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Recent laboratory experiments showed that at conditions resembling those near the tropopause region, small ice particles can be coated by a liquid H<sub>2</sub>SO<sub>4</sub>/H<sub>2</sub>O over-layer formed after the freezing of diluted sulfuric acid/water aerosol drops. Here, idealized radiative transfer tests are conducted to evaluate the impact that such an over-layer would have on the radiative effects produced by sub-visible cirrus clouds (SVCs). Spherical particle shape is assumed to keep the problem tractable. The calculations show that the over-layer increases both the shortwave (SW) and longwave (LW) cloud radiative effects (CRE), but the impact is small: ~0.02 W m<sup>−2</sup>, or even less, for the total (LW+SW) CRE at the top of the atmosphere. For the smallest ice particles, for which the over-layer is thickest, the fractional change in CRE can, however, reach ~20% for the SW CRE and over 50% for the LW CRE. The dependence of LW and SW CRE on particle size is also studied in the paper. Calculations for spherical and spheroidal uncoated ice particles show that even for high, optically thin cirrus, the total CRE can be negative, if the diameter of the particles is smaller than about 3–4 μm. Apart from the SVCs, this result could be relevant for contrail cirrus clouds, which are believed to consist of large numbers of very small ice particles.
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New atmospheric particles with diameters of 3–10 nm and their subsequent growth to cloud condensation nucleus have been observed at various places in the European boundary layer. These events have been observed simultaneously within wide geographical areas (over 1000 km) in connection to specific weather systems, the cold air behind cyclones. Here we show that atmospheric aerosol formation (i.e. nucleation and initial growth) is favoured by the outbreak of cold Arctic air over northern Europe. Aerosol formation was about twice as common in Arctic air as in sub-Polar air, and even more so compared to other air masses. The most important general factor favouring aerosol formation in Arctic air and marine air was weaker competing condensational sink (CS) for the precursor gases (less pre-existing aerosols), while high CS prevented aerosol formation in heated sub-Polar air and mid-latitude air. High SO<sub>2</sub> levels favoured nucleation in continental air and high UV-B radiation in sub-tropical air. The critical factor that determined if aerosol formation would start on a day with Arctic air was the UV-B radiation. The same applied to sub-Polar air and continental air, while increased SO<sub>2</sub> concentration could trigger formation in heated sub-Polar and mid-latitude air, and reduced CS could cause formation in mid-latitude, marine or mixed/transient air. We speculate that strong emissions of volatile organic compounds from the Boreal forest and strong boundary layer dynamics may have caused aerosol formation in sub-Polar air masses and air in transition from a marine to a continental character. The monthly frequency of Arctic air masses and the probability for photo-chemically driven aerosol formation explains the observed annual cycle in monthly particle formation frequency as well as much of the inter annual variability. The same cyclones that transport cold, clean air from the Arctic to Europe will also transport warm polluted air in the other direction, which help cause the Arctic Haze phenomena. The cyclones have a key role for the atmospheric aerosol life cycle in mid to high latitudes. Due to the observed growth to the size of CCN in one to two days, there is a potential feed back from the effects on the CCN population and cloud albedo even within the same weather system, but also on the climatic time scale.
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In an effort to improve our understanding of aerosol impacts on climate, we implement a desert dust module within a regional climate model (RegCM). The dust module includes emission, transport, gravitational settling, wet and dry removal and calculations of dust optical properties. The coupled RegCM-dust model is used to simulate two dust episodes observed over the Sahara region (a northeastern Africa dust outbreak, and a west Africa-Atlantic dust outbreak observed during the SHADE "Saharan Dust Experiment"), as well as a three month simulation over an extended domain covering the Africa-Europe sector. Comparisons with satellite and local aerosol optical depth measurements shows that the model captures the main spatial (both horizontal and vertical) and temporal features of the dust distribution. The main model deficiency occurs in the representation of certain dynamical patterns observed during the SHADE case which is associated with an active easterly wave that contributed to the generation of the dust outbreak. The model appears suitable to conduct long term simulations of the effects of Saharan dust on African and European climate.
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Nitrate photolysis in the wavelength range 250–1200 nm was studied on ice in a controlled laboratory experiment. Monolayer coverage of nitrate was achieved by dosing well-known amounts of HNO<sub>3</sub> from the gas phase onto a frozen water surface. Fluxes of HONO and NO<sub>2</sub> into the gas phase with time were quantified at temperatures between 193 K and 258 K and as a function of illumination wavelength in the range: 250–345 nm. Whereas HONO release showed a strong temperature dependence at colder temperatures, attributed to reversible adsorption processes, NO<sub>2</sub> fluxes were independent of temperature. The observed fluxes of HONO and NO<sub>2</sub> at high temperature were not affected by diffusion or adsorption processes, and could be used to estimate a quantum yield for HONO formation of (3.8±0.6)×10<sup>−4</sup>. A different wavelength dependence for HONO and NO<sub>2</sub> fluxes indicates that additional reactions besides nitrate photolysis and subsequent release of the products contribute to the emission of nitrogen oxides.
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We propose an innovative approach for analysing ground-based FTIR spectra which allows us to detect variabilities of lower and middle/upper tropospheric HDO/H<sub>2</sub>O ratios. We show that the proposed method is superior to common approaches. We estimate that lower tropospheric HDO/H<sub>2</sub>O ratios can be detected with a noise to signal ratio of 15% and middle/upper tropospheric ratios with a noise to signal ratio of 50%. The method requires the inversion to be performed on a logarithmic scale and to introduce an inter-species constraint. While common methods calculate the isotope ratio posterior to an independent, optimal estimation of the HDO and H<sub>2</sub>O profile, the proposed approach is an optimal estimator for the ratio itself. We apply the innovative approach to spectra measured continuously during 15 months and present, for the first time, an annual cycle of tropospheric HDO/H<sub>2</sub>O ratio profiles as detected by ground-based measurements. Outliers in the detected middle/upper tropospheric ratios are interpreted by backward trajectories.
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We have estimated impacts of alternative aviation routings on the radiative forcing. Changes in ozone and OH have been estimated in four Chemistry Transport Models (CTMs) participating in the TRADEOFF project. Radiative forcings due to ozone and methane have been calculated accordingly. In addition radiative forcing due to CO<sub>2</sub> is estimated based on fuel consumption. Three alternative routing cases are investigated; one scenario assuming additional polar routes and two scenarios assuming aircraft cruising at higher (+2000 ft) and lower (−6000 ft) altitudes. Results from the base case in year 2000 are included as a reference. Taking first a steady state backward looking approach, adding the changes in the forcing from ozone, CO<sub>2</sub> and CH<sub>4</sub>, the ranges of the models used in this work are −0.8 to −1.8 and 0.3 to 0.6 m Wm<sup>−2</sup> in the lower (−6000 ft) and higher (+2000 ft) cruise levels, respectively. In relative terms, flying 6000ft lower reduces the forcing by 5–10% compared to the current flight pattern, whereas flying higher, while saving fuel and presumably flying time, increases the forcing by about 2–3%. Taking next a forward looking approach we have estimated the integrated forcing (m Wm<sup>−2</sup> yr) over 20 and 100 years time horizons. The relative contributions from each of the three climate gases are somewhat different from the backward looking approach. The differences are moderate adopting 100 year time horizon, whereas under the 20 year horizon CO<sub>2</sub> naturally becomes less important relatively. Thus the forcing agents impact climate differently on various time scales. Also, we have found significant differences between the models for ozone and methane. We conclude that we are not yet at a point where we can include non-CO<sub>2</sub> effects of aviation in emission trading schemes. Nevertheless, the rerouting cases that have been studied here yield relatively small changes in the radiative forcing due to the radiatively active gases.
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Anthropogenic sulfate aerosol is a major contributor to shortwave radiative forcing of climate change by direct light scattering and by perturbing cloud properties and to local concentrations of atmospheric particulate matter. Here we analyze results from previously published calculations with an Eulerian transport model for atmospheric sulfur species in the Northern Hemisphere in June–July, 1997 to quantify the absolute and relative contributions of specific source regions (North America, Europe, and Asia) and SO<sub>2</sub>-to-sulfate conversion mechanisms (gas-phase, aqueous-phase and primary sulfate) to sulfate and SO<sub>2</sub> column burdens as a function of location and time. Although material emitted within a given region dominates the sulfate and SO<sub>2</sub> column burden in that region, examination of time series at specific locations shows that material imported from outside can make a substantial and occasionally dominant contribution. Frequently the major fraction of these exogenous contributions to the sulfate column burden was present aloft, thus minimally impacting air quality at the surface, but contributing substantially to the burden and, by implication, to radiative forcing and diminution of surface irradiance. Although the dominant sulfate formation pathway in the domain as a whole is aqueous-phase reaction in clouds (62%), in regions with minimum opportunity for aqueous-phase reaction gas-phase oxidation is dominant, albeit with considerable temporal variability depending on meteorological conditions. These calculations highlight the importance of transoceanic transport of sulfate, especially at the western margins of continents under the influence of predominantly westerly transport winds.
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Values of the scavenging coefficient determined from observations of ultrafine particles (with diameters in the range 10–510 nm) during rain events at a boreal forest site in Southern Finland between 1996 and 2001 were reported by Laakso et al. (2003a). The estimated range of the median values of the scavenging coefficient was [7×10<sup>−6</sup>–4×10<sup>−5</sup>] s<sup>−1</sup>, which is generally higher than model calculations based only on below-cloud processes (Brownian diffusion, interception, and typical phoretic and charge effects). <P> In the present study, in order to interpret these observed data on scavenging coefficients from Laakso et al. (2003a), we use a model that includes below-cloud scavenging processes, mixing of ultrafine particles from the boundary layer (BL) into cloud, followed by cloud condensation nuclei activation and in-cloud removal by rainfall. The range of effective scavenging coefficient predicted by the new model, corresponding to wide ranges of values of its input parameters, are compared with observations. Results show that ultrafine particle removal by rain depends on aerosol size, rainfall intensity, mixing processes between BL and cloud elements, in-cloud scavenged fraction, in-cloud collection efficiency, and in-cloud coagulation with cloud droplets. <P> The scavenging coefficients predicted by the new model are found to be significantly sensitive to the choice of representation of: (1) mixing processes; (2) raindrop size distribution; (3) phoretic effects in aerosol-raindrop collisions; and (4) cloud droplet activation. Implications for future studies of BL ultrafine particles scavenging are discussed.
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The historical total ozone measurements taken with Dobson Spectrophotometer #8 at Longyearbyen (78.2° N, 15.6° E), Svalbard, Norway, in the period 1950–1962 have been re-analyzed and homogenized based on the original measurement logs, using present-day procedures. In lack of sufficient calibration information, an empirical quality assessment was performed, based on a climatological comparison with ozone measurements in Tromsø, using TOMS data at both sites in the period 1979–2001, and ground-based Dobson data in the period 1950–1962. The assessment revealed that the C wavelength pair direct-sun (DS) measurements are most trustworthy (and most frequent), while the WMO standard reference mode AD direct-sun has a systematic bias. Zenith-blue (ZB) measurements at solar zenith angles (SZA) <78° were adjusted to DS data using different empirical functions before and after 1957 (the start of the International Geophysical Year). ZB measurements at larger SZAs were homogenized by means of a normalization function derived from days with measurements over a wide range of SZAs. Zenith-cloudy measurements, which are particularly frequent during the summer months, were homogenized by applying correction factors depending on the cloud type (high thin clouds and medium to low thick clouds). The combination of all measurements yields a total of 4685 single values, covering 1637 days from September 1950 to September 1962; moon measurements during the polar night add another 137 daily means. The re-evaluated data show a convincing consistence with measurements since 1979 (TOMS, SAOZ, Dobson) as well as with the 1957–1962 data stored at the World Ozone and UV Data Centre (WOUDC).
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The contribution of bromoform to the stratospheric bromine loading is estimated using the one-dimensional tropical mean model of Folkins and Martin (2005), which is constrained by observed mean profiles of temperature and humidity. In order to reach the stratosphere, bromoform needs to be lifted by deep convection into the tropical tropopause layer (TTL), above the level of zero radiative heating. The contribution of bromoform to stratospheric bromine then depends critically on the rate of removal of the degradation products of bromoform (collectively called Br<sub>y</sub> here) from the TTL, which is believed to be due to scavenging by falling ice. This relates the transport of short-lived bromine species into the stratosphere to processes of dehydration in the TTL. In the extreme case of dehydration occurring only through overshooting deep convection, the loss of Br<sub>y</sub> from the TTL may be negligible and consequently bromoform will fully contribute with its boundary layer mixing ratio to the stratospheric bromine loading, i.e. with 3 pptv for an assumed 1 pptv of bromoform in the boundary layer. For the other extreme that Br<sub>y</sub> is removed from the TTL almost instantaneously, the model calculations predict a contribution of about 0.5 pptv for the assumed 1 pptv of boundary layer bromoform. While this gives some constraints on the contribution of bromoform to stratospheric bromine, a key uncertainty in estimating the contribution of short-lived bromine source gases to the stratospheric bromine loading is the mechanism and rate of removal of Br<sub>y</sub> within the TTL.
