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A series of 7-week sampling campaigns were conducted in urban background sites of six European cities as follows: Duisburg (autumn), Prague (winter), Amsterdam (winter), Helsinki (spring), Barcelona (spring) and Athens (summer). The campaigns were scheduled to include seasons of local public health concern due to high particulate concentrations or findings in previously conducted epidemiological studies. Aerosol samples were collected in parallel with two identical virtual impactors that divide air particles into fine (PM<sub>2.5</sub>) and coarse (PM<sub>2.5-10</sub>) size ranges. From the collected filter samples, elemental (EC) and organic (OC) carbon contents were analysed with a thermal-optical carbon analyser (TOA); total Ca, Ti, Fe, Si, Al and K by energy dispersive X-ray fluorescence (ED-XRF); As, Cu, Ni, V, and Zn by inductively coupled plasma mass spectrometry (ICP/MS); Ca<sup>2+</sup>, succinate, malonate and oxalate by ion chromatography (IC); and the sum of levoglucosan+galactosan+mannosan (∑MA) by liquid chromatography mass spectrometry (LC/MS). The campaign means of PM<sub>2.5</sub> and PM<sub>2.5-10</sub> were 8.3-29.6 µg m<sup>-3</sup> and 5.4-28.7 µg m<sup>-3</sup>, respectively. The contribution of particulate organic matter (POM) to PM<sub>2.5</sub> ranged from 21% in Barcelona to 54% in Prague, while that to PM<sub>2.5-10</sub> ranged from 10% in Barcelona to 27% in Prague. The contribution of EC was higher to PM<sub>2.5</sub> (5-9%) than to PM<sub>2.5-10</sub> (1-6%) in all the six campaigns. Carbonate (C(CO<sub>3</sub>), that interferes with the TOA analysis, was detected in PM<sub>2.5-10</sub> of Athens and Barcelona but not elsewhere. It was subtracted from the OC by a simple integration method that was validated. The CaCO<sub>3</sub> accounted for 55% and 11% of PM<sub>2.5-10</sub> in Athens and Barcelona, respectively. It was anticipated that combustion emissions from vehicle engines affected the POM content in PM<sub>2.5</sub> of all the six sampling campaigns, but a comparison of mass concentration ratios of the selected inorganic and organic tracers of common sources of organic material to POM suggested also interesting differences in source dominance during the campaign periods: Prague (biomass and coal combustion), Barcelona (fuel oil combustion, secondary photochemical organics) and Athens (secondary photochemical organics). The on-going toxicological studies will clarify the health significance of these findings.
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Collections of samples were conducted for the determination of the size distributions of EC and OC during the intensive sampling campaigns of the POVA program, in two Alpine valleys of the French Alps, in summer and in winter. The comparison of concentrations obtained for samples collected in parallel with impactor- and filter-based methods is rather positive with slopes of 0.95 and 0.76 for OC and EC, respectively and correlations close to 1 (0.92 and 0.90 for OC and EC, respectively, n=26). This is an indication that the correction of pyrolysis seems to work for the impactor samples despite non even deposits. The size distributions of the concentrations of EC and OC present large evolutions between winter and summer, and between a suburban and a rural site. In winter, an overwhelming proportion of the mass fraction of both species is found in the droplet and accumulation modes, often (but not always) in association with sulfate and other chemical species resulting from secondary formation processes. Some indications of gas/particles exchanges can be found for the other parts of the size spectrum (the Aitken and super micron modes) in the case of the rural site. In summer, the changes are more drastic with, according to the case, a dominant droplet or accumulation mode. Particularly at the rural site, the large extent of processing of the aerosol due to gas/particles exchanges is evident for the Aitken and super micron modes, with increasing of the OC mass fractions in these size ranges. All of these observations give indications on the degree of internal vs. external mixing of the species investigated in the different modes.
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The IPCC has stressed the importance of producing unbiased estimates of the uncertainty in indirect aerosol forcing, in order to give policy makers as well as research managers an understanding of the most important aspects of climate change that require refinement. In this study, we use 3-D meteorological fields together with a radiative transfer model to examine the spatially-resolved uncertainty in estimates of the first indirect aerosol forcing. The global mean forcing calculated in the reference case is -1.30 Wm<sup>-2</sup>. Uncertainties in the indirect forcing associated with aerosol and aerosol precursor emissions, aerosol mass concentrations from different chemical transport models, aerosol size distributions, the cloud droplet parameterization, the representation of the in-cloud updraft velocity, the relationship between effective radius and volume mean radius, cloud liquid water content, cloud fraction, and the change in the cloud drop single scattering albedo due to the presence of black carbon are calculated. The aerosol burden calculated by chemical transport models and the cloud fraction are found to be the most important sources of uncertainty. Variations in these parameters cause an underestimation or overestimation of the indirect forcing compared to the base case by more than 0.6 Wm<sup>-2</sup>. Uncertainties associated with aerosol and aerosol precursor emissions, uncertainties in the representation of the aerosol size distribution (including the representation of the pre-industrial size distribution), and uncertainties in the representation of cloud droplet spectral dispersion effect cause uncertainties in the global mean forcing of 0.2~0.6 Wm<sup>-2</sup>. There are significant regional differences in the uncertainty associated with the first indirect forcing with the largest uncertainties in industrial regions (North America, Europe, East Asia) followed by those in the major biomass burning regions.
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Thermal/optical methods have been widely used for quantifying total carbon (TC), organic carbon (OC), and elemental carbon (EC) in ambient and source particulate samples. Thermally defined carbon fractions have been used for source identification. Temperature precision in thermal carbon analysis is critical to the allocation of carbon fractions. The sample temperature is determined by a thermocouple, which is usually located in the oven near the sample. Sample and thermocouple temperature may differ owing to different thermal properties between the sample filter punch and the thermocouple, or inhomogeneities in the heating zone. Quick-drying temperature-indicating liquids (Tempil Inc., South Plainfield, NJ) of different liquefying points are used as temperature calibration standards. These consist of chemicals that change their appearance at specific temperatures and can be optically monitored to determine the sample temperature. Temperature measures were evaluated for three different models of carbon analyzers. Sample temperatures were found to differ from sensor temperatures by 10 to 50°C. Temperature biases of 14 to 22°C during thermal analysis were found to change carbon fraction measurements. The temperature indicators allow calibration curves to be constructed that relate the sample temperature to the temperature measured by a thermocouple.
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A medium frequency spaced-antenna radar has been operating at Rothera station, Antarctica (67° S, 68° W) for two periods, between 1997-1998 and since 2002, measuring winds in the mesosphere and lower thermosphere. In this paper monthly mean winds are derived and presented along with three years of radiosonde balloon data for comparison with the HWM-93 model atmosphere and other high latitude southern hemisphere sites. The observed meridional winds are slightly more northwards than those predicted by the model above 80 km in the winter months and below 80 km in summer. In addition, the altitude of the summer time zero crossing of the zonal winds above the westward jet is overestimated by the model by up to 8 km. These data are then merged with the wind climatology obtained from falling sphere measurements made during the PORTA campaign at Rothera in early 1998 and the HWM-93 model atmosphere to generate a complete zonal wind climatology between 0 and 100 km as a benchmark for future studies at Rothera. A westwards (eastwards) maximum of 44 ms<sup>-1</sup> at 67 km altitude occurs in mid December (62 ms<sup>-1</sup> at 37 km in mid July). The 0 ms<sup>-1</sup> wind contour reaches a maximum altitude of 90 km in mid November and a minimum altitude of 18 km in January extending into mid March at 75 km and early October at 76 km.
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The erythemally weighted (UV) irradiance below the severely depleted Arctic vortices in spring 1996 and 1997 were substantially elevated. On average the UV increased 36 and 33% relative to the 1979-1981 mean assuming clear skies from day 80-100 in 1996 and 1997, respectively. On clear sky days large regions of the Arctic experienced maximum UV increases exceeding 70 and 50% on single days in 1996 and 1997, respectively. A minor fraction of these increases are not anthropogenic and have a dynamical origin as seen by comparison to 1982, when hardly any ozone depletion is expected.
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We report the first high-precision measurements of δ <sup>18</sup>O and Δ <sup>17</sup>O at high southern latitudes that can resolve changes in the isotopic composition of water vapor in the lowermost stratosphere and upper troposphere. A strong increase of δ <sup>18</sup>O with decreasing mixing ratio above the tropopause is evident in the data. Since also the water vapor mixing ratio decreases above the tropopause, the effect seen in the isotope data can be explained by mixing of moist air from the tropopause with dry stratospheric air. However, the source of this dry stratospheric air is not known; both fast transport from the extratropical tropopause or mixing with air from the dehydrated polar vortex are likely. The magnitude of the Δ <sup>17</sup>O-anomaly (departure from mass-dependent fractionation (MDF)) was below 2 per mil for each datapoint, and a zero anomaly in lower level stratospheric water vapor is possible. Various transport histories for the stratospheric data are discussed based on the mixing ratio and isotope data.
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As part of the LBA-SMOCC (Large-Scale Biosphere-Atmosphere Experiment in Amazonia - Smoke, Aerosols, Clouds, Rainfall, and Climate) 2002 campaign, we studied the emission of carbon monoxide (CO), carbon dioxide (CO<sub>2</sub>), and aerosol particles from Amazonian deforestation fires using an instrumented aircraft. Emission ratios for aerosol number (CN) relative to CO (ER<sub>CN/CO</sub>) fell in the range 14-32 cm<sup>-3</sup> ppb<sup>-1</sup> in most of the investigated smoke plumes. Particle number emission ratios have to our knowledge not been previously measured in tropical deforestation fires, but our results are in agreement with values usually found from tropical savanna fires. The number of particles emitted per amount biomass burned was found to be dependent on the fire conditions (combustion efficiency). Variability in ER<sub>CN/CO</sub> between fires was similar to the variability caused by variations in combustion behavior within each individual fire. This was confirmed by observations of CO-to-CO<sub>2</sub> emission ratios (ER<sub>CO/CO<sub>2</sub></sub>), which stretched across the same wide range of values for individual fires as for all the fires observed during the sampling campaign, reflecting the fact that flaming and smoldering phases are present simultaneously in deforestation fires. Emission factors (EF) for CO and aerosol particles were computed and a correction was applied for the residual smoldering combustion (RSC) fraction of emissions that are not sampled by the aircraft, which increased the EF by a factor of 1.5-2.1. Vertical transport of smoke from the boundary layer (BL) to the cloud detrainment layer (CDL) and the free troposphere (FT) was found to be a very common phenomenon. We observed a 20% loss in particle number as a result of this vertical transport and subsequent cloud processing, attributable to in-cloud coagulation. This small loss fraction suggests that this mode of transport is very efficient in terms of particle numbers and occurs mostly via non-precipitating clouds. The detrained aerosol particles released in the CDL and FT were larger than in the unprocessed smoke, mostly due to coagulation and secondary growth, and therefore more efficient at scattering radiation and nucleating cloud droplets. This process may have significant atmospheric implications on a regional and larger scale.
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SCIAMACHY CO<sub>2</sub> measurements show a large variability in total column CO<sub>2</sub> over the Sahara desert of up to 10%, which is not anticipated from in situ measurements and cannot be explained by results of atmospheric models. Comparisons with colocated aerosol measurements by TOMS and MISR over the Sahara indicate that the seasonal variation of SCIAMACHY-observed CO<sub>2</sub> strongly resembles seasonal variations of windblown dust. Correlation coefficients of monthly datasets of colocated MISR aerosol optical depth and SCIAMACHY CO<sub>2</sub> vary between 0.6 and 0.8, indicating that about half of the CO<sub>2</sub> variance is explained by aerosol optical depth. Radiative transfer model calculations confirm the role of dust and can explain the size of the errors. Sensitivity tests suggest that the remaining variance may largely be explained by variations in the vertical distribution of dust. Further calculations for a few typical aerosol classes and a broad range of atmospheric conditions show that the impact of aerosols on SCIAMACHY retrieved CO<sub>2</sub> is by far the largest over the Sahara, but may also reach significant levels elsewhere. Over the continents, aerosols lead mostly to overestimated CO<sub>2</sub> columns with the exception of biomass burning plumes and dark coniferous forests. Inverse modelling calculations confirm that aerosol correction of SCIAMACHY CO<sub>2</sub> measurements is needed to derive meaningful source and sink estimates. Methods for correcting aerosol-induced errors exist, but so far mainly on the basis of theoretical considerations. As demonstrated by this study, SCIAMACHY may contribute to a verification of such methods using real data.
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Using new in-situ field observations of the most abundant oxygenated VOCs (methanol, acetaldehyde, acetone, C<sub>3</sub>/C<sub>4</sub> carbonyls, MVK+MAC and acetic acid) we were able to constrain emission and deposition patterns above and within a loblolly pine <I>(Pinus taeda)</I> plantation with a sweetgum (<I>Liquidambar styraciflua</I>) understory. During the day canopy scale measurements showed significant emission of methanol and acetone, while methyl vinyl ketone and methacrolein, acetaldehyde and acetic acid were mainly deposited during the day. All oxygenated compounds exhibited strong losses during the night that could not be explained by conventional dry deposition parameterizations. Accompanying leaf level measurements indicated substantial methanol and acetone emissions from loblolly pine. The exchange of acetaldehyde was more complex. Laboratory measurements made on loblolly pine needles indicated that acetaldehyde may be either emitted or taken up depending on ambient concentrations, with the compensation point increasing exponentially with temperature, and that mature needles tended to emit more acetaldehyde than younger needles. Canopy scale measurements suggested mostly deposition. Short-term (approx. 2 h) ozone fumigation in the laboratory had no detectable impact on post-exposure emissions of methanol and acetone, but decreased the exchange rates of acetaldehyde. The emission of a variety of oxygenated compounds (e.g. carbonyls and alcohols) was triggered or significantly enhanced during laboratory ozone fumigation experiments. These results suggest that higher ambient ozone levels in the future might enhance the biogenic contribution of some oxygenated compounds. Those with sufficiently low vapor pressures may potentially influence secondary organic aerosol growth. Compounds recently hypothesized to be primarily produced in the canopy atmosphere via ozone plus terpenoid-type reactions can also originate from the oxidation reaction of ozone with leaf surfaces and inside the leaf. This needs to be taken into account when scaling up very reactive biogenic compounds.
