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This study investigates the rain-initiated mixing and variability in the mixing ratio of selected trace gases in the atmosphere over the central Amazon rain forest. It builds on comprehensive data from the Amazon Tall Tower Observatory (ATTO), spanning from 2013 to 2020 and comprising the greenhouse gases (GHGs) carbon dioxide (CO2) and methane (CH4); the reactive trace gases carbon monoxide (CO), ozone (O3), nitric oxide (NO), and nitrogen dioxide (NO2); and selected volatile organic compounds (VOCs). Based on more than 1000 analyzed rainfall events, the study resolves the trace gas mixing ratio patterns before, during, and after the rain events, along with vertical mixing ratio gradients across the forest canopy. The assessment of the rainfall events was conducted independently for daytime and nighttime periods, which allows us to elucidate the influence of solar radiation. The mixing ratios of CO2, CO, and CH4 clearly declined during rainfall, which can be attributed to the downdraft-related entrainment of pristine air from higher altitudes into the boundary layer, a reduction of the photosynthetic activity under increased cloud cover, and changes in the surface fluxes. Notably, CO showed a faster reduction than CO2, and the vertical gradient of CO2 and CO is steeper than for CH4. Conversely, the O3 mixing ratio increased across all measurement heights in the course of the rain-related downdrafts. Following the O3 enhancement by up to a factor of 2, NO, NO2, and isoprene mixing ratios decreased. The temporal and vertical variability of the trace gases is intricately linked to the diverse sink and source processes, surface fluxes, and free-troposphere transport. Within the canopy, several interactions unfold among soil, atmosphere, and plants, shaping the overall dynamics. Also, the mixing ratio of biogenic VOCs (BVOCs) clearly varied with rainfall, driven by factors such as light, temperature, physical transport, and soil processes. Our results disentangle the patterns in the trace gas mixing ratio in the course of sudden and vigorous atmospheric mixing during rainfall events. By selectively uncovering processes that are not clearly detectable under undisturbed conditions, our results contribute to a better understanding of the trace gas life cycle and its interplay with meteorology, cloud dynamics, and rainfall in the Amazon.

Abstract. The wet-season atmosphere in the central Amazon resembles natural conditions with minimal anthropogenic influence, making it one of the rare preindustrial-like continental areas worldwide. Previous long-term studies have analyzed the properties and sources of the natural Amazonian background aerosol. However, the vertical profile of the planetary boundary layer (PBL) has not been assessed systematically. Since 2017, such a profile assessment has been possible with the 325 m high tower at the Amazon Tall Tower Observatory (ATTO), located in a largely untouched primary forest in the central Amazon. This study investigates the variability of submicrometer aerosol concentration, size distribution, and optical properties at 60 and 325 m in the Amazonian PBL. The results show significant differences in aerosol volumes and scattering coefficients in the vertical gradient. The aerosol population was well-mixed throughout the boundary layer during the daytime but became separated upon stratification during the nighttime. We also found a significant difference in the spectral dependence of the scattering coefficients between the two heights. The analysis of downdrafts and the related rainfall revealed changes in the aerosol populations before and after rain events, with absorption and scattering coefficients decreasing as optically active particles are removed by wet deposition. The recovery of absorption and scattering coefficients is faster at 325 m than at 60 m. Convective events were concomitant with rapid increases in the concentrations of sub-50 nm particles, which were likely associated with downdrafts. We found that the aerosol population near the canopy had a significantly higher mass scattering efficiency than at 325 m. There was also a clear spectral dependence, with values for λ=450, 525, and 635 nm of 7.74±0.12, 5.49±0.11, and 4.15±0.11 m2 g−1, respectively, at 60 m, while at 325 m the values were 5.26±0.06, 3.76±0.05, and 2.46±0.04 m2 g−1, respectively. The equivalent aerosol refractive index results, which were obtained for the first time for the wet season in the central Amazon, show slightly higher scattering (real) components at 60 m compared to 325 m of 1.33 and 1.27, respectively. In contrast, the refractive index's absorptive (imaginary) component was identical for both heights, at 0.006. This study shows that the aerosol physical properties at 60 and 325 m are different, likely due to aging processes, and strongly depend on the photochemistry, PBL dynamics, and aerosol sources. These findings provide valuable insights into the impact of aerosols on climate and radiative balance and can be used to improve the representation of aerosols in global climate models.

The climate effects of atmospheric aerosol particles serving as cloud condensation nuclei (CCN) depend on chemical composition and hygroscopicity, which are highly variable on spatial and temporal scales. Here we present global CCN measurements, covering diverse environments from pristine to highly polluted conditions. We show that the effective aerosol hygroscopicity, κ, can be derived accurately from the fine aerosol mass fractions of organic particulate matter (ϵorg) and inorganic ions (ϵinorg) through a linear combination, κ = ϵorg ⋅ κorg + ϵinorg ⋅ κinorg. In spite of the chemical complexity of organic matter, its hygroscopicity is well captured and represented by a global average value of κorg = 0.12 ± 0.02 with κinorg = 0.63 ± 0.01 as the corresponding value for inorganic ions. By showing that the sensitivity of global climate forcing to changes in κorg and κinorg is small, we constrain a critically important aspect of global climate modelling.

AbstractSmoke from vegetation fires affects air quality, atmospheric cycling, and the climate in the Amazon rain forest. A major unknown has remained the quantity of long-range transported smoke from Africa in relation to local and regional fire emissions. Here we quantify the abundance, seasonality, and properties of African smoke in central Amazonia. We show that it accounts for ~ 60% of the black carbon concentrations during the wet season and ~ 30% during the dry season. The African smoke influences aerosol-radiation interactions across the entire Amazon, with the strongest impact on the vulnerable eastern basin, a hot spot of climate and land use change. Our findings further suggest that the direct influence of African smoke has been historically relevant for soil fertilization, the carbon and water cycles, and, thus, the development of the Amazon forest ecosystem, even in the pre-industrial era.

Abstract. The number concentration and properties of aerosol particles serving ascloud condensation nuclei (CCN) are important for understanding cloudproperties, including in the tropical Atlantic marine boundary layer (MBL), where marine cumulus clouds reflect incoming solar radiation and obscure thelow-albedo ocean surface. Studies linking aerosol source, composition, andwater uptake properties in this region have been conducted primarily duringthe summertime dust transport season, despite the region receiving a varietyof aerosol particle types throughout the year. In this study, we comparesize-resolved aerosol chemical composition data to the hygroscopicityparameter κ derived from size-resolved CCN measurements made duringthe Elucidating the Role of Clouds–Circulation Coupling in Climate (EUREC4A) and Atlantic Tradewind Ocean-Atmosphere Mesoscale Interaction Campaign (ATOMIC) campaigns from January to February 2020. Weobserved unexpected periods of wintertime long-range transport of Africansmoke and dust to Barbados. During these periods, the accumulation-mode aerosol particle and CCN number concentrations as well as the proportions ofdust and smoke particles increased, whereas the average κ slightlydecreased (κ=0.46±0.10) from marine backgroundconditions (κ=0.52±0.09) when the submicron particles were mostly composed of marine organics and sulfate. Size-resolved chemicalanalysis shows that smoke particles were the major contributor to theaccumulation mode during long-range transport events, indicating that smokeis mainly responsible for the observed increase in CCN numberconcentrations. Earlier studies conducted at Barbados have mostly focused onthe role of dust on CCN, but our results show that aerosol hygroscopicity and CCN number concentrations during wintertime long-range transport events over the tropical North Atlantic are also affected by African smoke. Ourfindings highlight the importance of African smoke for atmospheric processesand cloud formation over the Caribbean.

Abstract. Nucleation and condensation associated with biogenicvolatile organic compounds (BVOCs) are important aerosol formation pathways,yet their contribution to the upper-tropospheric aerosols remainsinconclusive, hindering the understanding of aerosol climate effects. Here,we develop new schemes describing these organic aerosol formation processesin the WRF-Chem model and investigate their impact on the abundance of cloudcondensation nuclei (CCN) in the upper troposphere (UT) over the AmazonBasin. We find that the new schemes significantly increase the simulated CCNnumber concentrations in the UT (e.g., up to ∼ 400 cm−3at 0.52 % supersaturation) and greatly improve the agreement with theaircraft observations. Organic condensation enhances the simulated CCNconcentration by 90 % through promoting particle growth, while organicnucleation, by replenishing new particles, contributes an additional 14 %.Deep convection determines the rate of these organic aerosol formationprocesses in the UT through controlling the upward transport of biogenicprecursors (i.e., BVOCs). This finding emphasizes the importance of thebiosphere–atmosphere coupling in regulating upper-tropospheric aerosolconcentrations over the tropical forest and calls for attention to itspotential role in anthropogenic climate change.

Air pollution is a major risk factor for human health. Chemical reactions in the epithelial lining fluid (ELF) of the human respiratory tract result in the formation of reactive oxygen species (ROS), which can lead to oxidative stress and adverse health effects. We use kinetic modeling to quantify the effects of fine particulate matter (PM2.5), ozone (O3), and nitrogen dioxide (NO2) on ROS formation, interconversion, and reactivity, and discuss different chemical metrics for oxidative stress, such as cumulative production of ROS and hydrogen peroxide (H2O2) to hydroxyl radical (OH) conversion. All three air pollutants produce ROS that accumulate in the ELF as H2O2, which serves as reservoir for radical species. At low PM2.5 concentrations (10 μg m-3), however, Fenton chemistry overwhelms the ROS buffering effect and leads to a tipping point in H2O2 fate, causing a strong nonlinear increase in OH production. This shift in ROS chemistry and the enhanced OH production provide a tentative mechanistic explanation for how the inhalation of PM2.5 induces oxidative stress and adverse health effects.

Airborne transmission by droplets and aerosols is important for the spread of viruses. Face masks are a well-established preventive measure, but their effectiveness for mitigating SARS-CoV-2 transmission is still under debate. We show that variations in mask efficacy can be explained by different regimes of virus abundance and related to population-average infection probability and reproduction number. For SARS-CoV-2, the viral load of infectious individuals can vary by orders of magnitude. We find that most environments and contacts are under conditions of low virus abundance (virus-limited) where surgical masks are effective at preventing virus spread. More advanced masks and other protective equipment are required in potentially virus-rich indoor environments including medical centers and hospitals. Masks are particularly effective in combination with other preventive measures like ventilation and distancing.

Low clouds play a key role in the Earth-atmosphere energy balance and influence agricultural production and solar-power generation. Smoke aloft has been found to enhance marine stratocumulus through aerosol-cloud interactions, but its role in regions with strong human activities and complex monsoon circulation remains unclear. Here we show that biomass burning aerosols aloft strongly increase the low cloud coverage over both land and ocean in subtropical southeastern Asia. The degree of this enhancement and its spatial extent are comparable to that in the Southeast Atlantic, even though the total biomass burning emissions in Southeast Asia are only one-fifth of those in Southern Africa. We find that a synergetic effect of aerosol-cloud-boundary layer interaction with the monsoon is the main reason for the strong semi-direct effect and enhanced low cloud formation in southeastern Asia.

Wildfires inject large amounts of black carbon (BC) particles into the atmosphere, which can reach the lowermost stratosphere (LMS) and cause strong radiative forcing. During a 14-month period of observations on board a passenger aircraft flying between Europe and North America, we found frequent and widespread biomass burning (BB) plumes, influencing 16 of 160 flight hours in the LMS. The average BC mass concentrations in these plumes (∼140 ng·m-3, standard temperature and pressure) were over 20 times higher than the background concentration (∼6 ng·m-3) with more than 100-fold enhanced peak values (up to ∼720 ng·m-3). In the LMS, nearly all BC particles were covered with a thick coating. The average mass equivalent diameter of the BC particle cores was ∼120 nm with a mean coating thickness of ∼150 nm in the BB plume and ∼90 nm with a coating of ∼125 nm in the background. In a BB plume that was encountered twice, we also found a high diameter growth rate of ∼1 nm·h-1 due to the BC particle coatings. The observed high concentrations and thick coatings of BC particles demonstrate that wildfires can induce strong local heating in the LMS and may have a significant influence on the regional radiative forcing of climate.

Reactive oxygen species (ROS) play a central role in adverse health effects of air pollutants. Respiratory deposition of fine air particulate matter can lead to the formation of ROS in epithelial lining fluid, potentially causing oxidative stress and inflammation. Secondary organic aerosols (SOA) account for a large fraction of fine particulate matter, but their role in adverse health effects is unclear. Here, we quantify and compare the ROS yields and oxidative potential of isoprene, β-pinene, and naphthalene SOA in water and surrogate lung fluid (SLF). In pure water, isoprene and β-pinene SOA were found to produce mainly OH and organic radicals, whereas naphthalene SOA produced mainly H2O2 and O2•-. The total molar yields of ROS of isoprene and β-pinene SOA were 11.8% and 8.2% in water and decreased to 8.5% and 5.2% in SLF, which can be attributed to ROS removal by lung antioxidants. A positive correlation between the total peroxide concentration and ROS yield suggests that organic (hydro)peroxides may play an important role in ROS formation from biogenic SOA. The total molar ROS yields of naphthalene SOA was 1.7% in water and increased to 11.3% in SLF. This strong increase is likely due to redox reaction cycles involving environmentally persistent free radicals (EPFR) or semiquinones, antioxidants, and oxygen, which may promote the formation of H2O2 and the adverse health effects of anthropogenic SOA from aromatic precursors.

Polycyclic aromatic hydrocarbons like benzo(a)pyrene (BaP) in atmospheric particulate matter pose a threat to human health because of their high carcinogenicity. In the atmosphere, BaP is mainly degraded through a multiphase reaction with ozone, but the fate and atmospheric transport of BaP are poorly characterized. Earlier modeling studies used reaction rate coefficients determined in laboratory experiments at room temperature, which may overestimate/underestimate degradation rates when applied under atmospheric conditions. Moreover, the effects of diffusion on the particle bulk are not well constrained, leading to large discrepancies between model results and observations. We show how regional and global distributions and transport of BaP can be explained by a new kinetic scheme that provides a realistic description of the temperature and humidity dependence of phase state, diffusivity, and reactivity of BaP-containing particles. Low temperature and humidity can substantially increase the lifetime of BaP and enhance its atmospheric dispersion through both the planetary boundary layer and the free troposphere. The new scheme greatly improves the performance of multiscale models, leading to better agreement with observed BaP concentrations in both source regions and remote regions (Arctic), which cannot be achieved by less-elaborate degradation schemes (deviations by multiple orders of magnitude). Our results highlight the importance of considering temperature and humidity effects on both the phase state of aerosol particles and the chemical reactivity of particulate air pollutants.

Terbuthylazine (TBA) is a widely used herbicide, and its heterogeneous reaction with OH radicals is important for assessing its potential to undergo atmospheric long-range transport and to affect the environment and public health. The apparent reaction rate coefficients obtained in different experimental investigations, however, vary by orders of magnitude depending on the applied experimental techniques and conditions. In this study, we used a kinetic multilayer model of aerosol chemistry with reversible surface adsorption and bulk diffusion (KM-SUB) in combination with a Monte Carlo genetic algorithm to simulate the measured decay rates of TBA. Two experimental data sets available from different studies can be described with a consistent set of kinetic parameters resolving the interplay of chemical reaction, mass transport, and shielding effects. Our study suggests that mass transport and shielding effects can substantially extend the atmospheric lifetime of reactive pesticides from a few days to weeks, with strong implications for long-range transport and potential health effects of these substances.

The allergenic potential of airborne proteins may be enhanced via post-translational modification induced by air pollutants like ozone (O3) and nitrogen dioxide (NO2). The molecular mechanisms and kinetics of the chemical modifications that enhance the allergenicity of proteins, however, are still not fully understood. Here, protein tyrosine nitration and oligomerization upon simultaneous exposure of O3 and NO2 were studied in coated-wall flow-tube and bulk solution experiments under varying atmospherically relevant conditions (5-200 ppb O3, 5-200 ppb NO2, 45-96% RH), using bovine serum albumin as a model protein. Generally, more tyrosine residues were found to react via the nitration pathway than via the oligomerization pathway. Depending on reaction conditions, oligomer mass fractions and nitration degrees were in the ranges of 2.5-25% and 0.5-7%, respectively. The experimental results were well reproduced by the kinetic multilayer model of aerosol surface and bulk chemistry (KM-SUB). The extent of nitration and oligomerization strongly depends on relative humidity (RH) due to moisture-induced phase transition of proteins, highlighting the importance of cloud processing conditions for accelerated protein chemistry. Dimeric and nitrated species were major products in the liquid phase, while protein oligomerization was observed to a greater extent for the solid and semi-solid phase states of proteins. Our results show that the rate of both processes was sensitive towards ambient ozone concentration, but rather insensitive towards different NO2 levels. An increase of tropospheric ozone concentrations in the Anthropocene may thus promote pro-allergic protein modifications and contribute to the observed increase of allergies over the past decades.

Mineral dust and secondary organic aerosols (SOA) account for a major fraction of atmospheric particulate matter, affecting climate, air quality and public health. How mineral dust interacts with SOA to influence cloud chemistry and public health, however, is not well understood. Here, we investigated the formation of reactive oxygen species (ROS), which are key species of atmospheric and physiological chemistry, in aqueous mixtures of SOA and mineral dust by applying electron paramagnetic resonance (EPR) spectrometry in combination with a spin-trapping technique, liquid chromatography-tandem mass spectrometry (LC-MS/MS), and a kinetic model. We found that substantial amounts of ROS including OH, superoxide as well as carbon- and oxygen-centred organic radicals can be formed in aqueous mixtures of isoprene, α-pinene, naphthalene SOA and various kinds of mineral dust (ripidolite, montmorillonite, kaolinite, palygorskite, and Saharan dust). The molar yields of total radicals were ∼0.02-0.5% at 295 K, which showed higher values at 310 K, upon 254 nm UV exposure, and under low pH (

Secondary organic aerosols (SOA) are a large source of uncertainty in our current understanding of climate change and air pollution. The phase state of SOA is important for quantifying their effects on climate and air quality, but its global distribution is poorly characterized. We developed a method to estimate glass transition temperatures based on the molar mass and molecular O:C ratio of SOA components, and we used the global chemistry climate model EMAC with the organic aerosol module ORACLE to predict the phase state of atmospheric SOA. For the planetary boundary layer, global simulations indicate that SOA are mostly liquid in tropical and polar air with high relative humidity, semi-solid in the mid-latitudes and solid over dry lands. We find that in the middle and upper troposphere SOA should be mostly in a glassy solid phase state. Thus, slow diffusion of water, oxidants and organic molecules could kinetically limit gas-particle interactions of SOA in the free and upper troposphere, promote ice nucleation and facilitate long-range transport of reactive and toxic organic pollutants embedded in SOA.

Air pollution and climate change are potential drivers for the increasing burden of allergic diseases. The molecular mechanisms by which air pollutants and climate parameters may influence allergic diseases, however, are complex and elusive. This article provides an overview of physical, chemical and biological interactions between air pollution, climate change, allergens, adjuvants and the immune system, addressing how these interactions may promote the development of allergies. We reviewed and synthesized key findings from atmospheric, climate, and biomedical research. The current state of knowledge, open questions, and future research perspectives are outlined and discussed. The Anthropocene, as the present era of globally pervasive anthropogenic influence on planet Earth and, thus, on the human environment, is characterized by a strong increase of carbon dioxide, ozone, nitrogen oxides, and combustion- or traffic-related particulate matter in the atmosphere. These environmental factors can enhance the abundance and induce chemical modifications of allergens, increase oxidative stress in the human body, and skew the immune system toward allergic reactions. In particular, air pollutants can act as adjuvants and alter the immunogenicity of allergenic proteins, while climate change affects the atmospheric abundance and human exposure to bioaerosols and aeroallergens. To fully understand and effectively mitigate the adverse effects of air pollution and climate change on allergic diseases, several challenges remain to be resolved. Among these are the identification and quantification of immunochemical reaction pathways involving allergens and adjuvants under relevant environmental and physiological conditions.

Hydroxyl radical-induced oxidation of proteins and peptides can lead to the cleavage of the peptide, leading to a release of fragments. Here, we used high-performance liquid chromatography tandem mass spectrometry (HPLC-MS/MS) and pre-column online ortho-phthalaldehyde (OPA) derivatization-based amino acid analysis by HPLC with diode array detection and fluorescence detection to identify and quantify free amino acids released upon oxidation of proteins and peptides by hydroxyl radicals. Bovine serum albumin (BSA), ovalbumin (OVA) as model proteins, and synthetic tripeptides (comprised of varying compositions of the amino acids Gly, Ala, Ser, and Met) were used for reactions with hydroxyl radicals, which were generated by the Fenton reaction of iron ions and hydrogen peroxide. The molar yields of free glycine, aspartic acid, asparagine, and alanine per peptide or protein varied between 4 and 55%. For protein oxidation reactions, the molar yields of Gly (∼32-55% for BSA, ∼10-21% for OVA) were substantially higher than those for the other identified amino acids (∼5-12% for BSA, ∼4-6% for OVA). Upon oxidation of tripeptides with Gly in C-terminal, mid-chain, or N-terminal positions, Gly was preferentially released when it was located at the C-terminal site. Overall, we observe evidence for a site-selective formation of free amino acids in the OH radical-induced oxidation of peptides and proteins, which may be due to a reaction pathway involving nitrogen-centered radicals.

Polycyclic aromatic hydrocarbons (PAHs) are hazardous pollutants, with increasing emissions in pace with economic development in East Asia, but their distribution and fate in the atmosphere are not yet well understood. We extended the regional atmospheric chemistry model WRF-Chem (Weather Research Forecast model with Chemistry module) to comprehensively study the atmospheric distribution and the fate of low-concentration, slowly degrading semivolatile compounds. The WRF-Chem-PAH model reflects the state-of-the-art understanding of current PAHs studies with several new or updated features. It was applied for PAHs covering a wide range of volatility and hydrophobicity, i.e. phenanthrene, chrysene and benzo[a]pyrene, in East Asia. Temporally highly resolved PAH concentrations and particulate mass fractions were evaluated against observations. The WRF-Chem-PAH model is able to reasonably well simulate the concentration levels and particulate mass fractions of PAHs near the sources and at a remote outflow region of East Asia, in high spatial and temporal resolutions. Sensitivity study shows that the heterogeneous reaction with ozone and the homogeneous reaction with the nitrate radical significantly influence the fate and distributions of PAHs. The methods to implement new species and to correct the transport problems can be applied to other newly implemented species in WRF-Chem.

Air pollution can cause oxidative stress and adverse health effects such as asthma and other respiratory diseases, but the underlying chemical processes are not well characterized. Here we present chemical exposure-response relations between ambient concentrations of air pollutants and the production rates and concentrations of reactive oxygen species (ROS) in the epithelial lining fluid (ELF) of the human respiratory tract. In highly polluted environments, fine particulate matter (PM2.5) containing redox-active transition metals, quinones, and secondary organic aerosols can increase ROS concentrations in the ELF to levels characteristic for respiratory diseases. Ambient ozone readily saturates the ELF and can enhance oxidative stress by depleting antioxidants and surfactants. Chemical exposure-response relations provide a quantitative basis for assessing the relative importance of specific air pollutants in different regions of the world, showing that aerosol-induced epithelial ROS levels in polluted megacity air can be several orders of magnitude higher than in pristine rainforest air.