Free Tropospheric Conditions Research Articles

Marine and terrestrial contributions to atmospheric deposition fluxes of methylated arsenic species

Arsenic, a toxic element from both anthropogenic and natural sources, reaches surface environments through atmospheric cycling and dry and wet deposition. Biomethylation volatilizes arsenic into the atmosphere and deposition cycles it back to the surface, affecting soil-plant systems. Chemical speciation of deposited arsenic is important for understanding further processing in soils and bioavailability. However, the range of atmospheric transport and source signature of arsenic species remain understudied. Here we report significant levels of methylated arsenic in precipitation, cloud water and aerosols collected under free tropospheric conditions at Pic du Midi Observatory (France) indicating long-range transport, which is crucial for atmospheric budgets. Through chemical analyses and moisture source diagnostics, we identify terrestrial and marine sources for distinct arsenic species. Estimated atmospheric deposition fluxes of methylated arsenic are similar to reported methylation rates in soils, highlighting atmospheric deposition as a significant, overlooked source of potentially bioavailable methylated arsenic species impacting plant uptake in soils.

Measurement report: Insights into the chemical composition and origin of molecular clusters and potential precursor molecules present in the free troposphere over the southern Indian Ocean: observations from the Maïdo Observatory (2150 m a.s.l., Réunion)

Abstract. New particle formation (NPF) in the free troposphere (FT) is thought to be a significant source of particles over the oceans. The entrainment of particles initially formed in the marine FT is further suspected to be a major contributor to cloud condensation nuclei (CCN) number concentrations in the marine boundary layer (BL). Yet, little is known about the process and, more broadly, about the composition of the marine FT, which remains poorly explored due to access difficulties. Here we report measurements performed in April 2018 at the Maïdo Observatory with a nitrate-based chemical ionization atmospheric pressure interface time-of-flight mass spectrometer, which have allowed the first molecular-level characterization of the remote marine FT composition. A number of molecules and clusters were identified and classified into nine groups according to their chemical composition; among the identified species, the groups containing methanesulfonic acid (MSA) and C2 amines show signals that are on average significantly higher when the site is under conditions representative of the marine FT (compared to the BL). The correlation analysis revealed apparent connections between the signals of the identified compounds and several variables concurrently measured at the site (under FT conditions) or related to air mass history, suggesting that oxalic acid, malonic acid, and observed C2 amines could be of terrestrial origin, with, in addition, a possible marine source for oxalic acid and amines, while iodic acid, sulfur species, and maleic acid have a dominant marine origin. Identification of FT conditions at the site was based on the analysis of the standard deviation of the wind direction; this parameter, which can easily be derived from continuous measurements at the site, is shown in the first part of the study to be a relevant tracer when compared to predictions from the Meso-NH atmospheric model. Similar to other high-altitude sites, FT conditions are mainly encountered at night at Maïdo; therefore, the link to NPF could not be established, and further research is needed to assess the composition of precursors to nanoparticle formation in the marine FT.

Experimental Determination of the Relationship Between Organic Aerosol Viscosity and Ice Nucleation at Upper Free Tropospheric Conditions

AbstractThis work presents measurements of the ice nucleating ability of secondary organic material recorded between −40 and −70°C and relative humidity with respect to ice (RHice) between 150% and 220%. For a subset of systems, temperature and humidity dependence of particle viscosity as well as dry glass transition temperature were characterized using the dual tandem differential mobility analyzer method. Eleven unique monoterpene, sesquiterpene and aromatic precursors were used to generate secondary organic material (SOM) using either an oxidation flow reactor (OFR) or an environmental chamber (EC). For the SOM for which viscosity was measured, the particle glass transition temperatures varied between 6 and 23°C (n = 8). Measurements were performed to verify that increased relative humidity did not plasticize the particles below −10°C at residence times similar to those in the ice nucleation instrument. No heterogeneous ice nucleation was observed at the ∼0.5% onset threshold for any of the materials generated. The ice nucleation occurs by the freezing of SOM solution droplets consistent with homogeneous freezing indicating that they form an aqueous solution, or the SOM particles required water saturation to freeze, indicating that they were hydrophobic. Experiments exploring the influence of functional groups and mass loading did not reveal any obvious influence of particle chemistry or generation conditions on the results. Close structural matches between known organic ice nucleating particles as precursor or formed products did not yield materials that promoted freezing. These experiments suggest that heterogeneous ice formation of glassy secondary organic materials is likely uncommon under upper free tropospheric conditions.

Measurement report: Ice-nucleating particles active ≥ −15 °C in free tropospheric air over western Europe

Abstract. Ice-nucleating particles (INPs) initiate ice formation in supercooled clouds, typically starting in western Europe at a few kilometres above the ground. However, little is known about the concentration and composition of INPs in the lower free troposphere (FT). Here, we analysed INPs active at −10 ∘C (INP−10) and −15 ∘C (INP−15) that were collected under FT conditions at the high-altitude observatory Jungfraujoch between January 2019 and March 2021. We relied on continuous radon measurements to distinguish FT conditions from those influenced by the planetary boundary layer. Median concentrations in the FT were 2.4 INP−10 m−3 and 9.8 INP−15 m−3, with a multiplicative standard deviation of 2.0 and 1.6 respectively. A majority of INPs were deactivated after exposure to 60 ∘C; thus, they probably originated from certain epiphytic bacteria or fungi. Subsequent heating to 95 ∘C deactivated another 15 % to 20 % of the initial INPs, which were likely other types of fungal INPs that might have been associated with soil organic matter or with decaying leaves. Very few INP−10 withstood heating to 95 ∘C, but on average 20 % of INP−15 in FT samples did so. This percentage doubled during Saharan dust intrusions, which had practically no influence on INP−10. Overall, the results suggest that aerosolised epiphytic microorganisms, or parts thereof, are responsible for the majority of primary ice formation in moderately supercooled clouds above western Europe.

Albedo susceptibility of northeastern Pacific stratocumulus: the role of covarying meteorological conditions

Abstract. Quantification of the radiative adjustment of marine low clouds to aerosol perturbations, regionally and globally, remains the largest source of uncertainty in assessing current and future climate. One of the important steps towards quantifying the role of aerosol in modifying cloud radiative properties is to quantify the susceptibility of cloud albedo and liquid water path (LWP) to perturbations in cloud droplet number concentration (Nd). We use 10 years of spaceborne observations from the polar-orbiting Aqua satellite to quantify the albedo susceptibility of marine low clouds to Nd perturbations over the northeast (NE) Pacific stratocumulus (Sc) region. Mutual information analysis reveals a dominating control of cloud state (e.g., LWP and Nd) on low-cloud albedo susceptibility, relative to the meteorological states that drive these cloud states. Through a LWP–Nd space decomposition of albedo susceptibilities, we show clear separation among susceptibility regimes (brightening or darkening), consistent with previously established mechanisms through which aerosol modulates cloud properties. These regimes include (i) thin non-precipitating clouds (LWP < 55 g m−2) that exhibit brightening (occurring 37 % of the time), corresponding to the Twomey effect; (ii) thicker non-precipitating clouds, corresponding to entrainment-driven negative LWP adjustments that manifest as a darkening regime (36 % of the time); and (iii) another brightening regime (22 % of the time) consisting of mostly precipitating clouds, corresponding to precipitation-suppression LWP positive adjustments. Overall, we find an annual-mean regional low-cloud brightening potential of 20.8±2.68 W m−2 ln(Nd)−1, despite an overall negative LWP adjustment for non-precipitating marine stratocumulus, owing to the high occurrence of the Twomey–brightening regime. Over the NE Pacific, clear seasonal covariabilities among meteorological factors related to the large-scale circulation are found to play an important role in grouping conditions favorable for each susceptibility regime. When considering the covarying meteorological conditions, our results indicate that for the northeastern Pacific stratocumulus, clouds that exhibit the strongest brightening potential occur most frequently within shallow marine boundary layers over a cool ocean surface with a stable atmosphere and a dry free troposphere above. Clouds that exhibit a darkening potential associated with negative LWP adjustments occur most frequently within deep marine boundary layers in which the atmospheric instability and the ocean surface are not strong and warm enough to produce frequent precipitation. Cloud brightening associated with warm-rain suppression is found to preferably occur either under unstable atmospheric conditions or humid free-tropospheric conditions that co-occur with a warm ocean surface.

Long-term characterisation of the vertical structure of the Saharan Air Layer over the Canary Islands using lidar and radiosonde profiles: implications for radiative and cloud processes over the subtropical Atlantic Ocean

Abstract. Every year, large-scale African dust outbreaks frequently pass over the Canary Islands (Spain). Here we describe the seasonal evolution of atmospheric aerosol extinction and meteorological vertical profiles on Tenerife over the period 2007–2018 using long-term micropulse lidar (MPL-3) and radiosonde observations. These measurements are used to categorise the different patterns of dust transport over the subtropical North Atlantic and, for the first time, to robustly describe the dust vertical distribution in the Saharan Air Layer (SAL) over this region. Three atmospheric scenarios dominate the aerosol climatology: dust-free (clean) conditions, the Saharan summer scenario (summer-SAL) and the Saharan winter scenario (winter-SAL). A relatively well-mixed marine boundary layer (MBL) was observed in the case of clean (dust-free) conditions; it was associated with rather constant lidar extinction coefficients (α) below 0.036 km−1 with minimum α (< 0.022 km−1) in the free troposphere (FT). The summer-SAL has been characterised as a dust-laden layer strongly affecting both the MBL (Δα = +48 % relative to clean conditions) and the FT. The summer-SAL appears as a well-stratified layer, relatively dry at lower levels (Δr∼-44 % at the SAL’s base, where r is the water vapour mixing ratio) but more humid at higher levels compared with clean FT conditions (Δr∼+332 % at 5.3 km), with a peak of α> 0.066 km−1 at ∼ 2.5 km. Desert dust is present up to ∼ 6.0 km, the SAL top based on the altitude of SAL's temperature inversion. In the winter-SAL scenario, the dust layer is confined to lower levels below 2 km altitude. This layer is characterised by a dry anomaly at lower levels (Δr∼ −38 % in comparison to the clean scenario) and a dust peak at ∼ 1.3 km height. Clean FT conditions were found above 2.3 km. Our results reveal the important role that both dust and water vapour play in the radiative balance within the summer-SAL and winter-SAL. The dominant dust-induced shortwave (SW) radiative warming in summer (heating rates up to +0.7 K d−1) is found slightly below the dust maximum. However, the dominant contribution of water vapour was observed as a net SW warming observed within the SAL (from 2.1 to 5.7 km) and as a strong cold anomaly near the SAL's top (−0.6 K d−1). The higher water vapour content found to be carried on the summer-SAL, despite being very low, represents a high relative variation in comparison to the very dry clean free troposphere in the subtropics. This relevant aspect should be properly taken into account in atmospheric modelling processes. In the case of the winter-SAL, we observed a dust-induced radiative effect dominated by SW heating (maximum heating of +0.7 K d−1 at 1.5 km, near the dust peak); both dust and atmospheric water vapour impact heating in the atmospheric column. This is the case of the SW heating within the SAL (maximum near the r peak), the dry anomaly at lower levels (Δr∼ −38 % at 1 km) and the thermal cooling (∼ 0.3 K d−1) from the temperature inversion upwards. Finally, we hypothesise that the SAL can impact heterogeneous ice nucleation processes through the frequent occurrence of mid-level clouds observed near the SAL top at relatively warm temperatures. A dust event that affected Tenerife on August 2015 is simulated using the regional DREAM model to assess the role of dust and water vapour carried within SAL in the ice nucleation processes. The modelling results reproduce the arrival of the dust plume and its extension over the island and confirm the observed relationship between the summer-SAL conditions and the formation of mid- and high-level clouds.

Chemical composition of nanoparticles from <i>α</i>-pinene nucleation and the influence of isoprene and relative humidity at low temperature

Abstract. Biogenic organic precursors play an important role in atmospheric new particle formation (NPF). One of the major precursor species is α-pinene, which upon oxidation can form a suite of products covering a wide range of volatilities. Highly oxygenated organic molecules (HOMs) comprise a fraction of the oxidation products formed. While it is known that HOMs contribute to secondary organic aerosol (SOA) formation, including NPF, they have not been well studied in newly formed particles due to their very low mass concentrations. Here we present gas- and particle-phase chemical composition data from experimental studies of α-pinene oxidation, including in the presence of isoprene, at temperatures (−50 and −30 ∘C) and relative humidities (20 % and 60 %) relevant in the upper free troposphere. The measurements took place at the CERN Cosmics Leaving Outdoor Droplets (CLOUD) chamber. The particle chemical composition was analyzed by a thermal desorption differential mobility analyzer (TD-DMA) coupled to a nitrate chemical ionization–atmospheric pressure interface–time-of-flight (CI-APi-TOF) mass spectrometer. CI-APi-TOF was used for particle- and gas-phase measurements, applying the same ionization and detection scheme. Our measurements revealed the presence of C8−10 monomers and C18−20 dimers as the major compounds in the particles (diameter up to ∼ 100 nm). Particularly, for the system with isoprene added, C5 (C5H10O5−7) and C15 compounds (C15H24O5−10) were detected. This observation is consistent with the previously observed formation of such compounds in the gas phase. However, although the C5 and C15 compounds do not easily nucleate, our measurements indicate that they can still contribute to the particle growth at free tropospheric conditions. For the experiments reported here, most likely isoprene oxidation products enhance the growth of particles larger than 15 nm. Additionally, we report on the nucleation rates measured at 1.7 nm (J1.7 nm) and compared with previous studies, we found lower J1.7 nm values, very likely due to the higher α-pinene and ozone mixing ratios used in the present study.

Dust and tropical PMx aerosols in Cape Verde: Sources, vertical distributions and stratified transport from North Africa

We investigated the sources and processes affecting the vertical distribution of tropical PMx aerosols (particulate matter -PM- smaller than 10, 2.5 and 1 μm, PM10, PM2.5 and PM1, respectively) in the low troposphere of Santo Antão and São Vicente islands, in Cape Verde archipelago, a region where a better understanding of aerosols is needed due to their involvement in tropical meteorology and their impact on air quality, ocean and climate. We found that local sources had a low-scale impact. From transect measurements at ground level, we found that PMx levels were predominantly low, except near to PMx sources, where distinctive PM1 / PM2.5 ratios were measured, linked to vehicle exhaust (0.96), biomass burning (0.67) and Cape Verdean dust (0.36) emissions. The depth of the marine boundary layer (MBL) and the vertical distributions of PMx showed wide variability prompted by meteorological conditions. The trade winds prevailed in the MBL, whereas other airflows were situated above it: North-Atlantic, African easterly airflow and Saharan Air Layer. Under North-Atlantic airflow conditions, the MBL extended to 1400 m above sea level (m.a.s.l.). Above this altitude, PMx concentrations decreased quickly (< 3 μg/m3) due to the free troposphere conditions. Under Saharan dust conditions, the MBL was confined to just 70 m.a.s.l., whereas a complex dust stratification was observed above, characterized by alternating dry air layers with high dust loads (PM10 ~ 100 μg/m3) and more humid air layers with lower aerosol loads (PM10 ~ 40 μg/m3). Within the dry easterly African airflow occurring above the marine stratocumulus typical of the MBL top (placed at 500 m.a.s.l.), we detected layers enriched in hydrophilic aerosols (PM10: ~ 8 μg/m3). These were imbedded in relatively humid air (RH ~48%), probably linked to secondary aerosol formation by in-cloud processes in the marine stratocumulus situated below. We found that PMx transport from North Africa, both under dust and dust-free conditions, is associated with complex vertical stratifications, even within the dusty Saharan Air Layer.

Long-term trends of black carbon and particle number concentration in the lower free troposphere in Central Europe

BackgroundThe implementation of emission mitigation policies in Europe over the last two decades has generally improved the air quality, which resulted in lower aerosol particle mass, particle number, and black carbon mass concentration. However, little is known whether the decreasing particle concentrations at a lower-altitude level can be observed in the free troposphere (FT), an important layer of the atmosphere, where aerosol particles have a longer lifetime and may affect climate dynamics. In this study, we used data from two high-Alpine observatories, Zugspitze-Schneefernerhaus (ZSF) and Jungfraujoch (JFJ), to assess the long-term trends on size-resolved particle number concentrations (PNCs) and equivalent black carbon (eBC) mass concentration separated for undisturbed lower FT conditions and under the influence of air from the planetary boundary layer (PBL) from 2009 to 2018.ResultsThe FT and PBL-influenced conditions were segregated for both sites. We found that the FT conditions in cold months were more prevalent than in warm months, while the measured aerosol parameters showed different seasonal patterns for the FT and PBL-influenced conditions. The pollutants in the PBL-influenced condition have a higher chance to be transported to high-altitudes due to the mountainous topography, leading to a higher concentration and more distinct seasonal variation, and vice versa. The long-term trends of the measured aerosol parameters were evaluated and the decreased aerosol concentrations were observed for both FT and PBL-influenced conditions. The observed decreasing trends in eBC concentration in the PBL-influenced condition are well consistent with the reported trends in total BC emission in Germany and Switzerland. The decreased concentrations in the FT condition suggest that the background aerosol concentration in the lower FT over Central Europe has correspondingly decreased. The change of back trajectories in the FT condition at ZSF and JFJ was further evaluated to investigate the other possible drivers for the decreasing trends.ConclusionsThe background aerosol concentration in the lower FT over Central Europe has significantly decreased during 2009–2018. The implementation of emission mitigation policies is the most decisive factor and the decrease of the regional airmass occurrence over Central Europe also has contributed to the decreasing trends.

Long-term Variability of Aerosol Optical Properties at Mauna Loa

ABSTRACT We investigated the variability of the aerosol scattering (σsp; 1974–2015) and absorption (σap; 2000–2015) coefficients at the Mauna Loa Observatory using surface in situ measurements. Although σsp decreased during the morning (1.85 ± 3.43 Mm–1 at 550 nm, 8–11 local standard time [LST]), it increased during the afternoon (3.72 ± 7.63 Mm–1 at 550 nm, 14–17 LST) due to the development of thermally induced boundary layer winds. No distinct diurnal variation was observed in σap. The obvious increase in σsp and σap during the spring under free troposphere conditions (8–11 LST) is attributed to long-range-transported aerosols from Asia, especially dust and pollution aerosols from Northeast Asia and biomass burning aerosols from Southeast Asia. Accordingly, σsp increased from 1974 till 2015 (at 1.89% year–1), whereas no significant trend was noted for either σsp or σap from 2000 till 2015. An increasing trend for σsp prevailed in air masses originating in Northeast Asia (+0.51 Mm–1 decade–1).

Retrieval of aerosol properties from ceilometer and photometer measurements: long-term evaluation with in situ data and statistical analysis at Montsec (southern Pyrenees)

Abstract. Given the need for accurate knowledge of aerosol microphysical and optical properties with height resolution, various algorithms combining vertically resolved and column-integrated aerosol information have been developed in the last years. Here we present new results of vertically resolved extensive aerosol optical properties (backscattering, scattering and extinction) and volume concentrations retrieved with the GRASP (Generalized Retrieval of Aerosol and Surface Properties) algorithm over a 3-year period. The range-corrected signal (RCS) at 1064 nm measured with a ceilometer and the aerosol optical depth (AOD) and sky radiances from a sun/sky photometer have been used as input for this algorithm. We perform a detailed evaluation of GRASP retrievals with simultaneous in situ measurements performed at the same height, at the Montsec mountaintop observatory (MSA) in the Pre-Pyrenees (northeastern Spain). This is the first long-term evaluation of various outputs of this algorithm; previous evaluations focused only on the study of aerosol volume concentration for short-term periods. In general, our results show good agreement between techniques although GRASP inversions yield higher values than those measured in situ. The statistical analysis of the extinction coefficient vertical profiles shows a clear seasonality as well as significant differences depending on the air mass origin. The observed seasonal cycle is mainly modulated by a higher development of the atmospheric boundary layer (ABL) during warm months, which favors the transport of pollutants to MSA, and higher influence of regional and North African episodes. On the other hand, in winter, MSA is frequently influenced by free-troposphere conditions and venting periods and therefore lower extinction coefficients that markedly decrease with height. This study shows the potentiality of implementing GRASP in ceilometer and lidar networks for obtaining aerosol optical properties and volume concentrations at multiple sites, which will definitely contribute to enhancing the representativeness of the aerosol vertical distribution as well as to providing useful information for satellite and global model evaluation.

Analysis of aerosol scattering properties and PM10 concentrations at a mountain site influenced by mineral dust transport

Aerosol scattering properties (ASP) i.e., scattering and backscattering coefficients (σsp, σbsp, 525 nm), scattering Ångström exponent (SAE, 450–635 nm) and backscatter ratio (b, 525 nm) along with PM10 concentrations were measured from November 2015 to October 2016 at a mountain site (1558 m a.s.l) located in the southwestern Mediterranean. ASP and PM10 average values obtained for the whole period were: 26.2 Mm−1, 3.5 Mm−1, 1.42, 0.139 and 12.4 μg/m3, respectively. The study was aimed at analyzing: a) the seasonal variability of the measured parameters, b) the impact of mineral dust from North Africa on PM10 and optical properties and c) the variation of ASP values and PM10 concentrations as a function of the mixing layer height. The extensive scattering properties had values ∼35% higher during the warm period, while SAE and b were similar during both the cold and warm seasons. σsp and σbsp increased under Saharan dust events (SDE). In contrast, SAE and b values showed a decrease due to the increase in coarse particle concentrations during this type of event. On non-event days, the lowest values of σsp and PM10 were recorded under free troposphere (FT) conditions (10.5 Mm−1, 3 μg/m3). Conversely, SAE recorded its highest value (∼2.00) under these conditions, pointing to a predominance of fine particles in this layer. Average values of σsp and PM10 increased with the increase in the height of the Planetary Boundary Layer (PBL), while the SAE value progressively decreased to a steady value of 1.50–1.60. The average value of the mass scattering efficiency (MSE) during the study period was 1.35 m2/g.

Recent Advances in Quantifying Wet Scavenging Efficiency of Black Carbon Aerosol

Black carbon (BC) aerosol is of great importance not only for its strong potential in heating air and impacts on cloud, but also because of its hazards to human health. Wet deposition is regarded as the main sink of BC, constraining its lifetime and thus its impact on the environment and climate. However, substantial controversial and ambiguous issues in the wet scavenging processes of BC are apparent in current studies. Despite of its significance, there are only a small number of field studies that have investigated the incorporation of BC-containing particles into cloud droplets and influencing factors, in particular, the in-cloud scavenging, because it was simplicitly considered in many studies (as part of total wet scavenging). The mass scavenging efficiencies (MSEs) of BC were observed to be varied over the world, and the influencing factors were attributed to physical and chemical properties (e.g., size and chemical compositions) and meteorological conditions (cloud water content, temperature, etc.). In this review, we summarized the MSEs and potential factors that influence the in-cloud and below-cloud scavenging of BC. In general, MSEs of BC are lower at low-altitude regions (urban, suburban, and rural sites) and increase with the rising altitude, which serves as additional evidence that atmospheric aging plays an important role in the chemical modification of BC. Herein, higher altitude sites are more representative of free-tropospheric conditions, where BC is usually more aged. Despite of increasing knowledge of BC–cloud interaction, there are still challenges that need to be addressed to gain a better understanding of the wet scavenging of BC. We recommend that more comprehensive methods should be further estimated to obtain high time-resolved scavenging efficiency (SE) of BC, and to distinguish the impact of in-cloud and below-cloud scavenging on BC mass concentration, which is expected to be useful for constraining the gap between field observation and modeling simulation results.

Wind Shear Effects on Radiatively and Evaporatively Driven Stratocumulus Tops

Abstract Direct numerical simulations resolving meter and submeter scales in the cloud-top region of stratocumulus are used to investigate the interactions between a mean vertical wind shear and in-cloud turbulence driven by evaporative and radiative cooling. There are three major results. First, a critical velocity jump exists, above which shear significantly broadens the entrainment interfacial layer (EIL), enhances cloud-top cooling, and increases the mean entrainment velocity; shear effects are negligible when the velocity jump is below . Second, a depletion velocity jump exists, above which shear-enhanced mixing reduces cloud-top radiative cooling, thereby weakening the large convective motions; shear effects remain localized within the EIL when the velocity jump is below . The critical velocity jump and depletion velocity jump are provided as a function of in-cloud and free-tropospheric conditions, and one finds and for typical subtropical conditions. Third, the individual contributions to the mean entrainment velocity from mixing, radiative cooling, and evaporative cooling strongly depend on the choice of the reference height where the entrainment velocity is calculated. This result implies that the individual contributions to the mean entrainment velocity should be estimated at a comparable height while deriving entrainment-rate parameterizations. A strong shear alters substantially the magnitude and the height where these individual contributions reach their maxima, which further demonstrates the importance of shear on the dynamics of stratocumulus clouds.

Seasonal Variation of Aerosol Size Distribution Data at the Puy de Dôme Station with Emphasis on the Boundary Layer/Free Troposphere Segregation

Aerosol particles are important due to their direct and indirect impacts on climate. Within the planetary boundary layer (BL), these particles have a relatively short lifetime due to their frequent removal process by wet deposition. When aerosols are transported into the free troposphere (FT), their atmospheric lifetime increases significantly, making them representative of large spatial areas. In this work, we use a combination of in situ measurements performed at the high altitude PUY (Puy de Dôme, 45°46′ N, 2°57′ E, 1465 m a.s.l) station, together with LIDAR profiles at Clermont-Ferrand for characterizing FT conditions, and further characterize the physical properties of aerosol in this poorly documented area of the atmosphere. First, a combination of four criteria was used to identify whether the PUY station lies within the FT or within the BL. Results show that the PUY station is located in BL with frequencies ranging from 50% during the winter, up to 97% during the summer. Then, the classification is applied to a year-long dataset (2015) of particle size distribution data to study the differences in particle physical characteristics (size distribution) and black carbon (BC) concentrations between the FT and the BL. Although BC, Aitken, and the accumulation mode particles concentrations were higher in the BL than in the FT in winter and autumn, they were measured to be higher in the FT compared to BL in spring. No significant difference between the BL and the FT concentrations was observed for the nucleation mode particles for all seasons, suggesting a continuous additional source of nucleation mode particles in the FT during winter and autumn. Coarse mode particle concentrations were found higher in the FT than in the BL for all seasons and especially during summer. This indicates an efficient long-range transport of large particles in the FT from distant sources (marine and desert) due to higher wind speeds in the FT compared to BL. For FT air masses, we used 204-h air mass back-trajectories combined with boundary layer height estimations from ECMWF ERA-Interim to assess the time they spent in the FT since their last contact with the BL and to evaluate the impact of this parameter on the aerosol properties. We observed that even after 75 h without any contact with the BL, FT aerosols preserve specific properties of their air mass type.

Adaptive selection of diurnal minimum variation: a statistical strategy to obtain representative atmospheric CO&amp;lt;sub&amp;gt;2&amp;lt;/sub&amp;gt; data and its application to European elevated mountain stations

Abstract. Critical data selection is essential for determining representative baseline levels of atmospheric trace gases even at remote measurement sites. Different data selection techniques have been used around the world, which could potentially lead to reduced compatibility when comparing data from different stations. This paper presents a novel statistical data selection method named adaptive diurnal minimum variation selection (ADVS) based on CO2 diurnal patterns typically occurring at elevated mountain stations. Its capability and applicability were studied on records of atmospheric CO2 observations at six Global Atmosphere Watch stations in Europe, namely, Zugspitze-Schneefernerhaus (Germany), Sonnblick (Austria), Jungfraujoch (Switzerland), Izaña (Spain), Schauinsland (Germany), and Hohenpeissenberg (Germany). Three other frequently applied statistical data selection methods were included for comparison. Among the studied methods, our ADVS method resulted in a lower fraction of data selected as a baseline with lower maxima during winter and higher minima during summer in the selected data. The measured time series were analyzed for long-term trends and seasonality by a seasonal-trend decomposition technique. In contrast to unselected data, mean annual growth rates of all selected datasets were not significantly different among the sites, except for the data recorded at Schauinsland. However, clear differences were found in the annual amplitudes as well as the seasonal time structure. Based on a pairwise analysis of correlations between stations on the seasonal-trend decomposed components by statistical data selection, we conclude that the baseline identified by the ADVS method is a better representation of lower free tropospheric (LFT) conditions than baselines identified by the other methods.

The Horizontal Ice Nucleation Chamber (HINC): INP measurements at conditions relevant for mixed-phase clouds at the High Altitude Research Station Jungfraujoch

Abstract. In this work we describe the Horizontal Ice Nucleation Chamber (HINC) as a new instrument to measure ambient ice-nucleating particle (INP) concentrations for conditions relevant to mixed-phase clouds. Laboratory verification and validation experiments confirm the accuracy of the thermodynamic conditions of temperature (T) and relative humidity (RH) in HINC with uncertainties in T of ±0.4 K and in RH with respect to water (RHw) of ±1.5 %, which translates into an uncertainty in RH with respect to ice (RHi) of ±3.0 % at T &gt; 235 K. For further validation of HINC as a field instrument, two measurement campaigns were conducted in winters 2015 and 2016 at the High Altitude Research Station Jungfraujoch (JFJ; Switzerland, 3580 m a. s. l. ) to sample ambient INPs. During winters 2015 and 2016 the site encountered free-tropospheric conditions 92 and 79 % of the time, respectively. We measured INP concentrations at 242 K at water-subsaturated conditions (RHw = 94 %), relevant for the formation of ice clouds, and in the water-supersaturated regime (RHw = 104 %) to represent ice formation occurring under mixed-phase cloud conditions. In winters 2015 and 2016 the median INP concentrations at RHw = 94 % was below the minimum detectable concentration. At RHw = 104 %, INP concentrations were an order of magnitude higher, with median concentrations in winter 2015 of 2.8 per standard liter (std L−1; normalized to standard T of 273 K and pressure, p, of 1013 hPa) and 4.7 std L−1 in winter 2016. The measurements are in agreement with previous winter measurements obtained with the Portable Ice Nucleation Chamber (PINC) of 2.2 std L−1 at the same location. During winter 2015, two events caused the INP concentrations at RHw = 104 % to significantly increase above the campaign average. First, an increase to 72.1 std L−1 was measured during an event influenced by marine air, arriving at the JFJ from the North Sea and the Norwegian Sea. The contribution from anthropogenic or other sources can thereby not be ruled out. Second, INP concentrations up to 146.2 std L−1 were observed during a Saharan dust event. To our knowledge this is the first time that a clear enrichment in ambient INP concentration in remote regions of the atmosphere is observed during a time of marine air mass influence, suggesting the importance of marine particles on ice nucleation in the free troposphere.

CCN production by new particle formation in the free troposphere

Abstract. Global models predict that new particle formation (NPF) is, in some environments, responsible for a substantial fraction of the total atmospheric particle number concentration and subsequently contributes significantly to cloud condensation nuclei (CCN) concentrations. NPF events were frequently observed at the highest atmospheric observatory in the world, on Chacaltaya (5240 m a.s.l.), Bolivia. The present study focuses on the impact of NPF on CCN population. Neutral cluster and Air Ion Spectrometer and mobility particle size spectrometer measurements were simultaneously used to follow the growth of particles from cluster sizes down to ∼ 2 nm up to CCN threshold sizes set to 50, 80 and 100 nm. Using measurements performed between 1 January and 31 December 2012, we found that 61 % of the 94 analysed events showed a clear particle growth and significant enhancement of the CCN-relevant particle number concentration. We evaluated the contribution of NPF, relative to the transport and growth of pre-existing particles, to CCN size. The averaged production of 50 nm particles during those events was 5072, and 1481 cm−3 for 100 nm particles, with a larger contribution of NPF compared to transport, especially during the wet season. The data set was further segregated into boundary layer (BL) and free troposphere (FT) conditions at the site. The NPF frequency of occurrence was higher in the BL (48 %) compared to the FT (39 %). Particle condensational growth was more frequently observed for events initiated in the FT, but on average faster for those initiated in the BL, when the amount of condensable species was most probably larger. As a result, the potential to form new CCN was higher for events initiated in the BL (67 % against 53 % in the FT). In contrast, higher CCN number concentration increases were found when the NPF process initially occurred in the FT, under less polluted conditions. This work highlights the competition between particle growth and the removal of freshly nucleated particles by coagulation processes. The results support model predictions which suggest that NPF is an effective source of CCN in some environments, and thus may influence regional climate through cloud-related radiative processes.

Processes controlling the seasonal variations in &amp;lt;sup&amp;gt;210&amp;lt;/sup&amp;gt;Pb and &amp;lt;sup&amp;gt;7&amp;lt;/sup&amp;gt;Be at the Mt. Cimone WMO-GAW global station, Italy: a model analysis

Abstract. We apply the Global Modeling Initiative (GMI) chemistry and transport model driven by NASA's MERRA assimilated meteorological data to simulate the seasonal variations in two radionuclide aerosol tracers (terrigenous 210Pb and cosmogenic 7Be) at the WMO-GAW station of Mt. Cimone (44°12′ N, 10°42′ E; 2165 m a.s.l.; Italy), which is representative of free-tropospheric conditions most of the year, during 2005 with an aim to understand the roles of transport and precipitation scavenging processes in controlling their seasonality. The total precipitation field in the MERRA data set is evaluated with the Global Precipitation Climatology Project (GPCP) observations, and generally good agreement is found. The model reproduces reasonably the observed seasonal pattern of 210Pb concentrations, characterized by a wintertime minimum due to lower 222Rn emissions and weaker uplift from the boundary layer and summertime maxima resulting from strong convection over the continent. The observed seasonal behavior of 7Be concentrations shows a winter minimum, a summer maximum, and a secondary spring maximum. The model captures the observed 7Be pattern in winter–spring, which is linked to the larger stratospheric influence during spring. However, the model tends to underestimate the observed 7Be concentrations in summer, partially due to the sensitivity to spatial sampling in the model. Model sensitivity experiments indicate a dominant role of precipitation scavenging (vs. dry deposition and convection) in controlling the seasonality of 210Pb and 7Be concentrations at Mt. Cimone.

Experimental particle formation rates spanning tropospheric sulfuric acid and ammonia abundances, ion production rates, and temperatures

AbstractBinary nucleation of sulfuric acid and water as well as ternary nucleation involving ammonia are thought to be the dominant processes responsible for new particle formation (NPF) in the cold temperatures of the middle and upper troposphere. Ions are also thought to be important for particle nucleation in these regions. However, global models presently lack experimentally measured NPF rates under controlled laboratory conditions and so at present must rely on theoretical or empirical parameterizations. Here with data obtained in the European Organization for Nuclear Research CLOUD (Cosmics Leaving OUtdoor Droplets) chamber, we present the first experimental survey of NPF rates spanning free tropospheric conditions. The conditions during nucleation cover a temperature range from 208 to 298 K, sulfuric acid concentrations between 5 × 105 and 1 × 109 cm−3, and ammonia mixing ratios from zero added ammonia, i.e., nominally pure binary, to a maximum of ~1400 parts per trillion by volume (pptv). We performed nucleation studies under pure neutral conditions with zero ions being present in the chamber and at ionization rates of up to 75 ion pairs cm−3 s−1 to study neutral and ion‐induced nucleation. We found that the contribution from ion‐induced nucleation is small at temperatures between 208 and 248 K when ammonia is present at several pptv or higher. However, the presence of charges significantly enhances the nucleation rates, especially at 248 K with zero added ammonia, and for higher temperatures independent of NH3 levels. We compare these experimental data with calculated cluster formation rates from the Atmospheric Cluster Dynamics Code with cluster evaporation rates obtained from quantum chemistry.