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A long-term ozone loss time series is necessary to understand the evolution of ozone in Antarctica. Therefore, we construct the time series using ground-based, satellite and bias-corrected multi-sensor reanalysis (MSR) data sets for the period 1989–2010. The trends in ozone over 1979–2010 are also estimated to further elucidate its evolution in the wake of decreasing halogen levels in the stratosphere. Our analysis with ground-based observations shows that the average ozone loss in the Antarctic is about −33 to −50% (−90 to −155 DU (Dobson Unit)) in 1989–1992, and then stayed at around −48% (−160 DU). The ozone loss in the warmer winters (e.g. 2002 and 2004) is lower (−37 to −46%), and in the very cold winters (e.g. 2003 and 2006) it is higher (−52 to −55%). These loss estimates are in good agreement with those estimated from satellite observations, where the differences are less than ±3%. The ozone trends based on the equivalent effective Antarctic stratospheric chlorine (EEASC) and piecewise linear trend (PWLT) functions for the vortex averaged ground-based, Total Ozone Mapping Spectrometer/Ozone Monitoring Instrument (TOMS/OMI), and MSR data averaged over September–November exhibit about −4.6 DU yr<sup>−1</sup> over 1979–1999, corroborating the role of halogens in the ozone decrease during the period. The ozone trends computed for the 2000–2010 period are about +1 DU yr<sup>−1</sup> for EEASC and +2.6 DU yr<sup>−1</sup> for the PWLT functions. The larger positive PWLT trends for the 2000–2010 period indicate the influence of dynamics and other basis functions on the increase of ozone. The trends in both periods are significant at 95% confidence intervals for all analyses. Therefore, our study suggests that Antarctic ozone shows a significant positive trend toward its recovery, and hence, leaves a clear signature of the successful implementation of the Montreal Protocol.
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Laboratory chamber experiments are the main source of data on the mechanism of oxidation and the secondary organic aerosol (SOA) forming potential of volatile organic compounds. Traditional methods of representing the SOA formation potential of an organic do not fully capture the dynamic, multi-generational nature of the SOA formation process. We apply the Statistical Oxidation Model (SOM) of Cappa and Wilson (2012) to model the formation of SOA from the formation of the four C<sub>12</sub> alkanes, dodecane, 2-methyl undecane, cyclododecane and hexylcyclohexane, under both high- and low-NO<sub>x</sub> conditions, based upon data from the Caltech chambers. In the SOM, the evolution of reaction products is defined by the number of carbon (<i>N</i><sub>C</sub>) and oxygen (<i>N</i><sub>O</sub>) atoms, and the model parameters are (1) the number of oxygen atoms added per reaction, (2) the decrease in volatility upon addition of an oxygen atom and (3) the probability that a given reaction leads to fragmentation of the molecules. Optimal fitting of the model to chamber data is carried out using the measured SOA mass concentration and the aerosol O:C atomic ratio. The use of the kinetic, multi-generational SOM is shown to provide insights into the SOA formation process and to offer promise for application to the extensive library of existing SOA chamber experiments that is available.
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Continuous black carbon (BC) observations were conducted from 1999 through 2009 by an Aethalometer (AE10) and from 2006 through 2011 by a Multi-Angle Absorption Photometer (MAAP) at Neumayer Station (NM) under stringent contamination control. Considering the respective observation period, BC concentrations measured by the MAAP were somewhat higher (median ± standard deviation: 2.1 ± 2.0 ng m<sup>−3</sup>) compared to the AE10 results (1.6 ± 2.1 ng m<sup>−3</sup>). Neither for the AE10 nor for the MAAP data set a significant long-term trend could be detected. Consistently a pronounced seasonality was observed with both instruments showing a primary annual maximum between October and November and a minimum in April with a maximum/minimum ratio of 4.5/1.6 = 3.8 and 2.7/0.64 = 4.2 for the MAAP and AE10 data, respectively. Occasionally a secondary summer maximum in January/February was visible. With the aim to assess the impact of BC on optical properties of the aerosol at NM, we evaluated the BC data along with particle scattering coefficients measured by an integrating nephelometer. We found the mean single scattering albedo of ω<sub>550</sub> = 0.992 ± 0.0090 (median: 0.994) at a wavelength of 550 nm with a range of values from 0.95 to 1.0.
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The D/H isotope ratio is used to attribute boundary layer humidity changes to the set of contributing fluxes for a case following a snowstorm in which a snow pack of about 10 cm vanished. Profiles of H<sub>2</sub>O and CO<sub>2</sub> mixing ratio, D/H isotope ratio, and several thermodynamic properties were measured from the surface to 300 m every 15 min during four winter days near Boulder, Colorado. Coeval analysis of the D/H ratios and CO<sub>2</sub> concentrations find these two variables to be complementary with the former being sensitive to daytime surface fluxes and the latter particularly indicative of nocturnal surface sources. Together they capture evidence for strong vertical mixing during the day, weaker mixing by turbulent bursts and low level jets within the nocturnal stable boundary layer during the night, and frost formation in the morning. The profiles are generally not well described with a gradient mixing line analysis because D/H ratios of the end members (i.e., surface fluxes and the free troposphere) evolve throughout the day which leads to large uncertainties in the estimate of the D/H ratio of surface water flux. A mass balance model is constructed for the snow pack, and constrained with observations to provide an optimal estimate of the partitioning of the surface water flux into contributions from sublimation, evaporation of melt water in the snow and evaporation from ponds. Results show that while vapor measurements are important in constraining surface fluxes, measurements of the source reservoirs (soil water, snow pack and standing liquid) offer stronger constraint on the surface water balance. Measurements of surface water are therefore essential in developing observational programs that seek to use isotopic data for flux attribution.
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Atmospheric sulfur (S) deposition via precipitation, particles and gases was investigated at ten sites in Northern China. Measurements were performed continuously between December 2007 and November 2010. The total S deposition flux in the target area ranged from 35.0 to 100.7 kg S ha<sup>−1</sup> yr<sup>−1</sup>, noticeably higher than the values documented in Europe, North America, and East Asia. The ten-site, 3-yr average total S deposition was 64.8 kg S ha<sup>−1</sup> yr<sup>−1</sup>, with 68% attributed to dry deposition (mainly SO<sub>2</sub>) and the rest to wet deposition. Consequently, the spatial distribution of the total flux was consistent to that of dry deposition, that is, higher values were observed at industrial and urban sites than at agricultural and rural sites. However, the seasonal variation in the total S deposition was not obvious across the entire year because of opposite seasonal trends in wet and dry deposition. It was found that the wet deposition, without significant spatial and interannual differences, was influenced by the volume of precipitation, the air-column concentrations of S compounds and in-cloud scavenging. Similar to the wet deposition, the dry-deposited sulfate was also less dependent on the surface concentration. Nevertheless, the regional differences in SO<sub>2</sub> dry deposition were mostly explained by the ambient concentration, which is closely associated with local emissions. As expected, the spatial pattern of total S deposition resembled that of the emission inventory, indicating the dramatic anthropogenic imprints on the regional S budget. Although at most of the study sites the "acid equivalents" deposition of S was comparable to that of nitrogen (N), the importance of S in the acidification risks was more pronounced at the industrial sites. The ten-site, 3-yr mean total "acid equivalents" deposition of S and N was estimated to be 8.4 (range: 4.2–11.6) keq ha<sup>−1</sup> yr<sup>−1</sup>, which exceeds the critical loads for natural ecosystems in Northern China. Taking these findings and our previous studies together, a multi-pollutant perspective and joint mitigation strategies to abate SO<sub>2</sub> and NH<sub>3</sub> simultaneously in the target area are recommended to protect natural ecosystems from excess acid deposition.
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Starting on 7 February 2009, southeast Australia was devastated by large bushfires, which burned an area of about 3000 km<sup>2</sup> on this day alone. This event was extraordinary, because a large number of combustion products were transported into the uppermost troposphere and lower stratosphere within a few days. Various biomass burning products released by the fire were observed by the Michelson Interferometer for Passive Atmospheric Sounding (MIPAS) on the Envisat satellite. We tracked the plume using MIPAS C<sub>2</sub>H<sub>2</sub>, HCN and HCOOH single-scan measurements on a day-to-day basis. The measurements were compared with a high-resolution model run of the Global Environmental Multiscale Air Quality (GEM-AQ) model. Generally there is good agreement between the spatial distribution of measured and modelled pollutants. Both MIPAS and GEM-AQ show a fast southeastward transport of the pollutants to New Zealand within one day. During the following 3–4 days, the plume remained northeastward of New Zealand and was located at altitudes of 15 to 18 km. Thereafter its lower part was transported eastward, followed by westward transport of its upper part. On 17 February the eastern part had reached southern South America and on 20 February the central South Atlantic. On the latter day a second relic of the plume was observed moving eastward above the South Pacific. Between 20 February and the first week of March, the upper part of the plume was transported westward over Australia and the Indian Ocean towards southern Africa. First evidence for entry of the pollutants into the stratosphere was found in MIPAS data of 11 February, followed by larger amounts on 17 February and the days thereafter. From MIPAS data, C<sub>2</sub>H<sub>2</sub>/HCN and HCOOH/HCN enhancement ratios of 0.76 and 2.16 were calculated for the first days after the outbreak of the fires, which are considerably higher than the emission ratios assumed for the model run and at the upper end of values found in literature. From the temporal decrease of the enhancement ratios, mean lifetimes of 16–20 days and of 8–9 days were calculated for measured C<sub>2</sub>H<sub>2</sub> and HCOOH. The respective lifetimes calculated from the model data are 18 and 12 days.
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Using the satellite temperature measurements from the Stratospheric Sounding Units (SSU) and Microwave Sounding Units (MSU including the advanced microwave sounding unit, AMSU) since 1979, the trends and uncertainties in the fifth Coupled Model Intercomparison Project (CMIP5) model simulations from the middle troposphere to the upper stratosphere (5–50 km) have been explored. The temperature trend discrepancies between the new generation reanalyses are investigated. Both the temporal character of the global mean temperature and the regional spatial pattern of the temperature trends are discussed. The results show that the CMIP5 model simulations reproduced common stratospheric cooling and tropospheric warming features although a significant discrepancy among the selected models was observed. <br><br> For the temporal variation of the global mean temperature, the CMIP5 simulations reproduce the volcanic signal and were highly consistent with the SSU measurements in the upper stratosphere. In contrast, the CFSR and MERRA reanalyses (excluding ERA-I) exhibit a different result from the CMIP5 simulations. For the spatial variation of the temperature trends, the CMIP5 simulations displayed a different latitudinal-longitudinal pattern from SSU/MSU measurements in all six layers from the middle troposphere to the upper stratosphere. The CFSR reanalysis shows a good spatial correlation with satellite observations in the troposphere but poor spatial correlation in the stratosphere. The ERA-I and MERRA reanalyses have good spatial correlation in the upper stratosphere and an even better spatial correlation in the troposphere. <br><br> Generally, the CMIP5 simulations significantly underestimated the stratospheric cooling in the tropics and substantially overestimated the cooling over the Antarctic in the MSU observations. The largest trend spread among the seven CMIP5 simulations is seen in both the south- and north-polar regions in the stratosphere and troposphere. The tropospheric spread values are generally smaller than the stratospheric spread values.
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This study presents a total of four years of sub-micron aerosol particle size distribution measurements in the southern African savannah, an environment with few previous observations covering a full seasonal cycle and the size range below 100 nm. During the first 19 months, July 2006–January 2008, the measurements were carried out at Botsalano, a semi-clean location, whereas during the latter part, February 2008–May 2010, the measurements were carried out at Marikana (approximately 150 km east of Botsalano), which is a more polluted location with both pyrometallurgical industries and informal settlements nearby. <br><br> The median total concentration of aerosol particles was more than four times as high at Marikana than at Botsalano. In the size ranges of 12–840 nm, 50–840 nm and 100–840 nm the median concentrations were 1856, 1278 and 698 particles cm<sup>−3</sup> at Botsalano and 7805, 3843 and 1634 particles cm<sup>−3</sup> at Marikana, respectively. <br><br> The diurnal variation of the size distribution for Botsalano arose as a result of frequent regional new particle formation. However, for Marikana the diurnal variation was dominated by the morning and evening household burning in the informal settlements, although regional new particle formation was even more frequent than at Botsalano. The effect of the industrial emissions was not discernible in the size distribution at Marikana although it was clear in the sulphur dioxide diurnal pattern, indicating the emissions to be mostly gaseous. <br><br> Seasonal variation was strongest in the concentration of particles larger than 100 nm, which was clearly elevated at both locations during the dry season from May to September. In the absence of wet removal during the dry season, the concentration of particles larger than 100 nm had a correlation above 0.7 with CO for both locations, which implies incomplete burning to be an important source of aerosol particles during the dry season. However, the sources of burning differ: at Botsalano the rise in concentration originates from regional wild fires, while at Marikana domestic heating in the informal settlements is the main source. <br><br> Air mass history analysis for Botsalano identified four regional scale source areas in southern Africa and enabled the differentiation between fresh and aged rural background aerosol originating from the clean sector, i.e., western sector with very few large anthropogenic sources. Comparison to size distributions published for other comparable environments in Northern Hemisphere shows southern African savannah to have a unique combination of sources and meteorological parameters. The observed strong link between combustion and seasonal variation is comparable only to the Amazon basin; however, the lack of long-term observations in the Amazonas does not allow a quantitative comparison. <br><br> All the data presented in the figures, as well as the time series of monthly mean and median size distributions are included in numeric form as a Supplement to provide a reference point for the aerosol modelling community.
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Biogenic volatile organic compounds (BVOC) emitted from vegetation are important for the formation of secondary pollutants such as ozone and secondary organic aerosols (SOA) in the atmosphere. Therefore, BVOC emission are an important input for air quality models. To model these emissions with high spatial resolution, the accuracy of the underlying vegetation inventory is crucial. We present a BVOC emission model that accommodates different vegetation inventories and uses satellite-based measurements of greenness instead of pre-defined vegetation periods. This approach to seasonality implicitly treats effects caused by water or nutrient availability, altitude and latitude on a plant stand. Additionally, we test the influence of proposed seasonal variability in enzyme activity on BVOC emissions. In its present setup, the emission model calculates hourly emissions of isoprene, monoterpenes, sesquiterpenes and the oxygenated volatile organic compounds (OVOC) methanol, formaldehyde, formic acid, ethanol, acetaldehyde, acetone and acetic acid. In this study, emissions based on three different vegetation inventories are compared with each other and diurnal and seasonal variations in Europe are investigated for the year 2006. Two of these vegetation inventories require information on tree-cover as an input. We compare three different land-cover inventories (USGS GLCC, GLC2000 and Globcover 2.2) with respect to tree-cover. The often-used USGS GLCC land-cover inventory leads to a severe reduction of BVOC emissions due to a potential miss-attribution of broad-leaved trees and reduced tree-cover compared to the two other land-cover inventories. To account for uncertainties in the land-cover classification, we introduce land-cover correction factors for each relevant land-use category to adjust the tree-cover. The results are very sensitive to these factors within the plausible range. For June 2006, total monthly BVOC emissions decreased up to −27% with minimal and increased up to +71% with maximal factors, while in January 2006, the changes in monthly BVOC emissions were −54 and +56% with minimal and maximal factors, respectively. The new seasonality approach leads to a reduction in the annual emissions compared with non-adjusted data. The strongest reduction occurs in OVOC (up to −32%), the weakest in isoprene (as little as −19%). If also enzyme seasonality is taken into account, however, isoprene reacts with the steepest decrease of annual emissions, which are reduced by −44% to −49%, annual emissions of monoterpenes reduce between −30 and −35%. The sensitivity of the model to changes in temperature depends on the climatic zone but not on the vegetation inventory. The sensitivity is higher for temperature increases of 3 K (+31% to +64%) than decreases by the same amount (−20 to −35%). The climatic zones "Cold except summer" and "arid" are most sensitive to temperature changes in January for isoprene and monoterpenes, respectively, while in June, "polar" is most sensitive to temperature for both isoprene and monoterpenes. Our model predicts the oxygenated volatile organic compounds to be the most abundant fraction of the annual European emissions (3571–5328 Gg yr<sup>−1</sup>), followed by monoterpenes (2964–4124 Gg yr<sup>−1</sup>), isoprene (1450–2650 Gg yr<sup>−1</sup>) and sesquiterpenes (150–257 Gg yr<sup>−1</sup>). We find regions with high isoprene emissions (most notably the Iberian Peninsula), but overall, oxygenated VOC dominate with 43–45% (depending on the vegetation inventory) contribution to the total annual BVOC emissions in Europe. Isoprene contributes between 18–21%, monoterpenes 33–36% and sesquiterpenes contribute 1–2%. We compare the concentrations of biogenic species simulated by an air quality model with measurements of isoprene and monoterpenes in Hohenpeissenberg (Germany) for both summer and winter. The agreement between observed and modelled concentrations is better in summer than in winter. This can partly be explained with the difficulty to model weather conditions in winter accurately, but also with the increased anthropogenic influence on the concentrations of BVOC compounds in winter. Our results suggest that land-cover inventories used to derive tree-cover must be chosen with care. Also, uncertainties in the classification of land-cover pixels must be taken into account and remain high. This problem must be addressed together with the remote sensing community. Our new approach using a greenness index for addressing seasonality of vegetation can be implemented easily in existing models. The importance of OVOC for air quality should be more deeply addressed by future studies, especially in smog chambers. Also, the fate of BVOC from the dominant region of the Iberian Peninsula should be studied more in detail.
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Numerical simulations were carried out in a high-resolution two-dimensional framework to increase our understanding of aerosol indirect effects in mixed-phase stratiform clouds. Aerosol characteristics explored include insoluble particle type, soluble mass fraction, influence of aerosol-induced freezing point depression and influence of aerosol number concentration. Simulations were analyzed with a focus on the processes related to liquid phase microphysics, and ice formation was limited to droplet freezing. Of the aerosol properties investigated, aerosol insoluble mass type and its associated freezing efficiency was found to be most relevant to cloud lifetime. Secondary effects from aerosol soluble mass fraction and number concentration also alter cloud characteristics and lifetime. These alterations occur via various mechanisms, including changes to the amount of nucleated ice, influence on liquid phase precipitation and ice riming rates, and changes to liquid droplet nucleation and growth rates. Alteration of the aerosol properties in simulations with identical initial and boundary conditions results in large variability in simulated cloud thickness and lifetime, ranging from rapid and complete glaciation of liquid to the production of long-lived, thick stratiform mixed-phase cloud.
