Summary of PM2.5 measurement artifacts associated with the Teledyne T640 PM Mass Monitor under controlled chamber experimental conditions using polydisperse ammonium sulfate aerosols and biomass smoke.

Particulate matter (PM) is a major primary pollutant emitted during wildland fires that has the potential to pose significant health risks to individuals/communities who live and work in areas impacted by smoke events. Limiting exposure is the principle measure available to mitigate health impacts of smoke and therefore the accurate determination of ambient PM concentrations during wildland fire events is critical to protecting public health. However, monitoring air pollutants in smoke impacted environments has proven challenging in that measurement interferences or sampling conditions can result in both positive and negative artifacts. The EPA has performed research on methods for the measurement of PM2.5 in a series of laboratory-based studies including evaluation in smoke. This manuscript will summarize the results of the laboratory-based evaluation of federal equivalent method (FEM) monitors for PM2.5 with particular attention being given to the Teledyne-API Model T640 PM Mass monitor, as compared to the filter-based federal reference method (FRM). The T640 is an optical-based PM monitor and has been gaining wide use by state and local agencies in monitoring for PM2.5 U.S. National Ambient Air Quality Standards (NAAQS) attainment. At present, the T640 (includes both T640 and T640×) comprises ~44% of the PM2.5 FEM monitors in U.S. regulatory monitoring networks. In addition, the T640 has increasingly been employed for the higher time resolution comparison/evaluation of low-cost PM sensors including during smoke impacted events. Results from controlled non-smoke laboratory studies using generated ammonium sulfate aerosols demonstrated a generally negative T640 measurement artifact that was significantly related to the PM2.5 concentration and particle size distribution. Results from biomass burning chamber studies demonstrated positive and negative artifacts significantly associated with PM2.5 concentration and optical wavelength-dependent absorption properties of the smoke aerosol.Implications: The results detailed in this paper will provide state and local air monitoring agencies with the tools and knowledge to address PM2.5 measurement challenges in areas frequently impacted by wildland fire smoke. The observed large positive and negative artifacts in the T640 PM mass determination have the potential to result in false exceedances of the PM2.5 NAAQS or in the disqualification of monitoring data through an exceptional event designation. In addition, the observed artifacts in smoke impacted air will have a detrimental effect on providing reliable public information when wildfires occur and also in identifying reference measurements for small sensor evaluation studies. Other PM2.5 FEMs such as the BAM-1022 perform better in smoke and are comparable to the filter-based FRM. Care must be taken in choosing high time resolution FEM monitors that will be operated at smoke impacted sites. Accurate methods, such as the FRM and BAM-1022 will reduce the burden of developing and reviewing exceptional event request packages, data loss/disqualification, and provide states with tools to adequately evaluate public exposure risks and provide accurate public health messaging during wildfire/smoke events.

Comparison of ozone measurement methods in biomass burning smoke: an evaluation under field and laboratory conditions.

In recent years wildland fires in the United States have had significant impacts on local and regional air quality and negative human health outcomes. Although the primary health concerns from wildland fires come from fine particulate matter (PM2.5), large increases in ozone (O3) have been observed downwind of wildland fire plumes (DeBell et al., 2004; Bytnerowicz et al., 2010; Preisler et al., 2010; Jaffe et al., 2012; Bytnerowicz et al., 2013; Jaffe et al., 2013; Lu et al., 2016; Lindaas et al., 2017; McClure and Jaffe, 2018; Liu et al., 2018; Baylon et al., 2018; Buysse et al., 2019). Conditions generated in and around wildland fire plumes, including the presence of interfering chemical species, can make the accurate measurement of O3 concentrations using the ultraviolet (UV) photometric method challenging if not impossible. UV photometric method instruments are prone to interferences by volatile organic compounds (VOCs) that are present at high concentrations in wildland fire smoke. Four different O3 measurement methodologies were deployed in a mobile sampling platform downwind of active prescribed grassland fire lines in Kansas and Oregon and during controlled chamber burns at the United States Forest Service, Rocky Mountain Research Station Fire Sciences Laboratory in Missoula, Montana. We demonstrate that the Federal Reference Method (FRM) nitric oxide (NO) chemiluminescence monitors and Federal Equivalent Method (FEM) gas-phase (NO) chemical scrubber UV photometric O3 monitors are relatively interference-free, even in near-field combustion plumes. In contrast, FEM UV photometric O3 monitors using solid-phase catalytic scrubbers show positive artifacts that are positively correlated with carbon monoxide (CO) and total gas-phase hydrocarbon (THC), two indicator species of biomass burning. Of the two catalytic scrubber UV photometric methods evaluated, the instruments that included a Nafion® tube dryer in the sample introduction system had artifacts an order of magnitude smaller than the instrument with no humidity correction. We hypothesize that Nafion®-permeating VOCs (such as aromatic hydrocarbons) could be a significant source of interference for catalytic scrubber UV photometric O3 monitors and that the inclusion of a Nafion® tube dryer assists with the mitigation of these interferences. The chemiluminescence FRM method is highly recommended for accurate measurements of O3 in wildland fire plume studies and at regulatory ambient monitoring sites frequently impacted by wildland fire smoke.

Uncertainty in collocated mobile measurements of air quality.

Mobile mapping of air pollution has the potential to provide pollutant concentration data at unprecedented spatial scales. Characterizing instrument performance in the mobile context is challenging, but necessary to analyze and interpret the resulting data. We used robust statistical methods to assess mobile platform performance using data collected with the Aclima Inc. mobile air pollution measurement and data acquisition platform installed on three Google Street View cars. They were driven throughout the greater Denver metropolitan area between July 25, 2014 and August 14, 2014, measuring ozone (O3), nitrogen dioxide (NO2), nitric oxide (NO), black carbon (BC), and size-resolve particle number counts (PN) between 0.3 µm and 5.0 µm diameter. August 6, 2014 was dedicated to parked and moving collocations among the three cars, allowing an assessment of measurement precision and bias. We used the median absolute deviation (MAD) to estimate instrument precision from outdoor, parked collocations. Bias was assessed by measurements obtained from parked cars using the standard deviation of median values over a collocated measurement period, as well as by Passing-Bablok regression statistics while the cars were moving and collocated. For the moving collocation periods, we compared the distribution of 1-σ standard deviations among the 3 cars to the estimated distribution assuming only measurement uncertainty (precision and bias). The distribution of mobile measurements agreed well with the theoretical uncertainty distribution at the lower end of the distribution for O3, NO2, and PN. We assert that the difference between the actual and theoretical distributions is due to real spatial variability between pollutants. The agreement between the parked car estimates of uncertainty and that measured during the mobile collocations (at the lower quantiles) provides evidence that on-road collocation while parked could be sufficient for estimating measurement uncertainties of a mobile platform, even when extended to the moving environment.

Particulate matter, nitrogen oxides, ozone, and select volatile organic compounds during a winter sampling period in Logan, Utah, USA.

Particulate matter mass (PM), trace gaseous pollutants, and select volatile organic compounds (VOCs) with meteorological variables were measured in Logan, Utah (Cache Valley), for >4 weeks during winter 2017 as part of the Utah Winter Fine Particle Study (UWFPS). Higher PM levels for short time periods and lower ozone (O3) levels were present due to meteorological and mountain valley conditions. Nitrogenous pollutants were relatively strongly correlated with PM variables. Diurnal cycles of NOx, O3, and fine PM(PM 2.5) (aerodynamic diameter <2.5 µm [PM2.5]) suggested formation from NOx. O3 levels increased from early morning into midafternoon, and NOx and PM2.5 increased throughout the morning, followed by sharp decreases. Toluene/benzene and xylenes/benzene ratios and VOC correlations with nitrogenous and PM species were indicative of local traffic sources. Wind sector comparisons suggested that pollutant levels were lower when winds were from nearby mountains to the east versus winds from northerly or southerly origins. Implications: The Cache Valley in Idaho and Utah has been designated a PM2.5 nonattainment area that has been attributed to air pollution buildup during winter stagnation events. To inform state implementation plans for PM2.5 in Cache Valley and other PM2.5 nonattainment areas in Utah, a state and multiagency federal research effort known as the UWFPS was conducted in winter 2017. As part of the UWFPS, the U.S. Environmental Protection Agency (EPA) measured ground-based PM species and their precursors, VOCs, and meteorology in Logan, Utah. Results reported here from the EPA study in Logan provide additional understanding of wintertime air pollution conditions and possible sources of PM and gaseous pollutants as well as being useful for future PM control strategies in this area.

Multigenerational Theoretical Study of Isoprene Peroxy Radical 1-5-Hydrogen Shift Reactions that Regenerate HO x Radicals and Produce Highly Oxidized Molecules.

A computational protocol is employed to glean new insight into the kinetics of several 1,5-hydrogen atom (H) shift reactions subsequent to first- and second-generation OH/O2 additions to isoprene. The M06-2X density functional was initially used with the Nudged Elastic Band (NEB) method to determine the potential energy surface of OH/O2 addition reactions, the 1,5-H shift reactions, and the fragmentation exit channels. The Master Equation Solver for Multi-Energy Well Reactions (MESMER) was applied to determine the rate constants for OH addition and the 1,5-H shifts. M06-2X was capable of quantifying the rate constants of OH addition to the first and second double bonds of isoprene with deviations less than 17% from the experimentally determined values. However, M06-2X underestimated the 1,5-H shift rate constants of second-generation isoprene peroxy radicals. Consequently, MN15, ωB97X-D, and CBS-QB3 methods were employed to compute average barrier heights to first- and second-generation 1,5-H shifts. In the first generation, the rate constants of H abstraction by ß-(1,2) and (4,3) isoprene hydroxy-peroxy radicals from the neighboring hydroxyl group are 1.1 × 10-3 and 2.4 × 10-3 s-1, respectively. These values are determined primarily by the barrier of the H shift reaction and, to a smaller albeit nonnegligible extent, by the stability of the resulting alkoxy radical and the exit barrier leading to C-C bond dissociation. In contrast, the average second-generation rate constant of 1,5-H shifts from H-R-OH sites to the peroxy radical is 1.8 × 10-1 s-1, with tunneling playing the significant role of increasing this value relative to first-generation 1,5-H shifts. Under low NO x conditions, first-generation isoprene oxidation reactions may recycle HO x at levels ranging from 10 to 30% due in large part to 1,5-H shifts, with the recycling efficiency being sensitive to HO2 concentrations and temperature. HO x recycling is expected to increase to levels beyond 80% in second-generation reactions of oxidized isoprene species because of isoprene epoxydiol (IEPOX) formation and further 1,5-H shifts that are kinetically favorable.

Size-Selective Sampling Performance of Six Low-Volume "Total" Suspended Particulate (TSP) Inlets.

Several low-volume inlets (flow rates ≤16.7 liters per minute (Lpm)) are commercially available as components of low-cost, portable ambient particulate matter samplers. Because the inlets themselves do not contain internal fractionators, they are often assumed to representatively sample "total" mass concentrations from the ambient air, independent of aerodynamic particle size and wind speed. To date, none of these so-called "TSP" inlets have been rigorously tested under controlled conditions. To determine their actual size-selective performance under conditions of expected use, wind tunnel tests of six commonly used omnidirectional, low-volume inlets were conducted using solid, polydisperse aerosols at wind speeds of 2, 8, and 24 km/hr. With the exception of axially-oriented, isokinetic sharp-edge nozzles operating at 5 and 10 Lpm, all low-volume inlets showed some degree of non-ideal sampling performance as a function of aerodynamic particle size and wind speed. Depending upon wind speed and assumed ambient particle size distribution, total mass concentration measurements were estimated to be negatively biased by as much as 66%. As expected from particle inertial considerations, inlet efficiency tended to degrade with increasing wind speed and particle size, although some exceptions were noted. The implications of each inlet's non-ideal behavior are discussed with regards to expected total mass concentration measurement during ambient sampling and the ability to obtain representative sampling for size ranges of interest, such as PM2.5 and PM10. Overall test results will aid in low-volume inlet selection and with proper interpretation of results obtained with their ambient field use.

Development of Polydisperse Aerosol Generation and Measurement Procedures for Wind Tunnel Evaluation of Size-Selective Aerosol Samplers.

Accurate development and evaluation of inlets for representatively collecting ambient particulate matter typically involves use of monodisperse particles in aerosol wind tunnels. However, the resource requirements of using monodisperse aerosols for inlet evaluation creates the need for more rapid and less-expensive techniques to enable determination of size-selective performance in aerosol wind tunnels. The goal of recent wind tunnel research at the U.S. EPA was to develop and validate the use of polydisperse aerosols which provide more rapid, less resource-intensive test results which still meet data quality requirements necessary for developing and evaluating ambient aerosol inlets. This goal was successfully achieved through comprehensive efforts regarding polydisperse aerosol generation, dispersion, collection, extraction, and analysis over a wide range of aerodynamic particle sizes. Using proper experimental techniques, a sampler's complete size-selective efficiency curve can be estimated with polydisperse aerosols in a single test, as opposed to the use of monodisperse aerosols which require conducting multiple tests using several different particle sizes. While this polydisperse aerosol technique is not proposed as a regulatory substitute for use of monodisperse aerosols, the use of polydisperse aerosols is advantageous during an inlet's development where variables of sampling flow rate and inlet geometry are often iteratively evaluated before a final inlet design can be successfully achieved. Complete Standard Operating Procedures for the generation, collection, and analysis of polydisperse calibration aerosols are available from EPA as downloadable files. The described experimental methods will be of value to other researchers during development of ambient sampling inlets and size-selective evaluation of the inlets in aerosol wind tunnels.

Revisiting the size selective performance of EPA's high-volume total suspended particulate matter (Hi-Vol TSP) sampler.

Under the National Ambient Air Quality Standard (NAAQS) for airborne lead, measurements are conducted by means of a high-volume total suspended particulate matter (Hi-Vol TSP) sampler. In the decade between 1973 and 1983, there were 12 publications that explored the sampling characteristics and effectiveness of the Hi-Vol TSP, yet there persists uncertainty regarding its performance. This article presents an overview of the existing literature on the performance of the Hi-Vol TSP, and identifies the reported sampler effectiveness with respect to four factors: particle size (reported effectiveness of 7%-100%), wind speed (-36% to 100%), sampler orientation (7%-100%), and operational state (107%-140%). Effectiveness of the Hi-Vol TSP was evaluated with a solid, polydisperse aerosol in a controlled wind tunnel setting. Isokinetic samplers were deployed alongside the Hi-Vol TSP to investigate three wind speeds (2, 8, and 24 km h-1), three sampler orientations (0°, 45°, 90°), and two operational states (on, off) for aerosols with aerodynamic diameters from 5 to 35 µm. Results indicate that particle diameter was the largest determining factor of effectiveness followed by wind speed. Orientation of the sampler did not have a significant effect at 2 and 8 km h-1 but did at 24 km h-1. In a passive state, the Hi-Vol TSP was collected between 1% and 7% of available aerosol depending on particle size and wind speed. Results of this research do not invalidate results of previous studies but rather contribute to our overall understanding of the Hi-Vol TSP's size-selective performance. While results generally agreed with previous studies, the Hi-Vol TSP was found to exhibit less dependence on these four factors than previously reported.