Chunrong Jia

Distributions of personal VOC exposures: A population-based analysis

Information regarding the distribution of volatile organic compound (VOC) concentrations and exposures is scarce, and there have been few, if any, studies using population-based samples from which representative estimates can be derived. This study characterizes distributions of personal exposures to ten different VOCs in the U.S. measured in the 1999--2000 National Health and Nutrition Examination Survey (NHANES). Personal VOC exposures were collected for 669 individuals over 2-3 days, and measurements were weighted to derive national-level statistics. Four common exposure sources were identified using factor analyses: gasoline vapor and vehicle exhaust, methyl tert-butyl ether (MBTE) as a gasoline additive, tap water disinfection products, and household cleaning products. Benzene, toluene, ethyl benzene, xylenes chloroform, and tetrachloroethene were fit to log-normal distributions with reasonably good agreement to observations. 1,4-Dichlorobenzene and trichloroethene were fit to Pareto distributions, and MTBE to Weibull distribution, but agreement was poor. However, distributions that attempt to match all of the VOC exposure data can lead to incorrect conclusions regarding the level and frequency of the higher exposures. Maximum Gumbel distributions gave generally good fits to extrema, however, they could not fully represent the highest exposures of the NHANES measurements. The analysis suggests that complete models for the distribution of VOC exposures require an approach that combines standard and extreme value distributions, and that carefully identifies outliers. This is the first study to provide national-level and representative statistics regarding the VOC exposures, and its results have important implications for risk assessment and probabilistic analyses.

Ozone Artifacts and Carbonyl Measurements Using Tenax GR, Tenax TA, Carbopack B, and Carbopack X Adsorbents

Abstract Four popular thermally desorbable adsorbents used for air sampling (Tenax TA, Tenax GR, Carbopack B, and Carbopack X) are examined for the potential to form artifacts with ozone (O3) at environmental concentrations. The performance of these adsorbents for the ketone and alde-hyde species identified as O3-adsorbent artifacts was also characterized, including recovery, linearity, and method detection limits (MDLs). Using gas chromatography/mass spectrometry, 13 different artifacts were identified and confirmed for both Tenax TA and Tenax GR, 9 for Carbopack B, but none for Carbopack X. Several O3 artifacts not reported previously were identified, including: pentanal, 3-hexanone, 2-hexanone, hexanal, 3-heptanone, and heptanal with Tenax TA; pentanal, 3-hexanone, 2-hexanone, hexanal, and 3-heptanone on Tenax GR; and 1-octene and 1-nonene with Carbopack B. Levels of straight-chain aldehyde artifacts rapidly diminished after a few cycles of adsorbent conditioning/O3 exposure, and concentrations could be predicted using a first-order model. Phenyl-substituted carbonyl artifacts (benzalde-hyde and acetophenone) persisted on Tenax TA and GR even after 10 O3 exposure-conditioning cycles. O3 breakthrough through the adsorbent bed was most rapid in adsorbents that yielded the highest levels of artifacts. Overall, artifact composition and concentration are shown to depend on O3 concentration and dose, conditioning method, and adsorbent type and age. Calibrations showed good linearity, and most compounds had reasonable recoveries, for example, 90 ±15% for Tenax TA, 97 ±23% for Tenax GR, 101 ±24% for Carbopack B, and 79 ±25% (91 ±9% for n-aldehydes) for Carbopack X. Benzeneacetaldehyde recovery was notably poorer (22–63% across the four adsorbents). MDLs for several compounds were relatively high, up to 5 ng. By accounting for both artifact formation and method performance, this work helps to identify which carbonyl compounds can be measured using thermally desorbable adsorbents and which may be prone to bias because of the formation of O3- adsorbent artifacts.