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This report addresses the effects of pollution on the development of precipitation in clean ("pristine") and polluted ("hazy") environments in the Eastern Mediterranean by using the Integrated Community Limited Area Modeling System (ICLAMS) (an extended version of the Regional Atmospheric Modeling System, RAMS). The use of this model allows one to investigate the interactions of the aerosols with cloud development. The simulations show that the onset of precipitation in hazy clouds is delayed compared to pristine conditions. Adding small concentrations of GCCN to polluted clouds promotes early-stage rain. The addition of GCCN to pristine clouds has no effect on precipitation amounts. Topography was found to be more important for the distribution of precipitation than aerosol properties. Increasing by 15% the concentration of hygroscopic dust particles for a case study over the Eastern Mediterranean resulted in more vigorous convection and more intense updrafts. The clouds that were formed extended about three kilometers higher, delaying the initiation of precipitation by one hour. Prognostic treatment of the aerosol concentrations in the explicit cloud droplet nucleation scheme of the model, improved the model performance for the twenty-four hour accumulated precipitation. The spatial distribution and the amounts of precipitation were found to vary greatly between the different aerosol scenarios. These results indicate the large uncertainty that remains and the need for more accurate description of aerosol feedbacks in atmospheric models and climate change predictions.
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Methanol (CH<sub>3</sub>OH) and formic acid (HCOOH) are among the most abundant volatile organic compounds present in the atmosphere. In this work, we derive the global distributions of these two organic species using for the first time the Infrared Atmospheric Sounding Interferometer (IASI) launched onboard the MetOp-A satellite in 2006. This paper describes the method used and provides a first critical analysis of the retrieved products. The retrieval process follows a two-step approach in which global distributions are first obtained on the basis of a simple radiance indexing (transformed into brightness temperatures), and then mapped onto column abundances using suitable conversion factors. For methanol, the factors were calculated using a complete retrieval approach in selected regions. In the case of formic acid, a different approach, which uses a set of forward simulations for representative atmospheres, has been used. In both cases, the main error sources are carefully determined: the average relative error on the column for both species is estimated to be about 50%, increasing to about 100% for the least favorable conditions. The distributions for the year 2009 are discussed in terms of seasonality and source identification. Time series comparing methanol, formic acid and carbon monoxide in different regions are also presented.
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We have combined chemical and micrometeorological measurements to investigate the formation and distribution of HONO throughout a forest canopy. HONO was measured simultaneously at two heights, close to the forest floor and just above canopy. The turbulent exchange between the forest and the atmosphere above was studied using vertical profiles of eddy covariance measurements of wind velocity, sonic temperature, water vapour and CO<sub>2</sub>. HONO mixing ratios at both heights showed typical diel cycles with low daytime values (~80 ppt) and high nighttime values (up to 500 ppt), but were influenced by various sources and sinks leading to mixing ratio differences (above canopy minus below) of up to +240 ppt at nighttime. In the late afternoon and early night mixing ratios increased at higher rates near the forest floor, indicating a possible ground source. Due to the simultaneous decoupling of the forest from the air layer above the canopy, mixing ratio differences reached about −170 ppt. From the late night until the early morning mixing ratios above the forest were typically higher than close to the forest floor. For some cases, this could be attributed to advection above the forest, which only partly penetrated the canopy. Measured photolysis frequencies above and below the forest canopy differed by a factor of 10–25 resulting in HONO lifetimes of about 10 min above and 100–250 min below the canopy at noontime. However, these differences of the main daytime HONO sink were not evident in the mixing ratio differences, which were close to zero during the morning hours. Effective turbulent exchange due to a complete coupling of the forest to the air layer above the canopy in the morning has offset the differences caused by the daytime photolytic sink and added to the interplay between different HONO production and loss processes.
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Aerosols containing biological components can have a significant effect on human health by causing primarily irritation, infection and allergies. Specifically, airborne fungi can cause a wide array of adverse responses in humans depending on the type and quantity present. In this study we used chemical biomarkers for analyzing fungi-containing aerosols in the eastern Mediterranean region during the year 2009 in order to quantify annual fungal abundances. The prime marker for fungi used in this study was ergosterol, and its concentrations were compared with those of mannitol and arabitol which were recently suggested to also correlate with fungal spores concentrations (Bauer et al., 2008a). Back trajectory analysis, inorganic ions, humidity and temperature were used in an attempt to identify sources as well as the dependence on seasonal and environmental conditions. We found that the ambient concentrations of ergosterol, arabitol and mannitol range between 0 and 2.73 ng m<sup>−3</sup>, 1.85 and 58.27 ng m<sup>−3</sup>, 5.57 and 138.03 ng m<sup>−3</sup>, respectively. The highest levels for all biomarkers were during the autumn, probably from local terrestrial sources, as deduced from the inorganic ions and back trajectory analysis. Significant correlations were observed between arabitol and mannitol during the entire year except for the winter months. Both sugars correlated with ergosterol only during the spring and autumn. We conclude that mannitol and arabitol might not be specific biomarkers for fungi and that the observed correlations during spring and autumn may be attributed to high levels of vegetation during spring blossoms and autumn decomposing.
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The composition and physical properties of aged atmospheric aerosol were characterized at a remote sampling site on the northern coast of Crete, Greece during the Finokalia Aerosol Measurement Experiment in May 2008 (FAME-2008). A reduced Dry-Ambient Aerosol Size Spectrometer (DAASS) was deployed to measure the aerosol water content and volumetric growth factor of fine particulate matter. The particles remained wet even at relative humidity (RH) as low as 20%. The aerosol was acidic during most of the measurement campaign, which likely contributed to the water uptake at low RH. The water content observations were compared to the thermodynamic model E-AIM, neglecting any contribution of the organics to aerosol water content. There was good agreement between the water measurements and the model predictions. Adding the small amount of water associated with the organic aerosol based on monoterpene water absorption did not change the quality of the agreement. These results strongly suggest that the water uptake by aged organic aerosol is relatively small (a few percent of the total water for the conditions during FAME-08) and generally consistent with what has been observed in laboratory experiments. The water concentration measured by a Q-AMS was well correlated with the DAASS measurements and in good agreement with the predicted values for the RH of the Q-AMS inlet. This suggests that, at least for the conditions of the study, the Q-AMS can provide valuable information about the aerosol water concentrations if the sample is not dried.
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Measurements of significant concentrations of IO, I<sub>2</sub> and BrO in a semi-polluted coast environment at Roscoff, in North-West France, have been made as part of the Reactive Halogens in the Marine Boundary Layer (RHaMBLe) campaign undertaken in September 2006. We use a one-dimensional column model, with idealised I<sub>2</sub> emissions predicted using macroalgael maps and tidal data from the littoral area surrounding Roscoff, to investigate the probable causes for these observations. The coupled microphysical and chemical aerosol model simulates mixed-phase halogen chemistry using two separate particle modes, seasalt and non-seasalt, each comprising of eight size-sections. This work confirms the finding of a previous study that the BrO measurements are most likely caused by unknown, local sources. We find that the remote observations of IO and I<sub>2</sub> are best replicated using the I<sub>2</sub> recycling mechanism suggested by previous studies, but that such a mechanism is not wholly necessary. However in-situ measurements of I<sub>2</sub> can only be explained by invoking an I<sub>2</sub> recycling mechanism. We suggest that focussed observations of the changes in NO<sub>x</sub> and NO<sub>y</sub> concentrations, as well as changes in the nitrate fraction of the non-seasalt aerosol mode, in the presence of I<sub>2</sub> bursts could be used to determine the atmospheric relevance of the predicted I<sub>2</sub> recycling mechanism.
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The column abundance of NO<sub>3</sub> was measured over Table Mountain Facility, CA (34.4° N, 117.7° W) from May 2003 through September 2004, using lunar occultation near full moon with a grating spectrometer. The NO<sub>3</sub> column retrieval was performed with the differential optical absorption spectroscopy (DOAS) technique using both the 623 and 662 nm NO<sub>3</sub> absorption bands. Other spectral features such as Fraunhofer lines and absorption from water vapor and oxygen were removed using solar spectra obtained at different airmass factors. We observed a seasonal variation, with nocturnally averaged NO<sub>3</sub> columns between 5−7 × 10<sup>13</sup> molec cm<sup>−2</sup> during October through March, and 5−22 × 10<sup>13</sup> molec cm<sup>−2</sup> during April through September. A subset of the data, with diurnal variability vastly different from the temporal profile obtained from one-dimensional stratospheric model calculations, clearly has boundary layer contributions; this was confirmed by simultaneous long-path DOAS measurements. However, even the NO<sub>3</sub> columns that did follow the modeled time evolution were often much larger than modeled stratospheric partial columns constrained by realistic temperatures and ozone concentrations. This discrepancy is attributed to substantial tropospheric NO<sub>3</sub> in the free troposphere, which may have the same time dependence as stratospheric NO<sub>3</sub>.
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Diurnal variations in hydroxyl (OH) in the stratosphere and mesosphere are analyzed using measurements from the Aura Microwave Limb Sounder (MLS). The primary driver for OH diurnal variations is the ultraviolet actinic flux that initiates the photochemical production of reactive hydrogen species. The magnitude of this flux is governed largely by changes in solar zenith angle (SZA) throughout the day, and OH diurnal variations are well approximated by an exponential function of the secant of SZA. Measured OH concentrations are fit to a function of the form exp[−βsec(SZA)], where the parameter β is a function of altitude. We examine the magnitude of β and show that it is related to the optical depths of ultraviolet absorption by ozone and molecular oxygen. Values of β from SLIMCAT model simulations show the same vertical structure as those from MLS and the average level of agreement between model and measurements is 6%. The vertical profile of β from MLS can be represented by a simple analytic formulation involving the ozone and water vapor photodissociation rates. This formulation is used to infer the altitude dependence of the primary production mechanisms for OH: the reaction of excited-state atomic oxygen with water vapor versus the direct photodissociation of water vapor.
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An inventory of anthropogenic primary aerosol emissions in China was developed for 1990–2005 using a technology-based approach. Taking into account changes in the technology penetration within industry sectors and improvements in emission controls driven by stricter emission standards, a dynamic methodology was derived and implemented to estimate inter-annual emission factors. Emission factors of PM<sub>2.5</sub> decreased by 7%–69% from 1990 to 2005 in different industry sectors of China, and emission factors of TSP decreased by 18%–80% as well, with the measures of controlling PM emissions implemented. As a result, emissions of PM<sub>2.5</sub> and TSP in 2005 were 11.0 Tg and 29.7 Tg, respectively, less than what they would have been without the adoption of these measures. Emissions of PM<sub>2.5</sub>, PM<sub>10</sub> and TSP presented similar trends: they increased in the first six years of 1990s and decreased until 2000, then increased again in the following years. Emissions of TSP peaked (35.5 Tg) in 1996, while the peak of PM<sub>10</sub> (18.8 Tg) and PM<sub>2.5</sub> (12.7 Tg) emissions occurred in 2005. Although various emission trends were identified across sectors, the cement industry and biofuel combustion in the residential sector were consistently the largest sources of PM<sub>2.5</sub> emissions, accounting for 53%–62% of emissions over the study period. The non-metallic mineral product industry, including the cement, lime and brick industries, accounted for 54%–63% of national TSP emissions. There were no significant trends of BC and OC emissions until 2000, but the increase after 2000 brought the peaks of BC (1.51 Tg) and OC (3.19 Tg) emissions in 2005. Although significant improvements in the estimation of primary aerosols are presented here, there still exist large uncertainties. More accurate and detailed activity information and emission factors based on local tests are essential to further improve emission estimates, this especially being so for the brick and coke industries, as well as for coal-burning stoves and biofuel usage in the residential sector.
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The scheme to propagate correlations between on-line and off-line state variables in atmospheric inversions using the fixed-lag Kalman smoother proposed in Bruhwiler et al. (2005) is explained as a process to impose a balanced constraint on the on-line state variables. It is then extended to the fixed-lag ensemble square root Kalman smoother and fixed-lag square root sigma-point Kalman smoother, allowing us to treat nonlinear observation operators easily. Further, to constrain the posterior fluxes within their feasible ranges, the constrained fixed-lag Kalman smoother is presented and the variable transform technique is proposed for the other two smoothers. Comparisons between various methods and observational data are conducted using a synthetic inversion of atmospheric CH<sub>4</sub> fluxes. The results indicate that our developed methods are good alternatives to existing methods for conducting sequential inversion of atmospheric trace gases. It is also shown that the benefit to include the correlations between on-line and off-line state variables is case dependent.
