Anthropogenic Control over Wintertime Oxidation of Atmospheric Pollutants

Anthropogenic air pollutants such as nitrogen oxides (NO(x) = NO + NO(2)), sulfur dioxide (SO(2)), and volatile organic compounds (VOC), among others, are emitted to the atmosphere throughout the year from energy production and use, transportation, and agriculture. These primary pollutants lead to the formation of secondary pollutants such as fine particulate matter (PM(2.5)) and ozone (O(3)) and perturbations to the abundance and lifetimes of short-lived greenhouse gases. Free radical oxidation reactions driven by solar radiation govern the atmospheric lifetimes and transformations of most primary pollutants and thus their spatial distributions. During winter in the mid and high latitudes, where a large fraction of atmospheric pollutants are emitted globally, such photochemical oxidation is significantly slower. Using observations from a highly instrumented aircraft, we show that multi-phase reactions between gas-phase NO(x) reservoirs and aerosol particles, as well as VOC emissions from anthropogenic activities, lead to a suite of atypical radical precursors dominating the oxidizing capacity in polluted winter air, and thus, the distribution and fate of primary pollutants on a regional to global scale

Validation of Regional CO2 Concentrations in the ECMWF Real-Time Analysis and Carbon-Tracker Reanalysis with Airborne Observations from ACT-A Field Campaign

Through verifying against hundreds of hours of airborne in-situ measurements from the NASA-sponsored Atmospheric Carbon and Transport America (ACT-A) field campaign, this study systematically examines the regional uncertainties and biases of the carbon dioxide (CO2) concentrations from two of the state-of-the-art global analysis products, namely the real-time analysis from the European Center (EC) for Medium Range Forecasting and NOAAs near real-time Carbon Tracker (CT) reanalysis. It is found that both the EC and CT-NRT analyses agree reasonably well with the independent ACT-A flight-level CO2 measurements in the free troposphere but the uncertainties are considerably larger in the boundary layer during both the summer months of 2016 and the winter months of 2017. There are also strong variabilities in accuracy and bias between seasons, and across three different subregions in the United States (Mid-Atlantic, Midwest and South). Overall, the analysis uncertainties of the EC and CT-NRT analyses in terms of root-mean square deviations against airborne data are comparable to each other, both of which are between 1-2 ppm in the free troposphere but can be as large as 10 ppm near the surface, which are grossly consistent with the difference between the two analyses. The current study not only provides systematic uncertainty estimates for both analysis products over North America but also demonstrated that these two independent estimates can be used to approximate the overall regional CO2 analysis uncertainties. Both statistics are important in future studies in quantifying the uncertainties of regional carbon concentration and flux estimates, as well as in assessing the impact of regional transport through more refined regional modeling and analysis systems

Observation-based modeling of ozone chemistry in the Seoul metropolitan area during the Korea-United States Air Quality Study (KORUS-AQ)

The Seoul Metropolitan Area (SMA) has a population of 24 million and frequently experiences unhealthy levels of ozone (O3). In this work, measurements taken during the Korea-United States Air Quality Study (KORUS-AQ, 2016) are used to explore regional gradients in O3 and its chemical precursors, and an observationally-constrained 0-D photochemical box model is used to quantify key aspects of O3 production including its sensitivity to precursor gases. Box model performance was evaluated by comparing modeled concentrations of select secondary species to airborne measurements. These comparisons indicate that the steady state assumption used in 0-D box models cannot describe select intermediate species, highlighting the importance of having a broad suite of trace gases as model constraints. When fully constrained, aggregated statistics of modeled O3 production rates agreed with observed changes in O3, indicating that the box model was able to represent the majority of O3 chemistry. Comparison of airborne observations between urban Seoul and a downwind receptor site reveal a positive gradient in O3 coinciding with a negative gradient in NOx, no gradient in CH2O, and a slight positive gradient in modeled rates of O3 production. Together, these observations indicate a radical-limited (VOC-limited) O3 production environment in the SMA. Zero-out simulations identified C7+ aromatics as the dominant VOC contributors to O3 production, with isoprene and anthropogenic alkenes making smaller but appreciable contributions. Simulations of model sensitivity to decreases in NOx produced results that were not spatially uniform, with large increases in O3 production predicted for urban Seoul and decreases in O3 production predicted for far-outlying areas. The policy implications of this work are clear: Effective O3 mitigation strategies in the SMA must focus on reducing local emissions of C7+ aromatics, while reductions in NOx emissions may increase O3 in some areas but generally decrease the regional extent of O3 exposure

Insights into hydroxyl measurements and atmospheric oxidation in a California forest

The understanding of oxidation in forest atmospheres is being challenged by measurements of unexpectedly large amounts of hydroxyl (OH). A significant number of these OH measurements were made by laser-induced fluorescence in low-pressure detection chambers (called Fluorescence Assay with Gas Expansion (FAGE)) using the Penn State Ground-based Tropospheric Hydrogen Oxides Sensor (GTHOS). We deployed a new chemical removal method to measure OH in parallel with the traditional FAGE method in a California forest. The new method gives on average only 40–60% of the OH from the traditional method and this discrepancy is temperature dependent. Evidence indicates that the new method measures atmospheric OH while the traditional method is affected by internally generated OH, possibly from oxidation of biogenic volatile organic compounds. The improved agreement between OH measured by this new technique and modeled OH suggests that oxidation chemistry in at least one forest atmosphere is better understood than previously thought

Exposure to endocrine-disrupting chemicals in the USA: a population-based disease burden and cost analysis

Background Endocrine-disrupting chemicals (EDCs) contribute to disease and dysfunction and incur high associated costs (>1% of the gross domestic product [GDP] in the European Union). Exposure to EDCs varies widely between the USA and Europe because of differences in regulations and, therefore, we aimed to quantify disease burdens and related economic costs to allow comparison. Methods We used existing models for assessing epidemiological and toxicological studies to reach consensus on probabilities of causation for 15 exposure–response relations between substances and disorders. We used Monte Carlo methods to produce realistic probability ranges for costs across the exposure–response relation, taking into account uncertainties. Estimates were made based on population and costs in the USA in 2010. Costs for the European Union were converted to US$(€1=$1·33). Findings The disease costs of EDCs were much higher in the USA than in Europe ($340 billion [2·33$217 billion [1·28%]). The difference was driven mainly by intelligence quotient (IQ) points loss and intellectual disability due to polybrominated diphenyl ethers (11 million IQ points lost and 43 000 cases costing $266 billion in the USA vs 873 000 IQ points lost and 3290 cases costing$12·6 billion in the European Union). Accounting for probability of causation, in the European Union, organophosphate pesticides were the largest contributor to costs associated with EDC exposure ($121 billion), whereas in the USA costs due to pesticides were much lower ($42 billion). Interpretation EDC exposure in the USA contributes to disease and dysfunction, with annual costs taking up more than 2% of the GDP. Differences from the European Union suggest the need for improved screening for chemical disruption to endocrine systems and proactive prevention. Funding Endocrine Society, Ralph S French Charitable Foundation, and Broad Reach Foundation. © 2016 Elsevier Lt