Regional and hemispheric impacts of anthropogenic and biomass burning emissions on summertime CO and O3 in the North Atlantic lower free troposphere

Abstract

We report summertime measurements of CO and O3 obtained during 2001–2003 at the PICO‐NARE mountaintop station in the Azores. Frequent events of elevated CO mixing ratios were observed. On the basis of backward trajectories arriving in the free troposphere and global simulations of biomass burning plumes, we attribute nearly all these events to North American pollution outflow and long‐range transport of biomass burning emissions. There was a high degree of interannual variability in CO levels: median [CO] ranged from 65 ppbv in 2001 to 104 ppbv in 2003. The highest concentrations were associated with transport of Siberian fire emissions during summer 2003, when Siberian fire activity was unusually high. Ozone mixing ratios also increased (by up to ∼30 ppbv) during the fire events. These findings demonstrate the significant hemispheric scale impact that biomass burning events have on background CO and O3 levels. O3 enhancements of similar magnitude were also observed in North American pollution outflow. O3 and CO were correlated during North American outflow events, with a slope averaging 1.0 (d[O3]/d[CO], ppbv/ppbv) when no fire impact was present. This slope is more than 80% larger than early 1990s observations made in the eastern United States and nearshore outflow region, even after accounting for declining U.S. CO emissions and for CO loss during transport to the Azores, and is not consistent with simple dilution of U.S. outflow with marine background air. We conclude that a significantly larger amount of O3 production occurred in the air sampled during this study, and we suggest several potential reasons for this, each of which could imply potentially significant shortcomings in current estimates of the hemispheric impact of North American emissions on tropospheric ozone and should be evaluated in future studies.