Items

Advanced search

Observations of total alkyl nitrates within the Sacramento Urban Plume

During the summer of 2001, NO2, total peroxy nitrates (ΣPNs), total alkyl nitrates (ΣANs), HNO3, volatile organic compounds (VOC), CO2, O3, and meteorological variables were measured at Granite Bay, CA. The diurnal variation in ΣPNs, ΣANs and HNO3 were all strongly correlated with sunlight, indicating both that they are photochemically produced and that they have a lifetime of a few hours at this site. The mixing ratios of ΣANs ranged as high as 2 ppbv. Mixing ratios at night averaged 0.4 ppbv. Odd-oxygen (Ox=O3+NO2) and ΣANs were strongly correlated reflecting both the common chemical source terms and the similar lifetimes of both species. Several approaches to interpreting the simultaneous variations of Ox and ΣANs are described, and used to derive a best estimate of the ΣAN yield from the VOC mixture at this site of 4.2% and an estimate of the range that is consistent with the observations of 3.9–5.8%. A yield of 4.2% implies termination of the HOx catalytic cycle by ΣAN formation once every 24 cycles. Analysis of the HNO3 observations in combination with the ΣAN and O3 measurements suggests that NOx terminations limit the HOx chain length to between 4.7 and 6.3.
Supersaturation, dehydration, and denitrification in Arctic cirrus

A polar cirrus case study is discussed with the help of a one-dimensional model with explicit aerosol and ice microphysics. It is demonstrated that continuous cooling of air in regions with small amounts of ice and slow ice deposition rates of water vapor drives significant in-cloud supersaturations over ice, with potentially important consequences for heterogeneous halogen activation. Radiatively important cloud properties such as ice crystal size distributions are investigated, showing the presence of high number concentrations of small crystals in the cloud top region at the tropopause, broad but highly variable size spectra in the cloud interior, and mostly large crystals at the cloud base. It is found that weakly forced Arctic cirrostratus are highly efficient at dehydrating upper tropospheric air. Estimating nitric acid uptake in cirrus with an unprecedented treatment of diffusion-limited trapping in growing ice crystals suggests that such clouds could also denitrify upper tropospheric air masses efficiently, but a closer comparison to suitable observations is needed to draw a definite conclusion on this point. It is also shown that low temperatures, high ice supersaturations, and the absence of ice above but close to the cloud top region cause efficient uptake of nitric acid in background aerosol particles.
Observations and model calculations of trace gas scavenging in a dense Saharan dust plume during MINATROC

An intensive field measurement campaign was performed in July/August 2002 at the Global Atmospheric Watch station Izaña on Tenerife to study the interaction of mineral dust aerosol and tropospheric chemistry (MINATROC). A dense Saharan dust plume, with aerosol masses exceeding 500 µg m-3, persisted for three days. During this dust event strongly reduced mixing ratios of ROx (HO2, CH3O2 and higher organic peroxy radicals), H2O2, NOx (NO and NO2) and O3 were observed. A chemistry boxmodel, constrained by the measurements, has been used to study gas phase and heterogeneous chemistry. It appeared to be difficult to reproduce the observed HCHO mixing ratios with the model, possibly related to the representation of precursor gas concentrations or the absence of dry deposition. The model calculations indicate that the reduced H2O2 mixing ratios in the dust plume can be explained by including the heterogeneous removal reaction of HO2 with an uptake coefficient of 0.2, or by assuming heterogeneous removal of H2O2 with an accommodation coefficient of 5x10-4. However, these heterogeneous reactions cannot explain the low ROx mixing ratios observed during the dust event. Whereas a mean daytime net ozone production rate (NOP) of 1.06 ppbv/hr occurred throughout the campaign, the reduced ROx and NOx mixing ratios in the Saharan dust plume contributed to a reduced NOP of 0.14-0.33 ppbv/hr, which likely explains the relatively low ozone mixing ratios observed during this event.
The contribution of sulphuric acid to atmospheric particle formation and growth: a comparison between boundary layers in Northern and Central Europe

Atmospheric gaseous sulphuric acid was measured and its influence on particle formation and growth was investigated building on aerosol data. The measurements were part of the EU-project QUEST and took place at two different measurement sites in Northern and Central Europe (Hyytiälä, Finland, March-April 2003 and Heidelberg, Germany, March-April 2004). From a comprehensive data set including sulphuric acid, particle number size distributions and meteorological data, particle growth rates, particle formation rates and source rates of condensable vapors were inferred. Growth rates were determined in two different ways, from particle size distributions as well as from a so-called timeshift analysis. Moreover, correlations between sulphuric acid and particle number concentration between 3 and 6 nm were examined and the influence of air masses of different origin was investigated. Measured maximum concentrations of sulphuric acid were in the range from 1x106 to 16x106cm-3. The gaseous sulphuric acid lifetime with respect to condensation on aerosol particles ranged from 2 to 33min in Hyytiälä and from 0.5 to 8 min in Heidelberg. Most calculated values (growth rates, formation rates, vapor source rates) were considerably higher in Central Europe (Heidelberg), due to the more polluted air and higher preexistent aerosol concentrations. Close correlations between H2SO4 and nucleation mode particles (size range: 3-6 nm) were found on most days at both sites. The percentage contribution of sulphuric acid to particle growth was below 10% at both places and to initial growth below 20%. An air mass analysis indicated that at Heidelberg new particles were formed predominantly in air advected from southwesterly directions.
The effects of lightning-produced NOx and its vertical distribution on atmospheric chemistry: sensitivity simulations with MATCH-MPIC

The impact of different assumptions concerning the source magnitude as well as the vertical placement of lightning-produced nitrogen oxides is studied using the global chemistry transport model MATCH-MPIC. The responses of NOx, O3, OH, HNO3 and peroxyacetyl-nitrate (PAN) are investigated. A marked sensitivity to both parameters is found. NOx burdens globally can be enhanced by up to 100% depending on the vertical placement and source magnitude strength. In all cases, the largest enhancements occur in the tropical upper troposphere, where lifetimes of most trace gases are longer and where they thus become more susceptible to long-range transport by large-scale circulation patterns. Comparison with observations indicate that 0 and 20 Tg(N)/yr production rates of NOx from lightning are too low and too high, respectively. However, no single intermediate production rate or vertical distribution can be singled out as best fitting the observations, due to the large scatter in the datasets. This underscores the need for further measurement campaigns in key regions, such as the tropical continents.
Validation of SCIAMACHY AMC-DOAS water vapour columns

A first validation of water vapour total column amounts derived from measurements of the SCanning Imaging Absorption spectroMeter for Atmospheric CHartographY (SCIAMACHY) in the visible spectral region has been performed. For this purpose, SCIAMACHY water vapour data have been determined for the year 2003 using an extended version of the Differential Optical Absorption Spectroscopy (DOAS) method, called Air Mass Corrected (AMC-DOAS). The SCIAMACHY results are compared with corresponding water vapour measurements by the Special Sensor Microwave Imager (SSM/I) and with model data from the European Centre for Medium-Range Weather Forecasts (ECMWF). In confirmation of previous results it could be shown that SCIAMACHY derived water vapour columns are typically slightly lower than both SSM/I and ECMWF data, especially over ocean areas. However, these deviations are much smaller than the observed scatter of the data which is caused by the different temporal and spatial sampling and resolution of the data sets. For example, the overall difference with ECMWF data is only -0.05 g/cm2 whereas the typical scatter is in the order of 0.5 g/cm2. Both values show almost no variation over the year. In addition, first monthly means of SCIAMACHY water vapour data have been computed. The quality of these monthly means is currently limited by the availability of calibrated SCIAMACHY spectra. Nevertheless, first comparisons with ECMWF data show that SCIAMACHY (and similar instruments) are able to provide a new independent global water vapour data set.
Polar organic compounds in rural PM2.5 aerosols from K-puszta, Hungary, during a 2003 summer field campaign: Sources and diel variations

In the present study, we examined PM2.5 continental rural background aerosols, which were collected during a summer field campaign at K-puszta, Hungary (4 June-10 July 2003), a mixed coniferous/deciduous forest site characterized by intense solar radiation during summer. Emphasis was placed on polar oxygenated organic compounds that provide information on aerosol sources and source processes. The major components detected at significant atmospheric concentrations were: (a) photo-oxidation products of isoprene including the 2-methyltetrols (2-methylthreitol and 2-methylerythritol) and 2-methylglyceric acid, (b) levoglucosan, a marker for biomass burning, (c) malic acid, an intermediate in the oxidation of unsaturated fatty acids, and (d) the sugar alcohols, arabitol and mannitol, markers for fungal spores. Diel patterns with highest concentrations during day-time were observed for the 2-methyltetrols, which can be regarded as supporting evidence for their fast photochemical formation from locally emitted isoprene. In addition, a diel pattern with highest concentrations during day-time was observed for the fungal markers, suggesting that the release of fungal fragments that are associated with the PM2.5 aerosol is enhanced during that time. Furthermore, a diel pattern was also found for levoglucosan with the highest concentrations at night when wood burning may take place in the settlements around the sampling site. In contrast, malic acid did not show day/night differences but was found to follow quite closely the particulate and organic carbon mass. This is interpreted as an indication that malic acid is formed in photochemical reactions which have a much longer overall time-scale than that of isoprene photo-oxidation, and the sources of its precursors are manifold, including both anthropogenic and natural emissions. On the basis of the high concentrations found for the isoprene oxidation products during day-time, it can be concluded that rapid photo-oxidation of isoprene is an important atmospheric chemistry process that contributes to secondary organic aerosol (SOA) formation at K-puszta during summer.
Comparison of microwave satellite humidity data and radiosonde profiles: A survey of European stations

A method to compare upper tropospheric humidity (UTH) from satellite and radiosonde data has been applied to the European radiosonde stations. The method uses microwave data as a benchmark for monitoring the performance of the stations. The present study utilizes three years (2001-2003) of data from channel 18 (183.31±1.00 GHz) of the Advanced Microwave Sounding Unit-B (AMSU-B) aboard the satellites NOAA-15 and NOAA-16. The comparison is done in the radiance space, the radiosonde data were transformed to the channel radiances using a radiative transfer model. The comparison results confirm that there is a dry bias in the UTH measured by the radiosondes. This bias is highly variable among the stations and the years. This variability is attributed mainly to the differences in the radiosonde humidity measurements. The analysis also shows a difference between daytime and nighttime soundings which is attributed to radiation error in the radiosonde data. The dry bias due to this error alone correspond to approximately 11% relative error in the UTH measurements.
The UV-A and visible solar irradiance spectrum: inter-comparison of absolutely calibrated, spectrally medium resolution solar irradiance spectra from balloon- and satellite-borne measurements

Within the framework of the ENVISAT/-SCIAMACHY satellite validation, solar irradiance spectra are absolutely measured at moderate resolution in the UV/visible spectral range (in the UV from 316.7-418 nm and the visible from 400-652 nm at a full width half maximum resolution of 0.55 nm and 1.48 nm, respectively) from aboard the azimuth-controlled LPMA/DOAS balloon gondola at around 32 km balloon float altitude. After accounting for the atmospheric extinction due to Rayleigh scattering and gaseous absorption (O3 and NO2), the measured solar spectra are compared with previous observations. Our solar irradiance spectrum perfectly agrees within +0.03% with the re-calibrated Kurucz et al. (1984) solar spectrum (Fontenla et al., 1999, called MODTRAN 3.7) in the visible spectral range (415-650 nm), but it is +2.1% larger in the (370-415 nm) wavelength interval, and -4% smaller in the UV-A spectral range (316.7-370 nm), when the Kurucz spectrum is convolved to the spectral resolution of our instrument. Similar comparisons of the SOLSPEC (Thuillier et al., 1997, 1998a, b) and SORCE/SIM (Harder et al., 2000) solar spectra with MODTRAN 3.7 confirms our findings with the values being -0.5%, +2%, and -1.4% for SOLSPEC -0.33%, -0.47%, and -6.2% for SORCE/SIM, respectively. Comparison of the SCIAMACHY solar spectrum from channels 1 to 4 (- re-calibrated by the University of Bremen -) with MODTRAN 3.7 indicates an agreement within -0.4% in the visible spectral range (415-585 nm), -1.6% within the 370-415 nm, and -5.7% within 325-370 nm wavelength interval, in agreement with the results of the other sensors. In agreement with findings of Skupin et al. (2002) our study emphasizes that the present ESA SCIAMACHY level 1 calibration is systematically +15% larger in the considered wavelength intervals when compared to all available other solar irradiance measurements.
Naturally driven variability in the global secondary organic aerosol over a decade

In order to investigate the variability of the secondary organic aerosol (SOA) distributions and budget and provide a measure for the robustness of the conclusions on human induced changes of SOA, a global 3-dimensional chemistry transport model describing both the gas and the particulate phase chemistry of the troposphere has been applied. The response of the global budget of SOA to temperature and moisture changes as well as to biogenic emission changes over a decade (1984-1993) has been evaluated. The considered emissions of biogenic non-methane volatile organic compounds (VOC) are driven by temperature, light and vegetation. They vary between 756 and 810 Tg Cy-1 and are therefore about 5.5 times higher than the anthropogenic VOC emissions. All secondary aerosols (sulphuric, nitrates and organics) are computed on-line together with the aerosol associated water. Over the studied decade, the computed natural variations (8%) in the chemical SOA production from biogenic VOC oxidation equal the chemical SOA production from anthropogenic VOC oxidation. Maximum values are calculated for 1990 (warmer and drier) and minimum values for 1986 (colder and wetter). The SOA computed variability results from a 7% increase in biogenic VOC emissions from 1986 to 1990 combined with 8.5% and 6% increases in the wet and dry deposition of SOA and leads to about 11.5% increase in the SOA burden of biogenic origin. The present study also demonstrates the importance of the hydrological cycle in determining the built up and fate of SOA in the atmosphere. It also reveals the existence of significant positive and negative feedback mechanisms in the atmosphere responsible for the non linear relationship between emissions of biogenic VOC and SOA burden.