Search

Accurate and reliable predictions and an understanding of future changes in the stratosphere are major aspects of the subject of climate change. Simulating the interaction between chemistry and climate is of particular importance, because continued increases in greenhouse gases and a slow decrease in halogen loading are expected. These both influence the abundance of stratospheric ozone. In recent years a number of coupled chemistry–climate models (CCMs) with different levels of complexity have been developed. They produce a wide range of results concerning the timing and extent of ozone-layer recovery. Interest in reducing this range has created a need to address how the main dynamical, chemical, and physical processes that determine the long-term behavior of ozone are represented in the models and to validate these model processes through comparisons with observations and other models. A set of core validation processes structured around four major topics (transport, dynamics, radiation, and stratospheric chemistry and microphysics) has been developed. Each process is associated with one or more model diagnostics and with relevant datasets that can be used for validation. This approach provides a coherent framework for validating CCMs and can be used as a basis for future assessments. Similar efforts may benefit other modeling communities with a focus on earth science research as their models increase in complexity.

During polar spring, periods of elevated tropospheric bromine drive near complete removal of surface ozone. These events impact the tropospheric oxidative capacity and are an area of active research with multiple approaches for representing the underlying processes in global models. We present a method for parameterizing emissions of molecular bromine (Br2) over the Arctic using satellite retrievals of bromine monoxide (BrO) from the Ozone Monitoring Instrument (OMI). OMI retrieves column BrO with daily near global coverage, and we use the GEOS‐Chem chemical mechanism, run online within the Goddard Earth Observing System Earth System Model to identify hotspots of BrO likely associated with polar processes. To account for uncertainties in modeling background BrO, hotspots are only identified where the difference between OMI and modeled columns exceeds a statistical threshold. The resulting hotspot columns are a lower‐limit for the portion of OMI BrO attributable to bromine explosion events. While these hotspots are correlated with BrO measured in the lower troposphere over the Arctic Ocean, a case study of missing detections of near‐surface BrO is identified. Daily flux of Br2 is estimated from hotspot columns of BrO using internal model parameters. When the emissions are applied, BrO hotspots are modeled with a 5% low bias. The sensitivity of the resulting ozone simulations to the treatment of background uncertainties in the BrO column is demonstrated. While periods of isolated, large (>50%) decreases in surface ozone are modeled, this technique does not simulate the low ozone observed at coastal stations and consistently underestimates ozone loss during March. Plain Language Summary: During polar spring, high levels of bromine‐containing molecules drive near complete removal of surface ozone (O3), impacting the chemistry of the troposphere and the biological uptake of mercury. Global models currently have multiple mechanisms for representing the underlying processes that produce brominated molecules in polar regions. We estimate molecular bromine (Br2) emissions from measurements of bromine monoxide (BrO) collected over the Arctic by a satellite instrument. An atmospheric model, run without polar emissions of Br2, is used to estimate how much of the satellite BrO signal is due to background processes in the stratosphere and troposphere and isolate the portion of the signal likely associated with Arctic emissions. We account for uncertainties in the model representation of background BrO using a statistical threshold. Because of the catalytic nature of bromine‐mediated ozone depletion, we focus our initial efforts on developing a lower‐limit estimate of Arctic emissions. The amount of BrO attributed to polar processes and the resulting impact on O3 are sensitive to the magnitude of the statistical threshold, with a better representation of surface O3 achieved with a lower threshold. While the satellite‐based emissions result in periodic decreases in surface O3 in late spring, modeled O3 is consistently high with respect to observations, particularly during early spring. Key Points: BrO hotspots are isolated from satellite signals using modeled columns of BrO and a bias threshold to account for model uncertaintiesWe estimate Arctic Br2 emissions from BrO signals and demonstrate the sensitivity of modeled O3 to the BrO hotspot detection thresholdSimulations with satellite‐based Br2 emissions overestimate springtime Arctic surface O3 with few ozone depleting events modeled in March [ABSTRACT FROM AUTHOR]

Trends in the composition of the lower atmosphere (0-1500m altitude) and surface air quality over the Baltimore/Washington area and surrounding states were investigated for the period from 1997 to 2011. We examined emissions of ozone precursors from monitors and inventories as well as ambient ground-level and aircraft measurements to characterize trends in air pollution. The US EPA Continuous Emissions Monitoring System (CEMS) program reported substantial decreases in emission of summertime nitrogen oxides (NOx) from power plants, up to ~80% in the mid-Atlantic States. These large reductions in emission of NOx are reflected in a sharp decrease of ground-level concentrations of NOx starting around 2003. The decreasing trend of tropospheric column CO observed by aircraft is ~0.8 Dobson unit (DU) per year, corresponding to ~35 ppbv yr-1 in the lower troposphere (the surface to 1500m above ground level). Satellite observations of long-term, near-surface CO show a ~40% decrease over western Maryland between 2000 and 2011; the same magnitude is indicated by aircraft measurements above these regions upwind of the Baltimore/Washington airshed. With decreasing emissions of ozone precursors, the ground-level ozone in the Baltimore/Washington area shows a 0.6 ppbv yr-1 decrease in the past 15 yr. Since photochemical production of ozone is substantially influenced by ambient temperature, we introduce the climate penalty factor (CPF) into the trend analysis of long-term aircraft measurements. After compensating for inter-annual variations in temperature, historical aircraft measurements indicate that the daily net production of tropospheric ozone over the Baltimore/Washington area decreased from ~20 ppbv day-1 in the late 1990s to ~7 ppbv day-1 in the early 2010s during ozone season. A decrease in the long-term column ozone is observed as ~0.2 DUyr-1 in the lowest 1500 m, corresponding to an improvement of ~1.3 ppbv yr-1. Our aircraft measurements were conducted on days when severe ozone pollution was forecasted, and these results represent the decreasing trend in high ozone events over the past 15 yr. Back trajectory cluster analysis demonstrates that emissions of air pollutants from Ohio and Pennsylvania through Maryland influence the column abundances of downwind ozone in the lower atmosphere. The trends in air pollutants reveal the success of regulations implemented over the past decades and the importance of region-wide emission controls in the eastern United States. [ABSTRACT FROM AUTHOR]

Emission of bromine from sea-salt aerosol, frost flowers, ice leads, and snow results in the nearly complete removal of surface ozone during Arctic spring. Regions of enhanced total column BrO observed by satellites have traditionally been associated with these emissions. However, airborne measurements of BrO and O3 within the convective boundary layer (CBL) during the ARCTAS and ARCPAC field campaigns at times bear little relation to enhanced column BrO. We show that the locations of numerous satellite BrO “hotspots” during Arctic spring are consistent with observations of total column ozone and tropopause height, suggesting a stratospheric origin to these regions of elevated BrO. Tropospheric enhancements of BrO large enough to affect the column abundance are also observed, with important contributions originating from above the CBL. Closure of the budget for total column BrO, albeit with significant uncertainty, is achieved by summing observed tropospheric partial columns with calculated stratospheric partial columns provided that natural, short-lived biogenic bromocarbons supply between 5 and 10 ppt of bromine to the Arctic lowermost stratosphere. Proper understanding of bromine and its effects on atmospheric composition requires accurate treatment of geographic variations in column BrO originating from both the stratosphere and troposphere., Engineering and Applied Sciences