Review of Sunset OC/EC Instrument Measurements During the EPA's Sunset Carbon Evaluation Project.

To evaluate the feasibility of the Sunset semicontinuous organic and elemental carbon (OC/EC) monitor, the U.S. Environmental Protection Agency (EPA) sponsored the deployment of this monitor at Chemical Speciation Network (CSN) sites with OC and EC measurements via quartz fiber filter collection in Chicago, Illinois; Houston, Texas; Las Vegas, Nevada; St. Louis, Missouri; Rubidoux, California; and Washington, D.C. Houston, St. Louis, and Washington also had collocated Aethalometer black carbon (BC) measurements. Sunset OC generally compared well with the CSN OC (r2 = 0.73 across five sites); the Sunset/CSN OC ratio was, on average, 1.06, with a range among sites of 0.96 to 1.12. Sunset thermal EC and CSN EC did not compare as well, with an overall r2 of 0.22, in part because 26% of the hourly Sunset EC measurements were below the detection limit. Sunset optical EC had a much better correlation to CSN EC (r2 = 0.67 across all sites), with an average Sunset/CSN ratio of 0.90 (range of 0.7 to 1.08). There was also a high correlation of Sunset optical EC with Aethalometer BC (r2 = 0.77 across all sites), though with a larger bias (average Sunset/Aethalometer ratio of 0.56). When the Sunset instrument was working well, OC and OptEC data were comparable to CSN OC and EC.

An evaluation of mass absorption cross-section for optical carbon analysis on Teflon filter media.

Black carbon (BC) or elemental carbon (EC) is a by-product of incomplete fuel combustion, and contributes adversely to human health, visibility, and climate impacts. Previous studies have examined nondestructive techniques for particle light attenuation measurements on Teflon® filters to estimate BC. The incorporation of an inline Magee Scientific OT21 transmissometer into the MTL AH-225 robotic weighing system provides the opportunity to perform optical transmission measurements on Teflon filters at the same time as the gravimetric mass measurement. In this study, we characterize the performance of the inline OT21, and apply it to determine the mass absorption cross-section (MAC) of PM2.5 BC across the United States. We analyzed 5393 archived Teflon® filters from the Chemical Speciation Network (CSN) collected during 2010-2011 and determined MAC by comparing light attenuation on Teflon® filters to corresponding thermal EC on quartz-fiber filters. Results demonstrated the importance of the initial transmission (I0) value used in light attenuation calculations. While light transmission varied greatly within filter lots, the average I0 of filter blanks during the sampling period provided an estimate for archived filters. For newly collected samples, it is recommended that filter-specific I0 measurements be made (i.e., same filter before sample collection). The estimated MAC ranged from 6.9 to 9.4 m2/g and varied by region and season across the United States, indicating that using a default value may lead to under- or overestimated BC concentrations. An analysis of the chemical composition of these samples indicated good correlation with EC for samples with higher EC content as a fraction of total PM2.5 mass, while the presence of light-scattering species such as crustal elements impacted the correlation affecting the MAC estimate. Overall, the method is demonstrated to be a quick, cost-effective approach to estimate BC from archived and newly sampled Teflon® filters by combining both gravimetric and BC measurements. IMPLICATIONS: Robotic optical analysis is a valid, cost-effective means to obtain a vast amount of BC data from archived and current routine filters. A tailored mass absorption cross-section by region and season is necessary for a more representative estimate of BC. Initial light transmission measurements play an important role due to the variability in blank filter transmission. Combining gravimetric mass and BC analysis on a single Teflon® filter reduces costs for monitoring agencies and maximizes data collection.

Field assessment of the Village Green Project: an autonomous community air quality monitoring system.

Continuous, long-term, and time-resolved measurement of outdoor air pollution has been limited by logistical hurdles and resource constraints. Measuring air pollution in more places is desired to address community concerns regarding local air quality impacts related to proximate sources, to provide data in areas lacking regional air monitoring altogether, or to support environmental awareness and education. This study integrated commercially available technologies to create the Village Green Project (VGP), a durable, solar-powered air monitoring park bench that measures real-time ozone, PM2.5, and meteorological parameters. The data are wirelessly transmitted via cellular modem to a server, where automated quality checks take place before data are provided to the public nearly instantaneously. Over 5500 h of data were successfully collected during the first ten months of pilot testing in Durham, North Carolina, with about 13 days (5.5%) of downtime because of low battery power. Additional data loss (4-14% depending on the measurement) was caused by infrequent wireless communication interruptions and instrument maintenance. The 94.5% operational time via solar power was within 1.5% of engineering calculations using historical solar data for the location. The performance of the VGP was evaluated by comparing the data to nearby air monitoring stations operating federal equivalent methods (FEM), which exhibited good agreement with the nearest benchmark FEMs for hourly ozone (r(2) = 0.79) and PM2.5 (r(2) = 0.76).

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.

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.

Evaluation of methods for analysis of lead in air particulates: an intra-laboratory and inter-laboratory comparison.

In 2008, the United States Environmental Protection Agency (USEPA) set a new National Ambient Air Quality Standard (NAAQS) for lead in total suspended particulate matter (Pb-TSP) which called for significant decreases in the allowable limits. The Federal Reference Method (FRM) for Pb-TSP promulgated in 1978 prescribes analysis of Pb by flame atomic absorption spectroscopy (FAAS), but the new limits approach the limits of quantitation of FAAS. On August 2, 2013, the USEPA finalized a new FRM for Pb-TSP. This new FRM describes two extraction methods and analysis by inductively coupled plasma-mass spectrometry (ICP-MS). The study described here was performed to evaluate the use of ICP-MS in the analysis of Pb-TSP for implementation of this new FRM. A multi-laboratory study of the new FRM demonstrated acceptable intra- and inter-laboratory precision and comparability for glass fiber, quartz, and PTFE filters, and acceptable accuracy for the analysis of three National Institute of Standards and Technology (NIST) Standard Reference Materials (SRMs). A comparison was made between analytical results obtained using the 1978 FRM and those obtained using the new FRM. The results demonstrate that the ICP-MS method performs acceptably for the determination of Pb-TSP with lower limits of quantitation and strong inter- and intra-laboratory precision.

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.

A multi-level model of blood lead as a function of air lead.

National and local declines in lead (Pb) in blood (PbB) over the past several years coincide with the decline in ambient air Pb (PbA) concentrations. The objective of this work is to evaluate how the relationship between PbB levels and PbA levels has changed following the phase out of leaded gasoline and tightened controls on industrial Pb emissions over the past 30 years among a national population sample. Participant-level data from the National Health and Nutrition Examination Survey (NHANES) were employed for two time periods (1988-1994 and 1999-2008), and the model was corrected for housing, demographic, socioeconomic, and other covariates present in NHANES. NHANES data for PbB and covariates were merged with PbA data from the U.S. Environmental Protection Agency. Linear mixed effects models (LMEs) were run to assess the relationship of PbB with PbA; sample weights were omitted, given biases encountered with the use of sample weights in LMEs. The 1988-1994 age-stratified results found that ln(PbB) was statistically significantly associated with ln(PbA) for all age groups. The consistent influence of PbA on PbB across age groups for the years 1988-1994 suggests a ubiquitous exposure unrelated to age of the sample population. The comparison of effect estimates for ln(PbA) shows a statistically significant effect estimate and ANOVA results for ln(PbB) for the 6- to 11-year and 12- to 19-year age groups during 1999-2008. The more recent finding suggests that PbA has less consistent influence on PbB compared with other factors.

Harmonization of uncertainties of X-ray fluorescence data for PM2.5 air filter analysis.

The U.S. Environmental Protection Agency (EPA)'s PM2.5 Chemical Speciation Network (CSN) and the Interagency Monitoring of Protected Visual Environments (IMPROVE) network use X-ray fluorescence (XRF) analysis to quantify trace elements in samples of fine particles less than 2.5 microns in aerodynamic diameter (PM2.5). Methods for calculating uncertainty values for XRF results vary considerably among laboratories and instrument makes and models. To support certain types of modeling and data analysis, uncertainty estimates are required that are consistent within and between monitoring programs, and that are independent of the laboratories that performed the analyses and the analytical instrumentation used. The goal of this work was to develop a consensus model for uncertainties associated with XRF analysis of PM2.5 filter samples. The following important components of uncertainty are included in the model described herein: variability in peak area, calibration, field sampling, and attenuation of X-ray intensity for light elements. This paper includes a detailed analysis of how attenuation uncertainties for light elements are derived. For the remaining uncertainty components included in the model, an approach and recommendations are presented to ensure that laboratories performing this type of analysis can use similar equations and parameterizations. By applying this uniform approach, it is illustrated how the uncertainties reported by the CSN and IMPROVE network laboratories can be brought into very good agreement. The proposed method is best applied at the time of data generation, but retrospective estimation of uncertainties in existing data-sets is also possible. This paper serves to document the equations used for calculating the uncertainties in speciated PM2.5 data currently being posted on EPA's Air Quality System database for the PM2.5 CSN program.

The national ambient air monitoring strategy: rethinking the role of national networks.

A current re-engineering of the United States routine ambient monitoring networks intended to improve the balance in addressing both regulatory and scientific objectives is addressed in this paper. Key attributes of these network modifications include the addition of collocated instruments to produce multiple pollutant characterizations across a range of representative urban and rural locations in a new network referred to as the National Core Monitoring Network (NCore). The NCore parameters include carbon monoxide (CO), sulfur dioxide (SO2), reactive nitrogen (NOy), ozone (O3), and ammonia (NH3) gases and the major fine particulate matter (PM2.5) aerosol components (ions, elemental and organic carbon fractions, and trace metals). The addition of trace gas instruments, deployed at existing chemical speciation sites and designed to capture concentrations well below levels of national air quality standards, is intended to support both long-term epidemiological studies and regional-scale air quality model evaluation. In addition to designing the multiple pollutant NCore network, steps were taken to assess the current networks on the basis of spatial coverage and redundancy criteria, and mechanisms were developed to facilitate incorporation of continuously operating particulate matter instruments.