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Attribution of stratospheric ozone trends to chemistry and transport: a modelling study

The decrease of the concentration of ozone depleting substances (ODSs) in the stratosphere over the past decade raises the question to what extent observed changes in stratospheric ozone over this period are consistent with known changes in the chemical composition and possible changes in atmospheric transport. Here we present a series of ozone sensitivity calculations with a stratospheric chemistry transport model (CTM) driven by meteorological reanalyses from the European Centre for Medium-Range Weather Forecasts, covering the period 1978–2009. In order to account for the reversal in ODS trends, ozone trends are analysed as piecewise linear trends over two periods, 1979–1999 and 2000–2009. Modelled column ozone (TO3) inter-annual variability and trends are in excellent agreement with observations from the Total Ozone Mapping Spectrometer (TOMS) and Solar Backscatter UV (SBUV/2) as well as the Global Ozone Monitoring Experiment (GOME/GOME2) and Scanning Imaging Absorption Spectrometer for Atmospheric Chartography (SCIAMACHY) instruments. In the period 1979–1999, modelled TO3 trends at mid-latitudes are dominated by changes in in situ gas-phase chemistry, which contribute to about 50% or more of the TO3 trend in most seasons. Changes in meteorology contribute around 35% to mid-latitude TO3 trends, with strong differences between different seasons. In springtime, export of ozone depleted air from polar latitudes contributes about 35–50% to the modelled TO3 trend at SH mid-latitudes and about 15–30% at NH mid-latitudes. Over the period 2000–2009 positive linear trends in modelled TO3, which agree well with observed TO3 trends, are dominated by changes in meteorology, as expected for the yet small decrease in stratospheric halogen loading over this period. While the TO3 trends themselves are not statistically significant over the period 2000–2009, changes in linear trends between 1978–1999 and 2000–2009 are significant at mid- and high latitudes of both hemisphere during most seasons. However, changes in meteorology have contributed substantially to these TO3 trend changes.
Measurement of the ambient organic aerosol volatility distribution: application during the Finokalia Aerosol Measurement Experiment (FAME-2008)

A variable residence time thermodenuder (TD) was combined with an Aerodyne Aerosol Mass Spectrometer (AMS) and a Scanning Mobility Particle Sizer (SMPS) to measure the volatility distribution of aged organic aerosol in the Eastern Mediterranean during the Finokalia Aerosol Measurement Experiment in May of 2008 (FAME-2008). A new method for the quantification of the organic aerosol volatility distribution was developed combining measurements of all three instruments together with an aerosol dynamics model. Challenges in the interpretation of ambient thermodenuder-AMS measurements include the potential resistances to mass transfer during particle evaporation, the effects of particle size on the evaporated mass fraction, the changes in the AMS collection efficiency and particle density as the particles evaporate partially in the TD, and finally potential losses inside the TD. Our proposed measurement and data analysis method accounts for all of these problems combining the AMS and SMPS measurements. The AMS collection efficiency of the aerosol that passed through the TD was found to be approximately 10% lower than the collection efficiency of the aerosol that passed through the bypass. The organic aerosol measured at Finokalia is approximately 2 or more orders of magnitude less volatile than fresh laboratory-generated monoterpene (α-pinene, β-pinene and limonene under low NOx conditions) secondary organic aerosol. This low volatility is consistent with its highly oxygenated AMS mass spectrum. The results are found to be highly sensitive to the mass accommodation coefficient of the evaporating species. This analysis is based on the assumption that there were no significant reactions taking place inside the thermodenuder.
Comparison of global inventories of CO emissions from biomass burning derived from remotely sensed data

We compare five global inventories of monthly CO emissions named VGT, ATSR, MODIS, GFED3 and MOPITT based on remotely sensed active fires and/or burned area products for the year 2003. The objective is to highlight similarities and differences by focusing on the geographical and temporal distribution and on the emissions for three broad land cover classes (forest, savanna/grassland and agriculture). Globally, CO emissions for the year 2003 range between 365 Tg CO (GFED3) and 1422 Tg CO (VGT). Despite the large uncertainty in the total amounts, some common spatial patterns typical of biomass burning can be identified in the boreal forests of Siberia, in agricultural areas of Eastern Europe and Russia and in savanna ecosystems of South America, Africa and Australia. Regionally, the largest difference in terms of total amounts (CV > 100%) and seasonality is observed at the northernmost latitudes, especially in North America and Siberia where VGT appears to overestimate the area affected by fires. On the contrary, Africa shows the best agreement both in terms of total annual amounts (CV = 31%) and of seasonality despite some overestimation of emissions from forest and agriculture observed in the MODIS inventory. In Africa VGT provides the most reliable seasonality. Looking at the broad land cover types, the range of contribution to the global emissions of CO is 64–74%, 23–32% and 3–4% for forest, savanna/grassland and agriculture, respectively. These results suggest that there is still large uncertainty in global estimates of emissions and it increases if the comparison is carried by out taking into account the temporal (month) and spatial (0.5° × 0.5° cell) dimensions. Besides the area affected by fires, also vegetation characteristics and conditions at the time of burning should also be accurately parameterized since they can greatly influence the global estimates of CO emissions.
Evidence for the effectiveness of the Montreal Protocol to protect the ozone layer

The release of man-made ozone depleting substances (ODS, including chlorofluorocarbons and halons) into the atmosphere has led to a near-linear increase in stratospheric halogen loading since the early 1970s, which levelled off after the mid-1990s and then started to decline, in response to the ban of many ODS by the Montreal Protocol (1987). We developed a multiple linear regression model to test whether this already had a measurable effect on total ozone values observed by the global network of ground-based instruments. The model includes explanatory variables describing the influence of various modes of dynamical variability and of volcanic eruptions. In order to describe the anthropogenic influence a first version of the model contains a linear trend (LT) term, whereas a second version contains a term describing the evolution of Equivalent Effective Stratospheric Chlorine (EESC). By comparing the explained variance of these two model versions we evaluated, which of the two terms better describes the observed ozone evolution. For a significant majority of the stations, the EESC proxy fits the long term ozone evolution better than the linear trend term. Therefore, we conclude that the Montreal Protocol has started to show measurable effects on the ozone layer about twenty years after it became legally binding.
Ozone, carbon monoxide and nitrogen oxides time series at four alpine GAW mountain stations in central Europe

Long-term, ground based in-situ observations of ozone (O3) and its precursor gases nitrogen dioxide (NO2) and carbon monoxide (CO) from the four sites Hohenpeissenberg and Zugspitze (D), Sonnblick (A) and Jungfraujoch (CH) are presented for the period 1995–2007. These Central European alpine mountain observatories cover an altitude range of roughly 1000 to 3500 m. Comparable analytical methods and common quality assurance (QA) procedures are used at all sites. For O3 and CO, calibration is linked to primary calibrations (O3) or CO standards provided by the Central Calibration Laboratory (CCL) at NOAA/ESRL. All stations have been audited by the World Calibration Centre (WCC) for CO and O3 (WCC-Empa; CH). Data from long-term measurements of NO2 and CO are only available from Hohenpeissenberg and Jungfraujoch. Both sites show slightly decreasing mixing ratios of the primarily emitted NO2 and the partly anthropogenically emitted CO between 1995 and 2007. The findings are generally consistent with shorter observation periods at Zugspitze and Sonnblick and thus are considered to represent regional changes in Central European atmospheric composition at this altitude range. Over the same period, 1995–2007, the O3 mixing ratios have slightly increased at three of the four sites independent of wind sector. Trends are often more pronounced in winter and less in summer; highest declines of NO2 and CO are observed in winter and the lowest in summer, whereas the strongest O3 increase was detected in winter and lowest or even decline in summer, respectively. Weekly cycles demonstrate anthropogenic impact at all elevations with enhanced NO2 on working days compared to weekends. Enhanced O3 values on working days indicating photochemical production from anthropogenic precursors are only observed in summer, whereas in all other seasons anti-correlation with NO2 was found due to reduced O3 values on working days. Trends are discussed with respect to anthropogenic impacts and vertical mixing. The observed trends for NO2 at the alpine mountain sites are less pronounced than trends estimated based on emission inventories.
Physical properties of iodate solutions and the deliquescence of crystalline I2O5 and HIO3

Secondary aerosol produced from marine biogenic sources in algal-rich coastal locations will initially be composed of iodine oxide species, most likely I2O5, or its hydrated form HIO3, formed as a result of iodine gas-phase chemistry. At present, there is no quantitative hygroscopic data for these compounds and very little data available for iodate solutions (HIO3 and I2O5 share a common aqueous phase). With increased interest in the role of such aerosol in the marine atmosphere, we have conducted studies of (i) the deliquescence behaviour of crystalline HIO3 and I2O5 at 273–303 K, (ii) the efflorescence behaviour of aqueous iodate solution droplets, and (iii) properties (water activity, density, and viscosity) of subsaturated and saturated iodate solutions. The deliquescence of I2O5 crystals at 293 K was observed to occur at a relative humidity (DRH) of 80.8±1.0%, whereas for HIO3, a DRH of 85.0±1.0% was measured. These values are consistent with measured water activity values for saturated I2O5 and HIO3 solutions at 293 K of 0.80±0.01 and 0.84±0.01 respectively. At all temperatures, DRH values for HIO3 crystals were observed to be higher than for those of I2O5. The temperature-dependent DRH data, along with solubility and water activity data were used to evaluate the enthalpy of solution (ΔHsol) for HIO3 and I2O5. A ΔHsol value of 8.3±0.7 kJ mol−1 was determined for HIO3 which is consistent with a literature value of 8.8 kJ mol−1. For I2O5, we report for the first time its solubility at various temperatures and ΔHsol = 12.4±0.6 kJ mol−1. The measured water activity values confirm that aqueous iodate solutions are strongly non-ideal, consistent with previous reports of complex ion formation and molecular aggregation.
Wintertime pollution over the Eastern Indo-Gangetic Plains as observed from MOPITT, CALIPSO and tropospheric ozone residual data

A large wintertime increase in pollutants has been observed over the eastern parts of the Indo Gangetic Plains. We use improved version 4 carbon monoxide (CO) retrievals from the Measurements of Pollution in the Troposphere (MOPITT) along with latest version 3 aerosol data from the Cloud-Aerosol Lidar and Infrared Pathfinder Satellite Observations (CALIPSO) lidar instrument and the tropospheric ozone residual products to characterize this pollution pool. The feature is seen primarily in the lower troposphere from about November to February with strong concomitant increases in CO and aerosol optical depth (AOD). The signature of the feature is also observed in tropospheric ozone column data. The height resolved aerosol data from CALIPSO confirm the trapping of the pollution pool at the lowest altitudes. The observations indicate that MOPITT can capture this low altitude phenomenon even in winter conditions as indicated by the averaging kernels.
Technical Note: Formal blind intercomparison of HO2 measurements in the atmosphere simulation chamber SAPHIR during the HOxComp campaign

Hydroperoxy radical (HO2) concentrations were measured during the formal blind intercomparison campaign HOxComp carried out in Jülich, Germany, in 2005. Three instruments detected HO2 via chemical conversion to hydroxyl radicals (OH) and subsequent detection of the sum of OH and HO2 by laser induced fluorescence (LIF). All instruments were based on the same detection and calibration scheme. Because measurements by a MIESR instrument failed during the campaign, no absolute reference measurement was available, so that the accuracy of individual instruments could not be addressed. Instruments sampled ambient air for three days and were attached to the atmosphere simulation chamber SAPHIR during the second part of the campaign. Six experiments of one day each were conducted in SAPHIR, where air masses are homogeneously mixed, in order to investigate the performance of instruments and to determine potential interferences of measurements under well-controlled conditions. Linear correlation coefficients (R2) between measurements of the LIF instruments are generally high and range from 0.82 to 0.98. However, the agreement between measurements is variable. The regression analysis of the entire data set of measurements in SAPHIR yields slopes between 0.69 to 1.26 and intercepts are smaller than typical atmospheric daytime concentrations (less than 1 pptv). The quality of fit parameters improves significantly, when data are grouped into data subsets of similar water vapor concentrations. Because measurements of LIF instruments were corrected for a well-characterized water dependence of their sensitivities, this indicates that an unknown factor related to water vapor affected measurements in SAPHIR. Measurements in ambient air are also well-correlated, but regression parameters differ from results obtained from SAPHIR experiments. This could have been caused by differences in HO2 concentrations in the sampled air at the slightly different locations of instruments.
Volatile organic compound emissions from Larrea tridentata (creosotebush)

We present results from the CREosote ATmosphere Interactions through Volatile Emissions (CREATIVE 2009) field study in southern Arizona aimed at quantifying emission rates of VOCs from creosotebush (Larrea tridentata) during the summer 2009 monsoon season. This species was chosen because of its vast distribution in North and South American deserts and because its resins have been reported to contain a rich set of volatile organic compounds (VOC). While a variety of ecosystems have been investigated for VOC emissions, deserts remain essentially unstudied, partially because of their low biomass densities and water limitations. However, during the North American monsoon, a pronounced increase in rainfall from an extremely dry June (<5 mm precipitation) to a rainy July (>80 mm) occurs over large areas of the Sonoran desert in the southwestern United States and northwestern Mexico. We observed a strong diurnal pattern of branch emissions and ambient concentrations of an extensive suite of VOCs with maxima in early afternoon. These include VOCs typically observed in forest sites (oxygenated VOCs and volatile isoprenoids) as well as a large number of other compounds, some of which have not been previously described from any plant including 1-chloro-2-methoxy-benzene and isobutyronitrile. Although generally considered to be derived from anthropogenic sources, we observed emissions of aromatic compounds including benzene, and a broad range of phenolics. Dimethyl sulfide emissions from creosotebush were higher than reported from any previously studied plant suggesting that terrestrial ecosystems should be reconsidered as an important source of this climatically important gas. We also present direct, primary emission measurements of isoprene and its apparent oxidation products methyl vinyl ketone, methacrolein, and 3-methyl furan (the later three compounds are typically assumed to form from secondary reactions within the atmosphere), as well as a group of compounds considered to be fatty acid oxidation products. These results suggest that one important function of some VOCs in creosotebush is as an antioxidant. We also find that emissions of nitriles from creosotebush could represent a significant but previously unaccounted nitrogen loss from this arid ecosystem. Our results demonstrate the richness of creosotebush volatile emissions and highlight the need for further research into their atmospheric and ecological impacts.
Measurements of HONO during BAQS-Met

Measurements of nitrous acid (HONO) were performed as part of the 2007 Border Air Quality and Meteorology Study (BAQS-Met) at the Harrow, Ontario, Canada supersite between 20 June and 10 July 2007. Nitrous acid is an important precursor of the hydroxyl radical and understanding its chemistry is important to understanding daytime oxidation chemistry. The HONO measurements were made using a custom built Long Path Absorption Photometer (LOPAP). The goal of this work was to shed light on sources of daytime HONO in the border region. During the course of the campaign HONO mixing ratios consistently exceeded expected daytime values by more than a factor of 6. Mean daytime mixing ratios of 61 pptv were observed. While HONO decay began at sunrise, minimum HONO values were measured during the late afternoon. There was little difference between the daytime (mean = 1.5%) and night-time (mean = 1.7%) ratios of HONO/NO2, thus there was a very strong daytime source of HONO which is consistent with other recent studies. Correlations of daytime HONO production with a variety of chemical and meteorological parameters indicate that production is dependent on UV radiation, NO2 and water vapour but is not consistent with a simple gas phase process. Apparent rate constants for the production of HONO from photolyticaly excited NO2 and water vapour vary from 2.8–7.8×10−13 cm3 molec−1 s−1, during the campaign. These results appear to be consistent with the heterogeneous conversion of NO2 enhanced by photo-excitation.