Dynamic recycling of gaseous elemental mercury in the boundary layer of the Antarctic Plateau

International audienceGaseous elemental mercury (Hg0) was investigated in the troposphere and in the interstitial air extracted from the snow at Dome Concordia station (alt. 3320 m) on the Antarctic Plateau during January 2009. Measurements and modeling studies showed evidence of a very dynamic and daily cycling of Hg0 inside the mixing layer with a range of values from 0.2 ng m−3 up to 2.3 ng m−3. During low solar irradiation periods, fast Hg0 oxidation processes in a confined layer were suspected. Unexpectedly high Hg0 concentrations for such a remote place were measured under higher solar irradiation due to snow photochemistry. We suggest that a daily cycling of reemission/oxidation occurs during summer within the mixing layer at Dome Concordia. Hg0 concentrations showed a negative correlation with ozone mixing ratios, which contrasts with atmospheric mer- cury depletion events observed during the Arctic spring. Un- like previous Antarctic studies, we think that atmospheric Hg0 removal may not be the result of advection processes. The daily and dramatic Hg0 losses could be a consequence of surface or snow induced oxidation pathways. It remains however unclear whether halogens are involved. The cycling of other oxidants should be investigated together with Hg species in order to clarify the complex reactivity on the Antarctic plateau

Aerosol mass and black carbon concentrations, a two year record at NCO-P (5079 m, Southern Himalayas)

Aerosol mass and the absorbing fraction are important variables, needed to constrain the role of atmospheric particles in the Earth radiation budget, both directly and indirectly through CCN activation. In particular, their monitoring in remote areas and mountain sites is essential for determining source regions, elucidating the mechanisms of long range transport of anthropogenic pollutants, and validating regional and global models. Since March 2006, aerosol mass and black carbon concentration have been monitored at the Nepal Climate Observatory-Pyramid, a permanent high-altitude research station located in the Khumbu valley at 5079 m a.s.l. below Mt. Everest. The first two-year averages of PM<sub>1</sub> and PM<sub>1−10</sub> mass were 1.94 μg m<sup>−3</sup> and 1.88 μg m<sup>−3</sup>, with standard deviations of 3.90 μg m<sup>−3</sup> and 4.45 μg m<sup>−3</sup>, respectively, while the black carbon concentration average is 160.5 ng m<sup>−3</sup>, with a standard deviation of 296.1 ng m<sup>−3</sup>. Both aerosol mass and black carbon show well defined annual cycles, with a maximum during the pre-monsoon season and a minimum during the monsoon. They also display a typical diurnal cycle during all the seasons, with the lowest particle concentration recorded during the night, and a considerable increase during the afternoon, revealing the major role played by thermal winds in influencing the behaviour of atmospheric compounds over the high Himalayas. The aerosol concentration is subject to high variability: in fact, as well as frequent "background conditions" (55% of the time) when BC concentrations are mainly below 100 ng m<sup>−3</sup>, concentrations up to 5 μg m<sup>−3</sup> are reached during some episodes (a few days every year) in the pre-monsoon seasons. The variability of PM and BC is the result of both short-term changes due to thermal wind development in the valley, and long-range transport/synoptic circulation. At NCO-P, higher concentrations of PM<sub>1</sub> and BC are mostly associated with regional circulation and westerly air masses from the Middle East, while the strongest contributions of mineral dust arrive from the Middle East and regional circulation, with a special contribution from North Africa and South-West Arabian Peninsula in post-monsoon and winter season

Forecast, observation and modelling of a deep stratospheric intrusion event over Europe

A wide range of measurements was carried out in central and southeastern Europe within the framework of the EU-project STACCATO (Influence of Stratosphere-Troposphere Exchange in a Changing Climate on Atmospheric Transport and Oxidation Capacity) with the principle goal to create a comprehensive data set on stratospheric air intrusions into the troposphere along a rather frequently observed pathway over central Europe from the North Sea to the Mediterranean Sea. The measurements were based on predictions by suitable quasi-operational trajectory calculations using ECMWF forecast data. A predicted deep Stratosphere to Troposphere Transport (STT) event, encountered during the STACCATO period on 20-21 June 2001, could be followed by the measurements network almost from its inception. Observations provide evidence that the intrusion affected large parts of central and southeastern Europe. Especially, the ozone lidar observations on 20-21 June 2001 at Garmisch-Partenkirchen, Germany captured the evolution of two marked tongues of high ozone with the first one reaching almost a height of 2 km, thus providing an excellent data set for model intercomparisons and validation. In addition, for the first time to our knowledge concurrent measurements of the cosmogenic radionuclides <sup>10</sup>Be and <sup>7</sup>Be and their ratio <sup>10</sup>Be/<sup>7</sup>Be are presented together as stratospheric tracers in a case study of a stratospheric intrusion. The ozone tracer columns calculated with the FLEXPART model were found to be in good agreement with water vapour satellite images, capturing the evolution of the observed dry streamers of stratospheric origin. Furthermore, the time-height cross section of ozone tracer simulated with FLEXPART over Garmisch-Partenkirchen captures with many details the evolution of the two observed high-ozone filaments measured with the IFU lidar, thus demonstrating the considerable progress in model simulations. Finally, the modelled ozone (operationally available since October 1999) from the ECMWF (European Centre for Medium-Range Weather Forecasts) atmospheric model is shown to be in very good agreement with the observations during this case study, which provides the first successful validation of a chemical tracer that is used operationally in a weather forecast model. This suggests that coupling chemistry and weather forecast models may significantly improve both weather and chemical forecasts in the future

Aerosol-ozone correlations during dust transport episodes

Its location in the Mediterranean region and its physical characteristics render Mt. Cimone (44&deg;11&prime; N, 10&deg;42&prime; E), the highest peak of the Italian northern Apennines (2165 m asl), particularly suitable to study the transport of air masses from the north African desert area to Europe. During these northward transports 12 dust events were registered in measurements of the aerosol concentration at the station during the period June&ndash;December 2000, allowing the study of the impact of mineral dust transports on free tropospheric ozone concentrations, which were also measured at Mt. Cimone. Three-dimensional backward trajectories were used to determine the air mass origin, while TOMS Aerosol Index data for the Mt. Cimone area were used to confirm the presence of absorbing aerosol over the measurement site. <P style='line-height: 20px;'> A trajectory statistical analysis allowed identifying the main source areas of ozone and aerosols. The analysis of these back trajectories showed that central Europe and north and central Italy are the major pollution source areas for ozone and fine aerosol, whereas the north African desert regions were the most important source areas for coarse aerosol and low ozone concentrations. During dust events, the Mt. Cimone mean volume concentration for coarse particles was 6.18 &micro;m³/cm³ compared to 0.63 &micro;m³/cm³ in dust-free conditions, while the ozone concentrations were 4% to 21% lower than the monthly mean background values. Our observations show that surface ozone concentrations were lower than the background values in air masses coming from north Africa, and when these air masses were also rich in coarse particles, the lowest ozone values were registered. Moreover, preliminary results on the possible impact of the dust events on PM₁₀ and ozone values measured in Italian urban and rural areas showed that during the greater number of the considered dust events, significant PM₁₀ increases and ozone decreases have occurred in the Po valley

In situ physical and chemical characterisation of the Eyjafjallajökull aerosol plume in the free troposphere over Italy

Continuous measurements of physical and chemical properties at the Mt. Cimone (Italy) GAW-WMO (Global Atmosphere Watch, World Meteorological Organization) Global Station (2165 m a.s.l.) have allowed the detection of the volcanic aerosol plume resulting from the Eyjafjallajökull (Iceland) eruption of spring 2010. The event affected the Mt. Cimone site after a transport over a distance of more than 3000 km. Two main transport episodes were detected during the eruption period, showing a volcanic fingerprint discernible against the free tropospheric background conditions typical of the site, the first from April 19 to 21 and the second from 18 to 20 May 2010. This paper reports the modification of aerosol characteristics observed during the two episodes, both characterised by an abrupt increase in fine and, especially, coarse mode particle number. Analysis of major, minor and trace elements by different analytical techniques (ionic chromatography, particle induced X-ray emission–particle induced gamma-ray emission (PIXE–PIGE) and inductively coupled plasma mass spectrometry (ICP-MS)) were performed on aerosols collected by ground-level discrete sampling. The resulting database allows the characterisation of aerosol chemical composition during the volcanic plume transport and in background conditions. During the passage of the volcanic plume, the fine fraction was dominated by sulphates, denoting the secondary origin of this mode, mainly resulting from in-plume oxidation of volcanic SO2. By contrast, the coarse fraction was characterised by increased concentration of numerous elements of crustal origin, such as Fe, Ti, Mn, Ca, Na, and Mg, which enter the composition of silicate minerals. Data analysis of selected elements (Ti, Al, Fe, Mn) allowed the estimation of the volcanic plume's contribution to total PM10, resulting in a local enhancement of up to 9.5 μg m−3, i.e. 40% of total PM10 on 18 May, which was the most intense of the two episodes. These results appear significant, especially in light of the huge distance of Mt. Cimone from the source, confirming the widespread diffusion of the Eyjafjallajökull ashes over Europe

In situ physical and chemical characterisation of the Eyjafjallajökull aerosol plume in the free troposphere over Italy

Abstract. Continuous measurements of physical and chemical properties at the Mt. Cimone (Italy) GAW-WMO (Global Atmosphere Watch, World Meteorological Organization) Global Station (2165 m a.s.l.) have allowed the detection of the volcanic aerosol plume resulting from the Eyjafjallajökull (Iceland) eruption of spring 2010. The event affected the Mt. Cimone site after a transport over a distance of more than 3000 km. Two main transport episodes were detected during the eruption period, showing a volcanic fingerprint discernible against the free tropospheric background conditions typical of the site, the first from April 19 to 21 and the second from 18 to 20 May 2010. This paper reports the modification of aerosol characteristics observed during the two episodes, both characterised by an abrupt increase in fine and, especially, coarse mode particle number. Analysis of major, minor and trace elements by different analytical techniques (ionic chromatography, particle induced X-ray emission–particle induced gamma-ray emission (PIXE–PIGE) and inductively coupled plasma mass spectrometry (ICP-MS)) were performed on aerosols collected by ground-level discrete sampling. The resulting database allows the characterisation of aerosol chemical composition during the volcanic plume transport and in background conditions. During the passage of the volcanic plume, the fine fraction was dominated by sulphates, denoting the secondary origin of this mode, mainly resulting from in-plume oxidation of volcanic SO2. By contrast, the coarse fraction was characterised by increased concentration of numerous elements of crustal origin, such as Fe, Ti, Mn, Ca, Na, and Mg, which enter the composition of silicate minerals. Data analysis of selected elements (Ti, Al, Fe, Mn) allowed the estimation of the volcanic plume's contribution to total PM10, resulting in a local enhancement of up to 9.5 μg m−3, i.e. 40% of total PM10 on 18 May, which was the most intense of the two episodes. These results appear significant, especially in light of the huge distance of Mt. Cimone from the source, confirming the widespread diffusion of the Eyjafjallajökull ashes over Europe

Calibration and assessment of electrochemical low-cost sensors in remote alpine harsh environments

This work presents results from an original open-source low-cost sensor (LCS) system developed to measure tropospheric O3 in a remote high altitude alpine site. Our study was conducted at the Col Margherita Observatory (2543 m above sea level), in the Italian Eastern Alps. The sensor system mounts three commercial low-cost O3/NO2 sensors that have been calibrated before field deployment against a laboratory standard (Thermo Scientific; 49i-PS), calibrated against the standard reference photometer no. 15 calibration scale of the World Meteorological Organization (WMO). Intra- and intercomparison between the sensors and a reference instrument (Thermo Scientific; 49c) have been conducted for 7 months from May to December 2018. The sensors required an individual calibration, both in laboratory and in the field. The sensor's dependence on the environmental meteorological variables has been considered and discussed. We showed that it is possible to reduce the bias of one LCS by using the average coefficient values of another LCS working in tandem, suggesting a way forward for the development of remote field calibration techniques. We showed that it is possible reconstruct the environmental ozone concentration during the loss of reference instrument data in situations caused by power outages. The evaluation of the analytical performances of this sensing system provides a limit of detection (LOD) &lt;5 ppb (parts per billion), limit of quantification (LOQ) &lt;17 ppb, linear dynamic range (LDR) up to 250 ppb, intra-Pearson correlation coefficient (PCC) up to 0.96, inter-PCC &gt;0.8, bias &gt;3.5 ppb and ±8.5 at 95 % confidence. This first implementation of a LCS system in an alpine remote location demonstrated how to obtain valuable data from a low-cost instrument in a remote environment, opening new perspectives for the adoption of low-cost sensor networks in atmospheric sciences

Vertical distribution of aerosol optical properties in the Po Valley during the 2012 summer campaigns

Studying the vertical distribution of aerosol particle physical and chemical properties in the troposphere is essential to understand the relative importance of local emission processes vs. long-range transport for column-integrated aerosol properties (e.g. the aerosol optical depth, AOD, affecting regional climate) as well as for the aerosol burden and its impacts on air quality at the ground. The main objective of this paper is to investigate the transport of desert dust in the middle troposphere and its intrusion into the planetary boundary layer (PBL) over the Po Valley (Italy), a region considered one of the greatest European pollution hotspots for the frequency that particulate matter (PM) limit values are exceeded. Events of mineral aerosol uplift from local (soil) sources and phenomena of hygroscopic growth at the ground are also investigated, possibly affecting the PM concentration in the region as well. During the PEGASOS 2012 field campaign, an integrated observing–modelling system was set up based on near-surface measurements (particle concentration and chemistry), vertical profiling (backscatter coefficient profiles from lidar and radiosoundings) and Lagrangian air mass transport simulations by FLEXPART model. Measurements were taken at the San Pietro Capofiume supersite (44°39′ N, 11°37′ E; 11 m a.s.l.), located in a rural area relatively close to some major urban and industrial emissive areas in the Po Valley. Mt. Cimone (44°12′ N, 10°42′ E; 2165 m a.s.l.) WMO/GAW station observations are also included in the study to characterize regional-scale variability. Results show that, in the Po Valley, aerosol is detected mainly below 2000 m a.s.l. with a prevalent occurrence of non-depolarizing particles ( > 50 % throughout the campaign) and a vertical distribution modulated by the PBL daily evolution. Two intense events of mineral dust transport from northern Africa (19–21 and 29 June to 2 July) are observed, with layers advected mainly above 2000 m, but subsequently sinking and mixing in the PBL. As a consequence, a non-negligible occurrence of mineral dust is observed close to the ground (  ~7 % of occurrence during a 1-month campaign). The observations unambiguously show Saharan dust layers intruding the Po Valley mixing layer and directly affecting the aerosol concentrations near the surface. Finally, lidar observations also indicate strong variability in aerosol on shorter timescales (hourly). Firstly, these highlight events of hygroscopic growth of anthropogenic aerosol, visible as shallow layers of low depolarization near the ground. Such events are identified during early morning hours at high relative humidity (RH) conditions (RH  > 80 %). The process is observed concurrently with high PM1 nitrate concentration (up to 15 µg cm−3) and hence mainly explicable by deliquescence of fine anthropogenic particles, and during mineral dust intrusion episodes, when water condensation on dust particles could instead represent the dominant contribution. Secondly, lidar images show frequent events (mean daily occurrence of  ~ 22 % during the whole campaign) of rapid uplift of mineral depolarizing particles in afternoon–evening hours up to 2000 m a.s.l. height. The origin of such particles cannot be directly related to long-range transport events, being instead likely linked to processes of soil particle resuspension from agricultural lands

Significant variations of trace gas composition and aerosol properties at Mt. Cimone during air mass transport from North Africa &#8211; contributions from wildfire emissions and mineral dust

High levels of trace gas (O3 and CO) and aerosol (BC, fine and coarse particle volumes), as well as high scattering coefficient (&sigma;p) values, were recorded at the regional GAW-WMO station of Mt. Cimone (CMN, 2165 m a.s.l., Italy) during the period 26–30 August 2007. Analysis of air-mass circulation, aerosol chemical characterization and trace gas and aerosol enhancement ratios (ERs), showed that high O3 and aerosol levels were likely linked to (i) the transport of anthropogenic pollution from northern Italy, and (ii) the advection of air masses rich in mineral dust and biomass burning (BB) products from North Africa. In particular, during the advection of air masses from North Africa, the CO and aerosol levels (CO: 175 ppbv, BC: 1015 ng/m3, fine particle volume: 3.00 &mu;m3 cm&minus;3, &sigma;p: 84.5 Mm&minus;1) were even higher than during the pollution event (CO: 138 ppbv, BC: 733 ng/m3, fine particles volume: 1.58 &mu;m3 cm&minus;3, &sigma;p: 44.9 Mm). Moreover, despite the presence of mineral dust able to affect significantly the O3 concentration, the analysis of ERs showed that the BB event represented an efficient source of fine aerosol particles (e.g. BC), but also of the O3 recorded at CMN. In particular, the calculated O3/CO ERs (0.10–0.17 ppbv/ppbv) were in the range of values found in literature for relatively aged (2–4 days) BB plumes and suggested significant photochemical O3 production during the air-mass transport. For fine particles and &sigma;p, the calculated ERs was higher in the BB plumes than during the anthropogenic pollution events, stressing the importance of the identified BB event as a source of atmospheric aerosol able to affect the atmospheric radiation budget. These results suggest that episodes of mineral dust mobilization and wildfire emissions over North Africa could significantly influence radiative properties (as deduced from &sigma;p observations at CMN) and air quality over the Mediterranean basin and northern Italy

Carbonaceous aerosol in polar areas: First results and improvements of the sampling strategies

While more and more studies are being conducted on carbonaceous fractions—organic carbon (OC) and elemental carbon (EC)—in urban areas, there are still too few studies about these species and their effects in polar areas due to their very low concentrations; further, studies in the literature report only data from intensive campaigns, limited in time. We present here for the first time EC–OC concentration long-time data records from the sea-level sampling site of Ny-Ålesund, in the High Arctic (5 years), and from Dome C, in the East Antarctic Plateau (1 year). Regarding the Arctic, the median (and the interquartile range (IQR)) mass concentrations for the years 2011–2015 are 352 (IQR: 283–475) ng/m3 for OC and 4.8 (IQR: 4.6–17.4) ng/m3 for EC, which is responsible for only 3% of total carbon (TC). From both the concentration data sets and the variation of the average monthly concentrations, the influence of the Arctic haze on EC and OC concentrations is evident. Summer may be interested by high concentration episodes mainly due to long-range transport (e.g., from wide wildfires in the Northern Hemisphere, as happened in 2015). The average ratio of EC/OC for the summer period is 0.05, ranging from 0.02 to 0.10, and indicates a clean environment with prevailing biogenic (or biomass burning) sources, as well as aged, highly oxidized aerosol from long-range transport. Contribution from ship emission is not evident, but this result may be due to the sampling time resolution. In Antarctica, a 1 year-around data set from December 2016 to February 2018 is shown, which does not present a clear seasonal trend. The OC median (and IQR) value is 78 (64–106) ng/m3; for EC, it is 0.9 (0.6–2.4) ng/m3, weighing for 3% on TC values. The EC/OC ratio mean value is 0.20, with a range of 0.06–0.35. Due to the low EC and OC concentrations in polar areas, correction for the blank is far more important than in campaigns carried out in other regions, largely affecting uncertainties in measured concentrations. Through the years, we have thus developed a new sampling strategy that is presented here for the first time: samplers were modified in order to collect a larger amount of particulates on a small surface, enhancing the capability of the analytical method since the thermo-optical analyzer is sensitive to carbonaceous aerosol areal density. Further, we have recently coupled such modified samplers with a sampling strategy that makes a more reliable blank correction of every single sample possible