Aerosol Size Distribution Measurements Research Articles

Chemical composition and trajectories of atmospheric particles at the Machu Picchu Peruvian Antarctic scientific station (62.09º S, 58.47º W)

Antarctica is a remote and relatively pristine region, but the regional transport of aerosols may be a source of pollution, especially in the Antarctic Peninsula. Few studies have characterized atmospheric aerosols and evaluated the contribution of their emission sources. The Peruvian Antarctic research station Machu Pichu (ECAMP, by its Spanish acronym) is located on King George Island in the Antarctic Peninsula. During February 2020, atmospheric particulate mass (PM10 and PM2.5) was sampled and analyzed to characterize its elemental composition and was supplemented by measurements of equivalent black carbon and aerosol size distributions. Chemical elements were analyzed by inductively coupled plasma mass spectrometry (ICP-MS), multivariate techniques, and enrichment factors. The most abundant elements in PM10 and PM2.5 were Na, Fe, Mg, and Si, with the most important local sources being marine (Na, Mg, Mn, Ca) and crustal (Fe, Al, P). Sources of weathering (Ba and Si) from glacial thawing and sources of combustion linked to the use of oil (V) and emission of black carbon were recorded. Air mass back-trajectory analysis using the HYSPLIT model helped identify external sources of particulate matter in the air masses reaching the ECAMP site. Overall, this study supports the growing evidence of the anthropogenic impact of distant and local sources on the white continent.

Size-resolved aerosol at a Coastal Great Lakes Site: Impacts of new particle formation and lake spray.

The quantification of aerosol size distributions is crucial for understanding the climate and health impacts of aerosols, validating models, and identifying aerosol sources. This work provides one of the first continuous measurements of aerosol size distribution from 1.02 to 8671 nm near the shore of Lake Michigan. The data were collected during the Lake Michigan Ozone Study (LMOS 2017), a comprehensive air quality measurement campaign in May and June 2017. The time-resolved (2-min) size distribution are reported herein alongside meteorology, remotely sensed data, gravimetric filters, and gas-phase variables. Mean concentrations of key aerosol parameters include PM2.5 (6.4 μg m-3), number from 1 to 3 nm (1.80x104 cm-3) and number greater than 3 nm (8x103 cm-3). During the field campaign, approximately half of days showed daytime ultrafine burst events, characterized by particle growth from sub 10 nm to 25-100 nm. A specific investigation of ultrafine lake spray aerosol was conducted due to enhanced ultrafine particles in onshore flows coupled with sustained wave breaking conditions during the campaign. Upon closer examination, the relationships between the size distribution, wind direction, wind speed, and wave height did not qualitatively support ultrafine particle production from lake spray aerosol; statistical analysis of particle number and wind speed also failed to show a relationship. The alternative hypothesis of enhanced ultrafine particles in onshore flow originating mainly from new particle formation activity is supported by multiple lines of evidence.

Process Modeling of Aerosol‐Cloud Interaction in Summertime Precipitating Shallow Cumulus Over the Western North Atlantic

AbstractProcess modeling of Aerosol‐cloud interaction (ACI) is essential to bridging gaps between observational analysis and climate modeling of aerosol effects in the Earth system and eventually reducing climate projection uncertainties. In this study, we examine ACI in summertime precipitating shallow cumuli observed during the Aerosol Cloud meTeorology Interactions oVer the western ATlantic Experiment (ACTIVATE). Aerosols and precipitating shallow cumuli were extensively observed with in‐situ and remote‐sensing instruments during two research flight cases on 02 June and 07 June, respectively, during the ACTIVATE summer 2021 deployment phase. We perform observational analysis and large‐eddy simulation (LES) of aerosol effect on precipitating cumulus in these two cases. Given the measured aerosol size distributions and meteorological conditions, LES is able to reproduce the observed cloud properties by aircraft such as liquid water content (LWC), cloud droplet number concentration (Nc) and effective radius reff. However, it produces smaller liquid water path (LWP) and larger Nc compared to the satellite retrievals. Both 02 and 07 June cases are over warm waters of the Gulf Stream and have a cloud top height over 3 km, but the 07 June case is more polluted and has larger LWC. We find that the Na‐induced LWP adjustment is dominated by precipitation feedback for the 2 June precipitating case and there is no clear entrainment feedback in both cases. An increase of cloud fraction due to a decrease of aerosol number concentration is also shown in the simulations for the 02 June case.

On the formation of biogenic secondary organic aerosol in chemical transport models: an evaluation of the WRF-CHIMERE (v2020r2) model with a focus over the Finnish boreal forest

Abstract. We present an evaluation of the regional chemical transport model (CTM) WRF-CHIMERE (v2020r2) for the formation of biogenic secondary organic aerosol (BSOA) with a focus over the Finnish boreal forest. Formation processes of biogenic aerosols are still affected by different sources of uncertainties, and model predictions vary greatly depending on the levels of details of the adopted chemical and emissions schemes. In this study, air quality simulations were conducted for the summer of 2019 using different organic aerosol (OA) schemes (as currently available in the literature) to treat the formation of BSOA. First, we performed a set of simulations in the framework of the volatility basis set (VBS) scheme carrying different assumptions for the treatment of the aging processes of BSOA. The results of the model were compared against high-resolution (i.e., 1 h) organic aerosol mass and size distribution measurements performed at the Station for Measuring Ecosystem–Atmosphere Relations (SMEAR-II) site located in Hyytiälä, in addition to other gas-phase species such as ozone (O3), nitrogen oxides (NOx), and biogenic volatile organic compound (BVOC) measurements of isoprene (C5H10) and monoterpenes. We show that WRF-CHIMERE could reproduce well the diurnal variation of the measured OA concentrations for all the investigated scenarios (along with the standard meteorological parameters) as well as the increase in concentrations during specific heat wave episodes. However, the modeled OA concentrations varied greatly between the schemes used to describe the aging processes of BSOA, as also confirmed by an additional evaluation using organic carbon (OC) measurement data retrieved from the EBAS European databases. Comparisons with isoprene and monoterpene air concentrations revealed that the model captured the observed monoterpene concentrations, but isoprene was largely overestimated, a feature that was mainly attributed to the overstated biogenic emissions of isoprene. We investigated the potential consequences of such an overestimation by inhibiting isoprene emissions from the modeling system. Results indicated that the modeled BSOA concentrations increased in the northern regions of the domain (e.g., Finland) compared to southern European countries, possibly due to a shift in the reactions of monoterpene compounds against available radicals, as further suggested by the reduction in α-pinene modeled air concentrations. Finally, we briefly analyze the differences in the modeled cloud liquid water content (clwc) among the simulations carrying different chemical schemes for the treatment of the aging processes of BSOA. The results of the model indicated an increase in clwc values at the SMEAR-II site, for simulations with higher biogenic organic aerosol loads, most likely as a result of the increased number of biogenic aerosol particles capable of activating cloud droplets.

Comparison of aerosol spectrometers : accounting for evaporation and sampling losses

Measuring aerosol size distribution with precision is critical to understand the transmission of pathogens causing respiratory illnesses and to identify risk mitigation strategies. It is however a challenging task as the size of pathogen-carrying particles evolves over time due to evaporation. Although measurement techniques well established in the field of aerosol science are often used to characterize bioaerosols, their performance is seldom assessed with respect to evaporation and deposition in sampling lines. Four instruments providing aerosol size distribution were compared using oil and water-based particles. They each rely on different measurement principles: phase doppler anemometry, light scattering, electrical mobility and aerodynamic impaction. Size distributions of oil-based particles showed consistency across different measurement instruments, but significant discrepancies arose for water-based particles undergoing evaporation. These larger differences result from both evaporation and particle deposition in transit between the sampling point and the measurement inside the instrument. Phase doppler anemometry was best suited for precise size distribution measurement, as it eliminates the need for a sampling line, thereby preventing particle loss or evaporation during transit. With this instrument as a reference, empirical correction factors for evaporation and deposition were derived from dimensionless numbers and experimental data, enabling quantitative assessment of bioaerosol size distribution using different instruments. To obtain the size distribution at the source of the aerosol generation, complete drying of a salt solution was performed. Using the complete drying technique and accounting for losses, sampling instruments can reliably provide this critical information and allow for thorough risk assessment in the context of airborne transmission.

Impact of desert dust on new particle formation events and the cloud condensation nuclei budget in dust-influenced areas

Abstract. Detailed knowledge on the formation of new aerosol particles in the atmosphere from precursor gases, and their subsequent growth, commonly known as new particle formation (NPF) events, is one of the largest challenges in atmospheric aerosol science. High pre-existing particle loadings are expected to suppress the formation of new atmospheric aerosol particles due to high coagulation and condensation (CS) sinks. However, NPF events are regularly observed in conditions with high concentrations of pre-existing particles and even during intense desert dust intrusions that imply discrepancies between the observations and theory. In this study, we present a multi-site analysis of the occurrence of NPF events under the presence of desert dust particles in dust-influenced areas. Characterization of NPF events at five different locations highly influenced by desert dust outbreaks was done under dusty and non-dusty conditions using continuous measurements of aerosol size distribution in both fine and coarse size fractions. Contrary to common thought, our results show that the occurrence of NPF events is highly frequent during desert dust outbreaks, showing that NPF event frequencies during dusty conditions are similar to those observed during non-dusty conditions. Furthermore, our results show that NPF events also occur during intense desert dust outbreaks at all the studied sites, even at remote sites where the amounts of precursor vapours are expected to be low. Our results show that the condensation sink associated with coarse particles (CSC) represents up to the 60 % of the total CS during dusty conditions, which highlights the importance of considering coarse-fraction particles for NPF studies in desert-dust-influenced areas. However, we did not find a clear pattern of the effect of desert dust outbreaks on the strength of NPF events, with differences from site to site. The particle growth rate (GR) did not present a clear dependence on the CS during dusty and non-dusty conditions. This result, together with the fact that desert dust has different effects on the growth and formation rates at each site, suggests different formation and growth mechanisms at each site between dusty and non-dusty conditions, probably due to differences in precursor vapours' origins and concentrations as well as changes in the oxidative capacity of pre-existing particles and their effectiveness acting as CS. Further investigation based on multiplatform measurement campaigns and chamber experiments with state-of-the-art gaseous and particulate physical and chemical properties measurements is needed to better understand the role of catalyst components present in desert dust particles in NPF. Finally, our results reveal a significant impact of NPF events on the cloud condensation nuclei (CCN) budget during desert dust outbreaks at the studied sites. Therefore, since desert dust contributes to a major fraction of the global aerosol mass load, and since there is a foreseeable increase in the frequency, duration and intensity of desert dust episodes due to climate change, it is imperative to improve our understanding of the effect of desert dust outbreaks on NPF and the CCN budget for better climate change prediction.

Characterising a mobile reference station (MoRS) to quantify personal exposure to air quality

There is increasing clinical, epidemiological, and toxicological evidence linking exposure to air pollution with multiple health outcomes that lead to increased mortality and morbidity. Traditionally, fixed air quality monitors have been used to provide ambient air pollution measurements, but they have spatial and temporal limitations. Rapid advances in instrument miniaturisation have made novel sensing technologies more accessible but these are prone to high sensitivity and inaccuracies. To bridge the gap between fixed monitors and small sensors we have developed a Mobile Reference Station (MoRS) – a portable platform delivering high quality measurements of air pollutants using smaller, low power reference grade instruments at high time resolutions. MoRS enables the simultaneous measurement of a broad aerosol size distribution (10 nm–35 μm), gaseous pollutant concentrations (nitrogen dioxide (NO2) and ozone (O3)), environmental parameters (noise, relatively humidity (RH) and temperature) as well as collecting filter samples for laboratory analysis. The MoRS instrumentation is described and the major challenges in ensuring that high data quality standards are maintained are discussed. Laboratory and field tests were used to derive scaling factors for all the MoRSinstrumentation. Field testing of MoRS showed excellent intercomparability against reference instrumentation (R2 > 0.98) and good agreement with reference instruments in the ultrafine aerosol range, although there was an overestimation of fine particle aerosols. Measurements taken during example mainline train and London Underground (LU) journeys are displayed showing the value of the high-quality data derived from MoRS and how this can help to disentangle multiple confounding environmental pollutants and enrich epidemiological studies.

Empirical estimation of size-resolved scavenging coefficients derived from in-situ measurements at background sites in Korea during 2013–2020

Owing to insufficient detailed in-field observations for explaining and quantifying the wet-scavenging coefficients, especially those below-cloud (Λbelow), prediction of accurate aerosol concentrations and/or behaviors in the atmosphere remains challenging. As a pioneering effort, this study focused on establishing an empirical equation for size-resolved Λbelow, which represent the characteristics in Korea, using long-term aerosol number size distribution and meteorological variable measurements at two background sites in Korea (Baengnyeong and Jeju). The median Λbelow values derived from the total number concentrations were 8.06 × 10−6 s−1 for Baengnyeong and 1.04 × 10−5 s−1 for Jeju, which are similar to or slightly lower than the Λbelow reported by previous in-situ studies. These may be caused by differences in the precipitation rates, precipitation drop sizes, aerosol chemical/hygroscopic properties, and aerosol size distributions at the measurement sites. Although the derived parameterization can cover a wide range (10 nm to 10 μm), the derived equation for the fourth-degree polynomial shows a high correlation coefficient of 0.81, indicating that the measured and fitted Λbelow converge within a narrow range. Moreover, the variation in Λbelow is relatively constant for aerosol diameters larger than ∼1 μm, similar to those derived from theoretical equations rather than empirical equations in previous studies. This study is thus expected to contribute to improving the below-cloud scavenging module implemented in a chemical transport model by covering a wide range of aerosol diameters to avoid overestimation by extrapolation of Λbelow.

Effects of boundary layer dynamics and meteorology on ultrafine particle formation and growth

It is currently not well understood how the planetary boundary layer (PBL) dynamics affects the formation and growth of ultrafine particles in the atmosphere, because of the limited co-located aerosol size distributions and lidar measurements. Here we show, from long-term in-situ observations, a clear link between boundary layer processes and surface aerosol dynamics. Aerosol size distributions in the diameter range from 7 to 300 nm were measured with a scanning mobility particle sizer (SMPS) at the University of Alabama Huntsville campus in 2016, 2017, and 2022. The backscatter of larger aerosols was measured using a co-located lidar ceilometer. Meteorological surface parameters including temperature, relative humidity, station pressure, wind speed and direction, solar radiation, and precipitation were also measured. New particle formation (NPF) and long growth (over 12 h) events occurred most frequently during the winter, unlike many other locations where NPF events occur more frequently in spring and fall, indicating that cooler temperatures play important roles in ultrafine particle formation in the warm subtropical environment. During the summer with strong solar radiation, there were more short-time growth events (less than 6 h), likely associated with convection within the boundary layer. Our observations also show cold fronts affect the measured aerosol size distributions because the combination of precipitation scavenging and cleaner air can provide thermodynamic conditions favorable for NPF and aerosol growth. These results highlight the importance of meteorology on aerosol formation and growth.

Chemical precursors of new particle formation in coastal New Zealand

Abstract. To reduce uncertainties in climate predictions, we need to better understand aerosol formation in different environments. An important part of this is studying which chemical species are responsible for particle formation. While many advances have been made in this field, measurements are especially lacking from marine environments. Here, we measured the chemical composition of ambient anions over 7 months at Baring Head station, located in coastal New Zealand. This adds to our previous work which reported the aerosol size distribution measurements and investigated new particle formation and environmental conditions favouring new particle formation at the station. By combining the information on ion chemical composition with our previous work, we were able to study the chemical precursors of new particle formation. Our results showed that while over land new particle formation is likely driven by sulfuric acid and organic species, in clean marine air iodine oxoacids and sulfur species are likely important drivers of particle formation processes. These data were also used to characterise the diurnal and seasonal cycles of the most important anion groups and their geographical source regions. Bisulfate anions displayed a clear daytime maximum where as iodine oxoacids had morning and evening maximums. Highly oxygenated organic molecules, on the other hand, were most abundant during the night when the air was land-influenced. This data set is highly valuable and our results provide important information on the chemical species driving new particle formation at a remote Southern Hemisphere coastal site.

Seasonal significance of new particle formation impacts on cloud condensation nuclei at a mountaintop location

Abstract. New particle formation (NPF) events are defined as a sudden burst of aerosols followed by growth and can impact climate by growing to larger sizes and under proper conditions, potentially forming cloud condensation nuclei (CCN). Field measurements relating NPF and CCN are crucial in expanding regional understanding of how aerosols impact climate. To quantify the possible impact of NPF on CCN formation, it is important to not only maintain consistency when classifying NPF events but also consider the proper timeframe for particle growth to CCN-relevant sizes. Here, we analyze 15 years of direct measurements of both aerosol size distributions and CCN concentrations and combine them with novel methods to quantify the impact of NPF on CCN formation at Storm Peak Laboratory (SPL), a remote, mountaintop observatory in Colorado. Using the new automatic method to classify NPF, we find that NPF occurs on 50 % of all days considered in the study from 2006 to 2021, demonstrating consistency with previous work at SPL. NPF significantly enhances CCN during the winter by a factor of 1.36 and during the spring by a factor of 1.54, which, when combined with previous work at SPL, suggests the enhancement of CCN by NPF occurs on a regional scale. We confirm that events with persistent growth are common in the spring and winter, while burst events are more common in the summer and fall. A visual validation of the automatic method was performed in the study. For the first time, results clearly demonstrate the significant impact of NPF on CCN in montane North American regions and the potential for widespread impact of NPF on CCN.

Survival probability of new atmospheric particles: closure between theory and measurements from 1.4 to 100 nm

Abstract. The survival probability of freshly nucleated particles governs the influences of new particle formation (NPF) on atmospheric environments and the climate. It characterizes the probability of a particle avoiding being scavenged by the coagulation with pre-existing particles and other scavenging processes before the particle successfully grows up to a certain diameter. Despite its importance, measuring the survival probability has been challenging, which limits the knowledge of particle survival in the atmosphere and results in large uncertainties in predicting the influences of NPF. Here we report the proper methods to retrieve particle survival probability using the measured aerosol size distributions. Using diverse aerosol size distributions from urban Beijing, the Finnish boreal forest, a chamber experiment, and aerosol kinetic simulations, we demonstrate that each method is valid for a different type of aerosol size distribution, whereas misapplying the conventional methods to banana-type NPF events may underestimate the survival probability. Using these methods, we investigate the consistency between the measured survival probability of new particles and the theoretical survival probability against coagulation scavenging predicted using the measured growth rate and coagulation sink. With case-by-case and time- and size-resolved analysis of long-term measurement data from urban Beijing, we find that although both the measured and theoretical survival probabilities are sensitive to uncertainties and variations, they are, on average, consistent with each other for new particles growing from 1.4 (the cluster size) to 100 nm.

Using Novel Molecular-Level Chemical Composition Observations of High Arctic Organic Aerosol for Predictions of Cloud Condensation Nuclei.

Predictions of cloud droplet activation in the late summertime (September) central Arctic Ocean are made using κ-Köhler theory with novel observations of the aerosol chemical composition from a high-resolution time-of-flight chemical ionization mass spectrometer with a filter inlet for gases and aerosols (FIGAERO-CIMS) and an aerosol mass spectrometer (AMS), deployed during the Arctic Ocean 2018 expedition onboard the Swedish icebreaker Oden. We find that the hygroscopicity parameter κ of the total aerosol is 0.39 ± 0.19 (mean ± std). The predicted activation diameter of ∼25 to 130 nm particles is overestimated by 5%, leading to an underestimation of the cloud condensation nuclei (CCN) number concentration by 4–8%. From this, we conclude that the aerosol in the High Arctic late summer is acidic and therefore highly cloud active, with a substantial CCN contribution from Aitken mode particles. Variability in the predicted activation diameter is addressed mainly as a result of uncertainties in the aerosol size distribution measurements. The organic κ was on average 0.13, close to the commonly assumed κ of 0.1, and therefore did not significantly influence the predictions. These conclusions are supported by laboratory experiments of the activation potential of seven organic compounds selected as representative of the measured aerosol.

Measurements of Aerosol Size and Microphysical Properties: A Comparison Between Raman Lidar and Airborne Sensors

AbstractThis manuscript compares measurements of aerosol size distributions and microphysical properties retrieved from the Raman lidar BASIL with those obtained from a series of aircraft sensors during HyMeX‐SOP1. The attention is focused on a measurement session on 02 October 2012, with BASIL measurements revealing the presence of a lower aerosol layer extending up to 3.3 km and an elevated layer extending from 3.6 to 4.6 km. Aerosol size distribution and microphysical properties are determined from multi‐wavelength particle backscattering and extinction profile measurements through a retrieval approach based on Tikhonov regularization. A good agreement is found between BASIL and the microphysical sensors' measurements for all considered aerosol size and microphysical properties. Specifically, BASIL and in‐situ volume concentration values are in the range 2–5 μm3 cm−3 in the lower layer and in the range 1–3.5 μm3 cm−3 in the upper layer. Values of the effective radius values from BASIL and the in‐situ sensors are in the range 0.2–0.6 μm in both the lower and upper layer. Aerosol size distributions are determined at 2.2, 2.8, 4 and 4.3 km, with a good agreement between the Raman lidar and the microphysical sensors at all considered heights. We combined these size and microphysical results with Lagrangian back‐trajectory analyses and chemical composition measurements. From this combination of datasets we conclude that aerosol particles below 3 km were probably originated by wildfires in North America and/or by anthropogenic activities in North‐Eastern Europe, while aerosols above 3 km were also probably originated by wildfires in North America.

Frequent new particle formation at remote sites in the subboreal forest of North America

Abstract. The frequency and intensity of new particle formation (NPF) over remote forest regions in the temperate and boreal zones, and thus the importance of NPF for the aerosol budget and life cycle in the pristine atmosphere, remains controversial. Whereas NPF has been shown to occur relatively frequently at several sites in Scandinavia, it was found to be nearly absent at a mid-continental site in Siberia. To explore this issue further, we made measurements of aerosol size distributions between 10 and 420 nm diameter at two remote sites in the transition region between temperate and boreal forest in British Columbia, Canada. The measurements covered 23 d during the month of June 2019, at the time when NPF typically reaches its seasonal maximum in remote midlatitude regions. These are the first such measurements in a near-pristine region on the North American continent. Although the sites were only 150 km apart, there were clear differences in NPF frequency and intensity between them. At the Eagle Lake site, NPF occurred daily, and nucleation-mode particle concentrations reached above 5000 cm−3. In contrast, at the Nazko River site, there were only six NPF events in 11 d, and the nucleation-mode particle concentrations only reached about 800 cm−3. The reasons for this difference could not be conclusively resolved with the available data; they may include air mass origins, preexisting aerosols, and the density and type of forest cover in the surrounding regions. In contrast to observations in other temperate and boreal environments, we found that NPF at our sites occurred at nighttime just as frequently as during daytime. Together with the lack of identifiable sources of sulfuric acid precursor species in the fetch region of our sites, this suggests that nucleation of extremely low volatility organics was the predominant NPF mechanism. Our results indicate that extended measurement campaigns with a more comprehensive set of instrumentation to investigate the role of NPF in the remote forest regions of North America are essential for a deeper scientific understanding of this important process and its role in the global aerosol budget.

Passive Vaping from Sub-Ohm Electronic Cigarette Devices.

To investigate passive vaping due to sub-ohm electronic cigarettes (e-cigs), aerosol number size distribution measurements (6 nm–10 µm) were performed during volunteer-vaping sessions. E-liquids, with vegetable glycerin (VG) and propylene glycol (PG), with a VG/PG ratio of 50/50 (with nicotine) and 80/20 (without nicotine), were vaped with a double-coil, single aerosol exit hole at 25–80 W electric power, corresponding to 130–365 kW m−2 heat fluxes and with an octa-coil, four aerosol exit holes atomizers, at 50–150 W electric power, corresponding to 133–398 kW m−2 heat fluxes. At the lowest heat flux, lower particle number concentrations (NTot) were observed for the nicotine-liquid than for the nicotine-free liquid, also due to its higher content of PG, more volatile than VG. For the octa-coil atomizer, at 265 and 398 kW m−2, NTot decreased below the first-generation e-cig, whereas volume concentrations greatly increased, due to the formation of super micron droplets. Higher volume concentrations were observed for the 80/20 VG/PG liquid, because of VG vaporization and of its decomposition products, greater than for PG. For the double coil atomizer, increasing the electric power from 40 W (208 kW m−2) to 80 W (365 kW m−2) possibly led to a critical heat flow condition, causing a reduction of the number concentrations for the VG/PG 50/50 liquid, an increase for the 80/20 VG/PG liquid and a decrease of the volume concentrations for both of them. Coherently, the main mode was at about 0.1 µm on both metrics for both liquids. For the other tests, two main modes (1 and 2 µm) were observed in the volume size distributions, the latter becoming wider at 100 and 150 W (265 and 398 kW m−2), suggesting the increased emission of light condensable decomposition products. The lower aerosol emissions observed at 150 W than at 100 W suggest the formation of gas-phase decomposition products. The observation of low-count high-volume aerosols addresses the relevance of the volume metric upon measuring the second-hand concentration of the aerosols released by sub-ohm e-cigarettes.

Role of Criegee intermediates in the formation of sulfuric acid at a Mediterranean (Cape Corsica) site under influence of biogenic emissions

Abstract. Reaction of stabilized Criegee intermediates (SCIs) with SO2 was proposed as an additional pathway of gaseous sulfuric acid (H2SO4) formation in the atmosphere, supplementary to the conventional mechanism of H2SO4 production by oxidation of SO2 in reaction with OH radicals. However, because of a large uncertainty in mechanism and rate coefficients for the atmospheric formation and loss reactions of different SCIs, the importance of this additional source is not well established. In this work, we present an estimation of the role of SCIs in H2SO4 formation at a western Mediterranean (Cape Corsica) remote site, where comprehensive field observations including gas-phase H2SO4, OH radicals, SO2, volatile organic compounds (VOCs) and aerosol size distribution measurements were performed in July–August 2013 as a part of the project ChArMEx (Chemistry-Aerosols Mediterranean Experiment). The measurement site was under strong influence of local emissions of biogenic volatile organic compounds, including monoterpenes and isoprene generating SCIs in reactions with ozone, and, hence, presenting an additional source of H2SO4 via SO2 oxidation by the SCIs. Assuming the validity of a steady state between H2SO4 production and its loss by condensation on existing aerosol particles with a unity accommodation coefficient, about 90 % of the H2SO4 formation during the day could be explained by the reaction of SO2 with OH. During the night the oxidation of SO2 by OH radicals was found to contribute only about 10 % to the H2SO4 formation. The accuracy of the derived values for the contribution of OH + SO2 reaction to the H2SO4 formation is limited mostly by a large, at present factor of 2, uncertainty in the OH + SO2 reaction rate coefficient. The contribution of the SO2 oxidation by SCIs to the H2SO4 formation was evaluated using available measurements of unsaturated VOCs and steady-state SCI concentrations estimated by adopting rate coefficients for SCI reactions based on structure–activity relationships (SARs). The estimated concentration of the sum of SCIs was in the range of (1–3) × 103 molec. cm−3. During the day the reaction of SCIs with SO2 was found to account for about 10 % and during the night for about 40 % of the H2SO4 production, closing the H2SO4 budget during the day but leaving unexplained about 50 % of the H2SO4 formation during the night. Despite large uncertainties in used kinetic parameters, these results indicate that the SO2 oxidation by SCIs may represent an important H2SO4 source in VOC-rich environments, especially during nighttime.

Data imputation in in situ-measured particle size distributions by means of neural networks

Abstract. In air quality research, often only size-integrated particle mass concentrations as indicators of aerosol particles are considered. However, the mass concentrations do not provide sufficient information to convey the full story of fractionated size distribution, in which the particles of different diameters (Dp) are able to deposit differently on respiratory system and cause various harm. Aerosol size distribution measurements rely on a variety of techniques to classify the aerosol size and measure the size distribution. From the raw data the ambient size distribution is determined utilising a suite of inversion algorithms. However, the inversion problem is quite often ill-posed and challenging to solve. Due to the instrumental insufficiency and inversion limitations, imputation methods for fractionated particle size distribution are of great significance to fill the missing gaps or negative values. The study at hand involves a merged particle size distribution, from a scanning mobility particle sizer (NanoSMPS) and an optical particle sizer (OPS) covering the aerosol size distributions from 0.01 to 0.42 µm (electrical mobility equivalent size) and 0.3 to 10 µm (optical equivalent size) and meteorological parameters collected at an urban background region in Amman, Jordan, in the period of 1 August 2016–31 July 2017. We develop and evaluate feed-forward neural network (FFNN) approaches to estimate number concentrations at particular size bin with (1) meteorological parameters, (2) number concentration at other size bins and (3) both of the above as input variables. Two layers with 10–15 neurons are found to be the optimal option. Worse performance is observed at the lower edge (0.01<Dp<0.02 µm), the mid-range region (0.15<Dp<0.5 µm) and the upper edge (6<Dp<10 µm). For the edges at both ends, the number of neighbouring size bins is limited, and the detection efficiency by the corresponding instruments is lower compared to the other size bins. A distinct performance drop over the overlapping mid-range region is due to the deficiency of a merging algorithm. Another plausible reason for the poorer performance for finer particles is that they are more effectively removed from the atmosphere compared to the coarser particles so that the relationships between the input variables and the small particles are more dynamic. An observable overestimation is also found in the early morning for ultrafine particles followed by a distinct underestimation before midday. In the winter, due to a possible sensor drift and interference artefacts, the estimation performance is not as good as the other seasons. The FFNN approach by meteorological parameters using 5 min data (R2= 0.22–0.58) shows poorer results than data with longer time resolution (R2= 0.66–0.77). The FFNN approach using the number concentration at the other size bins can serve as an alternative way to replace negative numbers in the size distribution raw dataset thanks to its high accuracy and reliability (R2= 0.97–1). This negative-number filling approach can maintain a symmetric distribution of errors and complement the existing ill-posed built-in algorithm in particle sizer instruments.

Two-stage aerosol formation in low-temperature combustion

Low-temperature combustion is a promising strategy for reducing pollutant formation in internal combustion engines. However, there is a lack of understanding of how the chemistry governing the differences in ignition between low-temperature and conventional combustion affects the emission rates and physicochemical properties of particulate matter (aerosols). Here, we conducted combustion experiments in an atmospheric-pressure reactor controlled at constant equivalence ratio (ϕ = 2.3) and O2/N2 = 0.06, and at temperatures varied between 250 °C and 1035 °C. We used two fuels: toluene, which has high sooting propensity, and n-heptane, which has a comparatively lower sooting propensity but exhibits two-stage ignition that is not present in toluene combustion. We performed real-time measurements of aerosol size distributions, volatility, and light-absorption properties. We also performed offline molecular-size characterization. Aerosols emitted from both fuels were comprised of light-absorbing organics that are categorized as brown carbon. At the highest combustion temperature (1035 °C), the aerosol emissions from toluene combustion were a factor of 20 larger than n-heptane. The aerosol emissions from toluene combustion had more abundance of large molecular-size species, were less volatile, and were more light-absorbing than n-heptane. For both fuels, aerosol emission factors exhibited a steep drop with decreasing temperatures. However, there was a resurgence in aerosol emissions at lower temperatures with a peak at 290 °C for n-heptane combustion that was not observed for toluene. This is consistent with chemical kinetics simulations that show prominent two-stage ignition behavior for n-heptane, but not for toluene.

Efficacy of a portable, moderate-resolution, fast-scanning differential mobility analyzer for ambient aerosol size distribution measurements

Abstract. Ambient aerosol size distributions obtained with a compact scanning mobility analyzer, the “Spider” differential mobility analyzer (DMA), are compared to those obtained with a conventional mobility analyzer, with specific attention to the effect of mobility resolution on the measured size distribution parameters. The Spider is a 12 cm diameter radial differential mobility analyzer that spans the 10–500 nm size range with 30 s mobility scans. It achieves its compact size by operating at a nominal mobility resolution R=3 (sheath flow = 0.9 L min−1; aerosol flow = 0.3 L min−1) in place of the higher ratio of sheath flow to aerosol flow commonly used. The question addressed here is whether the lower resolution is sufficient to capture key characteristics of ambient aerosol size distributions. The Spider, operated at R=3 with 30 s up- and downscans, was co-located with a TSI 3081 long-column mobility analyzer, operated at R=10 with a 360 s sampling duty cycle. Ambient aerosol data were collected over 26 consecutive days of continuous operation, in Pasadena, CA. Over the 17–500 nm size range, the two instruments exhibit excellent correlation in the total particle number concentrations and geometric mean diameters, with regression slopes of 1.13 and 1.00, respectively. Our results suggest that particle sizing at a lower resolution than typically employed may be sufficient to obtain key properties of ambient size distributions, at least for these two moments of the size distribution. Moreover, it enables better counting statistics, as the wider transfer function for a given aerosol flow rate results in a higher counting rate.