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Organic compounds in the atmosphere vary widely in their molecular composition and chemical properties, so no single instrument can reasonably measure the entire range of ambient compounds. Over the past decade, a new generation of in situ, field-deployable mass spectrometers has dramatically improved our ability to detect, identify, and quantify these organic compounds, but no systematic approach has been developed to assess the extent to which currently available tools capture the entire space of chemical identity and properties that is expected in the atmosphere. Reduced-parameter frameworks that have been developed to describe atmospheric mixtures are exploited here to characterize the range of chemical properties accessed by a suite of instruments. Multiple chemical spaces (e.g. oxidation state of carbon vs. volatility, and oxygen number vs. carbon number) were populated with ions measured by several mass spectrometers, with gas- and particle-phase α-pinene oxidation products serving as the test mixture of organic compounds. Few gaps are observed in the coverage of the parameter spaces by the instruments employed in this work, though the full extent to which comprehensive measurement was achieved is difficult to assess due to uncertainty in the composition of the mixture. Overlaps between individual ions and regions in parameter space were identified, both between gas- and particle-phase measurements, and within each phase. These overlaps were conservatively found to account for little (

In California, emission control strategies have been implemented to reduce air pollutants. Here we estimate the changes in nitrogen oxides (NOx = NO + NO2) emissions in 2005-2010 using a state-of-the-art four-dimensional variational approach. We separately and jointly assimilate surface NO2 concentrations and tropospheric NO2 columns observed by Ozone Monitoring Instrument (OMI) into the regional-scale Sulfur Transport and dEposition Model (STEM) chemical transport model on a 12 × 12 km2 horizontal resolution grid in May 2010. The assimilation generates grid-scale top-down emission estimates, and the updated chemistry fields are evaluated with independent aircraft measurements during the NOAA California Nexus (CalNex) field experiment. The emission estimates constrained only by NO2 columns, only by surface NO2, and by both indicate statewide reductions of 26%, 29%, and 30% from ~0.3 Tg N/yr in the base year of 2005, respectively. The spatial distributions of the emission changes differ in these cases, which can be attributed to many factors including the differences in the observation sampling strategies and their uncertainties, as well as those in the sensitivities of column and surface NO2 with respect to NOx emissions. The updates in California's NOx emissions reduced the mean error in modeled surface ozone in the Western U.S., even though the uncertainties in some urban areas increased due to their NOx-saturated chemical regime. The statewide reductions in NOx emissions indicated from our observationally constrained emission estimates are also reflected in several independently developed inventories: ~30% in the California Air Resources Board bottom-up inventory, ~4% in the 2008 National Emission Inventory, and ~20% in the annual mean top-down estimates by Lamsal et al. using the global Goddard Earth Observing System (GEOS)-Chem model and OMI NO2 columns. Despite the grid-scale differences among all top-down and bottom-up inventories, they all indicate stronger emission reductions in the urban regions. This study shows the potential of using space-/ground-based monitoring data and advanced data assimilation approach to timely and independently update NOx emission estimates on a monthly scale and at a fine grid resolution. The well-evaluated results here suggest that these approaches can be applied more broadly.

Airborne and ground-based measurements during the CalNex (California Research at the Nexus of Air Quality and Climate Change) field study in May/June 2010 show a weekend effect in ozone in the South Coast Air Basin (SoCAB) consistent with previous observations. The well-known and much-studied weekend ozone effect has been attributed to weekend reductions in nitrogen oxide (NOx = NO + NO2) emissions, which affect ozone levels via two processes: (1) reduced ozone loss by titration and (2) enhanced photochemical production of ozone due to an increased ratio of non-methane volatile organic compounds (VOCs) to NOx. In accord with previous assessments, the 2010 airborne and ground-based data show an average decrease in NOx of 46 11% and 34 4%, respectively, and an average increase in VOC/NOx ratio of 48 8% and 43 22%, respectively, on weekends. This work extends current understanding of the weekend ozone effect in the SoCAB by identifying its major causes and quantifying their relative importance from the available CalNex data. Increased weekend production of a VOC-NOx oxidation product, peroxyacetyl nitrate, compared to a radical termination product, nitric acid, indicates a significant contribution from increased photochemical production on weekends. Weekday-to-weekend differences in the products of NOx oxidation show 45 13% and 42 12% more extensive photochemical processing and, when compared with odd oxygen (Ox = O3 + NO2), 51 14% and 22 17% greater ozone production efficiency on weekends in the airborne and ground-based data, respectively, indicating that both contribute to higher weekend ozone levels in the SoCAB. Copyright 2012 by the American Geophysical Union.

Ozone (O3), alkyl nitrates (RONO2), and other photochemical products were formed in the atmosphere downwind from the Deepwater Horizon (DWH) oil spill by photochemical reactions of evaporating hydrocarbons with NOx (=NO+NO2) emissions from spill response activities. Reactive nitrogen species and volatile organic compounds (VOCs) were measured from an instrumented aircraft during daytime flights in the marine boundary layer downwind from the area of surfacing oil. A unique VOC mixture, where alkanes dominated the hydroxyl radical (OH) loss rate, was emitted into a clean marine environment, enabling a focused examination of O3 and RONO 2 formation processes. In the atmospheric plume from DWH, the OH loss rate, an indicator of potential O3 formation, was large and dominated by alkanes with between 5 and 10 carbons per molecule (C 5-C10). Observations showed that NOx was oxidized very rapidly with a 0.8h lifetime, producing primarily C6-C10 RONO2 that accounted for 78% of the reactive nitrogen enhancements in the atmospheric plume 2.5h downwind from DWH. Both observations and calculations of RONO2 and O3 production rates show that alkane oxidation dominated O3 formation chemistry in the plume. Rapid and nearly complete oxidation of NOx to RONO2 effectively terminated O3 production, with O3 formation yields of 6.0±0.5 ppbv O3 per ppbv of NOx oxidized. VOC mixing ratios were in large excess of NOx, and additional NOx would have formed additional O3 in this plume. Analysis of measurements of VOCs, O3, and reactive nitrogen species and calculations of O3 and RONO2 production rates demonstrate that NOx-VOC chemistry in the DWH plume is explained by known mechanisms. Copyright 2012 by the American Geophysical Union.

The fate of deepwater releases of gas and oil mixtures is initially determined by solubility and volatility of individual hydrocarbon species; these attributes determine partitioning between air and water. Quantifying this partitioning is necessary to constrain simulations of gas and oil transport, to predict marine bioavailability of different fractions of the gas-oil mixture, and to develop a comprehensive picture of the fate of leaked hydrocarbons in the marine environment. Analysis of airborne atmospheric data shows massive amounts (∼258,000 kg/day) of hydrocarbons evaporating promptly from the Deepwater Horizon spill; these data collected during two research flights constrain air-water partitioning, thus bioavailability and fate, of the leaked fluid. This analysis quantifies the fraction of surfacing hydrocarbons that dissolves in the water column (∼33% by mass), the fraction that does not dissolve, and the fraction that evaporates promptly after surfacing (∼14% by mass). We do not quantify the leaked fraction lacking a surface expression; therefore, calculation of atmospheric mass fluxes provides a lower limit to the total hydrocarbon leak rate of 32,600 to 47,700 barrels of fluid per day, depending on reservoir fluid composition information. This study demonstrates a new approach for rapid-response airborne assessment of future oil spills. Copyright 2011 by the American Geophysical Union.

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. Copyright 2010 by the American Geophysical Union.

Unexpected high levels of OH and NO were recorded at the South Pole (SP) Atmospheric Research Observatory during the 1998-99 ISCAT field study. Model simulations suggest a major photochemical linkage between observed OH and NO. A detailed comparison of the observations with model predictions revealed good agreement for OH at NO levels between 120 and 380 pptv. However, the model tended to overestimate OH for NO levels < 120 pptv, while it underestimated OH at levels > 380 pptv. The reasons for these deviations appear not to involve NO directly but rather HOx radical scavenging for the low NO conditions and additional HOx sources for the high NO conditions. Because of the elevated levels of NO and highly activated HOx photochemistry, the SP was found to be a strong net source of surface ozone. It is quite likely that the strong oxidizing environment found at the South Pole extends over the entire polar plateau.