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Ice nucleating particles (INPs) play a crucial role in initiating ice crystal formation in clouds, influencing the dynamics and optical properties of clouds and their impacts on precipitation and the climate system. Despite their importance, there is limited knowledge about the vertical distribution of INPs. This study focuses on aircraft measurements conducted during spring 2018 above the boreal forest of Hyytiälä, Finland. Similarities between INP concentrations, activated fractions, particle concentrations, and size distributions observed at ground level and in the boundary layer aloft indicate that surface particles and INPs are efficiently transported and mixed within the boundary layer. INP concentrations observed in the boundary layer are best predicted by a parameterization describing near-surface INP concentrations driven by the abundance of biogenic aerosol in the Finnish boreal forest, suggesting that biogenic INPs are dominant in the boundary layer above the same environment. Most of the INP concentrations and activated fractions observed in the free troposphere are notably lower than in the boundary layer, and the distinct particle size distributions suggest that different aerosol populations, likely resulting from long-range transport, are present in the free troposphere. However, we show one case where higher INP concentrations are observed in the free troposphere and where a homogeneous particle population exists from the surface to the free troposphere. This indicates that surface particles and INPs from the boreal forest can occasionally reach the free troposphere, which is particularly important as the INPs in the free troposphere can further travel horizontally and/or vertically and impact cloud formation.

The purpose of this study is to understand the drivers of cloud droplet formation in orographic clouds. We used a combination of modeling, in situ, and remote sensing measurements at the high-altitude Helmos Hellenic Atmospheric Aerosol and Climate Change ((HAC)2) station, which is located at the top of Mt. Helmos (1314 m above sea level), Greece, during the Cloud–AerosoL InteractionS in the Helmos Background TropOsphere (CALISHTO) campaign in fall 2021 (https://calishto.panacea-ri.gr/, last access: 1 August 2024) to examine the origins of the aerosols (i.e., local aerosol from the planetary boundary layer (PBL) or long-range-transported aerosol from the free-tropospheric layer (FTL) contributing to the cloud condensation nuclei (CCN)), their characteristics (hygroscopicity, size distribution, and mixing state), and the vertical velocity distributions and resulting supersaturations. We found that the characteristics of the PBL aerosol were considerably different from FTL aerosol and use the aerosol particle number and equivalent mass concentration of the black carbon (eBC) in order to determine when (HAC)2 was within the FTL or PBL based on time series of the height of the PBL. During the (HAC)2 cloud events we sample a mixture of interstitial aerosol and droplet residues, which we characterize using a new approach that utilizes the in situ droplet measurements to determine time periods when the aerosol sample is purely interstitial. From the dataset we determine the properties (size distribution and hygroscopicity) of the pre-cloud, activated, and interstitial aerosol. The hygroscopicity of activated aerosol is found to be higher than that of the interstitial or pre-cloud aerosol. A series of closure studies with the droplet parameterization shows that cloud droplet concentration (Nd) and supersaturation can be predicted to within 25 % of observations when the aerosol size distributions correspond to pre-cloud conditions. The analysis of the characteristic supersaturation of each aerosol population indicates that droplet formation in clouds is aerosol-limited when formed in FTL air masses – hence droplet formation is driven by aerosol variations, while clouds formed in the PBL tend to be velocity-limited and droplet variations are driven by fluctuations in vertical velocity. Given that the cloud dynamics do not vary significantly between air masses, the variation in aerosol concentration and type is mostly responsible for these shifts in cloud microphysical state and sensitivity to aerosol. With these insights, the remote sensing of cloud droplets in such clouds can be used to infer either CCN spectra (when in the FTL) or vertical velocity (when in the PBL). In conclusion, we show that a coordinated measurement of aerosol and cloud properties, together with the novel analysis approaches presented here, allows for the determination of the drivers of droplet formation in orographic clouds and their sensitivity to aerosol and vertical velocity variations.

The majority of new particle formation (NPF) events observed in Hada Al Sham, western Saudi Arabia, during 2013–2015 showed an unusual progression where the diameter of a newly formed particle mode clearly started to decrease after the growth phase. Many previous studies refer to this phenomenon as aerosol shrinkage. We will opt to use the term decreasing mode diameter (DMD) event, as shrinkage bears the connotation of reduction in the sizes of individual particles, which does not have to be the case. While several previous studies speculate that ambient DMD events are caused by evaporation of semivolatile species, no concrete evidence has been provided, partly due to the rarity of the DMD events. The frequent occurrence and large number of DMD events in our observations allow us to perform statistically significant comparisons between the DMD and the typical NPF events that undergo continuous growth. In our analysis, we find no clear connection between DMD events and factors that might trigger particle evaporation at the measurement site. Instead, examination of air mass source areas and the horizontal distribution of anthropogenic emissions in the study region leads us to believe that the observed DMD events could be caused by advection of smaller, less-grown particles to the measurement site after the more-grown ones. Using a Lagrangian single-particle growth model, we confirm that the observed particle size development, including the DMD events, can be reproduced by non-volatile condensation and thus without evaporation. In fact, when considering increasing contributions from a semivolatile compound, we find deteriorating agreement between the measurements and the model. Based on these results, it seems unlikely that evaporation of semivolatile compounds would play a significant role in the DMD events at our measurement site. In the proposed non-volatile explanation, the DMD events are a result of the observed particles having spent an increasing fraction of their lifetime in a lower-growth environment, mainly enabled by the lower precursor vapor concentrations further away from the measurement site combined with decreasing photochemical production of condensable vapors in the afternoon. Correct identification of the cause of the DMD events is important as the fate and the climate relevance of the newly formed particles heavily depend on it – if the particles evaporated, their net contribution to larger and climatically active particle sizes would be greatly reduced. Our findings highlight the importance of considering transport-related effects in NPF event analysis, which is an often overlooked factor in such studies.

Active remote sensors equipped with the capability to detect polarization, a shape-relevant parameter, are essential to aerosol particle identification in the vertical domain. Most commonly, the linear particle depolarization ratio has been available at the shorter wavelengths of 355 and/or 532 nm. Recently, linear particle depolarization ratios at longer wavelengths (910, 1064, and 1565 nm) have emerged in lidar aerosol research. In this study, a synergy of three lidars, namely a PollyXT lidar, a Vaisala CL61 ceilometer, and a HALO Photonics StreamLine Pro Doppler lidar, as well as in situ aerosol and pollen observations have been utilized to investigate the spectral dependence of birch and pine pollen particles. We found that, regardless of the pollen type, the linear particle depolarization ratio was subject to the amount of pollen and its relative contribution to the aerosol mixture in the air. More specifically, during birch pollination, characteristic linear particle depolarization ratios of 5 ± 2 % (355 nm), 28 ± 6 % (532 nm), 23 ± 6 % (910 nm), and 33 ± 4 % (1565 nm) were retrieved at the pollen layer. Regarding the pine-dominant period, characteristic linear particle depolarization ratios of 6 ± 2 %, 43 ± 11 %, 22 ± 6 %, and 26 ± 3 % were determined at wavelengths of 355, 532, 910, and 1565 nm, respectively. For birch, the linear particle depolarization ratio at 1565 nm was the highest, followed by the 532 and 910 nm wavelengths, respectively. A sharp decrease at 355 nm was evident for birch pollen. For pine pollen, a maximum at the 532 nm wavelength was observed. There was no significant change in the linear particle depolarization ratio at 910 nm for the pollen types considered in this study. Given the low concentration of pollen in the air, the inclusion of the longer wavelengths (910 and 1565 nm) for the detection of birch and pine can be beneficial due to their sensitivity to trace large aerosol particles.

In this work, an analysis was performed to investigate how different long-range transport air masses can affect the microphysical properties of low-level clouds in a clean subarctic environment. The cloud measurements included in situ and remote sensing ground-based techniques and were conducted during eight Pallas Cloud Experiments (PaCEs) held in the autumn between 2004 and 2019. Each PaCE was carried out at the Pallas Atmosphere-Ecosystem Supersite, located in the Finnish subarctic region. Two cloud spectrometer ground setups were installed on the roof of the station to measure cloud microphysical properties: the cloud, aerosol and precipitation spectrometer (CAPS) and the forward-scattering spectrometer probe (FSSP). Air mass histories were analyzed using the Lagrangian FLEXible PARTicle dispersion model (FLEXPART) in order to investigate the differences between five distinct source regions (“Arctic”, “Eastern”, “Southern”, “Western” and “Local”). We observed clear differences in the cloud microphysical properties for the air mass source regions. Arctic air masses were characterized by low liquid water content (LWC), low cloud droplet number concentration (Nc) and comparatively large median volume and effective droplet diameter. The Western region (marine North Atlantic) differed from the Arctic by both higher Nc and LWC. The Eastern region (continental Eurasia) only had a little higher LWC than the Arctic but substantially higher Nc and a smaller droplet diameter. The Southern region (continental Europe) had high Nc and LWC and a very similar droplet diameter to the Eastern region. Finally, the relationship between Nc and droplet size (i.e., the Twomey effect) was characterized for the different source regions, indicating that all region clouds were sensitive to increases in Nc.

In this study, we modeled the aerosol particle formation along air mass trajectories arriving at the remote Arctic research stations Gruvebadet (67 m a.s.l.) and Zeppelin (474 m a.s.l.), Ny-Ålesund, during May 2018. The aim of this study was to improve our understanding of processes governing secondary aerosol formation in remote Arctic marine environments. We run the Lagrangian chemistry transport model ADCHEM, along air mass trajectories generated with FLEXPART v10.4. The air masses arriving at Ny-Ålesund spent most of their time over the open ice-free ocean. In order to capture the secondary aerosol formation from the DMS emitted by phytoplankton from the ocean surface, we implemented a recently developed comprehensive DMS and halogen multi-phase oxidation chemistry scheme, coupled with the widely used Master Chemical Mechanism (MCM). The modeled median particle number size distributions are in close agreement with the observations in the marine-influenced boundary layer near-sea-surface Gruvebadet site. However, while the model reproduces the accumulation mode particle number concentrations at Zeppelin, it overestimates the Aitken mode particle number concentrations by a factor of ∼5.5. We attribute this to the deficiency of the model to capture the complex orographic effects on the boundary layer dynamics at Ny-Ålesund. However, the model reproduces the average vertical particle number concentration profiles within the boundary layer (0–600 m a.s.l.) above Gruvebadet, as measured with condensation particle counters (CPCs) on board an unmanned aircraft system (UAS). The model successfully reproduces the observed Hoppel minima, often seen in particle number size distributions at Ny-Ålesund. The model also supports the previous experimental findings that ion-mediated H2SO4–NH3 nucleation can explain the observed new particle formation in the marine Arctic boundary layer in the vicinity of Ny-Ålesund. Precursors resulting from gas- and aqueous-phase DMS chemistry contribute to the subsequent growth of the secondary aerosols. The growth of particles is primarily driven via H2SO4 condensation and formation of methane sulfonic acid (MSA) through the aqueous-phase ozonolysis of methane sulfinic acid (MSIA) in cloud and deliquescent droplets.

Atmospheric new particle formation (NPF) is a crucial process driving aerosol number concentrations in the atmosphere; it can significantly impact the evolution of atmospheric aerosol and cloud processes. This study analyses at least 1 year of asynchronous particle number size distributions from six different locations in India. We also analyze the frequency of NPF and its contribution to cloud condensation nuclei (CCN) concentrations. We found that the NPF frequency has a considerable seasonal variability. At the measurement sites analyzed in this study, NPF frequently occurs in March–May (pre-monsoon, about 21 % of the days) and is the least common in October–November (post-monsoon, about 7 % of the days). Considering the NPF events in all locations, the particle formation rate (JSDS) varied by more than 2 orders of magnitude (0.001–0.6 cm−3 s−1) and the growth rate between the smallest detectable size and 25 nm (GRSDS-25 nm) by about 3 orders of magnitude (0.2–17.2 nm h−1). We found that JSDS was higher by nearly 1 order of magnitude during NPF events in urban areas than mountain sites. GRSDS did not show a systematic difference. Our results showed that NPF events could significantly modulate the shape of particle number size distributions and CCN concentrations in India. The contribution of a given NPF event to CCN concentrations was the highest in urban locations (4.3 × 103 cm−3 per event and 1.2 × 103 cm−3 per event for 50 and 100 nm, respectively) as compared to mountain background sites (2.7 × 103 cm−3 per event and 1.0 × 103 cm−3 per event, respectively). We emphasize that the physical and chemical pathways responsible for NPF and factors that control its contribution to CCN production require in situ field observations using recent advances in aerosol and its precursor gaseous measurement techniques.

Aerosol particles are a complex component of the atmospheric system which influence climate directly by interacting with solar radiation, and indirectly by contributing to cloud formation. The variety of their sources, as well as the multiple transformations they may undergo during their transport (including wet and dry deposition), result in significant spatial and temporal variability of their properties. Documenting this variability is essential to provide a proper representation of aerosols and cloud condensation nuclei (CCN) in climate models. Using measurements conducted in 2016 or 2017 at 62 ground-based stations around the world, this study provides the most up-to-date picture of the spatial distribution of particle number concentration (Ntot) and number size distribution (PNSD, from 39 sites). A sensitivity study was first performed to assess the impact of data availability on Ntot's annual and seasonal statistics, as well as on the analysis of its diel cycle. Thresholds of 50 % and 60 % were set at the seasonal and annual scale, respectively, for the study of the corresponding statistics, and a slightly higher coverage (75 %) was required to document the diel cycle. Although some observations are common to a majority of sites, the variety of environments characterizing these stations made it possible to highlight contrasting findings, which, among other factors, seem to be significantly related to the level of anthropogenic influence. The concentrations measured at polar sites are the lowest (∼ 102 cm−3) and show a clear seasonality, which is also visible in the shape of the PNSD, while diel cycles are in general less evident, due notably to the absence of a regular day–night cycle in some seasons. In contrast, the concentrations characteristic of urban environments are the highest (∼ 103–104 cm−3) and do not show pronounced seasonal variations, whereas diel cycles tend to be very regular over the year at these stations. The remaining sites, including mountain and non-urban continental and coastal stations, do not exhibit as obvious common behaviour as polar and urban sites and display, on average, intermediate Ntot (∼ 102–103 cm−3). Particle concentrations measured at mountain sites, however, are generally lower compared to nearby lowland sites, and tend to exhibit somewhat more pronounced seasonal variations as a likely result of the strong impact of the atmospheric boundary layer (ABL) influence in connection with the topography of the sites. ABL dynamics also likely contribute to the diel cycle of Ntot observed at these stations. Based on available PNSD measurements, CCN-sized particles (considered here as either >50 nm or >100 nm) can represent from a few percent to almost all of Ntot, corresponding to seasonal medians on the order of ∼ 10 to 1000 cm−3, with seasonal patterns and a hierarchy of the site types broadly similar to those observed for Ntot. Overall, this work illustrates the importance of in situ measurements, in particular for the study of aerosol physical properties, and thus strongly supports the development of a broad global network of near surface observatories to increase and homogenize the spatial coverage of the measurements, and guarantee as well data availability and quality. The results of this study also provide a valuable, freely available and easy to use support for model comparison and validation, with the ultimate goal of contributing to improvement of the representation of aerosol–cloud interactions in models, and, therefore, of the evaluation of the impact of aerosol particles on climate.

Based on the first measurements of gas-phase pyruvic acid (CH3C(O)C(O)OH) in the boreal forest, we derive effective emission rates of pyruvic acid and compare them with monoterpene emission rates over the diel cycle. Using a data-constrained box model, we determine the impact of pyruvic acid photolysis on the formation of acetaldehyde (CH3CHO) and the peroxy radicals CH3C(O)O2 and HO2 during an autumn campaign in the boreal forest. The results are dependent on the quantum yield (φ) and mechanism of the photodissociation of pyruvic acid and the fate of a likely major product, methylhydroxy carbene (CH3COH). With the box model, we investigate two different scenarios in which we follow the present IUPAC (IUPAC Task Group on Atmospheric Chemical Kinetic Data Evaluation, 2021) recommendations with φ = 0.2 (at 1 bar of air), and the main photolysis products (60 %) are acetaldehyde + CO2 with 35 % C–C bond fission to form HOCO and CH3CO (scenario A). In the second scenario (B), the formation of vibrationally hot CH3COH (and CO2) represents the main dissociation pathway at longer wavelengths (∼ 75 %) with a ∼ 25 % contribution from C–C bond fission to form HOCO and CH3CO (at shorter wavelengths). In scenario 2 we vary φ between 0.2 and 1 and, based on the results of our theoretical calculations, allow the thermalized CH3COH to react with O2 (forming peroxy radicals) and to undergo acid-catalysed isomerization to CH3CHO. When constraining the pyruvic acid to measured mixing ratios and independent of the model scenario, we find that the photolysis of pyruvic acid is the dominant source of CH3CHO with a contribution between ∼ 70 % and 90 % to the total production rate. We find that the photolysis of pyruvic acid is also a major source of the acetylperoxy radical, with contributions varying between ∼ 20 % and 60 % dependent on the choice of φ and the products formed. HO2 production rates are also enhanced, mainly via the formation of CH3O2. The elevated production rates of CH3C(O)O2 and HO2 and concentration of CH3CHO result in significant increases in the modelled mixing ratios of CH3C(O)OOH, CH3OOH, HCHO, and H2O2.

Lidar observations during the pollen season 2019 at the European Aerosol Research Lidar Network (EARLINET) station in Kuopio, Finland, were analyzed in order to optically characterize atmospheric pollen. Pollen concentration and type information were obtained by a Hirst-type volumetric air sampler. Previous studies showed the detectability of non-spherical pollen using depolarization ratio measurements. We present lidar depolarization ratio measurements at three wavelengths of atmospheric pollen in ambient conditions. In addition to the depolarization ratio detected with the multiwavelength Raman polarization lidar PollyXT at 355 and 532 nm, depolarization measurements of a co-located Halo Doppler lidar at 1565 nm were utilized. During a 4 d period of high birch (Betula) and spruce (Picea abies) pollen concentrations, unusually high depolarization ratios were observed within the boundary layer. Detected layers were investigated regarding the share of spruce pollen to the total pollen number concentration. Daily mean linear particle depolarization ratios of the pollen layers on the day with the highest spruce pollen share are 0.10 ± 0.02, 0.38 ± 0.23 and 0.29 ± 0.10 at 355, 532 and 1565 nm, respectively, whereas on days with lower spruce pollen share, depolarization ratios are lower with less wavelength dependence. This spectral dependence of the depolarization ratios could be indicative of big, non-spherical spruce pollen. The depolarization ratio of pollen particles was investigated by applying a newly developed method and assuming a backscatter-related Ångström exponent of zero. Depolarization ratios of 0.44 and 0.16 at 532 and 355 nm for the birch and spruce pollen mixture were determined.

According to current estimates, atmospheric new particle formation (NPF) produces a large fraction of aerosol particles and cloud condensation nuclei in the Earth's atmosphere, which have implications for health and climate. Despite recent advances, atmospheric NPF is still insufficiently understood in the lower troposphere, especially above the mixed layer (ML). This paper presents new results from co-located airborne and ground-based measurements in a boreal forest environment, showing that many NPF events (∼42 %) appear to start in the topmost part of the residual layer (RL). The freshly formed particles may be entrained into the growing mixed layer (ML) where they continue to grow in size, similar to the aerosol particles formed within the ML. The results suggest that in the boreal forest environment, NPF in the upper RL has an important contribution to the aerosol load in the boundary layer (BL).

The depolarization ratio is a valuable parameter for lidar-based aerosol categorization. Usually, the aerosol particle depolarization ratio is determined at relatively short wavelengths of 355 nm and/or 532 nm, but some multi-wavelength studies including longer wavelengths indicate strong spectral dependency. Here, we investigate the capabilities of Halo Photonics StreamLine Doppler lidars to retrieve the particle linear depolarization ratio at the 1565 nm wavelength. We utilize collocated measurements with another lidar system, PollyXT at Limassol, Cyprus, and at Kuopio, Finland, to compare the depolarization ratio observed by the two systems. For mineral-dust-dominated cases we find typically a slightly lower depolarization ratio at 1565 nm than at 355 and 532 nm. However, for dust mixed with other aerosol we find a higher depolarization ratio at 1565 nm. For polluted marine aerosol we find a marginally lower depolarization ratio at 1565 nm compared to 355 and 532 nm. For mixed spruce and birch pollen we find a slightly higher depolarization ratio at 1565 nm compared to 532 nm. Overall, we conclude that Halo Doppler lidars can provide a particle linear depolarization ratio at the 1565 nm wavelength at least in the lowest 2–3 km above ground.

Unmanned aerial systems (UASs) are increasingly being used as observation platforms for atmospheric applications. The Lower Atmospheric Process Studies at Elevation – a Remotely-piloted Aircraft Team Experiment (LAPSE-RATE) in Alamosa, Colorado, USA, on 14–20 July 2018 investigated and validated different UASs, measurement sensors and setup configurations. Flight teams from the Finnish Meteorological Institute (FMI) and Kansas State University (KSU) participated in LAPSE-RATE to measure and investigate properties of aerosol particles and gases in the lower atmosphere. During the experiment, the performance of different UAS configurations were investigated and confirmed to operate reliably, resulting in a scientifically sound observational dataset. As an example, concentration of aerosols – including two new particle formation events, CO2 and water vapor, and meteorological parameters in the atmospheric vertical profile were measured during the short experiment. Such observations characterizing atmospheric phenomena of this specific environment would have not been possible in any other way and, thus, demonstrate the power of UASs as new, promising tools in atmospheric and environmental research.

The effect of observational constraint on the ranges of uncertain physical and chemical process parameters was explored in a global aerosol–climate model. The study uses 1 million variants of the Hadley Centre General Environment Model version 3 (HadGEM3) that sample 26 sources of uncertainty, together with over 9000 monthly aggregated grid-box measurements of aerosol optical depth, PM2.5, particle number concentrations, sulfate and organic mass concentrations. Despite many compensating effects in the model, the procedure constrains the probability distributions of parameters related to secondary organic aerosol, anthropogenic SO2 emissions, residential emissions, sea spray emissions, dry deposition rates of SO2 and aerosols, new particle formation, cloud droplet pH and the diameter of primary combustion particles. Observational constraint rules out nearly 98 % of the model variants. On constraint, the ±1σ (standard deviation) range of global annual mean direct radiative forcing (RFari) is reduced by 33 % to −0.14 to −0.26 W m−2, and the 95 % credible interval (CI) is reduced by 34 % to −0.1 to −0.32 W m−2. For the global annual mean aerosol–cloud radiative forcing, RFaci, the ±1σ range is reduced by 7 % to −1.66 to −2.48 W m−2, and the 95 % CI by 6 % to −1.28 to −2.88 W m−2. The tightness of the constraint is limited by parameter cancellation effects (model equifinality) as well as the large and poorly defined “representativeness error” associated with comparing point measurements with a global model. The constraint could also be narrowed if model structural errors that prevent simultaneous agreement with different measurement types in multiple locations and seasons could be improved. For example, constraints using either sulfate or PM2.5 measurements individually result in RFari±1σ ranges that only just overlap, which shows that emergent constraints based on one measurement type may be overconfident.

Total hydroxyl radical (OH) reactivity measurements were conducted at the second Station for Measuring Ecosystem–Atmosphere Relations (SMEAR II), a boreal forest site located in Hyytiälä, Finland, from April to July 2016. The measured values were compared with OH reactivity calculated from a combination of data from the routine trace gas measurements (station mast) as well as online and offline analysis with a gas chromatographer coupled to a mass spectrometer (GC–MS) and offline liquid chromatography. Up to 104 compounds, mostly volatile organic compounds (VOCs) and oxidized VOCs, but also inorganic compounds, were included in the analysis, even though the data availability for each compound varied with time. The monthly averaged experimental total OH reactivity was found to be higher in April and May (ca. 20 s−1) than in June and July (7.6 and 15.4 s−1, respectively). The measured values varied much more in spring with high reactivity peaks in late afternoon, with values higher than in the summer, in particular when the soil was thawing. Total OH reactivity values generally followed the pattern of mixing ratios due to change of the boundary layer height. The missing reactivity fraction (defined as the difference between measured and calculated OH reactivity) was found to be high. Several reasons that can explain the missing reactivity are discussed in detail such as (1) missing measurements due to technical issues, (2) not measuring oxidation compounds of detected biogenic VOCs, and (3) missing important reactive compounds or classes of compounds with the available measurements. In order to test the second hypothesis, a one-dimensional chemical transport model (SOSAA) has been used to estimate the amount of unmeasured oxidation products and their expected contribution to the reactivity for three different short periods in April, May, and July. However, only a small fraction ( %) of the missing reactivity can be explained by modelled secondary compounds (mostly oxidized VOCs). These findings indicate that compounds measured but not included in the model as well as unmeasured primary emissions contribute the missing reactivity. In the future, non-hydrocarbon compounds from sources other than vegetation (e.g. soil) should be included in OH reactivity studies.

Atmospheric aerosols have significant effects on human health and the climate. A large fraction of these aerosols originates from secondary new particle formation (NPF), where atmospheric vapors form small particles that subsequently grow into larger sizes. In this study, we characterize NPF events observed at a rural background site of Hada Al Sham (21.802∘ N, 39.729∘ E), located in western Saudi Arabia, during the years 2013–2015. Our analysis shows that NPF events occur very frequently at the site, as 73 % of all the 454 classified days were NPF days. The high NPF frequency is likely explained by the typically prevailing conditions of clear skies and high solar radiation, in combination with sufficient amounts of precursor vapors for particle formation and growth. Several factors suggest that in Hada Al Sham these precursor vapors are related to the transport of anthropogenic emissions from the coastal urban and industrial areas. The median particle formation and growth rates for the NPF days were 8.7 cm−3 s−1 (J7 nm) and 7.4 nm h−1 (GR7−12 nm), respectively, both showing highest values during late summer. Interestingly, the formation and growth rates increase as a function of the condensation sink, likely reflecting the common anthropogenic sources of NPF precursor vapors and primary particles affecting the condensation sink. A total of 76 % of the NPF days showed an unusual progression, where the observed diameter of the newly formed particle mode started to decrease after the growth phase. In comparison to most long-term measurements, the NPF events in Hada Al Sham are exceptionally frequent and strong both in terms of formation and growth rates. In addition, the frequency of the decreasing mode diameter events is higher than anywhere else in the world.

Atmospheric new particle formation (NPF) is an important phenomenon in terms of global particle number concentrations. Here we investigated the frequency of NPF, formation rates of 10 nm particles, and growth rates in the size range of 10–25 nm using at least 1 year of aerosol number size-distribution observations at 36 different locations around the world. The majority of these measurement sites are in the Northern Hemisphere. We found that the NPF frequency has a strong seasonal variability. At the measurement sites analyzed in this study, NPF occurs most frequently in March–May (on about 30 % of the days) and least frequently in December–February (about 10 % of the days). The median formation rate of 10 nm particles varies by about 3 orders of magnitude (0.01–10 cm−3 s−1) and the growth rate by about an order of magnitude (1–10 nm h−1). The smallest values of both formation and growth rates were observed at polar sites and the largest ones in urban environments or anthropogenically influenced rural sites. The correlation between the NPF event frequency and the particle formation and growth rate was at best moderate among the different measurement sites, as well as among the sites belonging to a certain environmental regime. For a better understanding of atmospheric NPF and its regional importance, we would need more observational data from different urban areas in practically all parts of the world, from additional remote and rural locations in North America, Asia, and most of the Southern Hemisphere (especially Australia), from polar areas, and from at least a few locations over the oceans.

The concentrations of terpenoids (isoprene; monoterpenes, MTs; and sesquiterpenes, SQTs) and oxygenated volatile organic compounds (OVOCs; i.e. aldehydes, alcohols, acetates and volatile organic acids, VOAs) were investigated during 2 years at a boreal forest site in Hyytiälä, Finland, using in situ gas chromatograph mass spectrometers (GC-MSs). Seasonal and diurnal variations of terpenoid and OVOC concentrations as well as their relationship with meteorological factors were studied.Of the VOCs examined, C2–C7 unbranched VOAs showed the highest concentrations, mainly due to their low reactivity. Of the terpenoids, MTs showed the highest concentrations at the site, but seven different highly reactive SQTs were also detected. The monthly and daily mean concentrations of most terpenoids, aldehydes and VOAs were highly dependent on the temperature. The highest exponential correlation with temperature was found for a SQT (β-caryophyllene) in summer. The diurnal variations in the concentrations could be explained by sources, sinks and vertical mixing. The diurnal variations in MT concentrations were strongly affected by vertical mixing. Based on the temperature correlations and mixing layer height (MLH), simple proxies were developed for estimating the MT and SQT concentrations.To estimate the importance of different compound groups and compounds in local atmospheric chemistry, reactivity with main oxidants (hydroxyl radical, OH; nitrate radical, NO3; and ozone, O3) and production rates of oxidation products (OxPRs) were calculated. The MTs dominated OH and NO3 radical chemistry, but the SQTs greatly impacted O3 chemistry, even though the concentrations of SQT were 30 times lower than the MT concentrations. SQTs were also the most important for the production of oxidation products. Since the SQTs show high secondary organic aerosol (SOA) yields, the results clearly indicate the importance of SQTs for local SOA production.

Although elevated surface ozone (O3) concentrations are observed in many areas within southern Africa, few studies have investigated the regional atmospheric chemistry and dominant atmospheric processes driving surface O3 formation in this region. Therefore, an assessment of comprehensive continuous surface O3 measurements performed at four sites in continental South Africa was conducted. The regional O3 problem was evident, with O3 concentrations regularly exceeding the South African air quality standard limit, while O3 levels were higher compared to other background sites in the Southern Hemisphere. The temporal O3 patterns observed at the four sites resembled typical trends for O3 in continental South Africa, with O3 concentrations peaking in late winter and early spring. Increased O3 concentrations in winter were indicative of increased emissions of O3 precursors from household combustion and other low-level sources, while a spring maximum observed at all the sites was attributed to increased regional biomass burning. Source area maps of O3 and CO indicated significantly higher O3 and CO concentrations associated with air masses passing over a region with increased seasonal open biomass burning, which indicated CO associated with open biomass burning as a major source of O3 in continental South Africa. A strong correlation between O3 on CO was observed, while O3 levels remained relatively constant or decreased with increasing NOx, which supports a VOC-limited regime. The instantaneous production rate of O3 calculated at Welgegund indicated that ∼ 40 % of O3 production occurred in the VOC-limited regime. The relationship between O3 and precursor species suggests that continental South Africa can be considered VOC limited, which can be attributed to high anthropogenic emissions of NOx in the interior of South Africa. The study indicated that the most effective emission control strategy to reduce O3 levels in continental South Africa should be CO and VOC reduction, mainly associated with household combustion and regional open biomass burning.

After carbon dioxide (CO2), aerosol black carbon (BC) is considered to be the second most important contributor to global warming. This paper presents equivalent black carbon (eBC) (derived from an optical absorption method) data collected from three sites in the interior of South Africa where continuous measurements were conducted, i.e. Elandsfontein, Welgegund and Marikana, as well elemental carbon (EC) (determined by evolved carbon method) data at five sites where samples were collected once a month on a filter and analysed offline, i.e. Louis Trichardt, Skukuza, Vaal Triangle, Amersfoort and Botsalano.Analyses of eBC and EC spatial mass concentration patterns across the eight sites indicate that the mass concentrations in the South African interior are in general higher than what has been reported for the developed world and that different sources are likely to influence different sites. The mean eBC or EC mass concentrations for the background sites (Welgegund, Louis Trichardt, Skukuza, Botsalano) and sites influenced by industrial activities and/or nearby settlements (Elandsfontein, Marikana, Vaal Triangle and Amersfoort) ranged between 0.7 and 1.1, and 1.3 and 1.4 µg m−3, respectively. Similar seasonal patterns were observed at all three sites where continuous measurement data were collected (Elandsfontein, Marikana and Welgegund), with the highest eBC mass concentrations measured from June to October, indicating contributions from household combustion in the cold winter months (June–August), as well as savannah and grassland fires during the dry season (May to mid-October). Diurnal patterns of eBC at Elandsfontein, Marikana and Welgegund indicated maximum concentrations in the early mornings and late evenings, and minima during daytime. From the patterns it could be deduced that for Marikana and Welgegund, household combustion, as well as savannah and grassland fires, were the most significant sources, respectively.Possible contributing sources were explored in greater detail for Elandsfontein, with five main sources being identified as coal-fired power stations, pyrometallurgical smelters, traffic, household combustion, as well as savannah and grassland fires. Industries on the Mpumalanga Highveld are often blamed for all forms of pollution, due to the NO2 hotspot over this area that is attributed to NOx emissions from industries and vehicle emissions from the Johannesburg–Pretoria megacity. However, a comparison of source strengths indicated that household combustion as well as savannah and grassland fires were the most significant sources of eBC, particularly during winter and spring months, while coal-fired power stations, pyrometallurgical smelters and traffic contribute to eBC mass concentration levels year round.

Atmospheric trace metals can cause a variety of health-related and environmental problems. Only a few studies on atmospheric trace metal concentrations have been conducted in South Africa. Therefore the aim of this study was to determine trace metal concentrations in aerosols collected at a regional background site, i.e. Welgegund, South Africa. PM1, PM1–2. 5 and PM2. 5–10 samples were collected for 13 months, and 31 atmospheric trace metal species were detected. Atmospheric iron (Fe) had the highest concentrations in all three size fractions, while calcium (Ca) was the second-most-abundant species. Chromium (Cr) and sodium (Na) concentrations were the third- and fourth-most-abundant species, respectively. The concentrations of the trace metal species in all three size ranges were similar, with the exception of Fe, which had higher concentrations in the PM1 size fraction. With the exception of titanium (Ti), aluminium (Al) and manganese (Mg), 70 % or more of the trace metal species detected were in the smaller size fractions, which indicated the influence of industrial activities. However, the large influence of wind-blown dust was reflected by 30 % or more of trace metals being present in the PM2. 5–10 size fraction. Comparison of trace metals determined at Welgegund to those in the western Bushveld Igneous Complex indicated that at both locations similar species were observed, with Fe being the most abundant. However, concentrations of these trace metal species were significantly higher in the western Bushveld Igneous Complex. Fe concentrations at the Vaal Triangle were similar to levels thereof at Welgegund, while concentrations of species associated with pyrometallurgical smelting were lower. Annual average Ni was 4 times higher, and annual average As was marginally higher than their respective European standard values, which could be attributed to regional influence of pyrometallurgical industries in the western Bushveld Igneous Complex. All three size fractions indicated elevated trace metal concentrations coinciding with the end of the dry season, which could partially be attributed to decreased wet removal and increases in wind generation of particulates. Principal component factor analysis (PCFA) revealed four meaningful factors in the PM1 size fraction, i.e. crustal, pyrometallurgical-related and Au slimes dams. No meaningful factors were determined for the PM1–2. 5 and PM2. 5–10 size fractions, which was attributed to the large influence of wind-blown dust on atmospheric trace metals determined at Welgegund. Pollution roses confirmed the influence of wind-blown dust on trace metal concentrations measured at Welgegund, while the impact of industrial activities was also substantiated.

Biogenic volatile organic compounds (BVOCs) play an important role in the chemistry of the troposphere, especially in the formation of tropospheric ozone (O3) and secondary organic aerosols (SOA). Ecosystems produce and emit a large number of BVOCs. It is estimated on a global scale that approximately 90 % of annual BVOC emissions are from terrestrial sources. In this study, measurements of BVOCs were conducted at the Welgegund measurement station (South Africa), which is considered to be a regionally representative background site situated in savannah grasslands. Very few BVOC measurements exist for savannah grasslands and results presented in this study are the most extensive for this type of landscape. Samples were collected twice a week for 2 h during the daytime and 2 h during the night-time through two long-term sampling campaigns from February 2011 to February 2012 and from December 2013 to February 2015, respectively. Individual BVOCs were identified and quantified using a thermal desorption instrument, which was connected to a gas chromatograph and a mass selective detector. The annual median concentrations of isoprene, 2-methyl-3-butene-2-ol (MBO), monoterpene and sesquiterpene (SQT) during the first campaign were 14, 7, 120 and 8 pptv, respectively, and 14, 4, 83 and 4 pptv, respectively, during the second campaign. The sum of the concentrations of the monoterpenes were at least an order of magnitude higher than the concentrations of other BVOC species during both sampling campaigns, with α-pinene being the most abundant species. The highest BVOC concentrations were observed during the wet season and elevated soil moisture was associated with increased BVOC concentrations. However, comparisons with measurements conducted at other landscapes in southern Africa and the rest of the world that have more woody vegetation indicated that BVOC concentrations were, in general, significantly lower for savannah grasslands. Furthermore, BVOC concentrations were an order of magnitude lower compared to total aromatic concentrations measured at Welgegund. An analysis of concentrations by wind direction indicated that isoprene concentrations were higher from the western sector that is considered to be a relatively clean regional background region with no large anthropogenic point sources, while wind direction did not indicate any significant differences in the concentrations of the other BVOC species. Statistical analysis indicated that soil moisture had the most significant impact on atmospheric levels of MBO, monoterpene and SQT concentrations, whereas temperature had the greatest influence on isoprene levels. The combined O3 formation potentials of all the BVOCs measured calculated with maximum incremental reactivity (MIR) coefficients during the first and second campaign were 1162 and 1022 pptv, respectively. α-Pinene and limonene had the highest reaction rates with O3, whereas isoprene exhibited relatively small contributions to O3 depletion. Limonene, α-pinene and terpinolene had the largest contributions to the OH reactivity of BVOCs measured at Welgegund for all of the months during both sampling campaigns.

Atmospheric emissions, including particle number and size distribution, from a 726 MWth coal-fired power plant were studied experimentally from a power plant stack and flue-gas plume dispersing in the atmosphere. Experiments were conducted under two different flue-gas cleaning conditions. The results were utilized in a plume dispersion and dilution model taking into account particle formation precursor (H2SO4 resulted from the oxidation of emitted SO2) and assessment related to nucleation rates. The experiments showed that the primary emissions of particles and SO2 were effectively reduced by flue-gas desulfurization and fabric filters, especially the emissions of particles smaller than 200 nm in diameter. Primary pollutant concentrations reached background levels in 200–300 s. However, the atmospheric measurements indicated that new particles larger than 2.5 nm are formed in the flue-gas plume, even in the very early phases of atmospheric ageing. The effective number emission of nucleated particles were several orders of magnitude higher than the primary particle emission. Modelling studies indicate that regardless of continuing dilution of the flue gas, nucleation precursor (H2SO4 from SO2 oxidation) concentrations remain relatively constant. In addition, results indicate that flue-gas nucleation is more efficient than predicted by atmospheric aerosol modelling. In particular, the observation of the new particle formation with rather low flue-gas SO2 concentrations changes the current understanding of the air quality effects of coal combustion. The results can be used to evaluate optimal ways to achieve better air quality, particularly in polluted areas like India and China.

Four years of continuous aerosol number size distribution measurements from the Arctic Climate Observatory in Tiksi, Russia, are analyzed. Tiksi is located in a region where in situ information on aerosol particle properties has not been previously available. Particle size distributions were measured with a differential mobility particle sizer (in the diameter range of 7–500 nm) and with an aerodynamic particle sizer (in the diameter range of 0.5–10 μm). Source region effects on particle modal features and number, and mass concentrations are presented for different seasons. The monthly median total aerosol number concentration in Tiksi ranges from 184 cm−3 in November to 724 cm−3 in July, with a local maximum in March of 481 cm−3. The total mass concentration has a distinct maximum in February–March of 1.72–2.38 μg m−3 and two minimums in June (0.42 μg m−3) and in September–October (0.36–0.57 μg m−3). These seasonal cycles in number and mass concentrations are related to isolated processes and phenomena such as Arctic haze in early spring, which increases accumulation and coarse-mode numbers, and secondary particle formation in spring and summer, which affects the nucleation and Aitken mode particle concentrations. Secondary particle formation was frequently observed in Tiksi and was shown to be slightly more common in marine, in comparison to continental, air flows. Particle formation rates were the highest in spring, while the particle growth rates peaked in summer. These results suggest two different origins for secondary particles, anthropogenic pollution being the important source in spring and biogenic emissions being significant in summer. The impact of temperature-dependent natural emissions on aerosol and cloud condensation nuclei numbers was significant: the increase in both the particle mass and the CCN (cloud condensation nuclei) number with temperature was found to be higher than in any previous study done over the boreal forest region. In addition to the precursor emissions of biogenic volatile organic compounds, the frequent Siberian forest fires, although far away, are suggested to play a role in Arctic aerosol composition during the warmest months. Five fire events were isolated based on clustering analysis, and the particle mass and cloud condensation nuclei number were shown to be somewhat affected by these events. In addition, during calm and cold months, aerosol concentrations were occasionally increased by local aerosol sources in trapping inversions. These results provide valuable information on interannual cycles and sources of Arctic aerosols.

Combustion of fuels in the residential sector for cooking and heating results in the emission of aerosol and aerosol precursors impacting air quality, human health, and climate. Residential emissions are dominated by the combustion of solid fuels. We use a global aerosol microphysics model to simulate the impact of residential fuel combustion on atmospheric aerosol for the year 2000. The model underestimates black carbon (BC) and organic carbon (OC) mass concentrations observed over Asia, Eastern Europe, and Africa, with better prediction when carbonaceous emissions from the residential sector are doubled. Observed seasonal variability of BC and OC concentrations are better simulated when residential emissions include a seasonal cycle. The largest contributions of residential emissions to annual surface mean particulate matter (PM2.5) concentrations are simulated for East Asia, South Asia, and Eastern Europe. We use a concentration response function to estimate the human health impact due to long-term exposure to ambient PM2.5 from residential emissions. We estimate global annual excess adult (> 30 years of age) premature mortality (due to both cardiopulmonary disease and lung cancer) to be 308 000 (113 300–497 000, 5th to 95th percentile uncertainty range) for monthly varying residential emissions and 517 000 (192 000–827 000) when residential carbonaceous emissions are doubled. Mortality due to residential emissions is greatest in Asia, with China and India accounting for 50 % of simulated global excess mortality. Using an offline radiative transfer model we estimate that residential emissions exert a global annual mean direct radiative effect between −66 and +21 mW m−2, with sensitivity to the residential emission flux and the assumed ratio of BC, OC, and SO2 emissions. Residential emissions exert a global annual mean first aerosol indirect effect of between −52 and −16 mW m−2, which is sensitive to the assumed size distribution of carbonaceous emissions. Overall, our results demonstrate that reducing residential combustion emissions would have substantial benefits for human health through reductions in ambient PM2.5 concentrations.

South Africa has one of the largest industrialized economies in Africa. Emissions of air pollutants are particularly high in the Johannesburg-Pretoria metropolitan area, the Mpumalanga Highveld and the Vaal Triangle, resulting in local air pollution. This study presents and evaluates a setup for conducting modeling experiments over southern Africa with the Weather Research and Forecasting model including chemistry and aerosols (WRF-Chem), and analyzes the contribution of anthropogenic emissions to the total black carbon (BC) concentrations from September to December 2010. The modeled BC concentrations are compared with measurements obtained at the Welgegund station situated ca. 100 km southwest of Johannesburg. An evaluation of WRF-Chem with observational data from ground-based measurement stations, radiosondes, and satellites shows that the meteorology is modeled mostly reasonably well, but precipitation amounts are widely overestimated and the onset of the wet season is modeled approximately 1 month too early in 2010. Modeled daily mean BC concentrations show a temporal correlation of 0.66 with measurements, but the total BC concentration is underestimated in the model by up to 50 %. Sensitivity studies with anthropogenic emissions of BC and co-emitted species turned off show that anthropogenic sources can contribute up to 100 % to BC concentrations in the industrialized and urban areas, and anthropogenic BC and co-emitted species together can contribute up to 60 % to PM1 levels. Particularly the co-emitted species contribute significantly to the aerosol optical depth (AOD). Furthermore, in areas of large-scale biomass-burning atmospheric heating rates are increased through absorption by BC up to an altitude of about 600hPa.

Proxies for estimating nucleation mode number concentrations and further simplification for their use with satellite data have been presented in Kulmala et al. (2011). In this paper we discuss the underlying assumptions for these simplifications and evaluate the resulting proxies over an area in South Africa based on a comparison with a suite of ground-based measurements available from four different stations. The proxies are formulated in terms of sources (concentrations of precursor gases (NO2 and SO2) and UVB radiation intensity near the surface) and a sink term related to removal of the precursor gases due to condensation on pre-existing aerosols. A-Train satellite data are used as input to compute proxies. Both the input data and the resulting proxies are compared with those obtained from ground-based measurements. In particular, a detailed study is presented on the substitution of the local condensation sink (CS) with satellite aerosol optical depth (AOD), which is a column-integrated parameter. One of the main factors affecting the disagreement between CS and AOD is the presence of elevated aerosol layers. Overall, the correlation between proxies calculated from the in situ data and observed nucleation mode particle number concentrations (Nnuc) remained low. At the time of the satellite overpass (13:00–14:00 LT) the highest correlation is observed for SO2/CS (R2 = 0.2). However, when the proxies are calculated using satellite data, only NO2/AOD showed some correlation with Nnuc (R2 = 0.2). This can be explained by the relatively high uncertainties related especially to the satellite SO2 columns and by the positive correlation that is observed between the ground-based SO2 and NO2 concentrations. In fact, results show that the satellite NO2 columns compare better with in situ SO2 concentration than the satellite SO2 column. Despite the high uncertainties related to the proxies calculated using satellite data, the proxies calculated from the in situ data did not better predict Nnuc. Hence, overall improvements in the formulation of the proxies are needed.

Raman lidar data obtained over a 1 year period has been analysed in relation to aerosol layers in the free troposphere over the Highveld in South Africa. In total, 375 layers were observed above the boundary layer during the period 30 January 2010 to 31 January 2011. The seasonal behaviour of aerosol layer geometrical characteristics, as well as intensive and extensive optical properties were studied. The highest centre heights of free-tropospheric layers were observed during the South African spring (2520 ± 970 m a.g.l., also elsewhere). The geometrical layer depth was found to be maximum during spring, while it did not show any significant difference for the rest of the seasons. The variability of the analysed intensive and extensive optical properties was high during all seasons. Layers were observed at a mean centre height of 2100 ± 1000 m with an average lidar ratio of 67 ± 25 sr (mean value with 1 standard deviation) at 355 nm and a mean extinction-related Ångström exponent of 1.9 ± 0.8 between 355 and 532 nm during the period under study. Except for the intensive biomass burning period from August to October, the lidar ratios and Ångström exponents are within the range of previous observations for urban/industrial aerosols. During Southern Hemispheric spring, the biomass burning activity is clearly reflected in the optical properties of the observed free-tropospheric layers. Specifically, lidar ratios at 355 nm were 89 ± 21, 57 ± 20, 59 ± 22 and 65 ± 23 sr during spring (September–November), summer (December–February), autumn (March–May) and winter (June–August), respectively. The extinction-related Ångström exponents between 355 and 532 nm measured during spring, summer, autumn and winter were 1.8 ± 0.6, 2.4 ± 0.9, 1.8 ± 0.9 and 1.8 ± 0.6, respectively. The mean columnar aerosol optical depth (AOD) obtained from lidar measurements was found to be 0.46 ± 0.35 at 355 nm and 0.25 ± 0.2 at 532 nm. The contribution of free-tropospheric aerosols on the AOD had a wide range of values with a mean contribution of 46%.

Aromatic hydrocarbons are associated with direct adverse human health effects and can have negative impacts on ecosystems due to their toxicity, as well as indirect negative effects through the formation of tropospheric ozone and secondary organic aerosol, which affect human health, crop production and regional climate. Measurements of aromatic hydrocarbons were conducted at the Welgegund measurement station (South Africa), which is considered to be a regionally representative background site. However, the site is occasionally impacted by plumes from major anthropogenic source regions in the interior of South Africa, which include the western Bushveld Igneous Complex (e.g. platinum, base metal and ferrochrome smelters), the eastern Bushveld Igneous Complex (platinum and ferrochrome smelters), the Johannesburg–Pretoria metropolitan conurbation (> 10 million people), the Vaal Triangle (e.g. petrochemical and pyrometallurgical industries), the Mpumalanga Highveld (e.g. coal-fired power plants and petrochemical industry) and also a region of anticyclonic recirculation of air mass over the interior of South Africa. The aromatic hydrocarbon measurements were conducted with an automated sampler on Tenax-TA and Carbopack-B adsorbent tubes with heated inlet for 1 year. Samples were collected twice a week for 2 h during daytime and 2 h during night-time. A thermal desorption unit, connected to a gas chromatograph and a mass selective detector was used for sample preparation and analysis. Results indicated that the monthly median (mean) total aromatic hydrocarbon concentrations ranged between 0.01 (0.011) and 3.1 (3.2) ppb. Benzene levels did not exceed the local air quality standard limit, i.e. annual mean of 1.6 ppb. Toluene was the most abundant compound, with an annual median (mean) concentration of 0.63 (0.89) ppb. No statistically significant differences in the concentrations measured during daytime and night-time were found, and no distinct seasonal patterns were observed. Air mass back trajectory analysis indicated that the lack of seasonal cycles could be attributed to patterns determining the origin of the air masses sampled. Aromatic hydrocarbon concentrations were in general significantly higher in air masses that passed over anthropogenically impacted regions. Inter-compound correlations and ratios gave some indications of the possible sources of the different aromatic hydrocarbons in the source regions defined in the paper. The highest contribution of aromatic hydrocarbon concentrations to ozone formation potential was also observed in plumes passing over anthropogenically impacted regions.

Atmospheric lidar measurements were carried out at Elandsfontein measurement station, on the eastern Highveld approximately 150 km east of Johannesburg in South Africa throughout 2010. The height of the planetary boundary layer (PBL) top was continuously measured using a Raman lidar, PollyXT (POrtabLe Lidar sYstem eXTended). High atmospheric variability together with a large surface temperature range and significant seasonal changes in precipitation were observed, which had an impact on the vertical mixing of particulate matter, and hence, on the PBL evolution. The results were compared to radiosondes, CALIOP (Cloud-Aerosol Lidar with Orthogonal Polarization) space-borne lidar measurements and three atmospheric models that followed different approaches to determine the PBL top height. These models included two weather forecast models operated by ECMWF (European Centre for Medium-range Weather Forecasts) and SAWS (South African Weather Service), and one mesoscale prognostic meteorological and air pollution regulatory model TAPM (The Air Pollution Model). The ground-based lidar used in this study was operational for 4935 h during 2010 (49% of the time). The PBL top height was detected 86% of the total measurement time (42% of the total time). Large seasonal and diurnal variations were observed between the different methods utilised. High variation was found when lidar measurements were compared to radiosonde measurements. This could be partially due to the distance between the lidar measurements and the radiosondes, which were 120 km apart. Comparison of lidar measurements to the models indicated that the ECMWF model agreed the best with mean relative difference of 15.4%, while the second best correlation was with the SAWS model with corresponding difference of 20.1%. TAPM was found to have a tendency to underestimate the PBL top height. The wind speeds in the SAWS and TAPM models were strongly underestimated which probably led to underestimation of the vertical wind and turbulence and thus underestimation of the PBL top height. Comparison between ground-based and satellite lidar shows good agreement with a correlation coefficient of 0.88. On average, the daily maximum PBL top height in October (spring) and June (winter) was 2260 m and 1480 m, respectively. To our knowledge, this study is the first long-term study of PBL top heights and PBL growth rates in South Africa.

Southern Africa is a significant source region of atmospheric pollution, yet long-term data on pollutant concentrations and properties from this region are rather limited. A recently established atmospheric measurement station in South Africa, Welgegund, is strategically situated to capture regional background concentrations, as well as emissions from the major source regions in the interior of South Africa. We measured non-refractive submicron aerosols (NR-PM1) and black carbon over a one year period in Welgegund, and investigated the seasonal and diurnal patterns of aerosol concentration levels, chemical composition, acidity and oxidation level. Based on air mass back trajectories, four distinct source regions were determined for NR-PM1. Supporting data utilised in our analysis included particle number size distributions, aerosol absorption, trace gas concentrations, meteorological variables and the flux of carbon dioxide. The dominant submicron aerosol constituent during the dry season was organic aerosol, reflecting high contribution from savannah fires and other combustion sources. Organic aerosol concentrations were lower during the wet season, presumably due to wet deposition as well as reduced emissions from combustion sources. Sulfate concentrations were usually high and exceeded organic aerosol concentrations when air-masses were transported over regions containing major point sources. Sulfate and nitrate concentrations peaked when air masses passed over the industrial Highveld (iHV) area. In contrast, concentrations were much lower when air masses passed over the cleaner background (BG) areas. Air masses associated with the anti-cyclonic recirculation (ACBIC) source region contained largely aged OA. Positive Matrix Factorization (PMF) analysis of aerosol mass spectra was used to characterise the organic aerosol (OA) properties. The factors identified were oxidized organic aerosols (OOA) and biomass burning organic aerosols (BBOA) in the dry season and low-volatile (LV-OOA) and semi-volatile (SV-OOA) organic aerosols in the wet season. The results highlight the importance of primary BBOA in the dry season, which represented 33% of the total OA. Aerosol acidity and its potential impact on the evolution of OOA are also discussed.

Recent studies have shown very high frequencies of atmospheric new particle formation in different environments in South Africa. Our aim here was to investigate the causes for two or three consecutive daytime nucleation events, followed by subsequent particle growth during the same day. We analysed 108 and 31 such days observed in a polluted industrial and moderately polluted rural environments, respectively, in South Africa. The analysis was based on two years of measurements at each site. After rejecting the days having notable changes in the air mass origin or local wind direction, i.e. two major reasons for observed multiple nucleation events, we were able to investigate other factors causing this phenomenon. Clouds were present during, or in between most of the analysed multiple particle formation events. Therefore, some of these events may have been single events, interrupted somehow by the presence of clouds. From further analysis, we propose that the first nucleation and growth event of the day was often associated with the mixing of a residual air layer rich in SO2 (oxidized to sulphuric acid) into the shallow surface-coupled layer. The second nucleation and growth event of the day usually started before midday and was sometimes associated with renewed SO2 emissions from industrial origin. However, it was also evident that vapours other than sulphuric acid were required for the particle growth during both events. This was especially the case when two simultaneously growing particle modes were observed. Based on our analysis, we conclude that the relative contributions of estimated H2SO4 and other vapours on the first and second nucleation and growth events of the day varied from day to day, depending on anthropogenic and natural emissions, as well as atmospheric conditions.

The South African savannah region is a complex environment of air pollution and natural emissions influenced by a strong seasonal cycle in biomass burning and strong precipitation. However, the scarcity of long-term observations means that the knowledge of controlling aerosol processes in this environment is limited. Here we use a recent dataset of 18 months of aerosol size distribution observations trying to understand the annual cycle of cloud condensation nuclei (CCN). Our observations show that the concentration of CCN-sized particles remains, in line with previous studies, high throughout the year with the highest concentrations during the dry winter and the lowest during the wet summer. During the wet season with reduced anthropogenic and biomass burning primary emissions, this pool of CCN is partly filled by boundary layer nucleation with subsequent growth. The enhanced importance of formation and growth during the wet season is addressed to increased biogenic activity together with enhanced free tropospheric removal decreasing the concentration of pre-existing CCN. During the dry season, while frequent new particle formation takes place, particle growth is reduced due to reduced condensing vapour concentrations. Thus in the dry season particles are not able to grow to sizes where they may act as CCN nearly as efficiently as during the wet season. The observations are compared to simulations by a global aerosol model GLOMAP. To our surprise, the global aerosol model utilized to explain the observations was not capable of re-producing the characteristics of particle formation and the annual CCN cycle, despite earlier good performance in predicting the particle concentrations in a number of diverse environments, including the South African savannah region. While the average yearly CCN concentrations of modelled CCN is close to observed concentrations, the characteristics of nucleation bursts and subsequent growth are not captured satisfactory by the model. Our sensitivity tests using different nucleation parameterizations and condensing organic vapour production rates show that neither of these is likely to explain the differences between observed and modelled nucleation and growth rates. A sensitivity study varying 28 modelling parameters indicates that the main uncertainties in the result are due to uncertainties in biomass burning emissions during the dry season, and anthropogenic sulphur emissions during the wet season, both in terms or emitted mass and particle sizes. The uncertainties appear to be mostly related to uncertainties in primary particle emissions, including the emissions variability not captured by monthly emission inventories. The results of this paper also highlights the fact that deficiencies in emissions estimates may result in deficiencies in particle production fluxes, while the end product such as modelled CCN concentration may be in line with observations.

This study presents a total of four years of sub-micron aerosol particle size distribution measurements in the southern African savannah, an environment with few previous observations covering a full seasonal cycle and the size range below 100 nm. During the first 19 months, July 2006–January 2008, the measurements were carried out at Botsalano, a semi-clean location, whereas during the latter part, February 2008–May 2010, the measurements were carried out at Marikana (approximately 150 km east of Botsalano), which is a more polluted location with both pyrometallurgical industries and informal settlements nearby. The median total concentration of aerosol particles was more than four times as high at Marikana than at Botsalano. In the size ranges of 12–840 nm, 50–840 nm and 100–840 nm the median concentrations were 1856, 1278 and 698 particles cm−3 at Botsalano and 7805, 3843 and 1634 particles cm−3 at Marikana, respectively. The diurnal variation of the size distribution for Botsalano arose as a result of frequent regional new particle formation. However, for Marikana the diurnal variation was dominated by the morning and evening household burning in the informal settlements, although regional new particle formation was even more frequent than at Botsalano. The effect of the industrial emissions was not discernible in the size distribution at Marikana although it was clear in the sulphur dioxide diurnal pattern, indicating the emissions to be mostly gaseous. Seasonal variation was strongest in the concentration of particles larger than 100 nm, which was clearly elevated at both locations during the dry season from May to September. In the absence of wet removal during the dry season, the concentration of particles larger than 100 nm had a correlation above 0.7 with CO for both locations, which implies incomplete burning to be an important source of aerosol particles during the dry season. However, the sources of burning differ: at Botsalano the rise in concentration originates from regional wild fires, while at Marikana domestic heating in the informal settlements is the main source. Air mass history analysis for Botsalano identified four regional scale source areas in southern Africa and enabled the differentiation between fresh and aged rural background aerosol originating from the clean sector, i.e., western sector with very few large anthropogenic sources. Comparison to size distributions published for other comparable environments in Northern Hemisphere shows southern African savannah to have a unique combination of sources and meteorological parameters. The observed strong link between combustion and seasonal variation is comparable only to the Amazon basin; however, the lack of long-term observations in the Amazonas does not allow a quantitative comparison. All the data presented in the figures, as well as the time series of monthly mean and median size distributions are included in numeric form as a Supplement to provide a reference point for the aerosol modelling community.

Concentrations of 5 gases (HCl, HNO3, HONO, NH3, SO2) and 8 major inorganic ions in particles (Cl−, NO3−, SO42−, NH4+, Na+, K+, Mg2+, Ca2+) were measured with an online monitor MARGA 2S in two size ranges, Dp Dp < 10 μm, in Helsinki, Finland from November 2009 to May 2010. The results were compared with filter sampling, mass concentrations obtained from particle number size distributions, and a conventional SO2 monitor. The MARGA yielded lower concentrations than those analyzed from the filter samples for most ions. Linear regression yielded the following MARGA vs. filter slopes: 0.72 for Cl−, 0.90 for NO3−, 0.85 for SO42−, 0.91 for NH4+ , 0.49 for Na+, 3.0 for Mg2+, and 3.0 for Ca2+ and 0.90 for the MARGA vs. SO2 monitor. For K+ there were not enough data points to calculate a statistically significant linear regression. There were clear seasonal cycles in the concentrations of the nitrogen-containing gases: the median concentrations of HNO3, HONO, and NH3 were 0.09 ppb, 0.37 ppb, and 0.01 ppb in winter, respectively, and 0.15, 0.15, and 0.14 in spring, respectively. The gas-phase fraction of nitrogen decreased roughly with decreasing temperature, so that in the coldest period from January to February the median contribution was 28% but in April to May was 53%. There were also large fractionation variations that temperature alone cannot explain. HONO correlated well with NOx but a large fraction of the HONO-to-NOx ratios were larger than published ratios in a road traffic tunnel, suggesting that a large amount of HONO had other sources than vehicle exhaust. Aerosol acidity was estimated by calculating ion equivalent ratios. The sources of acidic aerosols were studied with trajectory statistics that showed that continental aerosol is mainly neutralized and marine aerosol acidic.

South Africa holds significant mineral resources, with a substantial fraction of these reserves occurring and being processed in a large geological structure termed the Bushveld Igneous Complex (BIC). The area is also highly populated by informal, semi-formal and formal residential developments. However, knowledge of air quality and research related to the atmosphere is still very limited in the area. In order to investigate the characteristics and processes affecting sub-micron particle number concentrations and formation events, air ion and aerosol particle size distributions and number concentrations, together with meteorological parameters, trace gases and particulate matter (PM) were measured for over two years at Marikana in the heart of the western BIC. The observations showed that trace gas (i.e. SO2, NOx, CO) and black carbon concentrations were relatively high, but in general within the limits of local air quality standards. The area was characterised by very high condensation sink due to background aerosol particles, PM10 and O3 concentration. The results indicated that high amounts of Aitken and accumulation mode particles originated from domestic burning for heating and cooking in the morning and evening, while during daytime SO2-based nucleation followed by the growth by condensation of vapours from industrial, residential and natural sources was the most probable source for large number concentrations of nucleation and Aitken mode particles. Nucleation event day frequency was extremely high, i.e. 86% of the analysed days, which to the knowledge of the authors is the highest frequency ever reported. The air mass back trajectory and wind direction analyses showed that the secondary particle formation was influenced both by local and regional pollution and vapour sources. Therefore, our observation of the annual cycle and magnitude of the particle formation and growth rates during nucleation events were similar to results previously published for a semi-clean savannah site in South Africa.

In this paper we introduce new in situ observations of atmospheric aerosols, especially chemical composition, physical and optical properties, on the eastern brink of the heavily polluted Highveld area in South Africa. During the observation period between 11 February 2009 and 31 January 2011, the mean particle number concentration (size range 10–840 nm) was 6310 cm3 and the estimated volume of sub-10 μm particles 9.3 μm3 m−3. The aerosol absorption and scattering coefficients at 637 nm were 8.3 Mm−1 and 49.5 Mm−1, respectively. The mean single-scattering albedo at 637 nm was 0.84 and the Ångström exponent of scattering was 1.5 over the wavelength range 450–635 nm. The mean O3, SO2, NOx and H2S-concentrations were 37.1, 11.5, 15.1 and 3.2 ppb, respectively. The observed range of concentrations was large and attributed to the seasonal variation of sources and regional meteorological effects, especially the anticyclonic re-circulation and strong winter-time inversions. In a global context, the levels of gases and particulates were typical for continental sites with strong anthropogenic influence, but clearly lower than the most polluted areas of south-eastern Asia. Of all pollutants observed at the site, ozone is the most likely to have adverse environmental effects, as the concentrations were high also during the growing season. The measurements presented here will help to close existing gaps in the ground-based global atmosphere observation system, since very little long-term data of this nature is available for southern Africa.

In this paper we describe and summarize the main achievements of the European Aerosol Cloud Climate and Air Quality Interactions project (EUCAARI). EUCAARI started on 1 January 2007 and ended on 31 December 2010 leaving a rich legacy including: (a) a comprehensive database with a year of observations of the physical, chemical and optical properties of aerosol particles over Europe, (b) comprehensive aerosol measurements in four developing countries, (c) a database of airborne measurements of aerosols and clouds over Europe during May 2008, (d) comprehensive modeling tools to study aerosol processes fron nano to global scale and their effects on climate and air quality. In addition a new Pan-European aerosol emissions inventory was developed and evaluated, a new cluster spectrometer was built and tested in the field and several new aerosol parameterizations and computations modules for chemical transport and global climate models were developed and evaluated. These achievements and related studies have substantially improved our understanding and reduced the uncertainties of aerosol radiative forcing and air quality-climate interactions. The EUCAARI results can be utilized in European and global environmental policy to assess the aerosol impacts and the corresponding abatement strategies.

This study is based on 18 months (20 July 2006–5 February 2008) of continuous measurements of aerosol particle size distributions, air ion size distributions, trace gas concentrations and basic meteorology in a semi-clean savannah environment in Republic of South Africa. New particle formation and growth was observed on 69% of the days and bursts of non-growing ions/sub-10 nm particles on additional 14% of the days. This new particle formation frequency is the highest reported from boundary layer so far. Also the new particle formation and growth rates were among the highest reported in the literature for continental boundary layer locations; median 10 nm formation rate was 2.2 cm−3 s−1 and median 10–30 nm growth rate 8.9 nm h−1. The median 2 nm ion formation rate was 0.5 cm−3 s−1 and the median ion growth rates were 6.2, 8.0 and 8.1 nm h−1 for size ranges 1.5–3 nm, 3–7 nm and 7–20 nm, respectively. The growth rates had a clear seasonal dependency with minimum during winter and maxima in spring and late summer. The relative contribution of estimated sulphuric acid to the growth rate was decreasing with increasing particle size and could explain more than 20% of the observed growth rate only for the 1.5–3 nm size range. Also the air mass history analysis indicated the highest formation and growth rates to be associated with the area of highest VOC (Volatile Organic Compounds) emissions following from biological activity rather than the highest estimated sulphuric acid concentrations. The frequency of new particle formation, however, increased nearly monotonously with the estimated sulphuric acid reaching 100% at H2SO4 concentration of 6 · 107 cm−3, which suggests the formation and growth to be independent of each other.

This review is based on ca. 260 publications, 93 of which included data on the temporal and spatial variation of the concentration of small ions (−3. However, concentrations up to 5000 cm−3 have been observed. The results are in agreement with observations of ion production rates in the atmosphere. We also summarised observations on the conversion of small ions to intermediate ions, which can act as embryos for new atmospheric aerosol particles. Those observations include the formation rates (J2[ion]) of 2-nm intermediate ions, growth rates (GR[ion]) of sub-3 nm ions, and information on the chemical composition of the ions. Unfortunately, there were only a few studies which presented J2[ion] and GR[ion]. Based on the publications, the formation rates of 2-nm ions were 0–1.1 cm−3 s−1, while the total 2-nm particle formation rates varied between 0.001 and 60 cm−3 s−1. Due to small changes in J2[ion], the relative importance of ions in 2-nm particle formation was determined by the large changes in J2[tot], and, accordingly the contribution of ions increased with decreasing J2[tot]. Furthermore, small ions were observed to activate for growth earlier than neutral nanometer-sized particles and at lower saturation ratio of condensing vapours.