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Limited effect of anthropogenic nitrogen oxides on secondary organic aerosol formation

Globally, secondary organic aerosol (SOA) is mostly formed from emissions of biogenic volatile organic compounds (VOCs) by vegetation, but it can be modified by human activities as demonstrated in recent research. Specifically, nitrogen oxides (NOx = NO + NO2) have been shown to play a critical role in the chemical formation of low volatility compounds. We have updated the SOA scheme in the global NCAR (National Center for Atmospheric Research) Community Atmospheric Model version 4 with chemistry (CAM4-chem) by implementing a 4-product volatility basis set (VBS) scheme, including NOx-dependent SOA yields and aging parameterizations. Small differences are found for the no-aging VBS and 2-product schemes; large increases in SOA production and the SOA-to-OA ratio are found for the aging scheme. The predicted organic aerosol amounts capture both the magnitude and distribution of US surface annual mean measurements from the Interagency Monitoring of Protected Visual Environments (IMPROVE) network by 50 %, and the simulated vertical profiles are within a factor of 2 compared to aerosol mass spectrometer (AMS) measurements from 13 aircraft-based field campaigns across different regions and seasons. We then perform sensitivity experiments to examine how the SOA loading responds to a 50 % reduction in anthropogenic nitric oxide (NO) emissions in different regions. We find limited SOA reductions of 0.9–5.6, 6.4–12.0 and 0.9–2.8 % for global, southeast US and Amazon NOx perturbations, respectively. The fact that SOA formation is almost unaffected by changes in NOx can be largely attributed to a limited shift in chemical regime, to buffering in chemical pathways (low- and high-NOx pathways, O3 versus NO3-initiated oxidation) and to offsetting tendencies in the biogenic versus anthropogenic SOA responses.
Viscous organic aerosol particles in the upper troposphere: diffusivity-controlled water uptake and ice nucleation?

New measurements of water diffusion in secondary organic aerosol (SOA) material produced by oxidation of α-pinene and in a number of organic/inorganic model mixtures (3-methylbutane-1,2,3-tricarboxylic acid (3-MBTCA), levoglucosan, levoglucosan/NH4HSO4, raffinose) are presented. These indicate that water diffusion coefficients are determined by several properties of the aerosol substance and cannot be inferred from the glass transition temperature or bouncing properties. Our results suggest that water diffusion in SOA particles is faster than often assumed and imposes no significant kinetic limitation on water uptake and release at temperatures above 220 K. The fast diffusion of water suggests that heterogeneous ice nucleation on a glassy core is very unlikely in these systems. At temperatures below 220 K, model simulations of SOA particles suggest that heterogeneous ice nucleation may occur in the immersion mode on glassy cores which remain embedded in a liquid shell when experiencing fast updraft velocities. The particles absorb significant quantities of water during these updrafts which plasticize their outer layers such that these layers equilibrate readily with the gas phase humidity before the homogeneous ice nucleation threshold is reached. Glass formation is thus unlikely to restrict homogeneous ice nucleation. Only under most extreme conditions near the very high tropical tropopause may the homogeneous ice nucleation rate coefficient be reduced as a consequence of slow condensed-phase water diffusion. Since the differences between the behavior limited or non limited by diffusion are small even at the very high tropical tropopause, condensed-phase water diffusivity is unlikely to have significant consequences on the direct climatic effects of SOA particles under tropospheric conditions.
Viscosity controls humidity dependence of N2O5 uptake to citric acid aerosol

The heterogeneous loss of dinitrogen pentoxide (N2O5) to aerosol particles has a significant impact on the night-time nitrogen oxide cycle and therefore the oxidative capacity in the troposphere. Using a 13N short-lived radioactive tracer method, we studied the uptake kinetics of N2O5 on citric acid aerosol particles as a function of relative humidity (RH). The results show that citric acid exhibits lower reactivity than similar dicarboxylic and polycarboxylic acids, with uptake coefficients between &sim; 3 × 10-4–&sim; 3 × 10-3 depending on humidity (17–70 % RH). At RH above 50 %, the magnitude and the humidity dependence can be best explained by the viscosity of citric acid as compared to aqueous solutions of simpler organic and inorganic solutes and the variation of viscosity with RH and, hence, diffusivity in the organic matrix. Since the diffusion rates of N2O5 in highly concentrated citric acid solutions are not well established, we present four different parameterizations of N2O5 diffusivity based on the available literature data or estimates for viscosity and diffusivity of H2O. Above 50 % RH, uptake is consistent with the reacto-diffusive kinetic regime whereas below 50 % RH, the uptake coefficient is higher than expected from hydrolysis of N2O5 within the bulk of the particles, and the uptake kinetics is most likely limited by loss on the surface only. This study demonstrates the impact of viscosity in highly oxidized and highly functionalized secondary organic aerosol material on the heterogeneous chemistry of N2O5 and may explain some of the unexpectedly low loss rates to aerosol derived from field studies.
Impact of future land-cover changes on HNO3 and O3 surface dry deposition

Dry deposition is a key component of surface–atmosphere exchange of compounds, acting as a sink for several chemical species. Meteorological factors, chemical properties of the trace gas considered and land surface properties are strong drivers of dry deposition efficiency and variability. Under both climatic and anthropogenic pressure, the vegetation distribution over the Earth has been changing a lot over the past centuries and could be significantly altered in the future. In this study, we perform a modeling investigation of the potential impact of land-cover changes between the present day (2006) and the future (2050) on dry deposition velocities at the surface, with special interest for ozone (O3) and nitric acid (HNO3), two compounds which are characterized by very different physicochemical properties. The 3-D chemistry-transport model LMDz-INCA is used, considering changes in vegetation distribution based on the three future projections, RCPs 2.6, 4.5 and 8.5, and present-day (2007) meteorology. The 2050 RCP 8.5 vegetation distribution leads to a rise of up to 7 % (+0.02 cm s−1) in the surface deposition velocity calculated for ozone (Vd,O3) and a decrease of −0.06 cm s−1 in the surface deposition velocity calculated for nitric acid (Vd,HNO3) relative to the present-day values in tropical Africa and up to +18 and −15 %, respectively, in Australia. When taking into account the RCP 4.5 scenario, which shows dramatic land-cover change in Eurasia, Vd,HNO3 increases by up to 20 % (annual-mean value) and reduces Vd,O3 by the same magnitude in this region. When analyzing the impact of surface dry deposition change on atmospheric chemical composition, our model calculates that the effect is lower than 1 ppb on annual-mean surface ozone concentration for both the RCP 8.5 and RCP 2.6 scenarios. The impact on HNO3 surface concentrations is more disparate between the two scenarios regarding the spatial repartition of effects. In the case of the RCP 4.5 scenario, a significant increase of the surface O3 concentration reaching locally by up to 5 ppb (+5 %) is calculated on average during the June–August period. This scenario also induces an increase of HNO3 deposited flux exceeding locally 10 % for monthly values. Comparing the impact of land-cover change to the impact of climate change, considering a 0.93 °C increase of global temperature, on dry deposition velocities, we estimate that the strongest increase over lands occurs in the Northern Hemisphere during winter, especially in Eurasia, by +50 % (+0.07 cm s−1) for Vd,O3 and +100 % (+0.9 cm s−1) for Vd,HNO3. However, different regions are affected by both changes, with climate change impact on deposition characterized by a latitudinal gradient, while the land-cover change impact is much more heterogeneous depending on vegetation distribution modification described in the future RCP scenarios. The impact of long-term land-cover changes on dry deposition is shown to be significant and to differ strongly from one scenario to another. It should therefore be considered in biosphere–atmospheric chemistry interaction studies in order to have a fully consistent picture.
OMI tropospheric NO2 profiles from cloud slicing: constraints on surface emissions, convective transport and lightning NOx

We derive annual and seasonal global climatologies of tropospheric NO2 profiles from OMI cloudy observations for the year 2006 using the cloud-slicing method on six pressure levels centered at about 280, 380, 500, 620, 720 and 820 hPa. A comparison between OMI and the TM4 model tropospheric NO2 profiles reveals striking overall similarities, which confer great confidence to the cloud-slicing approach to provide details that pertain to annual as well as seasonal means, along with localized discrepancies that seem to probe into particular model processes. Anomalies detected at the lowest levels can be traced to deficiencies in the model surface emission inventory, at mid-tropospheric levels to convective transport and horizontal advective diffusion, and at the upper tropospheric levels to model lightning NOx production and the placement of deeply transported NO2 plumes such as from the Asian summer monsoon. The vertical information contained in the OMI cloud-sliced NO2 profiles provides a global observational constraint that can be used to evaluate chemistry transport models (CTMs) and guide the development of key parameterization schemes.
Global temperature response to the major volcanic eruptions in multiple reanalysis data sets

The global temperature responses to the eruptions of Mount Agung in 1963, El Chichón in 1982, and Mount Pinatubo in 1991 are investigated using nine currently available reanalysis data sets (JRA-55, MERRA, ERA-Interim, NCEP-CFSR, JRA-25, ERA-40, NCEP-1, NCEP-2, and 20CR). Multiple linear regression is applied to the zonal and monthly mean time series of temperature for two periods, 1979–2009 (for eight reanalysis data sets) and 1958–2001 (for four reanalysis data sets), by considering explanatory factors of seasonal harmonics, linear trends, Quasi-Biennial Oscillation, solar cycle, and El Niño Southern Oscillation. The residuals are used to define the volcanic signals for the three eruptions separately, and common and different responses among the older and newer reanalysis data sets are highlighted for each eruption. In response to the Mount Pinatubo eruption, most reanalysis data sets show strong warming signals (up to 2–3 K for 1-year average) in the tropical lower stratosphere and weak cooling signals (down to −1 K) in the subtropical upper troposphere. For the El Chichón eruption, warming signals in the tropical lower stratosphere are somewhat smaller than those for the Mount Pinatubo eruption. The response to the Mount Agung eruption is asymmetric about the equator with strong warming in the Southern Hemisphere midlatitude upper troposphere to lower stratosphere. Comparison of the results from several different reanalysis data sets confirms the atmospheric temperature response to these major eruptions qualitatively, but also shows quantitative differences even among the most recent reanalysis data sets. The consistencies and differences among different reanalysis data sets provide a measure of the confidence and uncertainty in our current understanding of the volcanic response. The results of this intercomparison study may be useful for validation of climate model responses to volcanic forcing and for assessing proposed geoengineering by stratospheric aerosol injection, as well as to link studies using only a single reanalysis data set to other studies using a different reanalysis data set.
Spatial and temporal variations of the concentrations of PM10, PM2.5 and PM1 in China

Concentrations of PM10, PM2.5 and PM1 were monitored at 24 CAWNET (China Atmosphere Watch Network) stations from 2006 to 2014. The highest particulate matter (PM) concentrations were observed at the stations of Xian, Zhengzhou and Gucheng, on the Guanzhong Plain and the Huabei Plain (HBP). The second highest PM concentrations were observed in northeast China, followed by southern China. According to the latest air quality standards of China, 14 stations reached the PM10 standard, and only 7 stations, mainly rural and remote stations, reached the PM2.5 standard. The ratios of PM2.5 to PM10 showed a clear increasing trend from northern to southern China, because of the substantial contribution of coarse mineral aerosol in northern China. The ratios of PM1 to PM2.5 were higher than 80 % at most stations. PM concentrations tended to be highest in winter and lowest in summer at most stations, and mineral dust influenced the results in spring. A decreasing interannual trend was observed on the HBP and in southern China for the period 2006 to 2014, but an increasing trend occurred at some stations in northeast China. Bimodal and unimodal diurnal variation patterns were identified at urban stations. Both emissions and meteorological variations dominate the long-term PM concentration trend, while meteorological factors play a leading role in the short term.
Reactive uptake of ammonia to secondary organic aerosols: kinetics of organonitrogen formation

As a class of brown carbon, organonitrogen compounds originating from the heterogeneous uptake of NH3 by secondary organic aerosol (SOA) have received significant attention recently. In the current work, particulate organonitrogen formation during the ozonolysis of α-pinene and the OH oxidation of m-xylene in the presence of ammonia (34–125 ppb) was studied in a smog chamber equipped with a high resolution time-of-flight aerosol mass spectrometer and a quantum cascade laser instrument. A large diversity of nitrogen-containing organic (NOC) fragments was observed which were consistent with the reactions between ammonia and carbonyl-containing SOA. Ammonia uptake coefficients onto SOA which led to organonitrogen compounds were reported for the first time, and were in the range of &sim; 10-3–10−2, decreasing significantly to < 10-5 after 6 h of reaction. At the end of experiments (~ 6 h) the NOC mass contributed 8.9 ± 1.7 and 31.5 ± 4.4 wt % to the total α-pinene- and m-xylene-derived SOA, respectively, and 4–15 wt % of the total nitrogen in the system. Uptake coefficients were also found to be positively correlated with particle acidity and negatively correlated with NH3 concentration, indicating that heterogeneous reactions were responsible for the observed NOC mass, possibly limited by liquid phase diffusion. Under these conditions, the data also indicate that the formation of NOC can compete kinetically with inorganic acid neutralization. The formation of NOC in this study suggests that a significant portion of the ambient particle associated N may be derived from NH3 heterogeneous reactions with SOA. NOC from such a mechanism may be an important and unaccounted for source of PM associated nitrogen. This mechanism may also contribute to the medium or long-range transport and wet/dry deposition of atmospheric nitrogen.
Contributions of dust and biomass burning to aerosols at a Colorado mountain-top site

Visible Multifilter Rotating Shadowband Radiometer (vis-MFRSR) data were collected at Storm Peak Laboratory (SPL), a mountain-top facility in northwest Colorado, from 1999 to 2011 and in 2013. From 2011 to 2014, in situ measurements of aerosol light scattering were also obtained. Using these data sets together, the seasonal impact of dust and biomass burning is considered for the western USA. Analysis indicates that the median contributions to spring and summer aerosol optical depth (AOD) from dust and biomass-burning aerosols across the data set are comparable. The mean AOD is slightly greater in the summer, with significantly more frequent and short-duration high AOD measurements due to biomass-burning episodes than in the spring. The Ångström exponent showed a significant increase in the summer for both the in situ and vis-MFRSR data, suggesting an increase in combustion aerosols. Spring dust events are less distinguishable in the in situ data than the column measurement, suggesting that a significant amount of dust may be found above the elevation of SPL, 3220 m a.s.l. Twenty-two known case studies of intercontinental dust, regional dust, and biomass-burning events were investigated. These events were found to follow a similar pattern, in both aerosol loading and Ångström exponent, as the seasonal mean signal in both the vis-MFRSR and ground-based nephelometer. This data set highlights the wide-scale implications of a warmer, drier climate on visibility in the western USA.
Oceanic bromoform emissions weighted by their ozone depletion potential

At present, anthropogenic halogens and oceanic emissions of very short-lived substances (VSLSs) both contribute to the observed stratospheric ozone depletion. Emissions of the long-lived anthropogenic halogens have been reduced and are currently declining, whereas emissions of the biogenic VSLSs are expected to increase in future climate due to anthropogenic activities affecting oceanic production and emissions. Here, we introduce a new approach for assessing the impact of oceanic halocarbons on stratospheric ozone by calculating their ozone depletion potential (ODP)-weighted emissions. Seasonally and spatially dependent, global distributions are derived within a case-study framework for CHBr3 for the period 1999–2006. At present, ODP-weighted emissions of CHBr3 amount up to 50 % of ODP-weighted anthropogenic emissions of CFC-11 and to 9 % of all long-lived ozone depleting halogens. The ODP-weighted emissions are large where strong oceanic emissions coincide with high-reaching convective activity and show pronounced peaks at the Equator and the coasts with largest contributions from the Maritime Continent and western Pacific Ocean. Variations of tropical convective activity lead to seasonal shifts in the spatial distribution of the trajectory-derived ODP with the updraught mass flux, used as a proxy for trajectory-derived ODP, explaining 71 % of the variance of the ODP distribution. Future climate projections based on the RCP 8.5 scenario suggest a 31 % increase of the ODP-weighted CHBr3 emissions by 2100 compared to present values. This increase is related to a larger convective updraught mass flux in the upper troposphere and increasing emissions in a future climate. However, at the same time, it is reduced by less effective bromine-related ozone depletion due to declining stratospheric chlorine concentrations. The comparison of the ODP-weighted emissions of short- and long-lived halocarbons provides a new concept for assessing the overall impact of oceanic halocarbon emissions on stratospheric ozone depletion for current conditions and future projections.