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In order to use high resolution in-situ measurements to constrain regional emissions of carbon dioxide (CO<sub>2</sub>), we use a Lagrangian methodology based on diffusive backward trajectory tracer reconstructions. We use aircraft, tall tower and ground sites for CO<sub>2</sub> data collected nearby the CO<sub>2</sub> emission hot spot of the Tokyo Bay Area during the CONTRAIL campaign, from the MRI/JMA Tsukuba tall tower and from the World Data Centre for Greenhouse Gases (WDCGG). We calculated Bayesian inversions based on EDGAR 4 and CDIAC a priori fluxes. Estimated fluxes for the Tokyo Bay Area for the analyzed period between 2005 and 2009 range between 4.80×10<sup>−7</sup> and 3.45×10<sup>−6</sup> kg<sub>CO<sub>2</sub></sub> m<sup>2</sup> s<sup>−1</sup> with significant time variations. Significant differences in retrieved fluxes of up to 21% were found when CONTRAIL measurements were added to the dataset. No significant trend was found in the time series of spatially averaged retrieved fluxes.
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The impact of aerosol composition on cloud condensation nuclei (CCN) activity were analyzed in this study based on field experiments carried out at downtown Tianjin, China in September 2010. In the experiments, the CCN measurements were performed at supersaturation (SS) of 0.1%, 0.2% and 0.4% using a thermal-gradient diffusion chamber (DMT CCNC), whereas the aerosol size distribution and composition were simultaneously measured with a TSI SMPS and an Aerodyne Aerosol Mass Spectrometer (AMS), respectively. The results show that the influence of aerosol composition on CCN activity is notable under low SS (0.1%), and their influence decreased with increasing SS. For example, under SS of 0.1%, the CCN activity increases from 4.5±2.6% to 12.8±6.1% when organics fraction decrease from 30–40% to 10–20%. The rate of increase reached up to 184%. While under SS of 0.4%, the CCN activity increases only from 35.7±19.0% to 46.5±12.3% correspondingly. The calculated <i>N</i><sub>CCN</sub> based on the size-resolved activation ratio and aerosol number size distribution correlated well with observed <i>N</i><sub>CCN</sub> at high SS (0.4%), but this consistence decreased with the falling of SS. The slopes of linear fitted lines between calculated and observed <i>N</i><sub>CCN</sub> are 0.708, 0.947, and 0.995 at SS of 0.1%, 0.2% and 0.4% respectively. Moreover, the stand deviation (SD) of calculated <i>N</i><sub>CCN</sub> increased with the decreasing of SS. A case study of CCN closure analyses indicated that the calculated error of <i>N</i><sub>CCN</sub> could reach up to 34% at SS of 0.1% if aerosol composition were not included, and the calculated error decreased with the raising of SS. It is decreased to 9% at SS of 0.2%, and further decreased to 4% at SS of 0.4%.
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The type of Polar stratospheric clouds (PSCs) as well as their temporal and spatial extent are important for the occurrence of heterogeneous reactions in the polar stratosphere. The formation of PSCs depends strongly on temperature. However, the mechanisms of the formation of solid PSCs are still poorly understood. Recent satellite studies of Antarctic PSCs have shown that their formation can be associated with deep-tropospheric clouds which have the ability to cool the lower stratosphere radiatively and/or adiabatically. In the present study, lidar measurements aboard the Cloud-Aerosol Lidar and Infrared Pathfinder Satellite Observation (CALIPSO) satellite were used to investigate whether the formation of Arctic PSCs can be associated with deep-tropospheric clouds as well. Deep-tropospheric cloud systems have a vertical extent of more than 6.5 km with a cloud top height above 7 km altitude. PSCs observed by CALIPSO during the Arctic winter 2007/2008 were classified according to their type (STS, NAT, or ice) and to the kind of underlying tropospheric clouds. Our analysis reveals that 172 out of 211 observed PSCs occurred in connection with tropospheric clouds. 72% of these 172 observed PSCs occurred above deep-tropospheric clouds. We also find that the type of PSC seems to be connected to the characteristics of the underlying tropospheric cloud system. During the Arctic winter 2007/2008 PSCs consisting of ice were mainly observed in connection with deep-tropospheric cloud systems while no ice PSC was detected above cirrus. Furthermore, we find no correlation between the occurrence of PSCs and the top temperature of tropospheric clouds. Thus, our findings suggest that Arctic PSC formation is connected to adiabatice cooling, i.e. dynamic effects rather than radiative cooling.
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Refractory black carbon aerosols (rBC) from biomass burning and fossil fuel combustion are deposited to the Antarctic ice sheet and preserve a history of emissions and long-range transport from low- and mid-latitudes. Antarctic ice core rBC records may thus provide information with respect to past combustion aerosol emissions and atmospheric circulation. Here, we present six East Antarctic ice core records of rBC concentrations and fluxes covering the last two centuries with approximately annual resolution (cal. yr. 1800 to 2000). The ice cores were drilled in disparate regions of the high East Antarctic ice sheet, at different elevations and net snow accumulation rates. Annual rBC concentrations were log-normally distributed and geometric means of annual concentrations ranged from 0.10 to 0.18 μg kg<sup>−1</sup>. Average rBC fluxes were determined over the time periods 1800 to 2000 and 1963 to 2000 and ranged from 3.4 to 15.5 μg m<sup>−2</sup> a<sup>−1</sup> and 3.6 to 21.8 μg m<sup>−2</sup> a<sup>−1</sup>, respectively. Geometric mean concentrations spanning 1800 to 2000 increased linearly with elevation at a rate of 0.025 μg kg<sup>−1</sup>/500 m. Spectral analysis of the records revealed significant decadal-scale variability, which at several sites was comparable to decadal ENSO variability.
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As a consequence of dynamically variable meteorological conditions, springtime Arctic ozone levels exhibit significant interannual variability in the lower stratosphere. In winter 2011, the polar vortex was strong and cold for an unusually long time. Our research site, located at Eureka, Nunavut, Canada (80.05° N, 86.42° W), was mostly inside the vortex from October 2010 until late March 2011. The Bruker 125HR Fourier transform infrared spectrometer installed at the Polar Environment Atmospheric Research Laboratory at Eureka acquired measurements from 23 February to 6 April during the 2011 Canadian Arctic Atmospheric Chemistry Experiment Validation Campaign. These measurements showed unusually low ozone, HCl, and HNO<sub>3</sub> total columns compared to the previous 14 yr. To remove dynamical effects, we normalized these total columns by the HF total column. The normalized values of the ozone, HCl, and HNO<sub>3</sub> total columns were smaller than those from previous years, and confirmed the occurrence of chlorine activation and chemical ozone depletion. To quantify the chemical ozone loss, a three-dimensional chemical transport model, SLIMCAT, and the passive subtraction method were used. The chemical ozone depletion was calculated as the mean percentage difference between the measured ozone and the SLIMCAT passive ozone, and was found to be 35%.
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This study evaluates the significance of glyoxal acting as an intermediate species leading to secondary organic aerosol (SOA) formation from aromatic hydrocarbon photooxidation under humid conditions. Rapid SOA formation from glyoxal uptake onto aqueous (NH<sub>4</sub>)<sub>2</sub>SO<sub>4</sub> seed particles is observed in agreement with previous studies; however, glyoxal did not partition significantly to SOA (with or without aqueous seed) during aromatic hydrocarbon photooxidation within an environmental chamber (RH less than 80%). Rather, glyoxal influences SOA formation by raising hydroxyl (OH) radical concentrations. Four experimental approaches supporting this conclusion are presented in this paper: (1) increased SOA formation and decreased SOA volatility in the toluene + NO<sub>x</sub> photooxidation system with additional glyoxal was reproduced by matching OH radical concentrations through H<sub>2</sub>O<sub>2</sub> addition; (2) glyoxal addition to SOA seed formed from toluene + NO<sub>x</sub> photooxidation did not increase SOA volume under dark; (3) SOA formation from toluene + NO<sub>x</sub> photooxidation with and without deliquesced (NH<sub>4</sub>)<sub>2</sub>SO<sub>4</sub> seed resulted in similar SOA growth, consistent with a minor contribution from glyoxal uptake onto deliquesced seed and organic coatings; and (4) the fraction of a C<sub>4</sub>H<sub>9</sub><sup>+</sup> fragment (observed by Aerodyne High Resolution Time-of-Flight Aerosol Mass Spectrometer, HR-ToF-AMS) in SOA from 2-tert-butylphenol (BP) oxidation was unchanged in the presence of additional glyoxal despite enhanced SOA formation. This study suggests that glyoxal uptake onto aerosol during the oxidation of aromatic hydrocarbons is more limited than previously thought.
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In the past decades, regional air pollution characterized by photochemical smog and grey haze-fog has become a severe environmental problem in China. To investigate this, a field measurement campaign was performed in the Huabei region, located between 32–42° N latitude in eastern China, during the period 2 April–16 May 2006 as part of the project "Influence of Pollution on Aerosols and Cloud Microphysics in North China" (IPAC-NC). It appeared that strong pollution emissions from urban and industrial centers tend to accumulate in the lower atmosphere over the central area of Huabei. We observed widespread, very high SO<sub>2</sub> mixing ratios, about 20–40 ppbv at 0.5–1.5 km altitude and 10–30 ppbv at 1.5–3.0 km altitude. Average CO mixing ratios were 0.65–0.7 ppmv at 0.5–1.5 km altitude, and very high CO around 1 ppmv was observed during some flights, and even higher levels at the surface. We find the high pollution concentrations to be associated with enhanced levels of OH and HO<sub>2</sub> radicals, calculated with a chemical box model constrained by the measurements. In the upper part of the boundary layer and in the lower free troposphere, high CO and SO<sub>2</sub> compete with relatively less NO<sub>2</sub> in reacting with OH, being efficiently recycled through HO<sub>2</sub>, preventing a net loss of HO<sub>x</sub> radicals. In addition to reactive hydrocarbons and CO, the oxidation of SO<sub>2</sub> causes significant ozone production over Huabei (up to ~13% or 2.0 ppbv h<sup>−1</sup> at 0.8 km altitude). Our results indicate that the lower atmosphere over Huabei is not only strongly polluted but also acts as an oxidation pool, with pollutants undergoing very active photochemistry over this part of China.
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The vertical distribution of ambient biogenic volatile organic compounds (BVOC) concentrations within a hemiboreal forest canopy was investigated over a period of one year. Variability in temporal and spatial isoprene concentrations, ranging from 0.1 to 7.5 μg m<sup>−3</sup>, can be mainly explained by biogenic emissions from deciduous trees. Monoterpene concentrations exceeded isoprene largely and ranged from 0.01 to 140 μg m<sup>−3</sup> and during winter time anthropogenic contributions are likely. Variation in monoterpene concentrations were found to be largest right above the ground and the vertical profiles suggest a weak mixing leading to terpene accumulation in the lower canopy. Exceptionally high values were recorded during a heat wave in July 2010 with very high midday temperatures above 30 °C for several weeks. During summer months, monoterpene exceeded isoprene concentrations 6-fold and during winter 12-fold. During summer months, dominance of α-pinene in the lower and of limonene in the upper part of the canopy was observed, both accounting for up to 70% of the total monoterpene concentration. During wintertime, Δ<sup>3</sup>-carene was the dominant species, accounting for 60% of total monoterpene concentration in January. Possible biogenic monoterpene sources beside the foliage are the leaf litter, the soil and also resins exuding from stems. In comparison, the hemiboreal mixed forest canopy showed similar isoprene but higher monoterpene concentrations than the boreal forest and lower isoprene but substantially higher monoterpene concentrations than the temperate mixed forest canopies. These results have major implications for simulating air chemistry and secondary organic aerosol formation within and above hemiboreal forest canopies. Possible effects of in-cartridge oxidation reactions are discussed as our measurement technique did not include oxidant scavenging. A comparison between measurements with and without scavenging oxidants is presented.
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The partitioning of semivolatile organic compounds between the gas phase and aerosol particles is an important source of secondary organic aerosol (SOA). Gas-particle partitioning of organic and inorganic species is influenced by the physical state and water content of aerosols, and therefore ambient relative humidity (RH), as well as temperature and organic loading levels. We introduce a novel combination of the thermodynamic models AIOMFAC (for liquid mixture non-ideality) and EVAPORATION (for pure compound vapor pressures) with oxidation product information from the Master Chemical Mechanism (MCM) for the computation of gas-particle partitioning of organic compounds and water. The presence and impact of a liquid-liquid phase separation in the condensed phase is calculated as a function of variations in relative humidity, organic loading levels, and associated changes in aerosol composition. We show that a complex system of water, ammonium sulfate, and SOA from the ozonolysis of α-pinene exhibits liquid-liquid phase separation over a wide range of relative humidities (simulated from 30% to 99% RH). Since fully coupled phase separation and gas-particle partitioning calculations are computationally expensive, several simplified model approaches are tested with regard to computational costs and accuracy of predictions compared to the benchmark calculation. It is shown that forcing a liquid one-phase aerosol with or without consideration of non-ideal mixing bears the potential for vastly incorrect partitioning predictions. Assuming an ideal mixture leads to substantial overestimation of the particulate organic mass, by more than 100% at RH values of 80% and by more than 200% at RH values of 95%. Moreover, the simplified one-phase cases stress two key points for accurate gas-particle partitioning calculations: (1) non-ideality in the condensed phase needs to be considered and (2) liquid-liquid phase separation is a consequence of considerable deviations from ideal mixing in solutions containing inorganic ions and organics that cannot be ignored. Computationally much more efficient calculations relying on the assumption of a complete organic/electrolyte phase separation below a certain RH successfully reproduce gas-particle partitioning in systems in which the average oxygen-to-carbon (O:C) ratio is lower than ~0.6, as in the case of α-pinene SOA, and bear the potential for implementation in atmospheric chemical transport models and chemistry-climate models. A full equilibrium calculation is the method of choice for accurate offline (box model) computations, where high computational costs are acceptable. Such a calculation enables the most detailed predictions of phase compositions and provides necessary information on whether assuming a complete organic/electrolyte phase separation is a good approximation for a given aerosol system. Based on the group-contribution concept of AIOMFAC and O:C ratios as a proxy for polarity and hygroscopicity of organic mixtures, the results from the α-pinene system are also discussed from a more general point of view.
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We have integrated observations of tropospheric ozone, very short-lived (VSL) halocarbons and reactive iodine and bromine species from a wide variety of tropical data sources with the global CAM-Chem chemistry-climate model and offline radiative transfer calculations to compute the contribution of halogen chemistry to ozone loss and associated radiative impact in the tropical marine troposphere. The inclusion of tropospheric halogen chemistry in CAM-Chem leads to an annually averaged depletion of around 10% (~2.5 Dobson units) of the tropical tropospheric ozone column, with largest effects in the middle to upper troposphere. This depletion contributes approximately −0.10 W m<sup>−2</sup> to the radiative flux at the tropical tropopause. This negative flux is of similar magnitude to the ~0.33 W m<sup>−2</sup> contribution of tropospheric ozone to present-day radiative balance as recently estimated from satellite observations. We find that the implementation of oceanic halogen sources and chemistry in climate models is an important component of the natural background ozone budget and we suggest that it needs to be considered when estimating both preindustrial ozone baseline levels and long term changes in tropospheric ozone.
