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Atmospheric peroxyacetyl nitrate (PAN): a global budget and source attribution

Peroxyacetyl nitrate (PAN) formed in the atmospheric oxidation of non-methane volatile organic compounds (NMVOCs) is the principal tropospheric reservoir for nitrogen oxide radicals (NOx = NO + NO2). PAN enables the transport and release of NOx to the remote troposphere with major implications for the global distributions of ozone and OH, the main tropospheric oxidants. Simulation of PAN is a challenge for global models because of the dependence of PAN on vertical transport as well as complex and uncertain NMVOC sources and chemistry. Here we use an improved representation of NMVOCs in a global 3-D chemical transport model (GEOS-Chem) and show that it can simulate PAN observations from aircraft campaigns worldwide. The immediate carbonyl precursors for PAN formation include acetaldehyde (44% of the global source), methylglyoxal (30%), acetone (7%), and a suite of other isoprene and terpene oxidation products (19%). A diversity of NMVOC emissions is responsible for PAN formation globally including isoprene (37%) and alkanes (14%). Anthropogenic sources are dominant in the extratropical Northern Hemisphere outside the growing season. Open fires appear to play little role except at high northern latitudes in spring, although results are very sensitive to plume chemistry and plume rise. Lightning NOx is the dominant contributor to the observed PAN maximum in the free troposphere over the South Atlantic.
Observations of I2 at a remote marine site

Inorganic iodine plays a significant role in the photochemistry of the marine boundary layer, but the sources and cycling of iodine are not well understood. We report the first I2 observations in marine air that is not impacted by coastal macroalgal emissions or sea ice chemistry. The data clearly demonstrate that the very high I2 levels previously reported for coastal air are not representative of open ocean conditions. In this study, gas phase I2 was measured at the Cape Verde Atmospheric Observatory, a semi-remote site in the eastern tropical Atlantic, using atmospheric pressure chemical ionization tandem mass spectrometry. Atmospheric I2 levels typically increased beginning at sunset, leveled off after midnight, and then rapidly decreased at sunrise. There was also a smaller midday maximum in I2 that was probably caused by a measurement artifact. Ambient I2 mixing ratios ranged from <0.02–0.6 pmol mol−1 in May 2007 and <0.03–1.67 pmol mol−1 in May 2009. The sea-air flux implied by the nighttime buildup of I2 is too small to explain the observed daytime IO levels at this site. Iodocarbon measurements made in this region previously are also insufficient to explain the observed 1–2 pmol mol−1 of daytime IO. The observations imply the existence of an unknown daytime source of gas phase inorganic iodine. Carpenter et al. (2013) recently proposed that sea surface emissions of HOI are several times larger than the flux of I2. Such a flux could account for both the nighttime I2 and the daytime IO observations.
Retrieval of methane source strengths in Europe using a simple modeling approach to assess the potential of spaceborne lidar observations

We investigate the sensitivity of future spaceborne lidar measurements to changes in surface methane emissions. We use surface methane observations from nine European ground stations and a Lagrangian transport model to infer surface methane emissions for 2010. Our inversion shows the strongest emissions from the Netherlands, the coal mines in Upper Silesia, Poland, and wetlands in southern Finland. The simulated methane surface concentrations capture at least half of the daily variability in the observations, suggesting that the transport model is correctly simulating the regional transport pathways over Europe. With this tool we can test whether proposed methane lidar instruments will be sensitive to changes in surface emissions. We show that future lidar instruments should be able to detect a 50% reduction in methane emissions from the Netherlands and Germany, at least during summer.
The Arctic summer atmosphere: an evaluation of reanalyses using ASCOS data

The Arctic has experienced large climate changes over recent decades, the largest for any region on Earth. To understand the underlying reasons for this climate sensitivity, reanalysis is an invaluable tool. The Arctic System Reanalysis (ASR) is a regional reanalysis, forced by ERA-Interim at the lateral boundaries and incorporating model physics adapted to Arctic conditions, developed to serve as a state-of-the-art, high-resolution synthesis tool for assessing Arctic climate variability and monitoring Arctic climate change. We use data from Arctic Summer Cloud-Ocean Study (ASCOS) to evaluate the performance of ASR and ERA-Interim for the Arctic Ocean. The ASCOS field experiment was deployed on the Swedish icebreaker Oden north of 87° N in the Atlantic sector of the Arctic during August and early September 2008. Data were collected during the transits from and to Longyearbyen and the 3-week ice drift with Oden moored to a drifting multiyear ice floe. These data are independent and detailed enough to evaluate process descriptions. The reanalyses captures basic meteorological variations coupled to the synoptic-scale systems, but have difficulties in estimating clouds and atmospheric moisture. While ERA-Interim has a systematic warm bias in the lowest troposphere, ASR has a cold bias of about the same magnitude on average. The results also indicate that more sophisticated descriptions of cloud microphysics in ASR did not significantly improve the modeling of cloud properties compared to ERA-Interim. This has consequences for the radiation balance, and hence the surface temperature, and illustrate how a modeling problem in one aspect of the atmosphere, here the clouds, feeds back to other parameters, especially near the surface and in the boundary layer.
Size-resolved aerosol composition and its link to hygroscopicity at a forested site in Colorado

Aerosol hygroscopicity describes the ability of a particle to take up water and form a cloud droplet. Modeling studies have shown sensitivity of precipitation-producing cloud systems to the availability of aerosol particles capable of serving as cloud condensation nuclei (CCN), and hygroscopicity is a key parameter controlling the number of available CCN. Continental aerosol is typically assumed to have a representative hygroscopicity parameter, κ, of 0.3; however, in remote locations this value can be lower due to relatively large mass fractions of organic components. To further our understanding of aerosol properties in remote areas, we measured size-resolved aerosol chemical composition and hygroscopicity in a forested, mountainous site in Colorado during the six-week BEACHON-RoMBAS (Bio-hydro-atmosphere interactions of Energy, Aerosols, Carbon, H2O, Organics and Nitrogen–Rocky Mountain Biogenic Aerosol Study) campaign. This campaign followed a year-long measurement period at this site, and results from the intensive campaign shed light on the previously reported seasonal cycle in aerosol hygroscopicity. New particle formation events were observed routinely at this site and nucleation mode composition measurements indicated that the newly formed particles were predominantly organic. These events likely contribute to the dominance of organic species at smaller sizes, where aerosol organic mass fractions were between 70 and 90%. Corresponding aerosol hygroscopicity was observed to be in the range κ = 0.15–0.22, with hygroscopicity increasing with particle size. Aerosol chemical composition measured by an aerosol mass spectrometer and calculated from hygroscopicity measurements agreed very well during the intensive study, with an assumed value of κorg = 0.13 resulting in the best agreement.
Uncertainty analysis of projections of ozone-depleting substances: mixing ratios, EESC, ODPs, and GWPs

The rates at which ozone-depleting substances (ODSs) are removed from the atmosphere, which determine the lifetimes of these ODSs, are key factors for determining the rate of ozone layer recovery in the coming decades. We present here a comprehensive uncertainty analysis of future mixing ratios of ODSs, levels of equivalent effective stratospheric chlorine (EESC), ozone depletion potentials, and global warming potentials (GWPs), using, among other information, the 2013 WCRP/SPARC (World Climate Research Programme/Stratospheric Processes and their Role in Climate) assessment of lifetimes of ODSs and their uncertainties. The year EESC returns to pre-1980 levels, a metric commonly used to indicate a level of recovery from ODS-induced ozone depletion, is 2048 for midlatitudes and 2075 for Antarctic conditions based on the lifetimes from the SPARC assessment, which is about 2 and 4 yr, respectively, later than based on the lifetimes from the WMO (World Meteorological Organization) assessment of 2011. However, the uncertainty in this return to 1980 levels is much larger than the shift due to this change in lifetimes. The year EESC returns to pre-1980 levels ranges from 2039 to 2064 (95% confidence interval) for midlatitudes and from 2061 to 2105 for the Antarctic spring. The primary contribution to these ranges comes from the uncertainty in the lifetimes, with smaller contributions from uncertainties in other modeled parameters. The earlier years of the return estimates derived by the uncertainty analysis, i.e., 2039 for midlatitudes and 2061 for Antarctic spring, are comparable to a hypothetical scenario in which emissions of ODSs cease in 2014. The later end of the range, i.e., 2064 for midlatitudes and 2105 for Antarctic spring, can also be obtained by a scenario with an additional emission of about 7 Mt CFC-11 eq. (eq. – equivalent) in 2015, which is the same as about 2 times the projected cumulative anthropogenic emissions of all ODSs from 2014 to 2050, or about 12 times the projected cumulative HCFC emissions from 2014 to 2050.
Quantifying the contributions of natural emissions to ozone and total fine PM concentrations in the Northern Hemisphere

Accurate estimates of emissions from natural sources are needed for reliable predictions of ozone and fine particulate matter (PM2.5) using air quality models. In this study, the large-scale atmospheric chemistry transport model, DEHM (the Danish Eulerian Hemispheric Model) is further developed, evaluated and applied to study and quantify the contributions of natural emissions of VOCs, NOx, NH3, SO2, CH4, PM, CO and sea salt to the concentration of ozone and formation of PM2.5 for the year 2006. Natural source categories adopted in the recent model are vegetation, lightning, soils, wild animals and oceans. In this study, the model has been further developed to include more Biogenic Volatile Organic Compounds (BVOCs) and to implement a scheme for secondary organic aerosols as well as an updated description of sea-salt emissions. Our simulations indicate that in the Northern Hemisphere the contribution from natural emissions to the average annual ozone mixing ratios over land is between 4–30 ppbV. Among the natural emissions, BVOCs are found to be the most significant contributors to ozone formation in 2006, enhancing the average ozone mixing ratio by about 11% over the land areas of the Northern Hemisphere. The relative contribution of all the natural emissions to ozone is found to be highest in the northern part of South America by about 42%. Similarly, the highest contribution of all the natural sources to total fine particles over land is found to be in South America by about 74% and sea-salt aerosols demonstrated to play the most important role. However, over the rest of the regions in the model domain the largest contribution from the natural sources to PM2.5 in the specific year 2006 is due to wildfires. The contribution from natural emissions to the mean PM2.5 concentration over the land areas in the model domain is about 34%.
Suppression of new particle formation from monoterpene oxidation by NOx

The impact of nitrogen oxides (NOx = NO + NO2) on new particle formation (NPF) and on photochemical ozone production from real plant volatile organic compound (BVOC) emissions was studied in a laboratory setup. At high NOx conditions ([BVOC] / [NOx] < 7, [NOx] > 23 ppb) new particle formation was suppressed. Instead, photochemical ozone formation was observed resulting in higher hydroxyl radical (OH) and lower nitrogen monoxide (NO) concentrations. When [NO] was reduced back to levels below 1 ppb by OH reactions, NPF was observed. Adding high amounts of NOx caused NPF to be slowed by orders of magnitude compared to analogous experiments at low NOx conditions ([NOx] ~300 ppt), although OH concentrations were higher. Varying NO2 photolysis enabled showing that NO was responsible for suppression of NPF. This suggests that peroxy radicals are involved in NPF. The rates of NPF and photochemical ozone production were related by power law dependence with an exponent approaching −2. This exponent indicated that the overall peroxy radical concentration must have been similar when NPF occurred. Thus, permutation reactions of first-generation peroxy radicals cannot be the rate limiting step in NPF from monoterpene oxidation. It was concluded that permutation reactions of higher generation peroxy-radical-like intermediates limit the rate of new particle formation. In contrast to the strong effects on the particle numbers, the formation of particle mass was substantially less sensitive to NOx concentrations. If at all, yields were reduced by about an order of magnitude only at very high NOx concentrations.
Slower ozone production in Houston, Texas following emission reductions: evidence from Texas Air Quality Studies in 2000 and 2006

Airborne measurements from two Texas Air Quality Study (TexAQS) field campaigns have been used to investigate changes of ozone production in Houston, Texas, from 2000 to 2006, a period of major emission reduction measures for petrochemical and other sources. Simultaneous declines in nitrogen oxides (NOx = NO + NO2) and highly reactive volatile organic compounds (HRVOCs) were observed between the two periods. We simulate HOx (OH and HO2) and organic radicals with a box model, the Dynamically Simple Model of Atmospheric Chemical Complexity, constrained by available airborne observations. Parameters such as total radical production, total OH reactivity of VOCs and ozone production rate (OPR) are computed to characterize the change of ozone production between 2000 and 2006 in the Houston area. The reduction in HRVOCs led to a decline in total radical production by 20–50%. Ozone production rates in the Houston area declined by 40–50% from 2000 to 2006, to which the reduction in NOx and HRVOCs made large contributions. Despite the significant decline in OPR, ozone production efficiency held steady, and VOC-sensitive conditions dominated during times of most rapid ozone formation, while the slow ozone formation continued to be NOx-limited. Our results highlight the importance of a balanced approach of ongoing HRVOC controls with NOx controls to further reduce O3 levels in the Houston area.
Extreme haze pollution in Beijing during January 2013: chemical characteristics, formation mechanism and role of fog processing

Severe haze hovered over large areas of China in January 2013 right after the public release of PM2.5 data of major cities in China at the very first time. This historical severe haze emerged over the northern China with monthly average concentrations of PM2.5, SO2, and NO2 exceeding 225, 200, and 80 μg m−3, respectively. Surface aerosol mean concentration of Beijing in January 2013 reached record high (only slightly lower than 2006) compared to historical data from 2003–2012, but with the largest daily fluctuation. Anomalous meteorological conditions in 2013 compared to the mean climatology from 2007–2012 were especially favorable for the formation of haze, such as higher humidity, lower temperature, lower PBL height, lower wind speed, and the high frequency of fog occurrences. The field campaign in Beijing showed an extremely high PM2.5 average concentration of 299.2 ± 79.1μg m−3 with extremely low visibility of 0.92 ± 0.82 km during an episode of high relative humidity with fog events. High AOD (Aerosol Optical Depth) was observed during fog days but with relatively low Angstrom exponent (< 1.0), suggesting the modification of fog processing on the particle size. Major aerosol chemical species, such as SO42−, NO3−, NH4+, Cl−, K+, and C2O42− presented an explicit exponential growth relationship with relative humidity, suggesting the significant impact of aerosol hygroscopicity on the visibility impairment. SO42− increased &sim;5 folds while NO3−, NH4+, and C2O42− increased &sim;3 folds in the fog days compared to the non-fog days. Aerosol in fog days was much more acidic than that in non-fog days. The in situ aerosol pH ranged from −0.78 to 0.14 in fog days based on the E-AIM model simulation. Bisulfate (HSO42−) accounted for 52% of the total sulfate and free hydrogen ion (H+Aq) accounted for 27% of the total acids in average. Enhanced coal combustion during the winter heating season along with traffic and industrial emissions were recognized to be the major causes for this severe haze. Fog processing was found to be the major pathway of producing extremely high yields of secondary inorganic aerosol and impacting the neutralization process (i.e. aerosol acidity) in this study.