H. Oetjen

Extensive halogen-mediated ozone destruction over the tropical Atlantic Ocean

Increasing tropospheric ozone levels over the past 150 years have led to a significant climate perturbation; the prediction of future trends in tropospheric ozone will require a full understanding of both its precursor emissions and its destruction processes. A large proportion of tropospheric ozone loss occurs in the tropical marine boundary layer and is thought to be driven primarily by high ozone photolysis rates in the presence of high concentrations of water vapour. A further reduction in the tropospheric ozone burden through bromine and iodine emitted from open-ocean marine sources has been postulated by numerical models, but thus far has not been verified by observations. Here we report eight months of spectroscopic measurements at the Cape Verde Observatory indicative of the ubiquitous daytime presence of bromine monoxide and iodine monoxide in the tropical marine boundary layer. A year-round data set of co-located in situ surface trace gas measurements made in conjunction with low-level aircraft observations shows that the mean daily observed ozone loss is ∼50 per cent greater than that simulated by a global chemistry model using a classical photochemistry scheme that excludes halogen chemistry. We perform box model calculations that indicate that the observed halogen concentrations induce the extra ozone loss required for the models to match observations. Our results show that halogen chemistry has a significant and extensive influence on photochemical ozone loss in the tropical Atlantic Ocean boundary layer. The omission of halogen sources and their chemistry in atmospheric models may lead to significant errors in calculations of global ozone budgets, tropospheric oxidizing capacity and methane oxidation rates, both historically and in the future.

Simultaneous global observations of glyoxal and formaldehyde from space

[1] The first global simultaneous observations of glyoxal (CHOCHO) and formaldehyde (HCHO) columns retrieved from measurements by the Scanning Imaging Absorption Spectrometer for Atmospheric Cartography (SCIAMACHY) satellite instrument are presented and compared to model calculations. The global pattern of the distribution of CHOCHO is similar to that of HCHO. High values are observed over areas with large biogenic isoprene emissions (Central Africa, parts of South America, and Indonesia). Also regions with biomass burning and anthropogenic pollution exhibit elevated levels of CHOCHO. The ratio of the columns of CHOCHO to HCHO is generally of the order of 0.05 in regions having biogenic emissions, which is in reasonable agreement with the current understanding of the oxidation of hydrocarbons emitted by the biosphere. However and in contrast to our model, high values of both HCHO and CHOCHO are also observed over areas of the tropical oceans. This is tentatively attributed to outflow from the continents and local oceanic biogenic sources of the precursors of HCHO and CHOCHO. Citation: Wittrock, F., A. Richter, H. Oetjen, J. P. Burrows, M. Kanakidou, S. Myriokefalitakis, R. Volkamer, S. Beirle, U. Platt, and T. Wagner (2006), Simultaneous global observations of glyoxal and formaldehyde from space, Geophys. Res. Lett., 33, L16804, doi:10.1029/2006GL026310.

Modeling the weekly cycle of NOx and CO emissions and their impacts on O3 in the Los Angeles‐South Coast Air Basin during the CalNex 2010 field campaign

We developed a new nitrogen oxide (NOx) and carbon monoxide (CO) emission inventory for the Los Angeles-South Coast Air Basin (SoCAB) expanding the Fuel-based Inventory for motor-Vehicle Emissions and applied it in regional chemical transport modeling focused on the California Nexus of Air Quality and Climate Change (CalNex) 2010 field campaign. The weekday NOx emission over the SoCAB in 2010 is 620 t d−1, while the weekend emission is 410 t d−1. The NOx emission decrease on weekends is caused by reduced diesel truck activities. Weekday and weekend CO emissions over this region are similar: 2340 and 2180 t d−1, respectively. Previous studies reported large discrepancies between the airborne observations of NOx and CO mixing ratios and the model simulations for CalNex based on the available bottom-up emission inventories. Utilizing the newly developed emission inventory in this study, the simulated NOx and CO mixing ratios agree with the observations from the airborne and the ground-based in situ and remote sensing instruments during the field study. The simulations also reproduce the weekly cycles of these chemical species. Both the observations and the model simulations indicate that decreased NOx on weekends leads to enhanced photochemistry and increase of O3 and Ox (=O3 + NO2) in the basin. The emission inventory developed in this study can be extended to different years and other urban regions in the U.S. to study the long-term trends in O3 and its precursors with regional chemical transport models.

Impact of intercontinental pollution transport on North American ozone air pollution: an HTAP phase 2 multi-model study

The recent update on the US National Ambient Air Quality Standards (NAAQS) of the ground-level ozone (O3/ can benefit from a better understanding of its source contributions in different US regions during recent years. In the Hemispheric Transport of Air Pollution experiment phase 1 (HTAP1), various global models were used to determine the O3 source–receptor (SR) relationships among three continents in the Northern Hemisphere in 2001. In support of the HTAP phase 2 (HTAP2) experiment that studies more recent years and involves higher-resolution global models and regional models’ participation, we conduct a number of regional-scale Sulfur Transport and dEposition Model (STEM) air quality base and sensitivity simulations over North America during May–June 2010. STEM’s top and lateral chemical boundary conditions were downscaled from three global chemical transport models’ (i.e., GEOS-Chem, RAQMS, and ECMWF C-IFS) base and sensitivity simulations in which the East Asian (EAS) anthropogenic emissions were reduced by 20 %. The mean differences between STEM surface O3 sensitivities to the emission changes and its corresponding boundary condition model’s are smaller than those among its boundary condition models, in terms of the regional/period-mean (<10 %) and the spatial distributions. An additional STEM simulation was performed in which the boundary conditions were downscaled from a RAQMS (Realtime Air Quality Modeling System) simulation without EAS anthropogenic emissions. The scalability of O3 sensitivities to the size of the emission perturbation is spatially varying, and the full (i.e., based on a 100% emission reduction) source contribution obtained from linearly scaling the North American mean O3 sensitivities to a 20% reduction in the EAS anthropogenic emissions may be underestimated by at least 10 %. The three boundary condition models’ mean O3 sensitivities to the 20% EAS emission perturbations are ~8% (May–June 2010)/~11% (2010 annual) lower than those estimated by eight global models, and the multi-model ensemble estimates are higher than the HTAP1 reported 2001 conditions. GEOS-Chem sensitivities indicate that the EAS anthropogenic NOx emissions matter more than the other EAS O3 precursors to the North American O3, qualitatively consistent with previous adjoint sensitivity calculations. In addition to the analyses on large spatial–temporal scales relative to the HTAP1, we also show results on subcontinental and event scales that are more relevant to the US air quality management. The EAS pollution impacts are weaker during observed O3 exceedances than on all days in most US regions except over some high-terrain western US rural/remote areas. Satellite O3 (TES, JPL–IASI, and AIRS) and carbon monoxide (TES and AIRS) products, along with surface measurements and model calculations, show that during certain episodes stratospheric O3 intrusions and the transported EAS pollution influenced O3 in the western and the eastern US differently. Free-running (i.e., without chemical data assimilation) global models underpredicted the transported background O3 during these episodes, posing difficulties for STEM to accurately simulate the surface O3 and its source contribution. Although we effectively improved the modeled O3 by incorporating satellite O3 (OMI and MLS) and evaluated the quality of the HTAP2 emission inventory with the Royal Netherlands Meteorological Institute–Ozone Monitoring Instrument (KNMI–OMI) nitrogen dioxide, using observations to evaluate and improve O3 source attribution still remains to be further explored.

Weakening of the weekend ozone effect over California's South Coast Air Basin

We have observed lower nitrogen dioxide (NO2) and ozone (O3) during a hot weekend (summer 2010) from aircraft over the entire South Coast Air Basin (SoCAB). Surface concentrations of NO2, O3, and temperature from 1996 to 2014 corroborate that this lower O3 on weekends is increasingly likely in recent years. While higher surface O3 on the weekends (weekend ozone effect, WO3E) remains widespread, the spatial extent and the trend in the probability of WO3E occurrences (PWO3E) have decreased significantly compared to a decade ago. This decrease is mostly the result of lower O3 on hot weekends in recent years. PWO3E is lowest in the eastern SoCAB. The major decrease happened during the 2008 economic recession, after which PWO3E has stabilized at a 15–25% lower level throughout most of the basin. Future NOx reductions are likely to be increasingly effective at reducing O3 pollution initially under hot conditions in the coming decade.

Combining active and passive airborne remote sensing to quantify NO2 and Ox production near Bakersfield, CA.

Aims: The objective of this study is to demonstrate the integrated use of passive and active remote sensing instruments to quantify the rate of NO x emissions, and investigate the O x production rates from an urban area. Place and Duration of Study: A research flight on June 15, 2010was conducted over Bakersfield, CA and nearby areas with oil and natural gas production. Methodology: Three remote sensing instruments, namely the University of Colorado AMAX-DOAS, NOAA TOPAZ lidar, and NCAS Doppler lidar were deployed aboard the NOAA Twin Otter during summer 2010. Production rates of nitrogen dioxide (NO 2) and background corrected O x (background corrected O 3 + NO 2), O x’ were quantified using the horizontal flux divergence approach by flying closed loops near Bakersfield, CA. By making concurrent measurements of the trace gases as well as the wind fields, we have greatly reduced the uncertainty due to wind field in production rates. Results: We find that the entire region is a source for both NO 2 and O x’. NO 2 production

Simulation of semi-explicit mechanisms of SOA formation from glyoxal in a 3-D model

Christoph Knote1), Alma Hodzic1), Jose L. Jimenez2,3), Rainer Volkamer2,3), Sunil Baidar2,3), Jerome Brioude3,5), Jerome Fast4), Jessica B. Gilman3,5), Allen Goldstein9), Joost de Gouw3,5), Patrick Hayes2,3), B. Tom Jobson6), W. Berk Knighton7), William C. Kuster3,5), Hilke Oetjen8), John Orlando1), Chen Song4), Harald Stark3,5), Philip S. Stevens10), Ryan Thalman2,3), Geoff Tyndall1), Carsten Warneke3,5), Rebecca Washenfelder3,5), Eleanor Waxman2,3), Qi Zhang11)

Novel Pathways to Form Secondary Organic Aerosols: Glyoxal SOA in WRF/Chem

Current approaches to simulate secondary organic aerosols (SOA) in regional and global numerical models are based on parameterizations of the oxidation of precursor gases in the gas-phase and subsequent partitioning into particles. Recent findings suggest however that formation in the aqueous-phase of aerosols might contribute substantially to ambient SOA load. In this work we investigate the contribution of glyoxal to SOA through chemical processes associated with aerosols. Both a very simple and a more explicit mechanism of SOA formation from glyoxal was included in the regional chemistry transport model WRF/Chem. We simulated the first 2 weeks of June 2010 over the domain of California to make use of the extensive dataset collected during the CARES/CalNex field campaigns to evaluate our simulations. Contributions to total SOA mass were found to range from 1 to 15 % in the LA basin, and <1 to 9 % in the isoprene-rich eastern slopes of the Central Valley. We find that the simple approach previously used in box as well as global modeling studies gives the highest contributions. A combination of reversible partitioning and volume pathways can provide comparable amounts only if partitioning of glyoxal into the aerosol liquid-phase is instantaneous.