Mineral dust and tropospheric chemistry (MINATROC 2000) Special Issue,Atmospheric Chemistry and Physics. Editor(s): Y. Balkanski and R. van Dingenen

Aerosol physical properties were measured at the Monte Cimone Observatory (Italy) from 1 June till 6 July 2000. The measurement site is located in the transition zone between the continental boundary layer and the free troposphere (FT), at the border between the Mediterranean area and Central Europe, and is exposed to a variety of air masses. Sub-µm number size distributions, aerosol hygroscopicity near 90% RH, refractory size distribution at 270°C and equivalent black carbon mass were continuously measured. Number size distributions and hygroscopic properties indicate that the site is exposed to aged continental air masses, however during daytime it is also affected by upslope winds. The mixing of this transported polluted boundary layer air masses with relatively clean FT air leads to frequent nucleation events around local noon. Night-time size distributions, including fine and coarse fractions for each air mass episode, have been parameterized by a 3-modal lognormal distribution. Number and volume concentrations in the sub-?m modes are strongly affected by the air mass origin, with highest levels in NW-European air masses, versus very clean, free tropospheric air coming from the N-European sector. During a brief but distinct dust episode, the coarse mode is clearly enhanced. The observed hygroscopic behavior of the aerosol is consistent with the chemical composition described by Putaud et al. (2004), but no closure between known chemical composition and measured hygroscopicity could be made because the hygroscopic properties of the water-soluble organic matter (WSOM) are not known. The data suggest that WSOM is slightly-to-moderately hygroscopic (hygroscopic growth factor GF at 90% relative humidity between 1.05 and 1.51), and that this property may well depend on the air mass origin and history. External mixing of aerosol particles is observed in all air masses through the occurrence of two hygroscopicity modes (average GF of 1.22 and 1.37, respectively). However, the presence of "less" hygroscopic particles has mostly such a low occurrence rate that the average growth factor distribution for each air mass sector actually appears as a single mode. This is not the case for the dust episode, where the external mixing between less hygroscopic and more hygroscopic particles is very prominent, and indicating clearly the occurrence of a dust accumulation mode, extending down to 50 nm particles, along with an anthropogenic pollution mode. The presented physical measurements finally allow us to provide a partitioning of the sub-?m aerosol in four non-overlapping fractions (soluble/volatile, non-soluble/volatile, refractory/non-black carbon, black carbon) which can be associated with separate groups of chemical compounds determined with chemical-analytical techniques (ions, non-water soluble organic matter, dust, elemental carbon). All air masses except the free-tropospheric N-European and Dust episodes show a similar composition within the uncertainty of the data (53%, 37%, 5% and 5% respectively for the four defined fractions). Compared to these sectors, the dust episode shows a clearly enhanced refractory-non-BC fraction (17%), attributed to dust in the accumulation mode, whereas for the very clean N-EUR sector, the total refractory fraction is 25%, of which 13% non-BC and 12% BC.

Abstract. The EU-project MINATROC (MINeral dust And TROpospheric Chemistry) aims at enabling an estimation of the influence of mineral dust, a major, but to date largely ignored component of tropospheric aerosol, on tropospheric oxidant cycles. Within the scope of this project continuous atmospheric measurements of gas-phase HNO3 and SO2 were conducted in June and July 2000 at the CNR WMO station, situated on Monte Cimone (MTC) (44°11' N --10°42' E, 2165 m asl), Italy. African air transporting dust is occasionally advected over the Mediterranean Sea to the site, thus mineral aerosol emitted from Africa will encounter polluted air masses and provide ideal conditions to study their interactions. HNO3 and SO2 were measured with an improved CIMS (chemical ionization mass spectrometry) system for ground-based measurements that was developed and built at MPI-K Heidelberg. Since HNO3 is a very sticky compound special care was paid for the air-sampling and background-measurement system. Complete data sets could be obtained before, during and after major dust intrusions. For the first time these measurements might provide a strong observational indication of efficient uptake of gas-phase HNO3 by atmospheric mineral-dust aerosol particles.

A monitoring programme for halogenated climate-altering gases has been established in the frame of the SHARE EV-K2 -CNR project at the Nepal Climate Laboratory – Pyramid in the Himalayan range at the altitude of 5079 m a.s.l. The site is very well located to provide important insights on changes in atmospheric composition in a region that is of great significance for emissions of both anthropogenic and biogenic halogenated compounds. Measurements are performed since March 2006, with grab samples collected on a weekly basis. The first three years of data have been analysed. After the identification of the atmospheric background values for fourteen halocarbons, the frequency of occurrence of pollution events have been compared with the same kind of analysis for data collected at other global background stations. The analysis showed the fully halogenated species, whose production and consumption are regulated under the Montreal Protocol, show a significant occurrence of “above the baseline” values, as a consequence of their current use in the developing countries surrounding the region, meanwhile the hydrogenated gases, more recently introduced into the market, show less frequent spikes. Atmospheric concentration trends have been calculated as well, and they showed a fast increase, ranging from 5.7 to 12.6%, of all the hydrogenated species, and a clear decrease of methyl chloroform(-17.7%).The comparison with time series from other stations has also allowed to derive Meridional gradients, which are absent for long living well mixed species, while for the more reactive species, the gradient in creases inversely with respect to their atmospheric lifetime. The effect of long range transport and of local events on the atmospheric composition at the station has been analysed as well, allowing the identification of relevant source regions the Northern half of the Indian sub-continent. Also, at finer spatial scales, a smaller, local contribution of forest fires from the Khumbu valley has been detected.

In spite of being located at the heart of the highest mountain range in the world, the Himalayan Nepal Climate Observatory (5079 m a.s.l.) at the Ev-K2-CNR Pyramid is shown to be affected by the advection of pollution aerosols from the populated regions of southern Nepal and the Indo-Gangetic plains. Such an impact is observed along most of the period April 2006–March 2007 addressed here, with a minimum in the monsoon season. Backtrajectoryanalysis indicates long-range transport episodes occurring in this year to originate mainly in the west Asian deserts. At this high altitude site, the measured aerosol optical depth is observed to be about one order of magnitude lower than the one measured at Ghandi College (60 m a.s.l.), in the IndoGangetic basin. As for Ghandi College, and in agreement with the in situ ground observations at the Pyramid, the fine mode aerosol optical depth maximizes during winter and minimizes in the monsoon season. Conversely, total optical depth maximizes during the monsoon due to the occurrence of elevated, coarse particle layers. Possible origins of these particles are wind erosion from the surrounding peaks and hydrated/cloud-processed aerosols. Assessment of the aerosol radiative forcing is then expected to be hampered by the presence of these high altitude particle layers, which impede an effective, continuous measurement of anthropogenic aerosol radiative properties from sky radiance inversions and/or ground measurements alone. Even though the retrieved absorption coefficients of pollution aerosols were rather large (single scattering albedo of the order of 0.6–0.9 were observed in the month of April 2006), the corresponding low optical depths (0.03 at 500 nm) are expected to limit the relevant radiative forcing. Still, the high specific forcing of this aerosol and its capability of altering snow surface albedo provide good reasons for continuous monitoring.

A Kalman-filter based inverse emission estimation method for long-lived trace gases is presented for use in conjunction with a Lagrangian particle dispersion model like FLEXPART. The sequential nature of the approach allows tracing slow seasonal and interannual changes rather than estimating a single period-mean emission field. Other important features include the estimation of a slowly varying concentration background at each measurement station, the possibility to constrain the solution to non-negative emissions, the quantification of uncertainties, the consideration of temporal correlations in the residuals, and the applicability to potentially large inversion problems. The method is first demonstrated for a set of synthetic observations created from a prescribed emission field with different levels of (correlated) noise, which closely mimics true observations. It is then applied to real observations of the three halocarbons HFC-125, HFC-152a and HCFC-141b at the remote research stations Jungfraujoch and Mace Head for the quantification of emissions in Western European countries from 2006 to 2010. Estimated HFC-125 emissions are mostly consistent with national totals reported to the Kyoto protocol and show a generally increasing trend over the considered period. Results for HFC-152a are much more variable with estimated emissions being both higher and lower in different countries. The highest emissions of the order of 1000 Mg yr-1 are estimated for Italy which so far does not report HFC-152a emissions. Emissions of HCFC-141b show a continuing strong decrease as expected due to its ban under the Montreal Protocol. Emissions from France, however, were still rather large (near 1000 Mg yr-1) in the years 2006 and 2007 but strongly declined thereafter.

The possible minimal range of reduction in snow surface albedo due to dry deposition of black carbon (BC) in the pre-monsoon period (March–May) was estimated as a lower bound together with the estimation of its accuracy, based on atmospheric observations at the Nepal Climate Observatory – Pyramid (NCO-P) sited at 5079 m a.s.l. in the Himalayan region. A total BC deposition rate was estimated as 2.89 µg m-2 day -1 providing a total deposition of 266 µg m-2 for March–May at the site, based on a calculation with a minimal deposition velocity of (1.0×10 (-4) m s( -1)) with atmospheric data of equivalent BC concentration. Main BC size at NCO-P site was determined as 103.1–669.8 nm by correlation analyses between equivalent BC concentration and particulate size distributions in the atmosphere. The BC deposition from the size distribution data was also estimated. Itwas found that 8.7% of the estimated dry deposition corresponds to the estimated BC deposition from equivalent BC concentration data. If all the BC is deposited uniformly on the top 2-cm pure snow, the corresponding BC concentration is 26.0–68.2 µg kg-1, assuming snow density variations of 195–512 kg m-3 of Yala Glacier close to NCO-P site. Such a concentration of BC in snow could result in 2.0–5.2% albedo reductions. By assuming these albedo reductions continue throughout the year, and then applying simple numerical experiments with a glacier mass balance model, we estimated reductions would lead to runoff increases of 70–204 mm of water. This runoff is the equivalent of 11.6–33.9% of the annual discharge of a typical Tibetan glacier. Our estimates of BC concentration in snow surface for pre-monsoon season is comparable to those at similar altitudes in the Himalayan region, where glaciers and perpetual snow regions begin, in the vicinity of NCO-P. Our estimates from only BC are likely to represent a lower bound for snow albedo reductions, because we used a fixed slower deposition velocity. In addition, we excluded the effects of atmospheric wind and turbulence, snow aging, dust deposition, and snow albedo feedbacks. This preliminary study represents the first investigation of BC deposition and related albedo on snow, using atmospheric aerosol data observed at the southern slope in the Himalayas.

Physical and chemical characterizations of the atmospheric aerosol were carried out at Mt. Cimone (Italy) during the 4 June-4 July 2000 period. Particle size distributions in the size range 6nm-10µm were measured with a differential mobility analyzer (DMA) and an optical particle counter (OPC). Size-segregated aerosol was sampled using a 6-stage low pressure impactor. Aerosol samples were submitted to gravimetric and chemical analyses. Ionic, carbonaceous and refractory components of the aerosol were quantified. We compared the sub- and superµm aerosol mass concentrations determined by gravimetric measurements (mGM), chemical analyses (mmCA), and by converting particle size distribution to aerosol mass concentrations (mmSD). Mean random uncertainties associated with the determination of mmGM, mmCA, and mmSD were assessed. The three estimates of the sub-µm aerosol mass concentration agreed, which shows that within experimental uncertainty, the sub-µm aerosol was composed of the quantified components. The three estimates of the super-µm aerosol mass concentration did not agree, which indicates that random uncertainties and/or possible systematic errors in aerosol sampling, sizing or analyses were not adequately accounted for. Aerosol chemical composition in air masses from different origins showed differences, which were significant in regard to experimental uncertainties. During the Saharan dust advection period, coarse dust and fine anthropogenic particles were externally mixed. No anthropogenic sulfate could be found in the super-µm dust particles. In contrast, nitrate was shifted towards the aerosol super-µm fraction in presence of desert dust.

This study presents two years of continuous observations of physical aerosol properties at the GAW-WMO global station "Nepal Climate Observatory – Pyramid" (NCO-P, 27°57' N, 86°48' E), sited at 5079 m a.s.l. in the high Himalayan Khumbu Valley (Nepal). Measurements of aerosol number size distribution, aerosol optical depth (AOD) and single scattering albedo (SSA) are analysed from March 2006 to February 2008. By studying the temporal variations of coarse (1 µm < Dp < 10 µm) particle number concentration, 53 mineral Dust Transport Events (DTEs) are identified, accounting for 22.2% of the analysed data-set. Such events occurred prevalently during pre-monsoon (for 30.6% of the period) and winter (22.1%) seasons. However, uncommon cases of mineral dust transport are observed even during the monsoon season. The main sources of mineral dust reaching NCO-P are identified in the arid regions not far from the measurement site, i.e. from Tibetan Plateau, and Lot-Thar deserts, which account for 52% of the dust transport days. Moreover, a non-negligible contribution can be attributed to the Arabian Peninsula (17%) and the Indo-Gangetic Plains (16%), as indicated by three dimensional (3-D) back-trajectory analyses performed with LAGRANTO model. The observed DTEs lead to significant enhancements in the coarse aerosol number concentration (+513%) and coarse aerosol mass (+655%), as compared with average values observed in "dust-free" conditions ( 0.05 ± 0.11 cm(-3) and 3.4 ± 3.7 µg m(-3), respectively). During DTEs, SSA is higher (0.84–0.89) than on "dust-free" days (0.75–0.83), confirming the importance of this class of events as a driver of the radiative features of the regional Himalayan climate. Considering the dust events, a significant seasonal AOD increase (+37.5%) is observed in the post-monsoon, whereas lower increase (less than +11.1%) characterises the pre-monsoon and winter seasons confirming the influence of synoptic-scale mineral dust transports on the aerosol optical properties observed at NCO-P.

An intensive measurement campaign was performed in June 2000 at the Mt. Cimone station (44°11' N-10°42' E, 2165 m asl, the highest mountain in the northern Italian Apennines) to study photochemical ozone production in the lower free troposphere. In general, average mixing ratios of important trace gases were not very high (121 ± 20 ppbv CO, 0.284 ± 0.220 ppbv NOx, 1.15 ± 0.8 ppbv NOy, 58 ± 9 ppbv O3), which indicates a small contribution by local pollution. Those trace gas levels are representative of continental background air, which is further supported by the analysis of VOCs (e.g.: C2H6 = (905 ± 200) pptv, C3H8 = (268 ±110) pptv, C2H2 = (201 ± 102) pptv, C5H8 = (111 ± 124) pptv, benzene = (65 ± 33) pptv). Furthermore, significant diurnal variations for a number of trace gases (O3, CO, NOx, NOy, HCHO) indicate the presence of free tropospheric airmasses at nighttime as a consequence of local catabatic winds. Average mid-day peroxy radical concentrations at Mt. Cimone are of the order of 30 pptv. At mean NO concentrations of the order of 40 pptv this gives rise to significant in situ net O3 production of 0.1-0.3 ppbv/hr. The importance of O3 production is supported by correlations between O3, CO, NOz, and HCHO, and between HCHO, CO and NOy.