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Effects of stratospheric ozone recovery on photochemistry and ozone air quality in the troposphere

There has been significant stratospheric ozone depletion since the late 1970s due to ozone-depleting substances (ODSs). With the implementation of the Montreal Protocol and its amendments and adjustments, stratospheric ozone is expected to recover towards its pre-1980 level in the coming decades. In this study, we examine the implications of stratospheric ozone recovery for the tropospheric chemistry and ozone air quality with a global chemical transport model (GEOS-Chem). With a full recovery of the stratospheric ozone, the projected increases in ozone column range from 1% over the low latitudes to more than 10% over the polar regions. The sensitivity factor of troposphere ozone photolysis rate, defined as the percentage changes in surface ozone photolysis rate for 1% increase in stratospheric ozone column, shows significant seasonal variation but is always negative with absolute value larger than one. The expected stratospheric ozone recovery is found to affect the tropospheric ozone destruction rates much more than the ozone production rates. Significant decreases in surface ozone photolysis rates due to stratospheric ozone recovery are simulated. The global average tropospheric OH decreases by 1.7%, and the global average lifetime of tropospheric ozone increases by 1.5%. The perturbations to tropospheric ozone and surface ozone show large seasonal and spatial variations. General increases in surface ozone are calculated for each season, with increases by up to 0.8 ppbv in the remote areas. Increases in ozone lifetime by up to 13% are found in the troposphere. The increased lifetimes of tropospheric ozone in response to stratospheric ozone recovery enhance the intercontinental transport of ozone and global pollution, in particular for the summertime. The global background ozone attributable to Asian emissions is calculated to increase by up to 15% or 0.3 ppbv in the Northern Hemisphere in response to the projected stratospheric ozone recovery.
Local impact of solar variation on NO2 in the lower mesosphere and upper stratosphere from 2007 to 2012

MIPAS/ENVISAT data of nighttime NO2 volume mixing ratios (VMR) from 2007 until 2012 between 40 km and 62 km altitude are compared with the geomagnetic Ap index and solar Lyman-α radiation. The local impact of variations in geomagnetic activity and solar radiation on the VMR of NO2 in the lower mesosphere and upper stratosphere in the Northern Hemisphere is investigated by means of superposed epoch analysis. Observations in the Northern Hemisphere show a clear 27-day period of the NO2 VMR. This is positively correlated with the geomagnetic Ap index at 60–70° N geomagnetic latitude but also partially correlated with the solar Lyman-α radiation. However, the dependency of NO2 VMR on geomagnetic activity can be distinguished from the impact of solar radiation. This indicates a direct response of NOx (NO + NO2) to geomagnetic activity, probably due to precipitating particles. The response is detected in the range between 46 km and 52 km altitude. The NO2 VMR epoch maxima due to geomagnetic activity is altitude-dependent and can reach up to 0.4 ppb, leading to mean production rates of 0.029 ppb (Ap d)−1. Observations in the Southern Hemisphere do not have the same significance due to a worse sampling of geomagnetic storm occurances. Variabilities due to solar variation occur at the same altitudes at 60–70° S geomagnetic latitude but cannot be analyzed as in the Northern Hemisphere. This is the first study showing the direct impact of electron precipitation on NOx at those altitudes in the spring/summer/autumn hemisphere.
Air–snowpack exchange of bromine, ozone and mercury in the springtime Arctic simulated by the 1-D model PHANTAS – Part 1: In-snow bromine activation and its impact on ozone

To provide a theoretical framework towards a better understanding of ozone depletion events (ODEs) and atmospheric mercury depletion events (AMDEs) in the polar boundary layer, we have developed a one-dimensional model that simulates multiphase chemistry and transport of trace constituents from porous snowpack and through the atmospheric boundary layer (ABL) as a unified system. This paper constitutes Part 1 of the study, describing a general configuration of the model and the results of simulations related to reactive bromine release from the snowpack and ODEs during the Arctic spring. A common set of aqueous-phase reactions describes chemistry both within the liquid-like layer (LLL) on the grain surface of the snowpack and within deliquesced "haze" aerosols mainly composed of sulfate in the atmosphere. Gas-phase reactions are also represented by the same mechanism in the atmosphere and in the snowpack interstitial air (SIA). Consequently, the model attains the capacity of simulating interactions between chemistry and mass transfer that become particularly intricate near the interface between the atmosphere and the snowpack. In the SIA, reactive uptake on LLL-coated snow grains and vertical mass transfer act simultaneously on gaseous HOBr, a fraction of which enters from the atmosphere while another fraction is formed via gas-phase chemistry in the SIA itself. A "bromine explosion", by which HOBr formed in the ambient air is deposited and then converted heterogeneously to Br2, is found to be a dominant process of reactive bromine formation in the top 1 mm layer of the snowpack. Deeper in the snowpack, HOBr formed within the SIA leads to an in-snow bromine explosion, but a significant fraction of Br2 is also produced via aqueous radical chemistry in the LLL on the surface of the snow grains. These top- and deeper-layer productions of Br2 both contribute to the release of Br2 to the atmosphere, but the deeper-layer production is found to be more important for the net outflux of reactive bromine. Although ozone is removed via bromine chemistry, it is also among the key species that control both the conventional and in-snow bromine explosions. On the other hand, aqueous-phase radical chemistry initiated by photolytic OH formation in the LLL is also a significant contributor to the in-snow source of Br2 and can operate without ozone, whereas the delivery of Br2 to the atmosphere becomes much smaller after ozone is depleted. Catalytic ozone loss via bromine radical chemistry occurs more rapidly in the SIA than in the ambient air, giving rise to apparent dry deposition velocities for ozone from the air to the snow on the order of 10−3 cm s−1 during daytime. Overall, however, the depletion of ozone in the system is caused predominantly by ozone loss in the ambient air. Increasing depth of the turbulent ABL under windy conditions will delay the buildup of reactive bromine and the resultant loss of ozone, while leading to the higher column amount of BrO in the atmosphere. During the Arctic spring, if moderately saline and acidic snowpack is as prevalent as assumed in our model runs on sea ice, the shallow, stable ABL under calm weather conditions may undergo persistent ODEs without substantial contributions from blowing/drifting snow and wind-pumping mechanisms, whereas the column densities of BrO in the ABL will likely remain too low in the course of such events to be detected unambiguously by satellite nadir measurements.
Aircraft measurements of polar organic tracer compounds in tropospheric particles (PM10) over central China

Atmospheric aerosol samples were collected by aircraft at low to middle altitudes (0.8–3.5 km a.g.l.) over central East to West China during summer 2003 and spring 2004. The samples were analyzed for polar organic compounds using a technique of solvent extraction/BSTFA derivatization/gas chromatography–mass spectrometry. Biogenic secondary organic aerosol (SOA) tracers from the oxidation of isoprene were found to be more abundant in summer (3.3–138 ng m−3, mean 39 ng m−3) than in spring (3.2–42 ng m−3, 15 ng m−3), while α/β-pinene and β-caryophyllene SOA tracers showed similar abundances between these two seasons. A strong positive correlation (R2 = 0.83) between levoglucosan and β-caryophyllinic acid was found in the spring samples vs. a weak correlation (R2 = 0.17) in the summer samples, implying substantial contributions from biomass burning to the β-caryophyllinic acid production in spring. Two organic nitrogen species (oxamic acid and carbamide) were detected in the aircraft aerosol samples, and their concentrations were comparable to those of biogenic SOA tracers. Most of the primary organic aerosol (POA) and SOA tracers were less abundant at higher altitudes, suggesting they are of ground surface origin, either being directly emitted from anthropogenic/natural sources on the ground surface, or rapidly formed through photooxidation of their precursors emitted from the ground surface and then diluted during uplifting into the troposphere. This study demonstrates that primary biological aerosols, biogenic SOA, and organic nitrogen species are important components of organic aerosols in the troposphere over central China during warm seasons.
Impacts of fire emissions and transport pathways on the interannual variation of CO in the tropical upper troposphere

This study investigates the impacts of fire emission, convection, various climate conditions and transport pathways on the interannual variation of carbon monoxide (CO) in the tropical upper troposphere (UT), by evaluating the field correlation between these fields using multi-satellite observations and principle component analysis, and the transport pathway auto-identification method developed in our previous study. The rotated empirical orthogonal function (REOF) and singular value decomposition (SVD) methods are used to identify the dominant modes of CO interannual variation in the tropical UT and to study the coupled relationship between UT CO and its governing factors. Both REOF and SVD results confirm that Indonesia is the most significant land region that affects the interannual variation of CO in the tropical UT, and El Niño–Southern Oscillation (ENSO) is the dominant climate condition that affects the relationships between surface CO emission, convection and UT CO. In addition, our results also show that the impact of El Niño on the anomalous CO pattern in the tropical UT varies strongly, primarily due to different anomalous emission and convection patterns associated with different El Niño events. In contrast, the anomalous CO pattern in the tropical UT during La Niña period appears to be less variable among different events. Transport pathway analysis suggests that the average CO transported by the "local convection" pathway (ΔCOlocal) accounts for the differences of UT CO between different ENSO phases over the tropical continents during biomass burning season. ΔCOlocal is generally higher over Indonesia–Australia and lower over South America during El Niño years than during La Niña years. The other pathway ("advection within the lower troposphere followed by convective vertical transport") occurs more frequently over the west-central Pacific during El Niño years than during La Niña years, which may account for the UT CO differences over this region between different ENSO phases.
Dimers in α-pinene secondary organic aerosol: effect of hydroxyl radical, ozone, relative humidity and aerosol acidity

The formation of secondary organic aerosol (SOA) from both ozonolysis and hydroxyl radical (OH)-initiated oxidation of α-pinene under conditions of high nitric oxide (NO) concentrations with varying relative humidity (RH) and aerosol acidity was investigated in the University of North Carolina dual outdoor smog chamber facility. SOA formation from ozonolysis of α-pinene was enhanced relative to that from OH-initiated oxidation in the presence of initially high-NO conditions. However, no effect of RH on SOA mass was evident. Ozone (O3)-initiated oxidation of α-pinene in the presence of ammonium sulfate (AS) seed coated with organic aerosol from OH-initiated oxidation of α-pinene showed reduced nucleation compared to ozonolysis in the presence of pure AS seed aerosol. The chemical composition of α-pinene SOA was investigated by ultra-performance liquid chromatography/electrospray ionization high-resolution quadrupole time-of-flight mass spectrometry (UPLC/ESI-HR-Q-TOFMS), with a focus on the formation of carboxylic acids and high-molecular weight dimers. A total of eight carboxylic acids and four dimers were identified, constituting between 8 and 12% of the total α-pinene SOA mass. OH-initiated oxidation of α-pinene in the presence of nitrogen oxides (NOx) resulted in the formation of highly oxidized carboxylic acids, such as 3-methyl-1,2,3-butanetricarboxylic acid (MBTCA) and diaterpenylic acid acetate (DTAA). The formation of dimers was observed only in SOA produced from the ozonolysis of α-pinene in the absence of NOx, with increased concentrations by a factor of two at higher RH (50–90%) relative to lower RH (30–50%). The increased formation of dimers correlates with an observed increase in new particle formation at higher RH due to nucleation. Increased aerosol acidity was found to have a negligible effect on the formation of the dimers. SOA mass yield did not influence the chemical composition of SOA formed from α-pinene ozonolysis with respect to carboxylic acids and dimers. The results support the formation of the high-molecular weight dimers through gas-phase reactions of the stabilized Criegee Intermediate (sCI) formed from the ozonolysis of α-pinene. The high molecular weight and polar nature of dimers formed in the gas phase may explain increased particle number concentration as a result of homogenous nucleation. Since three of these dimers (i.e. pinyl-diaterpenyl dimer (MW 358), pinyl-diaterebyl dimer (MW 344) and pinonyl-pinyl dimer (MW 368)) have been observed in both laboratory-generated and ambient fine organic aerosol samples, we conclude that the dimers observed in this study can be used as tracers for the O3-initiated oxidation of α-pinene, and are therefore indicative of enhanced anthropogenic activities, and that the high molecular weight and low volatility dimers result in homogenous nucleation under laboratory conditions, increasing the particle number concentration.
Snow cover sensitivity to black carbon deposition in the Himalayas: from atmospheric and ice core measurements to regional climate simulations

We applied a climate-chemistry global model to evaluate the impact of black carbon (BC) deposition on the Himalayan snow cover from 1998 to 2008. Using a stretched grid with a resolution of 50 km over this complex topography, the model reproduces reasonably well the remotely sensed observations of the snow cover duration. Similar to observations, modelled atmospheric BC concentrations in the central Himalayas reach a minimum during the monsoon and a maximum during the post- and pre-monsoon periods. Comparing the simulated BC concentrations in the snow with observations is more challenging because of their high spatial variability and complex vertical distribution. We simulated spring BC concentrations in surface snow varying from tens to hundreds of μg kg−1, higher by one to two orders of magnitude than those observed in ice cores extracted from central Himalayan glaciers at high elevations (>6000 m a.s.l.), but typical for seasonal snow cover sampled in middle elevation regions (<6000 m a.s.l.). In these areas, we estimate that both wet and dry BC depositions affect the Himalayan snow cover reducing its annual duration by 1 to 8 days. In our simulations, the effect of anthropogenic BC deposition on snow is quite low over the Tibetan Plateau because this area is only sparsely snow covered. However, the impact becomes larger along the entire Hindu-Kush, Karakorum and Himalayan mountain ranges. In these regions, BC in snow induces an increase of the net short-wave radiation at the surface with an annual mean of 1 to 3 W m−2 leading to a localised warming between 0.05 and 0.3 °C.
CLAAS: the CM SAF cloud property data set using SEVIRI

An 8-year record of satellite-based cloud properties named CLAAS (CLoud property dAtAset using SEVIRI) is presented, which was derived within the EUMETSAT Satellite Application Facility on Climate Monitoring. The data set is based on SEVIRI measurements of the Meteosat Second Generation satellites, of which the visible and near-infrared channels were intercalibrated with MODIS. Applying two state-of-the-art retrieval schemes ensures high accuracy in cloud detection, cloud vertical placement and microphysical cloud properties. These properties were further processed to provide daily to monthly averaged quantities, mean diurnal cycles and monthly histograms. In particular, the per-month histogram information enhances the insight in spatio-temporal variability of clouds and their properties. Due to the underlying intercalibrated measurement record, the stability of the derived cloud properties is ensured, which is exemplarily demonstrated for three selected cloud variables for the entire SEVIRI disc and a European subregion. All data products and processing levels are introduced and validation results indicated. The sampling uncertainty of the averaged products in CLAAS is minimized due to the high temporal resolution of SEVIRI. This is emphasized by studying the impact of reduced temporal sampling rates taken at typical overpass times of polar-orbiting instruments. In particular, cloud optical thickness and cloud water path are very sensitive to the sampling rate, which in our study amounted to systematic deviations of over 10% if only sampled once a day. The CLAAS data set facilitates many cloud related applications at small spatial scales of a few kilometres and short temporal scales of a~few hours. Beyond this, the spatiotemporal characteristics of clouds on diurnal to seasonal, but also on multi-annual scales, can be studied.
Three years of aerosol mass, black carbon and particle number concentrations at Montsec (southern Pyrenees, 1570 m a.s.l.)

Time variation of mass particulate matter (PM1 and PM1&minus10), black carbon (BC) and number of particles (N3: number of particles with an aerodynamic diameter higher than 3 nm, and N10: higher than 10 nm) concentrations at the high-altitude site of Montsec (MSC) in the southern Pyrenees was interpreted for the period 2010–2012. At MSC, PM10 (12 μg m−3) and N7 (2140 # cm−3) three-year arithmetic average concentrations were higher than those measured at other high-altitude sites in central Europe during the same period (PM10: 3–9 μg m−3 and N: 634–2070 # cm−3). By contrast, BC concentrations at MSC (0.2 μg m−3) were equal to or even lower than those measured at these European sites (0.2–0.4 μg m−3). These differences were attributed to the higher relevance of Saharan dust transport and to the higher importance of the biogenic precursor emissions and new particle formation (NPF) processes, and to the lower influence of anthropogenic emissions at MSC. The different time variation of PM and BC concentrations compared with that of N suggests that these aerosol parameters were governed by diverse factors at MSC. Both PM and BC concentrations showed marked differences for different meteorological scenarios, with enhanced concentrations under North African air outbreaks (PM1&minus10: 13 μg m−3, PM1: 8 μg m−3 and BC: 0.3 μg m−3) and low concentrations when Atlantic advections occurred (PM1−10: 5 μg m−3, PM1: 4 μg m−3 and BC: 0.1 μg m−3). PM and BC concentrations increased in summer, with a secondary maximum in early spring, and were at their lowest in winter, due to the contrasting origin of the air masses in the warmer seasons (spring and summer) and in the colder seasons (autumn and winter). The maximum in the warmer seasons was attributed to long-range transport processes that mask the breezes and regional transport breaking the daily cycles of these pollutants. By contrast, PM and BC concentrations showed clear diurnal cycles, with maxima at midday in the colder seasons. A statistically significant weekly variation was also obtained for the BC concentrations, displaying a progressive increase from Tuesday to Saturday, followed by a significant decrease on Sunday and Monday. N concentrations depended more on local meteorological variables such as temperature and solar radiation intensity than on the origin of the air mass. Therefore, arithmetic averages as a function of meteorological episodes showed the highest concentrations of N during summer regional episodes (N3: 4461 # cm−3 and N7: 3021 # cm−3) and the lowest concentrations during winter regional scenarios (N3: 2496 # cm−3 and N7: 1073 # cm−3). This dependence on temperature and solar radiation also accounted for the marked diurnal cycle of N concentrations throughout the year, with a peak at midday and for the absence of a weekly pattern. Measurements carried out at MSC enabled us to characterize the tropospheric background aerosols in the western Mediterranean basin (WMB). Our results highlight the importance of the NPF processes in southern Europe, underline the high contribution of long-range dust transport with respect to central Europe and its prevalence in elevated layers, and reveal that MSC is much less affected by anthropogenic emissions than other high-altitude sites in central Europe.
Quantification of hydroxyacetone and glycolaldehyde using chemical ionization mass spectrometry

Chemical ionization mass spectrometry (CIMS) enables online, rapid, in situ detection and quantification of hydroxyacetone and glycolaldehyde. Two different CIMS approaches are demonstrated employing the strengths of single quadrupole mass spectrometry and triple quadrupole (tandem) mass spectrometry. Both methods are generally capable of the measurement of hydroxyacetone, an analyte with known but minimal isobaric interferences. Tandem mass spectrometry provides direct separation of the isobaric compounds glycolaldehyde and acetic acid using distinct, collision-induced dissociation daughter ions. The single quadrupole CIMS measurement of glycolaldehyde was demonstrated during the ARCTAS-CARB (Arctic Research of the Composition of the Troposphere from Aircraft and Satellites - California Air Resources Board) 2008 campaign, while triple quadrupole CIMS measurements of glycolaldehyde and hydroxyacetone were demonstrated during the BEARPEX (Biosphere Effects on Aerosols and Photochemistry Experiment) 2009 campaign. Enhancement ratios of glycolaldehyde in ambient biomass-burning plumes are reported for the ARCTAS-CARB campaign. BEARPEX observations are compared to simple photochemical box model predictions of biogenic volatile organic compound oxidation at the site.