6 h) resulted in a larger positive artifact. A quartz filter behind a Teflon filter (QBT) provides a consistent estimate of the positive artifact on the bare quartz filter irrespective of sample duration, though it overcorrects for the positive artifact by 16-20% (attributed to particulate matter volatilizing off the upstream Teflon filter). The quartz behind quartz (QBQ) approach provides a reasonable estimate of the positive artifact on the bare quartz filter for the 24 h samples but not for the shorter samples. A slight seasonal variation is observed in the absolute value of the positive artifact, with higher values observed during the summer months.