Tropospheric ozone and CO over North Atlantic for the past decade

We investigate how declines in US emissions of CO and O3 precursors have impacted the lower free troposphere over the North Atlantic. We use seasonal observations for O3 and CO from the PICO-NARE project for the period covering 2001 to 2010. Observations are used to verify model output generated by the GEOS-Chem 3-D global chemical transport model. Additional satellite data for CO from AIRS/Aqua and for O3 from TES/Aura were also used to provide additional comparisons; particularly for fall, winter, and spring when PICO-NARE coverage is sparse. We find GEOS-Chem captures the seasonal cycle for CO and O3 well compared to PICO-NARE data. For CO, GEOS-Chem is biased low, particularly in spring which is in agreement with findings from previous studies. GEOS-Chem is 24.7 +/- 5.2 ppbv (1-σ) low compared to PICO-NARE summer CO data while AIRS is 14.2 +/- 6.6 ppbv high. AIRS does not show nearly as much variation as seen with GEOS-Chem or the Pico data, and goes from being lower than PICO-NARE data in winter and spring, to higher in summer and fall. Both TES and GEOS-Chem match the seasonal ozone cycle well for all seasons when compared with observations. Model results for O3 show GEOS-Chem is 6.67 +/- 2.63 ppbv high compared to PICO-NARE summer measurements and TES was 3.91 +/- 4.2 ppbv higher. Pico data, model results, and AIRS all show declines in CO and O3 for the summer period from 2001 to 2010. Limited availability of TES data prevents us from using it in trend analysis. For summer CO Pico, GEOS-Chem, and AIRS results show declines of 1.32, 0.368, and 0.548 ppbv/year respectively. For summer O3, Pico and GEOS-Chem show declines of -0.726 and -0.583 ppbv/year respectively. In other seasons, both model and AIRS show declining CO, particularly in the fall. GEOS-Chem results show a fall decline of 0.798 ppbv/year and AIRS shows a decline of 0.8372 ppbv/year. Winter and spring CO declines are 0.393 and 0.307 for GEOS-Chem, and 0.455 and 0.566 for AIRS. GEOS-Chem shows declining O3 in other seasons as well; with fall being the season of greatest decrease and winter being the least. Model results for fall, winter, and spring are 0.856, 0.117, and 0.570 ppbv/year respectively. Given the availability of data we are most confident in summer results and thus find that summer CO and O3 have declined in lower free troposphere of the North Atlantic region of the Azores. Sensitivity studies for CO and O3 at Pico were conducted by turning off North American fossil fuel emissions in GEOS-Chem. Model results show that North America fossil fuel emissions contribute 8.57 ppbv CO and 4.03 ppbv O3 to Pico. The magnitude of modeled trends declines in all seasons without North American fossil fuel emissions except for summer CO. The increase in summer CO declines may be due to a decline of 5.24 ppbv/year trend in biomass burning emissions over the study period; this is higher than the 2.33 ppbv/year North American anthropogenic CO model decline. Winter O3 is the only season which goes from showing a negative trend to a positive trend.

Long-Range Pollution Transport: Trans-Atlantic Mechanisms and Lagrangian Modeling Methods

Over the past several decades, it has become apparent that anthropogenic activities have resulted in the large-scale enhancement of the levels of many trace gases throughout the troposphere. More recently, attention has been given to the transport pathway taken by these emissions as they are dispersed throughout the atmosphere. The transport pathway determines the physical characteristics of emissions plumes and therefore plays an important role in the chemical transformations that can occur downwind of source regions. For example, the production of ozone (O3) is strongly dependent upon the transport its precursors undergo. O3 can initially be formed within air masses while still over polluted source regions. These polluted air masses can experience continued O3 production or O3 destruction downwind, depending on the air mass's chemical and transport characteristics. At present, however, there are a number of uncertainties in the relationships between transport and O3 production in the North Atlantic lower free troposphere. The first phase of the study presented here used measurements made at the Pico Mountain observatory and model simulations to determine transport pathways for US emissions to the observatory. The Pico Mountain observatory was established in the summer of 2001 in order to address the need to understand the relationships between transport and O3 production. Measurements from the observatory were analyzed in conjunction with model simulations from the Lagrangian particle dispersion model (LPDM), FLEX-PART, in order to determine the transport pathway for events observed at the Pico Mountain observatory during July 2003. A total of 16 events were observed, 4 of which were analyzed in detail. The transport time for these 16 events varied from 4.5 to 7 days, while the transport altitudes over the ocean ranged from 2-8 km, but were typically less than 3 km. In three of the case studies, eastward advection and transport in a weak warm conveyor belt (WCB) airflow was responsible for the export of North American emissions into the FT, while transport in the FT was governed by easterly winds driven by the Azores/Bermuda High (ABH) and transient northerly lows. In the fourth case study, North American emissions were lofted to 6-8 km in a WCB before being entrained in the same cyclone's dry airstream and transported down to the observatory. The results of this study show that the lower marine FT may provide an important transport environment where O3 production may continue, in contrast to transport in the marine boundary layer, where O3 destruction is believed to dominate. The second phase of the study presented here focused on improving the analysis methods that are available with LPDMs. While LPDMs are popular and useful for the analysis of atmospheric trace gas measurements, identifying the transport pathway of emissions from their source to a receptor (the Pico Mountain observatory in our case) using the standard gridded model output, particularly during complex meteorological scenarios can be difficult can be difficult or impossible. The transport study in phase 1 was limited to only 1 month out of more than 3 years of available data and included only 4 case studies out of the 16 events specifically due to this confounding factor. The second phase of this study addressed this difficulty by presenting a method to clearly and easily identify the pathway taken by only those emissions that arrive at a receptor at a particular time, by combining the standard gridded output from forward (i.e., concentrations) and backward (i.e., residence time) LPDM simulations, greatly simplifying similar analyses. The ability of the method to successfully determine the source-to-receptor pathway, restoring this Lagrangian information that is lost when the data are gridded, is proven by comparing the pathway determined from this method with the particle trajectories from both the forward and backward models. A sample analysis is also presented, demonstrating that this method is more accurate and easier to use than existing methods using standard LPDM products. Finally, we discuss potential future work that would be possible by combining the backward LPDM simulation with gridded data from other sources (e.g., chemical transport models) to obtain a Lagrangian sampling of the air that will eventually arrive at a receptor.

Boreal forest fire impacts on lower troposphere carbon monoxide and ozone levels at the regional to hemispheric scales

Tropospheric ozone (O3) and carbon monoxide (CO) pollution in the Northern Hemisphere is commonly thought to be of anthropogenic origin. While this is true in most cases, copious quantities of pollutants are emitted by fires in boreal regions, and the impact of these fires on CO has been shown to significantly exceed the impact of urban and industrial sources during large fire years. The impact of boreal fires on ozone is still poorly quantified, and large uncertainties exist in the estimates of the fire-released nitrogen oxides (NO x ), a critical factor in ozone production. As boreal fire activity is predicted to increase in the future due to its strong dependence on weather conditions, it is necessary to understand how these fires affect atmospheric composition. To determine the scale of boreal fire impacts on ozone and its precursors, this work combined statistical analysis of ground-based measurements downwind of fires, satellite data analysis, transport modeling and the results of chemical model simulations. The first part of this work focused on determining boreal fire impact on ozone levels downwind of fires, using analysis of observations in several-days-old fire plumes intercepted at the Pico Mountain station (Azores). The results of this study revealed that fires significantly increase midlatitude summertime ozone background during high fire years, implying that predicted future increases in boreal wildfires may affect ozone levels over large regions in the Northern Hemisphere. To improve current estimates of NOx emissions from boreal fires, we further analyzed ΔNOy /ΔCO enhancement ratios in the observed fire plumes together with transport modeling of fire emission estimates. The results of this analysis revealed the presence of a considerable seasonal trend in the fire NOx /CO emission ratio due to the late-summer changes in burning properties. This finding implies that the constant NOx /CO emission ratio currently used in atmospheric modeling is unrealistic, and is likely to introduce a significant bias in the estimated ozone production. Finally, satellite observations were used to determine the impact of fires on atmospheric burdens of nitrogen dioxide (NO2 ) and formaldehyde (HCHO) in the North American boreal region. This analysis demonstrated that fires dominated the HCHO burden over the fires and in plumes up to two days old. This finding provides insights into the magnitude of secondary HCHO production and further enhances scientific understanding of the atmospheric impacts of boreal fires.

INCORPORATING REAL SCIENCE INTO THE SECONDARY CLASSROOM: AEROSOLS AND CLIMATE CHANGE

Climate science and climate change are included in the Next Generation Science Standards, curriculum standards that were released in 2013. How to incorporate these topics, especially climate change, has been a difficult task for teachers. A team of scientists are studying aerosols in the free troposphere; what their properties are, how they change while in the atmosphere and where they came from. Lessons were created based on this real, ongoing scientific research being conducted in the Azores. During these activities, students are exposed to what scientists actually do in the form of videos and participate in similar tasks such as conducting experiments, collecting data, and analyzing data. At the conclusion of the lessons, students will form conclusions based on the evidence they have at the time.

Free Troposphere Ozone and Carbon Monoxide over the North Atlantic for 2001-2011

Carbon Monoxide (CO) and Ozone (O3) are considered to be one of the most important atmospheric pollutants in the troposphere with both having significant effects on human health. Both are included in the U.S. E.P.A list of criteria pollutants. CO is primarily emitted in the source region whereas O3 can be formed near the source, during transport of the pollution plumes containing O3 precursors or in a receptor region as the plumes subside. The long chemical lifetimes of both CO and O3 enable them to be transported over long distances. This transport is important on continental scales as well, commonly referred to as inter-continental transport and affects the concentrations of both CO and O3 in downwind receptor regions, thereby having significant implications for their air quality standards. Over the period 2001-2011, there have been decreases in the anthropogenic emissions of CO and NOx in North America and Europe whereas the emissions over Asia have increased. How these emission trends have affected concentrations at remote sites located downwind of these continents is an important question. The PICO-NARE observatory located on the Pico Mountain in Azores, Portugal is frequently impacted by North American pollution outflow (both anthropogenic and biomass burning) and is a unique site to investigate long range transport from North America. This study uses in-situ observations of CO and O3 for the period 2001-2011 at PICO-NARE coupled with output from the full chemistry (with normal and fixed anthropogenic emissions) and tagged CO simulations in GEOS-Chem, a global 3-D chemical transport model of atmospheric composition driven by meteorological input from the Goddard Earth Observing System (GEOS) of the NASA Global Modeling and Assimilation Office, to determine and interpret the trends in CO and O3 concentrations over the past decade. These trends would be useful in ascertaining the impacts emission reductions in the United States have had over Pico and in general over the North Atlantic. A regression model with sinusoidal functions and a linear trend term was fit to the in-situ observations and the GEOS-Chem output for CO and O3 at Pico respectively. The regression model yielded decreasing trends for CO and O3 with the observations (-0.314 ppbv/year & -0.208 ppbv/year respectively) and the full chemistry simulation with normal emissions (-0.343 ppbv/year & -0.526 ppbv/year respectively). Based on analysis of the results from the full chemistry simulation with fixed anthropogenic emissions and the tagged CO simulation it was concluded that the decreasing trends in CO were a consequence of the anthropogenic emission changes in regions such as USA and Asia. The emission reductions in USA are countered by Asian increases but the former have a greater impact resulting in decreasing trends for CO at PICO-NARE. For O3 however, it is the increase in water vapor content (which increases O3 destruction) along the pathways of transport from North America to PICO-NARE as well as around the site that has resulted in decreasing trends over this period. This decrease is offset by increase in O3 concentrations due to anthropogenic influence which could be due to increasing Asian emissions of O3 precursors as these emissions have decreased over the US. However, the anthropogenic influence does not change the final direction of the trend. It can thus be concluded that CO and O3 concentrations at PICO-NARE have decreased over 2001-2011.