Heidi Hubbard

Workgroup Report: Indoor Chemistry and Health

Chemicals present in indoor air can react with one another, either in the gas phase or on surfaces, altering the concentrations of both reactants and products. Such chemistry is often the major source of free radicals and other short-lived reactive species in indoor environments. To what extent do the products of indoor chemistry affect human health? To address this question, the National Institute for Occupational Safety and Health sponsored a workshop titled “Indoor Chemistry and Health” on 12–15 July 2004 at the University of California–Santa Cruz. Approximately 70 experts from eight countries participated. Objectives included enhancing communications between researchers in indoor chemistry and health professionals, as well as defining a list of priority research needs related to the topic of the workshop. The ultimate challenges in this emerging field are defining exposures to the products of indoor chemistry and developing an understanding of the links between these exposures and various health outcomes. The workshop was a step toward meeting these challenges. This summary presents the issues discussed at the workshop and the priority research needs identified by the attendees.

Application of novel method to measure endogenous VOCs in exhaled breath condensate before and after exposure to diesel exhaust

Polar volatile organic compounds (PVOCs) such as aldehydes and alcohols are byproducts of normal human metabolism and thus are found in blood and exhaled breath. Perturbation of the normal patterns of such metabolites may reflect exposures to environmental stressors, disease state, and human activity. Presented herein is a specific methodology for assaying PVOC biomarkers in exhaled breath condensate (EBC) samples with application to a series of samples from a controlled chamber exposure to dilute diesel exhaust (DE) or to purified air. The collection/analysis method is based on condensation of normal (at rest) exhaled breaths for 10 min (resulting in 1-2 ml of liquid) with subsequent analyte adsorption onto Tenax cartridges followed by thermal desorption and analysis by gas chromatography/mass spectrometry (GC/MS). Analytical data have linearity of response (R(2)>0.98) across a range of 0-160 ng/ml with a detection limit ranging from 0.2 to 7 ng/ml depending on the compound. Statistical analyses of the results of the controlled exposure study indicate that metabolism, as reflected in simple breath-borne oxygenated species, is not affected by exposure to ambient airborne levels of DE. Linear mixed-effects models showed that PVOC biomarker levels are affected by gender and vary significantly among nominally healthy subjects. Differences among PVOCs analyzed in clinic air, purified chamber air, and chamber air containing dilute DE confirm that most of the compounds are likely of endogenous origin as the exogenous exposure levels did not perturb the EBC measurements.

Volatile polar metabolites in exhaled breath condensate (EBC): collection and analysis.

Environmental exposures, individual activities and disease states can perturb normal metabolic processes and be expressed as a change in the patterns of polar volatile organic compounds (PVOCs) present in biological fluids. We explore the measurement of volatile endogenous biomarkers to infer previous exposures to complex mixtures of environmental stressors. It is difficult to extract such compounds for ultra-trace level analysis due to their high solubility in water, especially when assaying complex liquid biological media such as exhaled breath condensate (EBC). Existing methods tend to be limited in sample volume processed and restricted in sample throughput. We have developed an alternative passive extraction method wherein a 2 ml sample is injected into a 75 ml glass bulb creating a small pool of liquid; a standard Tenax® sampling tube is inserted above the fluid and allowed to equilibrate with the headspace for ∼24 h. The biomarker compounds are preferentially transferred by diffusion from the aqueous sample onto the Tenax® adsorbent; blanks and calibration samples are similarly processed. Numerous samples can be simultaneously prepared and stored awaiting routine analysis for a suite of alcohols and aldehydes using thermal desorption gas chromatography-mass spectrometry (GC-MS). We have optimized the procedures and estimated the sensitivity, precision and extraction efficiency resulting from the preparation and analytical procedures using synthetic samples. We subsequently demonstrated the method using anonymous biological specimens of EBC from healthy adults. The ultimate goal is to develop normal ranges and patterns for PVOCs to infer population-based environmental health states with simple spot measurements based on outlier determinations.

The Influence of Declining Air Lead Levels on Blood Lead–Air Lead Slope Factors in Children

Background: It is difficult to discern the proportion of blood lead (PbB) attributable to ambient air lead (PbA), given the multitude of lead (Pb) sources and pathways of exposure. The PbB–PbA relationship has previously been evaluated across populations. This relationship was a central consideration in the 2008 review of the Pb national ambient air quality standards. Objectives: The objectives of this study were to evaluate the relationship between PbB and PbA concentrations among children nationwide for recent years and to compare the relationship with those obtained from other studies in the literature. Methods: We merged participant-level data for PbB from the National Health and Nutrition Examination Survey (NHANES) III (1988–1994) and NHANES 9908 (1999–2008) with PbA data from the U.S. Environmental Protection Agency. We applied mixed-effects models, and we computed slope factor, d[PbB]/d[PbA] or the change in PbB per unit change in PbA, from the model results to assess the relationship between PbB and PbA. Results: Comparing the NHANES regression results with those from the literature shows that slope factor increased with decreasing PbA among children 0–11 years of age. Conclusion: These findings suggest that a larger relative public health benefit may be derived among children from decreases in PbA at low PbA exposures. Simultaneous declines in Pb from other sources, changes in PbA sampling uncertainties over time largely related to changes in the size distribution of Pb-bearing particulate matter, and limitations regarding sampling size and exposure error may contribute to the variability in slope factor observed across peer-reviewed studies. Citation: Richmond-Bryant J, Meng Q, Davis A, Cohen J, Lu SE, Svendsgaard D, Brown JS, Tuttle L, Hubbard H, Rice J, Kirrane E, Vinikoor-Imler LC, Kotchmar D, Hines EP, Ross M. 2014. The Influence of declining air lead levels on blood lead–air lead slope factors in children. Environ Health Perspect 122:754–760; http://dx.doi.org/10.1289/ehp.1307072

Contribution of Particle-Size-Fractionated Airborne Lead to Blood Lead during the National Health and Nutrition Examination Survey, 1999–2008

The objective of this work is to examine associations between blood lead (PbB) and air lead (PbA) in particulate matter measured at different size cuts by use of PbB concentrations from the National Health and Nutrition Examination Survey and PbA concentrations from the U.S. Environmental Protection Agency for 1999-2008. Three size fractions of particle-bound PbA (TSP, PM10, and PM2.5) data with different averaging times (current and past 90-day average) were utilized. A multilevel linear mixed effect model was used to characterize the PbB-PbA relationship. At 0.15 μg/m(3), a unit decrease in PbA in PM10 was significantly associated with a decrease in PbB of 0.3-2.2 μg/dL across age groups and averaging times. For PbA in PM2.5 and TSP, slopes were generally positive but not significant. PbB levels were more sensitive to the change in PbA concentrations for children (1-5 and 6-11 years) and older adults (≥ 60 years) than teenagers (12-19 years) and adults (20-59 years). For the years following the phase-out of Pb in gasoline and a resulting upward shift in the PbA particle size distribution, PbA in PM10 was a statistically significant predictor of PbB. The results also suggest that age could affect the PbB-PbA association, with children having higher sensitivity than adults.

Methyl Bromide as a Building Disinfectant: Interaction with Indoor Materials and Resulting Byproduct Formation

Abstract Several buildings were contaminated with Bacillus anthracis in the fall of 2001. These events required consideration of how to disinfect large indoor spaces for continued worker occupation. The interactions of gaseous disinfectants with indoor materials may inhibit the disinfection process, cause persistence of the disinfectant, and lead to possible byproduct formation and persistence. Methyl bromide (CH3Br) is a candidate for disinfection/deactivation of biological agents in buildings. In this study, 24 indoor materials were exposed to CH3Br for 16 hr at concentrations ranging from 100 to 2500 ppm in 48–L electropolished stainless steel chambers. CH3Br concentrations were measured during and after disinfection. Its interactions with materials were observed to be small, with nearly complete and rapid desorption. Between 3% and 8% of CH3Br adsorbed to four materials (office partition, ceiling tile, particle–board, and gypsum wallboard with satin paint), and the degree of adsorption decreased with increasing relative humidity. The percentage of adsorption to all other materials was <2%. This result suggests that when designing disinfection events with CH3Br, loss to indoor materials can be neglected in terms of disinfectant dose calculations. Possible reaction products were identified and/or quantified before and after exposure to CH3Br. Several monomethylated and dimethylated aliphatic compounds were observed in chamber air at low concentrations after the exposures of six materials to CH3Br. Concentration increases also occurred for chemicals that were observed to naturally off–gas from materials before exposure to CH3Br, suggesting that CH3Br may play a role in enhancing the natural off–gassing of chemicals, for example, by competitive displacement of compounds that already existed in the materials. The results described in this paper should facilitate the design of building disinfection systems involving CH3Br.

Effect measure modification of blood lead–air lead slope factors

There is abundant literature finding that susceptibility factors, including race and ethnicity, age, and housing, directly influence blood lead levels. No study has explored how susceptibility factors influence the blood lead–air lead relationship nationally. The objective is to evaluate whether susceptibility factors act as effect measure modifiers on the blood lead–air lead relationship. Participant level blood lead data from the 1999 to 2008 National Health and Nutrition Examination Survey were merged with air lead data from the US Environmental Protection Agency. Linear mixed effects models were run with and without an air lead interaction term for age group, sex, housing age, or race/ethnicity to determine whether these factors are effect measure modifiers for all ages combined and for five age brackets. Age group and race/ethnicity were determined to be effect measure modifiers in the all-age model and for some age groups. Being a child (1–5, 6–11, and 12–19 years) or of Mexican-American ethnicity increased the effect estimate. Living in older housing (built before 1950) decreased the effect estimate for all models except for the 1–5-year group, where older housing was an effect measure modifier. These results are consistent with the peer-reviewed literature of time-activity patterns, ventilation, and toxicokinetics.