Industrial-era decline in Arctic methanesulfonic acid is offset by increased biogenic sulfate aerosol.

Marine phytoplankton are primary producers in ocean ecosystems and emit dimethyl sulfide (DMS) into the atmosphere. DMS emissions are the largest biological source of atmospheric sulfur and are one of the largest uncertainties in global climate modeling. DMS is oxidized to methanesulfonic acid (MSA), sulfur dioxide, and hydroperoxymethyl thioformate, all of which can be oxidized to sulfate. Ice core records of MSA are used to investigate past DMS emissions but rely on the implicit assumption that the relative yield of oxidation products from DMS remains constant. However, this assumption is uncertain because there are no long-term records that compare MSA to other DMS oxidation products. Here, we share the first long-term record of both MSA and DMS-derived biogenic sulfate concentration in Greenland ice core samples from 1200 to 2006 CE. While MSA declines on average by 0.2 µg S kg-1 over the industrial era, biogenic sulfate from DMS increases by 0.8 µg S kg-1. This increasing biogenic sulfate contradicts previous assertions of declining North Atlantic primary productivity inferred from decreasing MSA concentrations in Greenland ice cores over the industrial era. The changing ratio of MSA to biogenic sulfate suggests that trends in MSA could be caused by time-varying atmospheric chemistry and that MSA concentrations alone should not be used to infer past primary productivity.

California Case Study of Wildfires and Prescribed Burns: PM2.5 Emissions, Concentrations, and Implications for Human Health.

Wildfires are a significant threat to human health, in part through degraded air quality. Prescribed burning can reduce wildfire severity but can also lead to an increase in air pollution. The complexities of fires and atmospheric processes lead to uncertainties when predicting the air quality impacts of fire and make it difficult to fully assess the costs and benefits of an expansion of prescribed fire. By modeling differences in emissions, surface conditions, and meteorology between wildfire and prescribed burns, we present a novel comparison of the air quality impacts of these fire types under specific scenarios. One wildfire and two prescribed burn scenarios were considered, with one prescribed burn scenario optimized for potential smoke exposure. We found that PM2.5 emissions were reduced by 52%, from 0.27 to 0.14 Tg, when fires burned under prescribed burn conditions, considerably reducing PM2.5 concentrations. Excess short-term mortality from PM2.5 exposure was 40 deaths for fires under wildfire conditions and 39 and 15 deaths for fires under the default and optimized prescribed burn scenarios, respectively. Our findings suggest prescribed burns, particularly when planned during conditions that minimize smoke exposure, could be a net benefit for the impacts of wildfires on air quality and health.

Variability in Aromatic Aerosol Yields under Very Low NOx Conditions at Different HO2/RO2 Regimes.

Current chemical transport models generally use a constant secondary organic aerosol (SOA) yield to represent SOA formation from aromatic compounds under low NOx conditions. However, a wide range of SOA yields (10 to 42%) from m-xylene under low NOx conditions is observed in this study. The chamber HO2/RO2 ratio is identified as a key factor explaining SOA yield variability: higher SOA yields are observed for runs with a higher HO2/RO2 ratio. The RO2 + RO2 pathway, which can be increasingly significant under low NOx and HO2/RO2 conditions, shows a lower SOA-forming potential compared to the RO2 + HO2 pathway. While the traditional low-NOx chamber experiments are commonly used to represent the RO2 + HO2 pathway, this study finds that the impacts of the RO2 + RO2 pathway cannot be ignored under certain conditions. We provide guidance on how to best control for these two pathways in conducting chamber experiments to best obtain SOA yield curves and quantify the contributions from each pathway. On the global scale, the chemical transport model GEOS-Chem is used to identify regions characterized by lower surface HO2/RO2 ratios, suggesting that the RO2 + RO2 pathway is more likely to prove significant to overall SOA yields in those regions. Current models generally do not consider the RO2 + RO2 impacts on aromatic SOA formation, but preliminary sensitivity tests with updated SOA yield parameters based on such a pathway suggest that without this consideration, some types of SOA may be overestimated in regions with lower HO2/RO2 ratios.

Changing Nature of Organic Carbon over the United States.

Total organic carbon (TOC) mass concentrations are decreasing across the contiguous United States (CONUS). We investigate decadal trends in organic carbon (OC) thermal fractions [OC1 (volatilizes at 140 °C), OC2 (280 °C), OC3 (480 °C), OC4 (580 °C)] and pyrolyzed carbon (PC), reported at 121 locations in the Interagency Monitoring of Protected Visual Environments (IMPROVE) network from 2005 to 2015 for 23 regions across the CONUS. Reductions in PC and OC2 drive decreases in TOC (TOC = OC1 + OC2 + OC3 + OC4 + PC) mass concentrations. OC2 decreases by 40% from 2005 to 2015, and PC decreases by 34%. The largest absolute mass decreases occur in the eastern United States, and relative changes normalized to local concentrations are more uniform across the CONUS. OC is converted to organic mass (OM) using region- and season-specific OM:OC ratios. Simulations with GEOS-Chem reproduce OM trends and suggest that decreases across the CONUS are due to aerosol liquid water (ALW) chemistry. Individual model species, notably aerosol derived from isoprene oxidation products and formed in ALW, correlate significantly (p < 0.05) with OM2, even in arid regions. These findings contribute to literature that suggests air quality rules aimed at SO2 and NOx emissions induce the cobenefit of reducing organic particle mass through ALW chemistry, and these benefits extend beyond the eastern United States.

Air quality in Yanbu, Saudi Arabia.

UNLABELLED: Yanbu, on the Red Sea, is an affluent Saudi Arabian industrial city of modest size. Substantial effort has been spent to balance environmental quality, especially air pollution, and industrial development. We have analyzed six years of observations of criteria pollutants O3, SO2, particles (PM2.5 and PM10) and the known ozone precursors-volatile organic compounds (VOCs) and nitrogen oxides (NOx). The results suggest frequent VOC-limited conditions in which ozone concentrations increase with decreasing NOx and with increasing VOCs when NOx is plentiful. For the remaining circumstances ozone has a complex non-linear relationship with the VOCs. The interactions between these factors at Yanbu cause measurable impacts on air pollution including the weekend effect in which ozone concentrations stay the same or even increase despite significantly lower emissions of the precursors on the weekends. Air pollution was lower during the Eids (al-Fitr and al-Adha), Ramadan and the Hajj periods. During Ramadan, there were substantial night time emissions as the cycle everyday living is almost reversed between night and day. The exceedances of air pollution standards were evaluated using criteria from the U.S. Environmental Protection Agency (EPA), World Health Organization (WHO), the Saudi Presidency of Meteorology and Environment (PME) and the Royal Commission Environmental Regulations (RCER). The latter are stricter standards set just for Yanbu and Jubail. For the fine particles (PM2.5), an analysis of the winds showed a major impact from desert dust. This effect had to be taken into account but still left many occasions when standards were exceeded. Fewer exceedances were found for SO2, and fewer still for ozone. The paper presents a comprehensive view of air quality at this isolated desert urban environment. IMPLICATIONS: Frequent VOC-limited conditions are found at Yanbu in Saudi Arabia that increase ozone pollution if NOx is are reduced. In this desert environment, increased nightlife produces the highest levels of VOCs and NOx at night rather than the day. The effects increase during Ramadan. Fine particles peak twice a day-the morning peak is caused by traffic and increases with decreasing wind, potentially representing health concerns, but the larger afternoon peak is caused by the wind, and it increases with increasing wind speeds. These features suggest that exposure to pollutants must be redefined for such an environment.

Evaluation of ozone, nitrogen dioxide, and carbon monoxide at nine sites in Saudi Arabia during 2007.

UNLABELLED: This paper presents a one-year record of in situ air-quality data from nine sites throughout Saudi Arabia. The data set is composed of hourly measurements of ozone (O3), nitrogen dioxide (NO2), and carbon monoxide (CO) at six of the largest cities in Saudi Arabia (Riyadh, Jeddah, Makkah, Yanbu, Dammam, Hafouf) and two remote locations in the mountainous southwestern region of Alsodah for the year 2007. The authors found that international O3 and CO standards were routinely exceeded throughout the year at many sites, and that exceedances increased during Ramadan (Sep. 12-Oct. 13), the Islamic month of fasting when much of normal daily activity is shifted to nighttime hours. In general NO2 and CO levels were higher in Saudi cities compared to U.S. cities of comparable population, while O3 levels were lower. There was a general trend for O3 and NO2 to be negatively correlated in Saudi cities in contrast to U.S. cities where the correlation is positive, suggesting that ozone chemistry in Saudi Arabia is limited by volatile organic compound emissions. This may be caused by low biogenic emissions from vegetation. Pollutant levels were lower at most Saudi sites during the four day Hajj period (Dec. 18-21) but higher in Makkah which receives millions of visitors during Hajj. The authors also found that ozone levels were elevated during the weekend (Thursday & Friday) relative to weekday levels despite lower NO2, a phenomenon known as the "weekend effect." As little air quality data is available from Saudi Arabia in the English-language literature, this data set fills a knowledge gap and improves understanding of air quality in an important but under-reported region of the world. IMPLICATIONS: Air quality measurements at nine sites in Saudi Arabia provide a detailed look at spatial and temporal patterns of ozone (O3), nitrogen dioxide (NO2), and carbon monoxide (CO). NO2 and CO levels increased in most cities during the fasting month of Ramadan, whereas O3 levels decreased. This led to an increased frequency of CO exceedances based on international standards. NO2 and CO also increased in Makkah during the Hajj pilgrimage. In general, NO2 and O3 levels were anticorrelated at most sites, suggesting that O3 chemistry is limited by volatile organic compound emissions throughout much of Saudi Arabia.

Annual and weekly patterns of ozone and particulate matter in Jeddah, Saudi Arabia.

Air pollution has been an increasing concern within the Kingdom of Saudi Arabia and other Middle Eastern countries. In this work the authors present an analysis of daily ozone (O3), nitrogen oxide (NO(x)), and particulate matter (< 10 miccrom aerodynamic diameter; PM10) concentrations for two years (2010 and 2011) at sites in and around the coastal city of Jeddah, as well as a remote background site for comparison. Monthly and weekly variations, along with their implications and consequences, were also examined. O3 within Jeddah was remarkably low, and exhibited the so-called weekend effect--elevated O3 levels on the weekends, despite reduced emissions of O3 precursors on those days. Weekend O3 increases averaged between 12% and 14% in the city, suggesting that NO(x)/volatile organic compound (VOC) ratios within cities such as Jeddah may be exceptionally high. Sites upwind or far removed from Jeddah did not display this weekend effect. Based on these results, emission control strategies in and around Jeddah must carefully address NO(x)/VOC ratios so as to reduce O3 at downwind locations without increasing it within urban locations themselves. PM10 concentrations within Jeddah were elevated compared with North American cites of similar climatology though comparable to other large cities within the Middle East. Implications: Daily concentrations of O3, PM10, and NO(x) in and around the city of Jeddah, Saudi Arabia, are analyzed and compared with those of other reference cities. Extremely low O3 levels, along with a significant urban weekend effect (higher weekend O3, despite reduced NO(x) concentrations), is apparent, along with high levels of PM10 within the city. Urban O3 in Jeddah was found to be lower than that of other comparable cities, but the strong weekend effect suggests that care must be taken to reduce downwind O3 levels without increasing them within the city itself. Further research into the emissions and chemistry contributing to the reduced O3 levels within the city is warranted.

Air quality impacts of observationally constrained biomass burning heat flux inputs.

Biomass burning is a major contributor to ambient air pollution worldwide, and the accurate characterization of biomass burning plume behavior is an important consideration for air quality models that attempt to reproduce these emissions. Smoke plume injection height, or the vertical level into which the combustion emissions are released, is an important consideration for determining plume behavior, transport, and eventual impacts. This injection height is dependent on several fire properties, each with estimates and uncertainties in terms of historical fire emissions inventories. One such property is the fire heat flux, a fire property metric sometimes used to predict and parameterize plume injection heights in current chemical transport models. Although important for plume behavior, fire heat flux is difficult to predict and parameterize efficiently, and is therefore often held to fixed, constant values in these models, leading to potential model biases relative to real world conditions. In this study we collect observed heat flux estimates from satellite data products for three wildfire events over northern California and use these estimates in a regional chemical transport model to investigate and quantify the impacts of observationally constrained heat fluxes on the modeled injection height and downwind air quality. We find large differences between these observationally derived heat flux estimates and fixed model assumptions, with important implications for modeled behavior of plume dynamics and surface air quality impacts. Overall, we find that using observationally constrained heat flux estimates tends to reduce modeled injection heights for our chosen fires, resulting in large increases in surface particulate matter concentrations. While local wind conditions contribute to variability and additional uncertainties in the impacts of modified plume injection heights, we find observationally constrained heat fluxes to be an impactful and potentially useful tool towards the improvement of emissions inventory assumptions and parameterizations.

Considering the air quality impacts of bioenergy crop production: a case study involving Arundo donax.

The expanding production of bioenergy crops may impact regional air quality through the production of volatile organic compounds such as isoprene. To investigate the effects of isoprene-emitting crops on air quality, specifically ozone (O(3)) and secondary organic aerosol (SOA) formation, we performed a series of model runs using the Weather Research and Forecasting model with Chemistry (WRF/Chem) coupled with the Model of Emissions of Gases and Aerosols from Nature (MEGAN) simulating a proposed cropland conversion to the giant cane Arundo donax for biomass production. Cultivation of A. donax in the relatively clean air of northeastern Oregon resulted in an average increase in 8 h O(3) levels of 0.52 ppb, while SOA was largely unaffected (<+0.01 µg m(-3)). Conversions in U.S. regions with reduced air quality (eastern Texas and northern Illinois) resulted in average 8 h O(3) increases of 2.46 and 3.97 ppb, respectively, with daily increases up to 15 ppb in the Illinois case, and daytime SOA increases up to 0.57 µg m(-3). While cultivation of isoprene-emitting bioenergy crops may be appropriate at some scales and in some regions, other areas may experience increased O(3) and SOA, highlighting the need to consider isoprene emissions when evaluating potential regional impacts of bioenergy crop production.

Evaluating health outcome metrics and their connections to air pollution and vulnerability in Southern California's Coachella Valley.

The ongoing desiccation of California's Salton Sea has led to increasing concerns about air quality and health for its surrounding communities, including the nearby Coachella Valley - a region already experiencing severe air quality and health disparities. Here we explore spatial air pollution and human health disparities in the Coachella Valley with particular attention to disparities arising across population characteristics including both socioeconomic and demographic vulnerabilities. We use two different measures of respiratory and cardiovascular health outcomes at the individual and census tract levels - one measure based on a randomly sampled telephone survey and the other measure based on emergency room visitation data - to investigate the degree to which these health outcomes are connected to air pollution and socioeconomic metrics. We further investigate biases and differences between the health outcome metrics themselves and suggest opportunities to address them in future analyses and survey efforts. We find that more vulnerable communities are associated with higher levels of fine particulates, but lower levels of ozone. While emergency visit rates show a significant positive correlation with both pollutants, no such association is found when using surveyed health outcome data. The ratio of emergency visits versus survey rates shows a positive relationship with socioeconomic and demographic vulnerability, indicating that vulnerable communities are less likely to self-report diagnoses despite higher rates of respiratory or cardiovascular hospitalization. Additionally, survey respondents tend to show less vulnerability relative to their surrounding census-based demographics. These findings suggest the need for greater attention to health issues specifically within disadvantaged communities in the Coachella Valley, building upon and working within existing community networks and local resources, to better address current and projected health needs. Our findings also highlight disparities in air pollution exposure, health outcomes, and population characteristics in the Coachella Valley, providing context for crucial pollution reduction efforts in the face of increasing environmental threats.

Integrated effects of SCR, velocity, and Air-fuel Ratio on gaseous pollutants and CO2 emissions from China V and VI heavy-duty diesel vehicles.

Vehicle exhaust, an important source of air pollution, is affected by many factors, including driving conditions, combustion efficiencies, and the usage of emission control devices. In this study, the Portable Emission Measurement System (PEMS) was used to test the emissions from China V and China VI heavy-duty diesel vehicles to evaluate the integrated effects of Selective Catalytic Reduction (SCR), velocity, and air-fuel ratio on carbon dioxide (CO2) and nitrogen oxide (NOx) emissions. Our results reveal that the average distance-based CO2 and CO emission factors at high velocities (50-90 km/h) are 25% and 61% lower than those at low velocities (less than 50 km/h). The use of SCR increases CO2 emissions in the range of 70-90 km/h (an average increase of 10.9%). In addition, SCR leads to a 55% NOx emission reduction at low velocities and 89% at high velocities, with an overall average reduction of 84%. We also find that SCR leads to a significant reduction in the correlation between NOx emissions and air-fuel ratio (0.76 vs 0.47 for China V truck; 0.72 vs 0.05 for China VI truck), but it does not cause a drastic reduction in the correlation coefficients between CO2 emissions and air-fuel ratio, which can be used to detect whether SCR is working effectively.

Global tropospheric effects of aromatic chemistry with the SAPRC-11 mechanism implemented in GEOS-Chem version 9-02.

The Goddard Earth Observing System with chemistry (GEOS-Chem) model has been updated with the Statewide Air Pollution Research Center version 11 (SAPRC-11) aromatics chemical mechanism, with the purpose of evaluating global and regional effects of the most abundant aromatics (benzene, toluene, xylenes) on the chemical species important for tropospheric oxidation capacity. The model evaluation based on surface and aircraft observations indicates good agreement for aromatics and ozone. A comparison between scenarios in GEOS-Chem with simplified aromatic chemistry (as in the standard setup, with no ozone formation from related peroxy radicals or recycling of NOx) and with the SAPRC-11 scheme reveals relatively slight changes in ozone, the hydroxyl radical, and nitrogen oxides on a global mean basis (1 %-4 %), although remarkable regional differences (5 %-20 %) exist near the source regions. NO x decreases over the source regions and increases in the remote troposphere, due mainly to more efficient transport of peroxyacetyl nitrate (PAN), which is increased with the SAPRC aromatic chemistry. Model ozone mixing ratios with the updated aromatic chemistry increase by up to 5 ppb (more than 10 %), especially in industrially polluted regions. The ozone change is partly due to the direct influence of aromatic oxidation products on ozone production rates, and in part to the altered spatial distribution of NOx that enhances the tropospheric ozone production efficiency. Improved representation of aromatics is important to simulate the tropospheric oxidation.