Wildfires Increase Concentrations of Hazardous Air Pollutants in Downwind Communities.

Due in part to climate change, wildfire activity is increasing, with the potential for greater public health impact from smoke in downwind communities. Studies examining the health effects of wildfire smoke have focused primarily on fine particulate matter (PM2.5), but there is a need to better characterize other constituents, such as hazardous air pollutants (HAPs). HAPs are chemicals known or suspected to cause cancer or other serious health effects that are regulated by the United States (US) Environmental Protection Agency. Here, we analyzed concentrations of 21 HAPs in wildfire smoke from 2006 to 2020 at 309 monitors across the western US. Additionally, we examined HAP concentrations measured in a major population center (San Jose, CA) affected by multiple fires from 2017 to 2020. We found that concentrations of select HAPs, namely acetaldehyde, acrolein, chloroform, formaldehyde, manganese, and tetrachloroethylene, were all significantly elevated on smoke-impacted versus nonsmoke days (P < 0.05). The largest median increase on smoke-impacted days was observed for formaldehyde, 1.3 µg/m3 (43%) higher than that on nonsmoke days. Acetaldehyde increased 0.73 µg/m3 (36%), and acrolein increased 0.14 µg/m3 (34%). By better characterizing these chemicals in wildfire smoke, we anticipate that this research will aid efforts to reduce exposures in downwind communities.

Synthesis of lichen response to gaseous nitrogen: ammonia versus nitrogen dioxide.

The dominant chemical form of nitrogen pollution in the atmosphere in the U.S. is shifting from oxidized nitrogen, primarily from combustion of fossil fuels, to reduced nitrogen from agricultural animal waste and fertilizer applications. Does it matter to lichens? In this synthesis, we characterize U.S. air concentrations of the most ubiquitous gaseous forms of reduced and oxidized nitrogen, NO2 and NH3, respectively, and their direct effects on lichens. In the U.S., the 3-year average (2017-2019) of the annual mean for each monitoring site ranges up to 56.4 µg NO2 m-3 (~30 ppb) and 6 µg NH3 m-3 (~9 ppb). The spatial coverage of current routine monitoring of NO2 and NH3 likely does not accurately represent exposures of NO2 to ecosystems in rural areas or capture spikes of NH3 concentrations proximal to intensive agriculture, which are documented to exceed 700 µg NH3 m-3 (~1000 ppb) for short durations. Both NO2 and NH3 can act as nutrients to lichens, but as exposures rise, both can cause physiological stress and mortality that then change community composition and diversity. There is a growing body of evidence that lichen community composition is altered at current levels of exposure in the U.S. with estimated no effect or lowest effect concentrations from <1-3 µg m-3 NO2 and <1 µg m-3 NH3. Better spatial characterization of both NO2 and NH3 concentrations, especially near intensive agriculture, would help to characterize the extent of the impacts across the U.S. These findings are discussed in the context of U.S. air pollution policy.

Shifts in the composition of nitrogen deposition in the conterminous United States are discernable in stream chemistry.

Across the conterminous United States (U.S.), the composition of atmospheric nitrogen (N) deposition is changing spatially and temporally. Previously, deposition was dominated by oxidized N, but now reduced N (ammonia [NH3] + ammonium [NH4+]) is equivalent to oxidized N when deposition is averaged across the entire nation and, in some areas, reduced N dominates deposition. To evaluate if there are effects of this change on stream chemistry at the national scale, estimates of N deposition form (oxidized or reduced) from the National Atmospheric Deposition Program Total Deposition data were coupled with stream measurements from the U.S. Environmental Protection Agency (EPA) National Rivers and Streams Assessments (three stream surveys between 2000 and 2014). A recent fine-scaled N input inventory was used to identify watersheds (<1000 km2) where atmospheric deposition is the largest N source (n = 1906). Within these more atmospherically-influenced watersheds there was a clear temporal shift from a greater proportion of sites dominated by oxidized N deposition to a greater proportion of sites dominated by reduced forms of N deposition. We found a significant positive correlation between oxidized N deposition and stream NO3- concentrations, whereas the correlation between reduced N deposition and stream NO3- concentrations were significant but weaker. Sites dominated by atmospheric inputs of reduced N forms had higher stream total organic N and total N despite lower total N deposition on average. This higher stream concentration of total N is mainly driven by the higher concentration of total organic N, suggesting an interaction between elevated reduced N in deposition and living components of the ecosystem or soil organic matter dynamics. Regardless of the proportion of reduced to oxidized N forms in deposition, stream NH4+ concentrations were generally low, suggesting that N deposited in a reduced form is rapidly immobilized, nitrified and/or assimilated by watershed processes.

Beyond Particulate Matter Mass: Heightened Levels of Lead and Other Pollutants Associated with Destructive Fire Events in California.

As the climate warms, wildfire activity is increasing, posing a risk to human health. Studies have reported on particulate matter (PM) in wildfire smoke, yet the chemicals associated with PM have received considerably less attention. Here, we analyzed 13 years (2006-2018) of PM2.5 chemical composition data from monitors in California on smoke-impacted days. Select chemicals (e.g., aluminum and sulfate) were statistically elevated on smoke-impacted days in over half of the years studied. Other chemicals, mostly trace metals harmful to human health (e.g., copper and lead), were elevated during particular fires only. For instance, in 2018, lead was more than 40 times higher on smoke days on average at the Point Reyes monitoring station, due mostly to the Camp Fire, burning approximately 200 km away. There was an association between these metals and the combustion of anthropogenic material (e.g., the burning of houses and vehicles). Although still currently rare, these infrastructure fires are likely becoming more common and can mobilize trace metals in smoke far downwind, at levels generally unseen except in the most polluted areas of the country. We hope a better understanding of the chemicals in wildfire smoke will assist in the communication and reduction of public health risks.

The reduction of summer sulfate and switch from summertime to wintertime PM2.5 concentration maxima in the United States.

Exposure to particulate matter air pollution with a nominal mean aerodynamic diameter less than or equal to 2.5 µm (PM2.5) has been associated with health effects including cardiovascular disease and death. Here, we add to the understanding of urban and rural PM2.5 concentrations over large spatial and temporal scales in recent years. We used high-quality, publicly-available air quality monitoring data to evaluate PM2.5 concentration patterns and changes during the years 2000-2015. Compiling and averaging measurements collected across the U.S. revealed that PM2.5 concentrations from urban sites experienced seasonal maxima in both winter and summer. Within each year from 2000 to 2008, the maxima of urban summer peaks were greater than winter peaks. However, from 2012 to 2015, the maxima of urban summertime PM2.5 peaks were smaller than the urban wintertime PM2.5 maxima, due to a decrease in the magnitude of summertime maxima with no corresponding decrease in the magnitude of winter maxima. PM2.5 measurements at rural sites displayed summer peaks with magnitudes relatively similar to those of urban sites, and negligible to no winter peaks through the time period analyzed. Seasonal variations of urban and rural PM2.5 sulfate, PM2.5 nitrate, and PM2.5 organic carbon (OC) were also assessed. Summer peaks in PM2.5 sulfate decreased dramatically between 2000 and 2015, whereas seasonal PM2.5 OC and winter PM2.5 nitrate concentration maxima remained fairly consistent. These findings demonstrate that PM2.5 concentrations, especially those occurring in the summertime, have declined in the U.S. from 2000 to 2015. In addition, reduction strategies targeting sulfate have been successful and the decrease in PM2.5 sulfate contributed to the decline in total PM2.5.

Estimation of on-road NO2 concentrations, NO2/NOX ratios, and related roadway gradients from near-road monitoring data.

This paper describes a new regression modeling approach to estimate on-road nitrogen dioxide (NO2) and oxides of nitrogen (NOX) concentrations and near-road spatial gradients using data from a near-road monitoring network. Field data were collected in Las Vegas, NV at three monitors sited 20, 100, and 300 m from Interstate-15 between December, 2008 and January, 2010. Measurements of NO2 and NOX were integrated over 1-hour intervals and matched with meteorological data. Several mathematical transformations were tested for regressing pollutant concentrations against distance from the roadway. A logit-ln model was found to have the best fit (R2 = 94.7%) and also provided a physically realistic profile. The mathematical model used data from the near-road monitors to estimate on-road concentrations and the near-road gradient over which mobile source pollutants have concentrations elevated above background levels. Average and maximum on-road NO2 concentration estimates were 33 ppb and 105 ppb, respectively. Concentration gradients were steeper in the morning and late afternoon compared with overnight when stable conditions preclude mixing. Estimated on-road concentrations were also highest in the late afternoon. Median estimated on-road and gradient NO2 concentrations were lower during summer compared with winter, with a steeper gradient during the summer, when convective mixing occurs during a longer portion of the day On-road concentration estimates were higher for winds perpendicular to the road compared with parallel winds and for atmospheric stability with neutral-to-unstable atmospheric conditions. The concentration gradient with increasing distance from the road was estimated to be sharper for neutral-to-unstable conditions when compared with stable conditions and for parallel wind conditions compared with perpendicular winds. A regression of the NO2/NOX ratios yielded on-road ratios ranging from 0.25 to 0.35, substantially higher than the anticipated tail-pipe emissions ratios. The results from the ratios also showed that the diurnal cycle of the background NO2/NOX ratios were a driving factor in the on-road and downwind NO2/NOX ratios.

Trueness, precision, and detectability for sampling and analysis of organic species in airborne particulate matter.

Recovery, precision, limits of detection and quantitation, blank levels, calibration linearity, and agreement with certified reference materials were determined for two classes of organic components of airborne particulate matter, polycyclic aromatic hydrocarbons and hopanes, using typical sampling and gas chromatography/mass spectrometry analysis methods. These determinations were based on initial method proficiency tests and on-going internal quality control procedures. Recoveries generally ranged from 75% to 85% for all target analytes and collocated sample precision estimates were generally better than 20% for polycyclic aromatic hydrocarbons and better than 25% for hopanes. Results indicated substantial differences in data quality between the polycyclic aromatic hydrocarbons and hopanes. Polycyclic aromatic hydrocarbons demonstrated better collocated precision, lower method detection limits, lower blank levels, and better agreement with certified reference materials than the hopanes. The most serious area of concern was the disagreement between measured and expected values in the standard reference material for hopanes. With this exception, good data quality was demonstrated for all target analytes on all other data quality indicators.