Aerosol Proxy Research Articles

Multiple effects of relative humidity on heterogeneous ozonolysis of cooking organic aerosol proxies from heated peanut oil emissions

The exposure to cooking organic aerosols (COA) is closely related to people's daily lives. Despite extensive investigations into COA's model compounds like oleic acid, the intricacies of heterogeneous ozonolysis of real COA and the effects of ambient conditions like humidity remain elusive. In this work, the ozonolysis of COA proxies from heated peanut oil emissions was investigated using diffuse reflectance infrared Fourier transform (DRIFTS) spectroscopy, and proton transfer reaction time-of-flight mass spectrometer (PTR-ToF-MS). We found that humidity hinders the reaction between ozone and CC double bonds due to the competitive adsorption of water and ozone on COA. Although visible light has little influence on the ozonolysis of COA in the absence of humidity, the ozonolytic CO production is significantly promoted by visible light in the presence of humidity. It may be attributed to the formation of water-derived reactive oxygen species (ROS, mainly HO•) from the photosensitization of polycyclic aromatic hydrocarbons (PAHs) in COA. We also found that humidity can enhance the depolymerization of carboxylic acid dimers and hydrolysis of intrinsic acetals in the COA. Moreover, humidity promotes the release of VOCs during both the dark and light ozonolysis of COA. This work reveals the important roles of humidity-responsive and photo-responsive components in COA during its ozonolysis, and the change in VOC release may guide the control of human VOC exposure in indoor air.

Long-term relationships between summer clouds and aerosols over mid-high latitudes of the Northern Hemisphere

While the short-term relationship between clouds and aerosols is well known, no adequate data is available to verify the longer-term, annual to decadal, relationship. It is important to quantify the aerosol–cloud interaction (ACI) for mitigating uncertainty in climate prediction. Here the long-term ACI over the mid-to-high latitudes of the Northern Hemisphere was analyzed by using seasonally-resolved ion fluxes reconstructed from a southeastern Greenland ice core (SE-Dome ice core) as aerosol proxies, and satellite-based summer cloud amount between 1982 and 2014. As a result, SO42− flux in the ice core shows significant positive correlation with total cloud amounts (CCT\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$${CC}_{T}$$\\end{document}) and cloud droplet concentration (Nd\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$${N}_{d}$$\\end{document}) in the summer over the southeastern Greenland Sea, implying that the sulfate aerosols may contribute to the variability of CCT\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$${CC}_{T}$$\\end{document} via microphysical cloud processes. Significant positive correlations are persistent even under the constrained conditions when cloud formation factors such as relative humidity, air temperature at cloud height, and summer North Atlantic Oscillation are limited within ± 1σ variability. Hence sulfate aerosols should control the interannual variability of summer CCT\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$${CC}_{T}$$\\end{document} In terms of decadal changes, CCT\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$${CC}_{T}$$\\end{document} was approximately 3–5% higher in the 1960s–1970s than in the 1990s–2000s, which can be explained by changes in the, SO42-\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$${{{\ ext{SO}}}_{4}}^{2-}$$\\end{document} flux preserved in the SE-Dome ice core.

Technical note: In situ measurements and modelling of the oxidation kinetics in films of a cooking aerosol proxy using a quartz crystal microbalance with dissipation monitoring (QCM-D)

Abstract. Aerosols and films are found in indoor and outdoor environments. How they interact with pollutants, such as ozone, has a direct impact on our environment via cloud droplet formation and the chemical persistence of toxic aerosol constituents. The chemical reactivity of aerosol emissions is typically measured spectroscopically or by techniques such as mass spectrometry, directly monitoring the amount of material during a chemical reaction. We present a study which indirectly measures oxidation kinetics in a common cooking aerosol proxy using a low-cost quartz crystal microbalance with dissipation monitoring (QCM-D). We validated this approach by comparison with kinetics measured both spectroscopically and with high-intensity synchrotron radiation. Using microscopy, we found that the film morphology changed and film rigidity increased during oxidation. There was evidence of surface crust formation on oxidised particles, though this was not consistent for all experiments. Crucially, our kinetic modelling of these experimental data confirmed that the oleic acid decay rate is in line with previous literature determinations, which demonstrates that performing such experiments on a QCM-D does not alter the underlying mechanism. There is clear potential to take this robust and low-cost but sensitive method to the field for in situ monitoring of reactions outdoors and indoors.

Sensitivities of cloud radiative effects to large-scale meteorology and aerosols from global observations

Abstract. The radiative effects of clouds make a large contribution to the Earth's energy balance, and changes in clouds constitute the dominant source of uncertainty in the global warming response to carbon dioxide forcing. To characterize and constrain this uncertainty, cloud-controlling factor (CCF) analyses have been suggested that estimate sensitivities of clouds to large-scale environmental changes, typically in cloud-regime-specific multiple linear regression frameworks. Here, local sensitivities of cloud radiative effects to a large number of controlling factors are estimated in a regime-independent framework from 20 years (2001–2020) of near-global (60∘ N–60∘ S) satellite observations and reanalysis data using statistical learning. A regularized linear regression (ridge regression) is shown to skillfully predict anomalies of shortwave (R2=0.63) and longwave cloud radiative effects (CREs) (R2=0.72) in independent test data on the basis of 28 CCFs, including aerosol proxies. The sensitivity of CREs to selected CCFs is quantified and analyzed. CRE sensitivities to sea surface temperature and estimated inversion strength are particularly pronounced in low-cloud regions and generally in agreement with previous studies. The analysis of CRE sensitivities to three-dimensional wind field anomalies reflects the fact that CREs in tropical ascent regions are mainly driven by variability of large-scale vertical velocity in the upper troposphere. In the subtropics, CRE is sensitive to free-tropospheric zonal and meridional wind anomalies, which are likely to encapsulate information on synoptic variability that influences subtropical cloud systems by modifying wind shear and thus turbulence and dry-air entrainment in stratocumulus clouds, as well as variability related to midlatitude cyclones. Different proxies for aerosols are analyzed as CCFs, with satellite-derived aerosol proxies showing a larger CRE sensitivity than a proxy from an aerosol reanalysis, likely pointing to satellite aerosol retrieval biases close to clouds, leading to overestimated aerosol sensitivities. Sensitivities of shortwave CREs to all aerosol proxies indicate a pronounced cooling effect from aerosols in stratocumulus regions that is counteracted to a varying degree by a longwave warming effect. The analysis may guide the selection of CCFs in future sensitivity analyses aimed at constraining cloud feedback and climate forcings from aerosol–cloud interactions using data from both observations and global climate models.

Influence of acidity on liquid–liquid phase transitions of mixed secondary organic aerosol (SOA) proxy–inorganic aerosol droplets

Abstract. The phase state and morphology of aerosol particles play a critical role in determining their effect on climate. While aerosol acidity has been identified as a key factor affecting multiphase chemistry and phase transitions, the impact of acidity on the phase transition of multicomponent aerosol particles has not been extensively studied in situ. In this work, we employed aerosol optical tweezers (AOT) to probe the impact of acidity on the phase transition behavior of levitated aerosol particles. Our results revealed that higher acidity decreases the separation relative humidity (SRH) of aerosol droplets mixed with ammonium sulfate (AS) and secondary organic aerosol (SOA) proxy, such as 3-methylglutaric acid (3-MGA), 1,2,6-hexanetriol (HEXT) and 2,5-hexanediol (HEXD) across aerosol pH in atmospheric conditions. Phase separation of organic acids was more sensitive to acidity compared to organic alcohols. We found the mixing relative humidity (MRH) was consistently higher than the SRH in several systems. Phase-separating systems, including 3-MGA / AS, HEXT / AS and HEXD / AS, exhibited oxygen-to-carbon ratios (O:C) of 0.67, 0.50 and 0.33, respectively. In contrast, liquid–liquid phase separation (LLPS) did not occur in the high-O:C system of glycerol / AS, which had an O:C ratio of 1.00. Additionally, the morphology of 42 out of the 46 aerosol particles that underwent LLPS was observed to be a core–shell structure. Our findings provide a comprehensive understanding of the pH-dependent LLPS in individual suspended aerosol droplets and pave the way for future research on phase separation of atmospheric aerosol particles.

Molecular Self-Organization in Surfactant Atmospheric Aerosol Proxies.

ConspectusAerosols are ubiquitous in the atmosphere. Outdoors, they take part in the climate system via cloud droplet formation, and they contribute to indoor and outdoor air pollution, impacting human health and man-made environmental change. In the indoor environment, aerosols are formed by common activities such as cooking and cleaning. People can spend up to ca. 90% of their time indoors, especially in the western world. Therefore, there is a need to understand how indoor aerosols are processed in addition to outdoor aerosols.Surfactants make significant contributions to aerosol emissions, with sources ranging from cooking to sea spray. These molecules alter the cloud droplet formation potential by changing the surface tension of aqueous droplets and thus increasing their ability to grow. They can also coat solid surfaces such as windows ("window grime") and dust particles. Such surface films are more important indoors due to the higher surface-to-volume ratio compared to the outdoor environment, increasing the likelihood of surface film-pollutant interactions.A common cooking and marine emission, oleic acid, is known to self-organize into a range of 3-D nanostructures. These nanostructures are highly viscous and as such can impact the kinetics of aerosol and film aging (i.e., water uptake and oxidation). There is still a discrepancy between the longer atmospheric lifetime of oleic acid compared with laboratory experiment-based predictions.We have created a body of experimental and modeling work focusing on the novel proposition of surfactant self-organization in the atmosphere. Self-organized proxies were studied as nanometer-to-micrometer films, levitated droplets, and bulk mixtures. This access to a wide range of geometries and scales has resulted in the following main conclusions: (i) an atmospherically abundant surfactant can self-organize into a range of viscous nanostructures in the presence of other compounds commonly encountered in atmospheric aerosols; (ii) surfactant self-organization significantly reduces the reactivity of the organic phase, increasing the chemical lifetime of these surfactant molecules and other particle constituents; (iii) while self-assembly was found over a wide range of conditions and compositions, the specific, observed nanostructure is highly sensitive to mixture composition; and (iv) a "crust" of product material forms on the surface of reacting particles and films, limiting the diffusion of reactive gases to the particle or film bulk and subsequent reactivity. These findings suggest that hazardous, reactive materials may be protected in aerosol matrixes underneath a highly viscous shell, thus extending the atmospheric residence times of otherwise short-lived species.

Wind‐Driven and Seasonal Effects on Marine Aerosol Production in the Bellingshausen Sea, Antarctica

AbstractWe assessed satellite‐retrieved marine aerosol in the western Antarctic Peninsula (WAP) across a 12‐year period from coarse‐mode aerosol optical depth (AODC), often used as a proxy for sea spray aerosol (SSA), and marine aerosol optical depth (MAOD), a newly developed proxy for tropospheric marine aerosol. Across open ocean to coastal regions, daily fluctuations in nighttime and daytime winds, respectively, drove increasing MAOD and AODC. MAOD depicted strong correlations with wind speed across open ocean and weak correlations in coastal regions. In the open ocean, AODC exhibited a very weak significant correlation to wind speed and a weak significant correlation to sea surface temperature (SST). We thus observed that warmer SST enhanced the production of SSA, supporting prior studies. This is the first study to assess patterns of AODC in the WAP. In contrast to the tropical Pacific, seasonal patterns showed that biological activity likely contributed toward MAOD and AODC magnitudes.

Levels and distribution profiles of Per- and Polyfluoroalkyl Substances (PFAS) in a high Arctic Svalbard ice core

Per- and polyfluoroalkyl substances (PFAS) are a group of persistent organic contaminants of which some are toxic and bioaccumulative. Several PFAS can be formed from the atmospheric degradation of precursors such as fluorotelomer alcohols (FTOHs) as well as hydrochlorofluorocarbons (HFCs) and other ozone-depleting chlorofluorocarbon (CFC) replacement compounds. Svalbard ice cores have been shown to provide a valuable record of long-range atmospheric transport of contaminants to the Arctic. This study uses a 12.3 m ice core from the remote Lomonosovfonna ice cap on Svalbard to understand the atmospheric deposition of PFAS in the Arctic. A total of 45 PFAS were targeted, of which 26 were detected, using supercritical fluid chromatography (SFC) tandem mass spectrometry (MS/MS) and ultra-performance liquid chromatography (UPLC) MS/MS. C2 to C11 perfluoroalkyl carboxylic acids (PFCAs) were detected continuously in the ice core and their fluxes ranged from 2.5 to 8200 ng m−2 yr−1 (9.51–16,500 pg L−1). Trifluoroacetic acid (TFA) represented 71 % of the total mass of C2 – C11 PFCAs in the ice core and had increasing temporal trends in deposition. The distribution profile of PFCAs suggested that FTOHs were likely the atmospheric precursor to C8 – C11 PFCAs, whereas C2 – C6 PFCAs had alternative sources, such as HFCs and other CFC replacement compounds. Perfluorooctanesulfonic acid (PFOS) was also widely detected in 82 % of ice core subsections, and its isomer profile (81 % linear) indicated an electrochemical fluorination manufacturing source. Comparisons of PFAS concentrations with a marine aerosol proxy showed that marine aerosols were insignificant for the deposition of PFAS on Lomonosovfonna. Comparisons with a melt proxy showed that TFA and PFOS were mobile during meltwater percolation. This indicates that seasonal snowmelt and runoff from post-industrial accumulation on glaciers could be a significant seasonal source of PFAS to ecosystems in Arctic fjords.

Predicting liquid-liquid phase separation in ternary organic-organic-water mixtures.

Liquid-liquid phase separation (LLPS) affects the water uptake of aerosol particles in the atmosphere through Kelvin and Raoult effects. This study investigates LLPS in ternary mixtures containing water and two organic compounds, using a conductor-like screening model for real solvents (COSMO-RS). COSMO-RS found LLPS in all of the studied mixtures containing water and proxies for primary and secondary organic aerosol (POA and SOA, respectively), due to the limited solubility of the hydrophobic POA proxies in water. The computations predict additional three-phase states in some of the SOA-POA-water mixtures at relative humidity (RH) close to 100%, which was not observed in experiments, likely due to the relatively low RH (90%) used in the experiments. A computational method, such as COSMO-RS, allows for the estimation of new information on mixing states and mixtures that cannot be accessed experimentally. Comparison with experiments can also provide insight into which types of compounds may be present in SOA. Additionally, the possibility of LLPS can be assessed faster with rough estimates rather than by computing the whole phase diagram.

Acoustic levitation with polarising optical microscopy (AL-POM): water uptake in a nanostructured atmospheric aerosol proxy

We present acoustic levitation combined with polarising optical microscopy (AL-POM). Fatty acid aerosols were probed and a model fit revealed a ca. 5–6 orders of magnitude difference in water diffusion coefficient upon a phase transition between optically birefringent and non-birefringent phases.

Reactivity of aminophenols in forming nitrogen-containing brown carbon from iron-catalyzed reactions

Nitrogen-containing organic carbon (NOC) in atmospheric particles is an important class of brown carbon (BrC). Redox active NOC like aminophenols received little attention in their ability to form BrC. Here we show that iron can catalyze dark oxidative oligomerization of o- and p-aminophenols under simulated aerosol and cloud conditions (pH 1–7, and ionic strength 0.01–1 M). Homogeneous aqueous phase reactions were conducted using soluble Fe(III), where particle growth/agglomeration were monitored using dynamic light scattering. Mass yield experiments of insoluble soot-like dark brown to black particles were as high as 40%. Hygroscopicity growth factors (κ) of these insoluble products under sub- and super-saturated conditions ranged from 0.4–0.6, higher than that of levoglucosan, a prominent proxy for biomass burning organic aerosol (BBOA). Soluble products analyzed using chromatography and mass spectrometry revealed the formation of ring coupling products of o- and p-aminophenols and their primary oxidation products. Heterogeneous reactions of aminophenol were also conducted using Arizona Test Dust (AZTD) under simulated aging conditions, and showed clear changes to optical properties, morphology, mixing state, and chemical composition. These results highlight the important role of iron redox chemistry in BrC formation under atmospherically relevant conditions.

Glass Transition Temperatures of Individual Submicrometer Atmospheric Particles: Direct Measurement via Heated Atomic Force Microscopy Probe.

The phase (solid, semisolid, or liquid) of atmospheric aerosols is central to their ability to take up water or undergo heterogeneous reactions. In recent years, the unexpected prevalence of viscous organic particles has been shown through field measurements and global atmospheric modeling. The aerosol phase has been predicted using glass transition temperatures (Tg), which were estimated based on molecular weight, oxygen:carbon ratio, and chemical formulae of organic species present in atmospheric particles via studies of bulk materials. However, at the most important sizes for cloud nucleation (∼50-500 nm), particles are complex mixtures of numerous organic species, inorganic salts, and water with substantial particle-to-particle variability. To date, direct measurements of Tg have not been feasible for individual atmospheric particles. Herein, nanothermal analysis (NanoTA), which uses a resistively heated atomic force microscopy (AFM) probe, is combined with AFM photothermal infrared (AFM-PTIR) spectroscopy to determine the Tg and composition of individual particles down to 76 nm in diameter at ambient temperature and pressure. Laboratory-generated proxies for organic aerosol (sucrose, ouabain, raffinose, and maltoheptaose) had similar Tg values to bulk Tg values measured with differential scanning calorimetry (DSC) and the Tg predictions used in atmospheric models. Laboratory-generated phase-separated particles and ambient particles were analyzed with NanoTA + AFM-PTIR showing intraparticle variation in composition and Tg. These results demonstrate the potential for NanoTA + AFM-PTIR to increase our understanding of viscosity within submicrometer atmospheric particles with complex phases, morphologies, and compositions, which will enable improved modeling of aerosol impacts on clouds and climate.

Variations in the concentration, source activity, and atmospheric processing of PM2.5-associated water-soluble ionic species over Jammu, India.

Concentrations, sources, and atmospheric processing of water-soluble ionic species associated with PM2.5 collected from 2015 to 2017 were studied in Jammu, an urban location in the North-Western Himalayan Region (NWHR).Being ecologically sensitive and sparsely studied for dynamics in PM2.5 and associated WSIS, the present study is important for developing robust air pollution abatement strategies for the air-shed of NWHR. Twenty-four hourly PM2.5 samples were collected on weekly basis at a receptor site and analyzed for WSIS using ion chromatography system. On annual basis, total sum of WSIS (ΣWSIS) contributed about 28.5% of PM2.5, where the contribution of sulfate-nitrate-ammonium, a proxy for secondary inorganic aerosols (SIA), was found to be 18.7% of PM2.5. The ΣWSIS and PM2.5 concentration showed a seasonal cycle with the maximum concentration during winters and the minimum in summers. Mass fraction of ΣWSIS in PM2.5 showed an anti-phase seasonal pattern indicating more source activity during summers. Season-wise, dominant WSIS constituting PM2.5 were NO3-, SO42-, NH4+, and K+ during winters; whereas summer was marked with dominant contributions from SO42-, NH4+, Ca2+, and K+. Seasonal variability exhibited among SIA constituents underscored the crucial role of air temperature and relative humidity regime. It was observed that nss-K+ + NH4+ were sufficient to neutralize most of the acidic species arising from precursor gases (NOx and SOx). Using principal component analysis, five major sources and processes, viz. (a) biomass burning activities, (b) secondary inorganic aerosol formation, (c) input from re-suspended dust, (d) transported dust, and (e) fertilizer residue, were identified for the emissions of PM2.5-associated WSIS over Jammu. In future studies, impacts of dry and/or wet deposition of aerosol-associated WSIS on the crop productivity in the region should be studied.

The impact of sampling strategy on the cloud droplet number concentration estimated from satellite data

Abstract. Cloud droplet number concentration (Nd) is of central importance to observation-based estimates of aerosol indirect effects, being used to quantify both the cloud sensitivity to aerosol and the base state of the cloud. However, the derivation of Nd from satellite data depends on a number of assumptions about the cloud and the accuracy of the retrievals of the cloud properties from which it is derived, making it prone to systematic biases. A number of sampling strategies have been proposed to address these biases by selecting the most accurate Nd retrievals in the satellite data. This work compares the impact of these strategies on the accuracy of the satellite retrieved Nd, using a selection of in situ measurements. In stratocumulus regions, the MODIS Nd retrieval is able to achieve a high precision (r2 of 0.5–0.8). This is lower in other cloud regimes but can be increased by appropriate sampling choices. Although the Nd sampling can have significant effects on the Nd climatology, it produces only a 20 % variation in the implied radiative forcing from aerosol–cloud interactions, with the choice of aerosol proxy driving the overall uncertainty. The results are summarised into recommendations for using MODIS Nd products and appropriate sampling.

The impact of molecular self-organisation on the atmospheric fate of a cooking aerosol proxy

Abstract. Atmospheric aerosols influence the climate via cloud droplet nucleation and can facilitate the long-range transport of harmful pollutants. The lifetime of such aerosols can therefore determine their environmental impact. Fatty acids are found in organic aerosol emissions with oleic acid, an unsaturated fatty acid, being a large contributor to cooking emissions. As a surfactant, oleic acid can self-organise into nanostructured lamellar bilayers with its sodium salt, and this self-organisation can influence reaction kinetics. We developed a kinetic multi-layer model-based description of decay data we obtained from laboratory experiments of the ozonolysis of coated films of this self-organised system, demonstrating a decreased diffusivity for both oleic acid and ozone due to lamellar bilayer formation. Diffusivity was further inhibited by a viscous oligomer product forming in the surface layers of the film. Our results indicate that nanostructure formation can increase the reactive half-life of oleic acid by an order of days at typical indoor and outdoor atmospheric ozone concentrations. We are now able to place nanostructure formation in an atmospherically meaningful and quantifiable context. These results have implications for the transport of harmful pollutants and the climate.

Machine-Learning Based Analysis of Liquid Water Path Adjustments to Aerosol Perturbations in Marine Boundary Layer Clouds Using Satellite Observations

Changes in marine boundary layer cloud (MBLC) radiative properties in response to aerosol perturbations are largely responsible for uncertainties in future climate predictions. In particular, the relationship between the cloud droplet number concentration (Nd, a proxy for aerosol) and the cloud liquid water path (LWP) remains challenging to quantify from observations. In this study, satellite observations from multiple polar-orbiting platforms for 2006–2011 are used in combination with atmospheric reanalysis data in a regional machine learning model to predict changes in LWP in MBLCs in the Southeast Atlantic. The impact of predictor variables on the model output is analysed using Shapley values as a technique of explainable machine learning. Within the machine learning model, precipitation fraction, cloud top height, and Nd are identified as important cloud state predictors for LWP, with dynamical proxies and sea surface temperature (SST) being the most important environmental predictors. A positive nonlinear relationship between LWP and Nd is found, with a weaker sensitivity at high cloud droplet concentrations. This relationship is found to be dependent on other predictors in the model: Nd–LWP sensitivity is higher in precipitating clouds and decreases with increasing SSTs.

Isotopic evidence for bioaccumulation of aerosol lead in fish and wildlife of western Canada

Lead (Pb) is a toxic element which is released as a result of anthropogenic activities, and Pb stable isotope ratios provide a means to distinguish sources and transport pathways in receiving environments. In this study, isotopes of bioaccumulated Pb (204Pb, 206Pb, 207Pb, 208Pb) were examined for diverse terrestrial and aquatic biota from three areas in western Canada: (a) otter, marten, gulls, terns, and wood frogs in the Alberta Oil Sands Region (AOSR), (b) fish, plankton, and gulls of Great Slave Lake (Yellowknife, Northwest Territories), and (c) wolverine from the Yukon. Aquatic and terrestrial biota from different habitats and a broad geographic area showed a remarkable similarity in their Pb isotope composition (grand mean ± 1 standard deviation: 206Pb/207Pb = 1.189 ± 0.007, 208Pb/207Pb = 2.435 ± 0.009, n = 116). Comparisons with Pb isotope ratios of local sources and environmental receptors showed that values in biota were most similar to those of atmospheric Pb, either measured in local aerosols influenced by industrial activities in the AOSR or in lichens (an aerosol proxy) near Yellowknife and in the Yukon. Biotic Pb isotope ratios were different from those of local geogenic Pb. Although the Pb isotope measurements could not unambiguously identify the specific anthropogenic sources of atmospheric Pb in biota, initial evidence points to the importance of fossil fuels currently used in transportation and power generation. Further research should characterize bioavailable chemical species of Pb in aerosols and important emission sources in western Canada.

The evolution of surface structure during simulated atmospheric ageing of nano-scale coatings of an organic surfactant aerosol proxy

A nano-scale proxy for atmospheric surfactant organic films undergoes changes in morphology and hygroscopicity during simulated atmospheric processing.

Physical and chemical properties of black carbon and organic matter from different combustion and photochemical sources using aerodynamic aerosol classification

Abstract. The physical and chemical properties of black carbon (BC) and organic aerosols are important for predicting their radiative forcing in the atmosphere. During the Soot Aerodynamic Size Selection for Optical properties (SASSO) project and a EUROCHAMP-2020 transnational access project, different types of light-absorbing carbon were studied, including BC from catalytically stripped diesel exhaust, an inverted flame burner, a colloidal graphite standard (Aquadag) and controlled flaming wood combustion. Brown carbon (BrC) was also investigated in the form of organic aerosol emissions from wood burning (pyrolysis and smouldering) and from the nitration of secondary organic aerosol (SOA) proxies produced in a photochemical reaction chamber. Here we present insights into the physical and chemical properties of the aerosols, with optical properties presented in subsequent publications. The dynamic shape factor (χ) of BC particles and material density (ρm) of organic aerosols was investigated by coupling a charging-free Aerodynamic Aerosol Classifier (AAC) with a Centrifugal Particle Mass Analyzer (CPMA) and a Scanning Mobility Particle Sizer (SMPS). The morphology of BC particles was captured by transmission electron microscopy (TEM). For BC particles from the diesel engine and flame burner emissions, the primary spherule sizes were similar, around 20 nm. With increasing particle size, BC particles adopted more collapsed/compacted morphologies for the former source but tended to show more aggregated morphologies for the latter source. For particles emitted from the combustion of dry wood samples, the χ of BC particles and the ρm of organic aerosols were observed in the ranges 1.8–2.17 and 1.22–1.32 g cm−3, respectively. Similarly, for wet wood samples, the χ and ρm ranges were 1.2–1.85 and 1.44–1.60 g cm−3, respectively. Aerosol mass spectrometry measurements show no clear difference in mass spectra of the organic aerosols in individual burn phases (pyrolysis or smouldering phase) with the moisture content of the wood samples. This suggests that the effect moisture has on the organic chemical profile of wood burning emissions is through changing the durations of the different phases of the burn cycle, not through the chemical modification of the individual phases. In this study, the incandescence signal of a Single Particle Soot Photometer (SP2) was calibrated with three different types of BC particles and compared with that from an Aquadag standard that is commonly used to calibrate SP2 incandescence to a BC mass. A correction factor is defined as the ratio of the incandescence signal from an alternative BC source to that from the Aquadag standard and took values of 0.821 ± 0.002 (or 0.794 ± 0.005), 0.879 ± 0.003 and 0.843 ± 0.028 to 0.913 ± 0.009 for the BC particles emitted from the diesel engine running under hot (or cold idle) conditions, the flame burner and wood combustion, respectively. These correction factors account for differences in instrument response to BC from different sources compared to the standardised Aquadag calibration and are more appropriate than the common value of 0.75 recommended by Laborde et al. (2012b) when deriving the mass concentration of BC emitted from diesel engines. Quantifying the correction factor for many types of BC particles found commonly in the atmosphere may enable better constraints to be placed on this factor depending on the BC source being sampled and thus improve the accuracy of future SP2 measurements of BC mass concentrations.

An organic crystalline state in ageing atmospheric aerosol proxies: spatially resolved structural changes in levitated fatty acid particles

Abstract. Organic aerosols are key components of the Earth's atmospheric system. The phase state of organic aerosols is known to be a significant factor in determining aerosol reactivity, water uptake and atmospheric lifetime – with wide implications for cloud formation, climate, air quality and human health. Unsaturated fatty acids contribute to urban cooking emissions and sea spray aerosols. These compounds, exemplified by oleic acid and its sodium salt, are surface-active and have been shown to self-assemble into a variety of liquid-crystalline phases upon addition of water. Here we observe a crystalline acid–soap complex in acoustically levitated oleic acid–sodium oleate particles. We developed a synchrotron-based simultaneous small-angle and wide-angle X-ray scattering (SAXS and WAXS)–Raman microscopy system to probe physical and chemical changes in the proxy during exposure to humidity and the atmospheric oxidant ozone. We present a spatially resolved structural picture of a levitated particle during humidification, revealing a phase gradient consisting of a disordered liquid crystalline shell and crystalline core. Ozonolysis is significantly slower in the crystalline phase compared with the liquid phase, and a significant portion (34 ± 8 %) of unreacted material remains after extensive oxidation. We present experimental evidence of inert surface layer formation during ozonolysis, taking advantage of spatially resolved simultaneous SAXS–WAXS experiments. These observations suggest that atmospheric lifetimes of surface-active organic species in aerosols are highly phase-dependent, potentially impacting climate, urban air quality and long-range transport of pollutants such as polycyclic aromatic hydrocarbons (PAHs).