Assaying particle-bound polycyclic aromatic hydrocarbons from archived PM2.5 filters.

Airborne particulate matter contains numerous organic species, including several polycyclic aromatic hydrocarbons (PAHs) that are known or suspected carcinogens. Existing methods for measuring airborne PAHs are complex and costly, primarily because they are designed to collect both gas-phase and particle-phase PAH constituents. Here, we report an assay for measuring particle-bound PAHs in archived filters from the network of U.S. monitoring stations for particles less than 2.5 microm in diameter (PM2.5), without the need for deploying specialized samplers. PAHs are extracted from Teflon filters with dichloromethane, concentrated, and measured at trace levels using gas chromatography-mass spectrometry. Although PAHs with 3-6 aromatic rings can be assayed, results are only unambiguously accurate for compounds with 5- or 6-rings, due to variable vaporization losses of the more volatile 3- and 4-ring compounds during sampling and/or storage. The method was evaluated for sensitivity, recovery, precision, and agreement of paired air samples, using PM2.5 samplers locally in Chapel Hill, NC. Additionally, three sets of archived samples were analyzed from a study of PM2.5 in the Czech Republic. Levels of some 4-ring and all 5- and 6-ring PAHs in both the local and Czech samples were consistent with published results from investigations employing PAH-specific air samplers. This work strongly suggests that assessment of particle-bound 5- and 6-ring PAHs from archived PM2.5 filters is quantitatively robust. The assay may also be useful for selected 4-ring compounds, notably chrysene and benzo(a)anthracene, if PM2.5 filters are stored under refrigeration.

Modeling spatial and temporal variability of residential air exchange rates for the Near-Road Exposures and Effects of Urban Air Pollutants Study (NEXUS).

Air pollution health studies often use outdoor concentrations as exposure surrogates. Failure to account for variability of residential infiltration of outdoor pollutants can induce exposure errors and lead to bias and incorrect confidence intervals in health effect estimates. The residential air exchange rate (AER), which is the rate of exchange of indoor air with outdoor air, is an important determinant for house-to-house (spatial) and temporal variations of air pollution infiltration. Our goal was to evaluate and apply mechanistic models to predict AERs for 213 homes in the Near-Road Exposures and Effects of Urban Air Pollutants Study (NEXUS), a cohort study of traffic-related air pollution exposures and respiratory effects in asthmatic children living near major roads in Detroit, Michigan. We used a previously developed model (LBL), which predicts AER from meteorology and questionnaire data on building characteristics related to air leakage, and an extended version of this model (LBLX) that includes natural ventilation from open windows. As a critical and novel aspect of our AER modeling approach, we performed a cross validation, which included both parameter estimation (i.e., model calibration) and model evaluation, based on daily AER measurements from a subset of 24 study homes on five consecutive days during two seasons. The measured AER varied between 0.09 and 3.48 h(-1) with a median of 0.64 h(-1). For the individual model-predicted and measured AER, the median absolute difference was 29% (0.19 h­1) for both the LBL and LBLX models. The LBL and LBLX models predicted 59% and 61% of the variance in the AER, respectively. Daily AER predictions for all 213 homes during the three year study (2010-2012) showed considerable house-to-house variations from building leakage differences, and temporal variations from outdoor temperature and wind speed fluctuations. Using this novel approach, NEXUS will be one of the first epidemiology studies to apply calibrated and home-specific AER models, and to include the spatial and temporal variations of AER for over 200 individual homes across multiple years into an exposure assessment in support of improving risk estimates.

Health and household air pollution from solid fuel use: the need for improved exposure assessment.

BACKGROUND: Nearly 3 billion people worldwide rely on solid fuel combustion to meet basic household energy needs. The resulting exposure to air pollution causes an estimated 4.5% of the global burden of disease. Large variability and a lack of resources for research and development have resulted in highly uncertain exposure estimates. OBJECTIVE: We sought to identify research priorities for exposure assessment that will more accurately and precisely define exposure-response relationships of household air pollution necessary to inform future cleaner-burning cookstove dissemination programs. DATA SOURCES: As part of an international workshop in May 2011, an expert group characterized the state of the science and developed recommendations for exposure assessment of household air pollution. SYNTHESIS: The following priority research areas were identified to explain variability and reduce uncertainty of household air pollution exposure measurements: improved characterization of spatial and temporal variability for studies examining both short- and long-term health effects; development and validation of measurement technology and approaches to conduct complex exposure assessments in resource-limited settings with a large range of pollutant concentrations; and development and validation of biomarkers for estimating dose. Addressing these priority research areas, which will inherently require an increased allocation of resources for cookstove research, will lead to better characterization of exposure-response relationships. CONCLUSIONS: Although the type and extent of exposure assessment will necessarily depend on the goal and design of the cookstove study, without improved understanding of exposure-response relationships, the level of air pollution reduction necessary to meet the health targets of cookstove interventions will remain uncertain.

Atmospheric mercury in the Lake Michigan basin: influence of the Chicago/Gary urban area.

The relative importance of the Chicago/Gay urban area was investigated to determine its impact on atmospheric mercury (Hg) concentrations and wet deposition in the Lake Michigan basin. Event wet-only precipitation, total particulate, and vapor phase samples were collected for Hg, and trace element determinations from five sites around Lake Michigan from July 1994 through October 1995 as part of the Lake Michigan Mass Balance Study (LMMBS). In addition, intensive over-water measurements were conducted aboard the EPA research vessel Lake Guardian during the summer of 1994 and the winter of 1995 as part of the Atmospheric Exchange Over Lakes and Oceans Study. Atmospheric Hg concentrations were found to be significantly higher in the Chicago/Gary urban area than surrounding sites: Hg in precipitation was a factor of 2 and particulate Hg was a factor of 6 times higher. Overwater measurements found elevated Hg concentrations 19 km off shore of Chicago/Gary suggesting an enhanced near field atmospheric deposition to Lake Michigan. Meteorological transport analyses also determined that local sources in the Chicago/Gary urban area significantly impacted all of the LMMBS sites indicating a broad impact to the entire Lake Michigan basin.

Deposition and emission of gaseous mercury to and from Lake Michigan during the Lake Michigan Mass Balance Study (July, 1994-October, 1995).

This paper presents measurements of dissolved gaseous mercury (DGM) concentrations in Lake Michigan and the application of a mechanistic approach to estimate deposition and emission fluxes of gaseous mercury (Hg2+ and Hg0) to and from Lake Michigan. Measurements of DGM concentrations made during May and July, 1994 and January, 1995 indicate that Lake Michigan was supersaturated with DGM suggesting that transfer of Hg0 occurs from the water to the atmosphere. Over-water concentrations of gaseous Hg2+ were estimated from total gaseous Hg (TGM) concentrations measured at five sites in the basin and used to model dry deposition fluxes of Hg2+. The modeling approach combines estimates of dry deposited Hg2+ with known photochemical and biotic reduction rates to form Hg0, which is available for re-emission. The model accounts for temporal and spatial variations in the deposition velocity of gaseous Hg2+ and the transfer velocity of Hg0 using high temporal and spatial resolution meteorological data. The modeled DGM concentrations agree well with the observed DGM concentrations in Lake Michigan. The modeled dry deposition fluxes of Hg2+ (286-797 kg yr(-1)) are very similar to the emission fluxes of Hg0 (320-959 kg yr(-1)), depending on the gaseous Hg2+ concentration used in the model.

Chemical characterization of ambient particulate matter near the World Trade Center: elemental carbon, organic carbon, and mass reconstruction.

Concentrations of elemental carbon (EC), organic carbon matter (OM), particulate matter less than 2.5 microm (PM2.5), reconstructed soil, trace element oxides, and sulfate are reported from four locations near the World Trade Center (WTC) complex for airborne particulate matter (PM) samples collected from September 2001 through January 2002. Across the four sampling sites, daily mean concentrations ranged from 1.5 to 6.8 microg/m3 for EC, from 10.2 to 31.4 microg/m3 for OM, and from 22.6 to 66.2 microg/m3 for PM2.5. Highest concentrations of PM species were generally measured north and west of the WTC complex. Total carbon matter and sulfate constituted the largest fraction of reconstructed PM2.5 concentrations. Concentrations of PM species across all sites decreased from the period when fires were present at the WTC complex (before December 19, 2001) to the period after the fires. Averaged over all sites, concentrations decreased by 25.6 microg/m3 for PM2.5, 2.7 microg/m3 for EC, and 9.2 microg/m3 for OM from the fire period to after fire period.

Air levels of carcinogenic polycyclic aromatic hydrocarbons after the World Trade Center disaster.

The catastrophic collapse of the World Trade Center (WTC) on September 11, 2001, created an immense dust cloud followed by fires that emitted soot into the air of New York City (NYC) well into December. The subsequent cleanup used diesel equipment that further polluted the air until the following June. The particulate air pollutants contained mutagenic and carcinogenic polycyclic aromatic hydrocarbons (PAHs). By using an assay developed for archived samples of fine particles, we measured nine PAHs in 243 samples collected at or near Ground Zero from September 23, 2001, to March 27, 2002. Based on temporal trends of individual PAH levels, we differentiated between fire and diesel sources and predicted PAH levels between 3 and 200 d after the disaster. Predicted PAH air concentrations on September 14, 2001, ranged from 1.3 to 15 ng/m(3); these values are among the highest reported from outdoor sources. We infer that these high initial air concentrations resulted from fires that rapidly diminished over 100 d. Diesel sources predominated for the next 100 d, during which time PAH levels declined slowly to background values. Because elevated PAH levels were transient, any elevation in cancer risk from PAH exposure should be very small among nonoccupationally exposed residents of NYC. However, the high initial levels of PAHs may be associated with reproductive effects observed in the offspring of women who were (or became) pregnant shortly after September 11, 2001. Because no PAH-specific air sampling was conducted, this work provides the only systematic measurements, to our knowledge, of ambient PAHs after the WTC disaster.